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
  • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
  • G03C7/3335—Coloured coupling substances, e.g. for the correction of the coloured image containing an azo chromophore
• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/30—Hardeners

Definitions

• This invention relates to a light-sensitive silver halide color photographic material, more specifically to a light-sensitive silver halide color photographic material in which less fog occurs, processing fluctuation is small and also fluctuation between printers is small.
• the respective yellow, magenta and cyan dyes formed from couplers do not always have ideal absorption characteristics.
• a magenta dye generally absorbs blue light slightly in addition to green light which should be absorbed thereby, so that distortion of color reproducibility occurs.
• a coupler colored in yellow or magenta has been used before coupling reaction with an oxidized product of an aromatic primary amine color developing agent.
• the former coupler is the so-called colored magenta coupler
• the latter is the so-called colored cyan coupler.
• these colored magenta couplers have various problems that a large amount is required to be added due to small molar absorption coefficient, it is difficult to set their main absorptions to a preferred range, an masking effect is small due to low development activity, development activity is high but fog occurs easily, further, stability relative to light, heat or humidity is low, and a magenta dye formed by reacting with a color developing agent has short wavelength.
• these couplers are not satisfactory, and under the present situation, their characteristics are maintained somehow by using several couplers in combination.
• a high sensitivity fine particle silver halide emulsion and a high color forming magenta coupler have been used, so that characteristics required to a colored magenta coupler have been heightened to a great extent.
• processing fluctuation The fluctuation between printers has been greatly improved by using a colored magenta coupler disclosed in Japanese Provisional Patent Publication No. 16939/1992.
• fog is increased when said colored magenta coupler is used, and when a light-sensitive material is subjected to exposure and then color development processing, fluctuation of photographic characteristics (hereinafter referred to as "processing fluctuation") is increased due to change of conditions such as concentration, temperature and pH of a color developing agent in a color developing solution.
• An object of the present invention is to provide a light-sensitive silver halide color photographic material in which less fog occurs, processing fluctuation is small and also fluctuation between printers is small.
• the above object of the present invention can be accomplished by the following light-sensitive silver halide color photographic material.
• a light-sensitive silver halide color photographic material having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, characterized in that at least one green-sensitive silver halide emulsion layer contains at least one colored magenta coupler represented by the following formula (CM - I), and at least one photographic constituent layer contains at least one vinyl sulfone type hardener, wherein R1 represents a substituent; R2 represents an acylamino group, a sulfonamide group, an imide group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group or an alkoxycarbonylamino group; R3 represents a halogen atom or an alkoxy group; m represents an integer of 0 to 5; and n represents an integer of 0 to 4.
• R1 As the substituent represented by R1, there may be mentioned, for example, an alkyl group, an alkoxy group, an aryl group, an acylamino group, a sulfonamide group, a hydroxyl group, a halogen atom, an alkoxycarbonyl group, an acyl group, an carbamoyl group, a sulfamoyl group and a carboxyl group, and these groups may further have a substituent(s).
• R1 is preferably an alkyl group, an alkoxy group, a hydroxyl group or an acylamino group, most preferably an alkoxy group.
• the acylamino group represented by R2 may include, for example, a 2,4-di-t-pentylphenoxyacetamide group and a 4-(2,4-di-t-pentylphenoxy)butanamide group; the sulfonamide group, for example, a 4-dodecyloxyphenylsulfonamide group; the imide group, for example, an oxtadecenylsuccinimide group; the carbamoyl group, for example, a 4-(2,4-di-t-pentylphenoxy)butylaminocarbonyl group; the sulfamoyl group, for example, a tetradecanesulfamoyl group; the alkoxy group, for example, a methoxy group, an ethoxy group and an octyloxy group; the alkoxycarbonyl group, for example, a tetradecanoxycarbonyl group; and the alkoxy
• the halogen atom represented by R3 may include, for example, a chlorine atom, a bromine atom and a fluorine atom, and the alkoxy group may include, for example, a methoxy group and a dodecyloxy group.
• R3 is preferably a chlorine atom.
• m is preferably 1 or 2, and n is preferably 1.
• An amount of the colored magenta coupler of the present invention is preferably 0.01 to 1.0 g/m2, more preferably 0.03 to 0.3 g/m2 based on a light-sensitive material.
• the colored magenta coupler represented by the formula (CM - I) of the present invention can be generally synthesized by the so-called diazo coupling reaction which has been conventionally carried out, for example, a method disclosed in Japanese Patent Publication No. 6540/1971. That is, a desired colored coupler can be obtained by diazotizing an aniline derivative at 0 to - 10 °C in water, hydrated alcohol or hydrated acetone by using 1 to 5-fold moles of conc.
• the colored magenta coupler represented by the above formula (CM - I) of the present invention may be used alone or in combination of two or more kinds. In general, based on the principle of automasking, at least one magenta coupler which is substantially colorless is used in combination.
• the vinyl sulfone type hardener to be used in the present invention includes, for example, aromatic compounds as described in German Patent No. 11 00 942 and U.S. Patent No. 3,490,911; alkyl compounds bonded by hetero atoms as described in Japanese Patent Publications No. 29622/1969, No. 25373/1972 and No. 24259/1972; sulfonamide and ester type compounds as described in Japanese Patent Publication No. 8736/1972; 1,3,5-tris[ ⁇ -(vinylsulfonyl)-propionyl]hexahydro-s-triazine as described in Japanese Provisional Patent Publication No. 24435/1974; alkyl type compounds as described in Japanese Patent Publication No. 35807/1975 and Japanese Provisional Patent Publication No. 44164/1976; and compounds as described in Japanese Provisional Patent Publication No. 18944/1984.
• the vinyl sulfone type hardener preferably used in the present invention is represented by the following formula (H - I) L ( ⁇ SO2 - X) m
• n represents an integer of 2 to 10, more preferably 2 to 6.
• the m-valent linking group L may include, for example, an alkylene group, an arylene group or an m-valent group formed by combining these groups with at least one bond represented by -O-, -N(R1)-, -CO-, -SO-, -SO2-, -SO3-, -SO2N(R1)-, -COO-, -CON(R1)-, -N(R1)CON(R1)- and -N(-R1)CO2-, where R1 represents a hydrogen atom, an alkyl group or an aralkyl group each having 1 to 15 carbon atoms.
• R1s may be bonded to each other to form a ring.
• L may have a substituent(s), and examples of the substituent include a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group and an aryl group.
• the substituent may be further substituted by at least one group represented by X3-SO2-.
• X3 has the same meaning as X described above.
• a to v each represent an integer of 1 to 6, and only d may be 0.
• d, k, l and p are preferably 1 to 3, and a to v except for the above d, k, l and p are preferably 1 or 2.
• R1 is preferably hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly preferably hydrogen atom, a methyl group and an ethyl group.
• X may include, for example, the following.
• vinyl sulfone type hardeners are dissolved in water or in an organic solvent, and used in an amount of 0.005 to 20 % by weight, preferably 0.02 to 10 % by weight based on gelatin.
• the hardeners are added to a photographic layer by employing a batch system or an in-line addition system.
• the photographic layer to which these hardeners are added is not particularly limited, and for example, the object of the present invention can be accomplished even by adding the hardener to only one layer of the uppermost layer or the lowermost layer, or all the layers.
• the above hardeners have excellent diffusion property in photographic constituent layers. Thus, when all photographic constituent layers are coated simultaneously, even if the hardeners are added to any constituent layer to be coated simultaneously, the hardeners are diffused to almost all the layers of the photographic constituent layers to be coated simultaneously before hardening property is exhibited or while exhibiting hardening property, whereby all layers can be finally hardened almost uniformly.
• silver halide of the silver halide emulsion to be used in the light-sensitive silver halide photographic material of the present invention there may be used any silver halide used in a general silver halide emulsion using silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride.
• the silver halide grain to be used in the silver halide emulsion may be either a grain having a uniform distribution of a silver halide composition in the grain or a grain having a layered structure in which an inner portion and a surface layer have different silver halide compositions with each other.
• the silver halide grain may be either a grain of the type in which a latent image is mainly formed on a surface thereof or a grain of the type in which a latent image is mainly formed internally of the grain.
• the silver halide emulsion may have any grain size distribution. There may be used an emulsion having a wide grain size distribution (called “a polydispersed emulsion”) or an emulsion having a narrow grain size distribution (called “a monodispersed emulsion”) alone or in combination of several kinds thereof. Further, a mixture of a polydispersed emulsion and a monodispersed emulsion may be used.
• a polydispersed emulsion emulsion having a wide grain size distribution
• a monodispersed emulsion emulsion having a narrow grain size distribution
• a mixture of a polydispersed emulsion and a monodispersed emulsion may be used.
• silver halide emulsion there may be used a mixture of two or more kinds of silver halide emulsions prepared separately.
• the silver halide grain to be used in the present invention can be chemically sensitized by a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method and a noble metal sensitization method.
• the silver halide grains other than the silver halide grains spectrally sensitized by using a combination of the light-sensitive dyes of the present invention can be spectrally sensitized to a desired wavelength region by using a dye which has been known as a sensitizing dye in the photographic field.
• an antifoggant and a stabilizer may be added.
• gelatin As a binder (or protective colloid) to be used in the emulsion and others of the light-sensitive silver halide photographic material of !he present invention, gelatin is advantageously used.
• gelatin derivative a graft polymer of gelatin and other polymer, a protein, a sugar derivative, a cellulose derivative and a hydrophilic colloid including a synthetic hydrophilic polymer substance such as a homo- or copolymer.
• the photographic emulsion layer and other hydrophilic colloidal layers of the light-sensitive silver halide photographic material of the present invention can be hardened by crosslinking binder (or protective colloid) molecules and using a hardener for enhancing film strength alone or in combination thereof.
• a plasticizer or a dispersion (latex) of a synthetic polymer insoluble or difficultly soluble in water may be contained.
• a coupler may be used. Further, there may be used a competitive coupler having an color correction effect, and a compound which releases a photographically useful fragment such as a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a color adjusting agent, a hardener, a fogging agent, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer by coupling with an oxidized product of a color developing agent.
• a development accelerator a bleaching accelerator, a developer, a silver halide solvent, a color adjusting agent, a hardener, a fogging agent, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer by coupling with an oxidized product of a color developing agent.
• acylacetanilide type couplers may be preferably used. Among them, benzoylacetanilide type and pivaloylacetanilide type compounds are advantageous.
• magenta dye-forming coupler there may be used a 5-pyrazolone type coupler, a pyrazoloazole type coupler, a pyrazolobenzimidazole type coupler, an open chain acylacetonitrile type coupler and an indazole type coupler.
• a phenol or naphthol type coupler is generally used as a cyan dye-forming coupler.
• a coupler is incorporated into the light-sensitive material, known techniques used for conventional couplers may be applied. It is preferred that the coupler is dissolved in a high boiling point solvent, if necessary, in combination with a low boiling point solvent, dispersed in the form of fine grains, and added to the silver halide emulsion according to the present invention.
• a hydroquinone derivative, a UV absorber and an antifading agent may be used in combination without any problem.
• auxiliary layers such as a filter layer, an antihalation layer and an antiirradiation layer may be provided.
• a dye which flows out from the light-sensitive material during development processing, or bleached may be contained.
• a matting agent e.g., a lubricant, an image stabilizer, a UV absorber, a fluorescent brightener, a surfactant, a development accelerator, a development retarder and a bleaching accelerator.
• the photographic emulsion layer and other layers of the light-sensitive silver halide photographic material of the present invention may be provided on a baryta paper, a paper on which an ⁇ -olefin polymer is laminated, a paper support in which an ⁇ -olefin layer and the paper support are easily peeled off, a flexible reflective support such as a synthetic paper, a film comprising a semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, a reflective support on which a white pigment is coated, and a rigid material such as glass, metal and ceramics. Or else, they may be provided on a thin type reflective support having a thickness of 120 to 160 ⁇ m.
• the light-sensitive silver halide photographic material of the present invention contains a coupler
• generally known color photographic processings are carried out after exposure in order to obtain a dye image.
• the light-sensitive material may be processed immediately after color development by using a processing solution having bleaching ability and a processing solution having fixing ability, but may be processed by using a processing solution having bleaching ability and fixing ability (the so-called bleach-fixing solution).
• a processing solution having bleaching ability and fixing ability the so-called bleach-fixing solution.
• a bleaching agent to be used for said bleaching a metal complex salt of an organic acid is used.
• washing processing is generally carried out. Further, a stabilizing processing substitute for washing processing may be carried out, and both processing steps may be carried out in combination.
• Amounts in the multilayer light-sensitive color photographic material are represented by gram per 1 m2 of the light-sensitive material unless otherwise indicated. Further, silver halide and colloidal silver are represented by calculating them or. silver. Amounts of sensitizing dyes are represented by a molar number per mole of silver.
• Second layer antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling point solvent (Oil-1) 0.20 High boiling point solvent (Oil-2) 0.20 Gelatin 1.6
• Second layer intermediate layer (IL-1) Hardener (HH - 1) 0.09 Gelatin 1.3
• Third layer low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.4 Silver iodobromide emulsion (Em-2) 0.3 Sensitizing dye (S-1) 3.2 x 10 ⁇ 4 Sensitizing dye (S-2) 3.2 x 10 ⁇ 4 Sensitizing dye (S-3) 0.2 x 10 ⁇ 4 Cyan coupler (C-1) 0.50 Cyan coupler (C-2) 0.13 Colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.01 High boiling point solvent (Oil-1) 0.55 Gelatin 1.0
• a coating aid SU-2 a dispersing aid SU-1, and dyes AI-1 and AI-2 were suitably added to the respective layers.
• emulsions used in the above samples are shown below, all of which are monodispersed emulsions having high iodine content in inner portions.
• Samples 2 to 18 were prepared in the same manner as in Sample 1 except for changing the colored magenta coupler CM-A in the sixth layer and the seventh layer and the hardener HH-1 in the second layer, the fifth layer, the eighth layer and the eleventh layer to the same amounts of the compounds shown in Table 1, respectively.
• the processing solutions used in the respective processing steps had the following compositions.
• ⁇ Color developing solution> 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)-aniline ⁇ sultate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine ⁇ 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid ⁇ trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g made up to one liter with addition of water (pH 10.05).
• Print samples 1A to 18A were so prepared using Printer A that a gray portion of the color checker became gray with a reflectance of 18 %.
• Print samples 1B to 18B were prepared under the same conditions as in the case of using Printer A, and fluctuation between different printers were judged visually.
• Samples 1 to 18 were subjected to exposure with white light through step wedge for sensitometry, and then processed according to Processing A described above. Thereafter, the samples were measured by using green light to evaluate fog and sensitivity. The sensitivity was determined by a reciprocal of an exposure amount necessary for giving a density of fog + 0.3, and represented by a relative value when the value of Sample 1 was determined as 100. Further, the respective samples were subjected to exposure with white light through step wedge for sensitometry, and then processed in the same manner as in the above Processing A except for changing pH of the color developing solution in the above Processing A to 10.20 (hereinafter referred to as "Processing B") whereby increase of fog was compared with that in Processing A. The results are all shown in Table 1.
• a light-sensitive silver halide color photographic material in which less fog occurs, processing fluctuation is small and also fluctuation between printers is small can be provided.

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• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
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• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (1)

• 1991
  • 1991-08-29 JP JP24452791A patent/JPH0561163A/ja active Pending
• 1992
  • 1992-08-28 EP EP92307859A patent/EP0530039A1/fr not_active Withdrawn

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