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
  • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density

Definitions

• This invention relates to a process of forming silver halide color photographic images and particularly to a process of forming silver halide color photographic images excellent in color-hue reproduction.
• IIE spectral photosensitivity distribution and interimage effect
• a development inhibitor is released from a compound which produces imagewise development inhibitor upon reacting with the oxidized products of a developing agent (that is so-called a DIR compound) or a precursor thereof and thereby the developments of other color-sensitive layers can be inhibited by the resulting development inhibitor, so that an IIE can be produced to display the improvement effects of the color reproduction.
• the above-mentioned technique can contribute mainly to the improvements of the color purity among the color reproducibilities.
• the above-mentioned DIR compounds have also had a defect that a color hue may be varied if the magnitude and range of interimage action thereof cannot be well-controlled, though it can make a color purity higher.
• Japanese Patent Examined Publication No. 49-6207/1974 discloses a technique that the spectral photosensitivity distribution of blue-sensitive and red-sensitive silver halide emulsion layers (hereinafter abbreviated to a blue-sensitive and red-sensitive layers, respectively) are put close to that of a green-sensitive layer so as to reduce the color reproduction variations caused by a difference of light sources used for taking-pictures.
• the above-mentioned technique has the following defects; that the technique cannot only be used as a means for improving the colors having the afore-mentioned difficulties in color-hue reproducibility, but also the photosensitivity is seriously lowered; that the color reproducible regions are narrowed because the spectral photosensitivity distributions are overlapped among color-sensitive layers, though the technique can reduce the reproduction variations caused by changes in color-temperature; and, resultingly, that the resulting colors are made dark and dull without reproducing any highly chromatic colors.
• JP OPI Publication Japanese Patent Publication Open to Public Inspection
• JP OPI Publication No. 62-160449/1987
• each of the orientation of IIE is specified for every color-sensitive layer.
• JP OPI Publication No. 62-160448/1987 discloses a technique that a cyan photosensitive layer is so provided as to exert the IIE thereof upon a red-sensitive layer, resulting in the photosensitivity resembling falsewise the spectral photosensitivity of the human eye.
• an IIE color developable layer i.e., a cyan photosensitive layer
• this technique has such a defect as that a silver amount used is increased or that the production cost is made higher, and it cannot be said that the effects of the technique are satisfactory.
• This invention is to solve the above-mentioned problems. It is an object of the invention to provide a silver halide color photographic image-forming process excellent in color reproduction and particularly in skin-color and yellow-color reproduction.
• a silver halide color photographic image-forming process comprising; making a color original image on a silver halide color photographic light sensitive material for taking-picture use comprising a support having thereon a blue-sensitive silver halide emulsion layer (named B-layer), a green-sensitive silver halide emulsion layer (named G-layer) and a red-sensitive silver halide emulsion layer (named R-layer); and printing the color original image resulted from the light sensitive material on a silver halide color photographic light sensitive material for printing use comprising a support having thereon a yellow-dye forming layer (named Y-layer), a magenta-dye forming layer (named M-layer) and a cyan-dye forming layer (named C-layer); wherein both of the B- and Y-layer contain an yellow coupler represented by the following Formula [I]; wherein R1 represents an alkyl, cycloalkyl
• a wavelength ⁇ Bmax capable of giving a maximum sensitivity has a relation of, preferably, 400nm ⁇ ⁇ Bmax ⁇ 470nm and, more preferably, 410nm ⁇ ⁇ Bmax ⁇ 460nm.
• a wavelength ⁇ Gmax capable of giving a maximum sensitivity has a relation of, preferably, 525nm ⁇ ⁇ Gmax ⁇ 560nm.
• the spectral photosensitivity S G 570 at 570nm of the G-layer is, preferably, not more than 40% of the spectral photosensitivity at ⁇ Gmax .
• the skin-color portions of a resulting printed image are pink-like tinted so as to reproduce a preferable skin-color.
• Spectral photosensitivity S G 570 of a G-layer in the above-mentioned 570nm is to be, preferably, not more than 20% and, more preferably, not more than 15%.
• the spectral photosensitivity of a R-layer shall not be limitative, but wavelength ⁇ Rmax capable of giving a maximum photosensitivity has a relation of, preferably, 590nm ⁇ ⁇ Rmax ⁇ 640nm and, more preferably, 600nm ⁇ ⁇ Rmax ⁇ 630nm.
• the spectral photosensitivity of each of B-, G- and R-layers can be selectively obtained by taking any one of the various means.
• These means include, for example, a means for providing a spectral sensitization for a silver halide with a sensitizing dye having an absorption in an intended-wavelength region; another means for providing an objective spectral sensitization upon suitably optimizing the halide composition or distribution of silver halide; and a further means for controlling a spectral photosensitivity distribution so as to meet the objects by making use of a suitable optical absorbent.
• a variety of the well-known spectrally sensitizing dyes can be used.
• these dyes a cyanine dye, a merocyanine dye, a compounded merocyanine dye and so forth are preferably used.
• any well-known silver halides can be used for the silver halides of the photosensitive layers of silver halide color photographic light sensitive materials for taking-picture use.
• the photosensitive silver halides may be preferably comprised of silver iodobromide for use in light sensitive materials for taking-picture use. Besides the silver iodobromide, silver chloroiodobromide, silver bromide, silver chloride and so forth may also be used.
• Y-layer is a blue-sensitive layer
• M-layer is a green-sensitive layer
• C-layer is a red-sensitive layer.
• each of the photosensitive layers is applied with a silver halide emulsion containing silver chlorobromide as the halide composition thereof.
• a silver halide emulsion such as a silver chloride emulsion and a silver chlorobromide emulsion, which contains the halides comprising silver chloride in an average amount of not less than 90 mol%.
• the wavelength capable of giving a maximum value of S Y ( ⁇ ) is to be in a wavelength region within the range of 430nm to 460nm and that the wavelength ⁇ Y 50 is to be within the range of 485nm to 495nm on the longer wavelength side where ⁇ Y 50 corresponds to a wavelength capable of giving 50% of the maximum value of S Y ( ⁇ ).
• the color developing agents applicable to form images include, for example, the well-known aromatic primary amine color developing agents.
• aromatic primary amine color developing agents include, for example, the well-known aromatic primary amine color developing agents.
• a p-phenylene diamine derivative is preferably used for.
• 4-amino-3-methyl-N-ethyl-N-[ ⁇ -(methanesulfonamido)ethyl]-aniline is preferably used in particular.
• the alkyl groups represented by R1 include, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a dodecyl group and so forth.
• the alkyl groups represented by R1 also include those having a substituent.
• the substituents include, for example, a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group and a hydroxyl group.
• the cycloalkyl groups represented by R1 include, for example, a cyclopropyl group, a cyclohexyl group, an adamantyl group and so forth.
• the aryl groups represented by R1 include, for example, a phenyl group.
• the group represented by R1 is preferably, for example, a branched alkyl group.
• the groups preferably represented by R0 include, for example, an aryl group having 6 to 24 carbon atoms (such as a phenyl group, a p-tolyl group, an o-tolyl group and a 4-methoxyphenyl group), an alkoxy group having 1 to 14 carbon atoms (such as a methoxy group, an ethoxy group, a butoxy group, an n-octyloxy group, an n-tetradecyloxy group, a benzyloxy group and a methoxyethoxy group), an aryloxy group having 6 to 24 carbon atoms (such as a phenoxy group, a p-tolyloxy group, an o-tolyloxy group, a p-methoxyphenoxy group, a p-dimethylaminophenoxy group and an m-pentadecylphenoxy group), and a trifluoromethyl group.
• the groups represented by R3 each substitutable to a benzene ring include, for example, a halogen atom (such as a chlorine atom), an alkyl group (such as an ethyl group, an i-propyl group and a t-butyl group), an alkoxy group (such as a methoxy group), an aryloxy group (such as a phenyloxy group), an acyloxy group (such as a methylcarbonyloxy group and a benzoyloxy group), an acylamino group (such as an acetamido group and a phenylcarbonylamino group), a carbamoyl group (such as an N-methylcarbamoyl group and an N-phenylcarbamoyl group), an alkylsulfonamido group (such as an ethylsulfonylamino group), an arylsulfonamido group (such as
• Y1 represents a ballast group, for which the groups represented by the following Formula [II] are preferable.
• R4 represents an organic group comprising a linking group having a carbonyl or sulfonyl group.
• the groups each having a carbonyl group include, for example, an ester group, an amido group, a carbamoyl group, a ureido group, a urethane group and so forth.
• the groups each having a sulfonyl group include, for example, a sulfo group, a sulfonamido group, a sulfamoyl group, an aminosulfonamido group and so forth.
• J represents -N(R5)CO- or -CON(R5)-, in which R5 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
• the alkyl groups represented by R5 include, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a dodecyl group and so forth.
• the aryl groups represented thereby include, for example, a phenyl group, a naphthyl group and so forth.
• the heterocyclic groups represented thereby include, preferably, those each having 5- to 7-membered ring, such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group and so forth.
• the alkyl, aryl or heterocyclic groups each represented by R5 also include those having substituents.
• the substituents shall not be limited, but they include, typically, a halogen atom (such as a chlorine atom and so forth), an alkyl group (such as an ethyl group, a t-butyl group and so forth), an aryl group (such as a phenyl group, a p-methoxyphenyl group, a naphthyl group and so forth), an alkoxy group (such as an ethoxy group, a benzyloxy group and so forth), an aryloxy group (such as a phenoxy group and so forth), an alkylthio group (such as an ethylthio group and so forth), an arylthio group (such as a phenylthio group and so forth), an alkylsulfonyl group (such as a ⁇ -hydroxyethylsulfonyl
• X1 represents a group capable of splitting off upon coupling reaction with the oxidized product of a developing agent.
• the groups are represented by the following Formula [III] or [IV] and, among them, the group represented by Formula [IV] is preferable.
• R6 represents an aryl or heterocyclic group including those each having a substituent.
• Z1 represents the group consisting of non-metal atoms necessary to form a 5- or 6-membered ring upon associating with a nitrogen atom.
• the atomic groups necessary to form the group consisting of non-metal atoms include, for example, those of methylene, methine or substituted methine and those given below. (in which R A is synonymous with the above-denoted R5), -N-, -O-, -S-, -SO2-
• the yellow couplers represented by the foregoing Formula [I] are also allowed to form a bis-member upon bonding in the position of R1, R3 or Y1.
• the yellow coupler of the present invention is preferably represented by the following Formula [V].
• R1, R3 and J represent each the same groups as those represented by R1, R3 denoted in Formula [I] and J denoted in Formula [II];
• R2 represents an alkyl group having 1 to 5 carbon atoms;
• n is an integer of 0 or 1;
• R7 represents an alkylene group, an arylene group, an alkylenearylene group, an arylenealkylene group or -A-V1-B- (in which A and B represent each an alkylene group, an arylene group, an alkylenearylene group or an arylenealkylene group, and V1 represents a divalent linking group);
• R8 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group;
• P0 represents a bonding group having a carbonyl or sulfonyl unit;
• X1 represents a group capable of
• the alkylene groups each represented by R7 include, for example, a methylene group, an ethylene group, a propylene group, a butylene group and a hexylene group. These groups also include those having substituents, namely; those substituted with an alkyl group including, for example, a methyl-methylene group, an ethyl-ethylene group, a 1-methylethylene group, a 1-methyl-2-ethyl-ethylene group, a 2-decylethylene group, a 3-hexyl-propylene group and a 1-benzylethylene group; and those substituted with an aryl group including, for example, a 2-phenyl-ethylene group and a 3-naphthyl-propylene group.
• the arylene groups include, for example, a phenylene group and a naphthylene group.
• the alkylenearylene groups include, for example, a methylenephenylene group and so forth.
• the arylenealkylene groups include, for example, a phenylenemethylene group and so forth.
• alkylene, arylene, alkylenearylene or arylenealkylene groups represented by A and B are synonymous with those represented by R7 denoted in Formula [V]; and the divalent bonding groups represented by V1 include, for example, -O-, -S- and so forth.
• alkylene groups are particularly preferable.
• the alkyl groups represented by R8 include, for example, an ethyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, a hexadecyl group, an octadecyl group and so forth. These alkyl groups may also be straight-chained or branched.
• the cycloalkyl groups include, for example, a cyclohexyl group and so forth.
• the aryl groups include, for example, a phenyl group, a naphthyl group and so forth.
• the heterocyclic groups include, for example, a pyridyl group and so forth.
• the alkyl, cycloalkyl, aryl and heterocyclic groups each represented by R8 also include those having substituents.
• any substituents shall be applicable thereto without special limitation.
• the same substituents as those given for the foregoing R5 may be given, provided, however, that an organic group having a dissociative hydrogen atom having a pKa value of not higher than 9.5 (such as a phenolic hydrogen atom and so forth) are not preferable for the substituents to R8.
• P0 represents a linking group having a carbonyl or sulfonyl unit and, among them, the groups represented by the following Formula Group [VI] are preferable. and, more preferably, a linking group having a sulfonyl unit.
• R and R' represent each a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, provided, R and R' may also be the same with or the different from each other.
• R and R' include, for example, the same groups as given for R5. These groups also include those having the same substituents as given for R5.
• R and R' preferably represent each a hydrogen atom.
• the yellow couplers of the invention represented by the foregoing Formula [I] may be ordinarily used in an amount within the range of, preferably, 1x10 ⁇ 3 mols to 1 mol per 1 mol of silver halide used and, more preferably, 1x10 ⁇ 2 mols to 8x10 ⁇ 1 mols.
• the couplers of the invention may be used independently or in combination in the form of the mixture. It is also allowed to use them upon mixing them with any known yellow couplers.
• the coupler of the invention can be used in any layers of light sensitive materials. However, it is preferable to be used in light sensitive silver halide emulsions or the layer adjacent thereto and most preferable to be used in light sensitive emulsion layers.
• the coupler of the invention can be synthesized in any conventional well-known synthesizing processes including, typically, the synthesizing process described in JP OPI Publication No. 63-123047/1988.
• the coupler of the invention is used in an amount within the range of 1x10 ⁇ 5 mols to 1.0 ⁇ 2 mols, preferably 1x10 ⁇ 4 mols to 5x10 ⁇ 3 mols and more preferably 2x10 ⁇ 4 mols to 10 ⁇ 3 mols, each per sq. meter of a light sensitive material.
• couplers can be added into light sensitive layers in an oil-in-water type dispersion process which are known as an oil-protect process.
• a coupler is dissolved in a high-boiling organic solvent including phthalic acid esters such as dibutyl phthalate and dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate and trinonyl phosphate, or the coupler is dissolved in the combination thereof with a low-boiling organic solvent such as ethyl acetate and/or a water-soluble solvent; the resulting solution is then dispersed emulsionwise in an aqueous gelatin solution containing a surfactant; and the resulting coupler dispersion is then added into a photographic emulsion.
• a high-boiling organic solvent including phthalic acid esters such as dibutyl phthalate and dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate and trinonyl phosphate, or the coupler is dissolved in the combination thereof with a low-boiling organic solvent
• a coupler dispersion by adding water or an aqueous gelatin solution into a coupler solution containing a surfactant so that an oil drops-in water type dispersion can be prepared with accompanying a phase inversion. It is further allowed to mix a coupler dispersion with a photographic emulsion in a distillation, noodle-washing or ultrafiltration process, after removing a low-boiling organic solvent and so forth. It is still further allowed to disperse a coupler dispersion and add it into a photographic emulsion, in such a coupler dispersion process as described in U.S. Patent Nos. 4,933,270, 4,957,857, 4,990,431, 4,970,139, 5,013,640, 5,008,179, 5,024,929, 5,087,554, 5,089,380 and 5,091,296.
• the above-mentioned coupler may be used in an amount within the range of 0.05 mols to 0.5 mols and preferably 0.1 mols to 0.4 mols, each per mol of a silver halide content of an emulsion layer.
• the ratio by weight of a high-boiling organic solvent to a yellow coupler of the invention (hereinafter referred to as HBS/Coupler) is preferably not more than 1.5 and more preferably not more than 1.0.
• the blue-sensitive layer of the invention may be formed of a plurality of layers. Particularly, it is to be formed of, preferably, 2 to 4 layers and, more preferably, 2 to 3 layers.
• the light sensitive silver halide emulsions applicable to the invention include, particularly, a silver iodobromide emulsion, provided, it is to have an average silver iodide content within the range of, preferably 7 mol% or less, more preferably 1.0 to 6.5 mol% and, further preferably 1.5 to 6 mol%.
• the silver halide emulsions applicable to the invention can be physically or optically ripened and spectrally sensitized.
• the additives applicable to such a treatment as mentioned above are given in, for example, RD 17643, RD18716 and RD308119.
• Table 2 indicates the places of the RDs given the information of the additives.
• Couplers can also be applied in combination to the invention.
• the typical examples of these couplers are also given in the following RD17643 and RD308119.
• Table 4 indicates the places of the descriptions related thereto.
• Table 4 [Contents] [RD308119] [RD17643] Yellow coupler p.1001 VII-D p.25 VII-C ⁇ G Magenta coupler 1001 VII-D 25 VII-C ⁇ G Cyan coupler 1001 VII-D 25 VII-C ⁇ G Colored coupler 1002 VII-G 25 VII-G DIR coupler 1001 VII-F 25 VII-F BAR coupler 1002 VII-F Other organic residual group releasing coupler 1001 VII-F
• the additives applicable to the invention can be added in such a dispersion process as described in RD308119, p.1007, XIV.
• the auxiliary layers such as the filter layers or interlayers each described in the foregoing RD308119, VII-K can be provided.
• the light sensitive materials of the invention are allowed to have a variety of layer arrangements such as the regular, inverse and unit-layer arrangements, each described in RD308119, VII-K.
• the supports it is allowed to use a sheet of paper laminated with polyethylene and so forth, a polyethylene terephthalate film, a sheet of baryta paper, a cellulose triacetate film, and so forth.
• This invention can be applied to a variety of color light sensitive materials typically including a color negative film, a slide or TV color reversal film, a color paper, a color positive film and a color reversal paper.
• any generally known color development processes can be utilized.
• the light sensitive materials of the invention can be developed in any ordinary processes such as those described in, for example, the foregoing RD17643, pp.28 ⁇ 29, RD18716, p.647 and RD308119, XIX.
• the silver halide emulsions used in each of the light sensitive layers were prepared with reference to the process described in Example 1 given in JP OPI Publication No. 59-178447/1984.
• the resulting emulsions were the monodisperse type emulsions each having a distribution range of not more than 20%. After desalting and washing the resulting emulsions, they were each subjected to an optimum chemical ripening treatment in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate and were then added with sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole.
• Samples 2 through 5 were each prepared in the same manner as in Sample 1, except that coupler Y-1 used in Layers 14, 15 and 16 of Sample 1 were replaced by the couplers shown in Table 1 in the same mols with those of coupler Y-1.
• Table 5 Sample No. Couplers used in Layers 14 ⁇ 16 1 Y-1 2 Exemplified compound 6 3 Exemplified compound 56 4 Exemplified compound 1 5 Exemplified compound 3
• Sample 101 was prepared to provide the following layers 1 through 11 on a paper-made support polyethylene coated on the both sides.
• the amounts of each component coated will be shown in terms of g/m2, provide, however, the silver halide used therein will be shown the corresponding silver contents thereof.
• Sample 101 there further contained surfactant (ASU-1, ASU-2 and ASU-3), layer hardeners (AH-1, AH-2 and AH-3), anti-irradiation dyes (AAI-1, AAI-2, AAI-3 and AAI-4) and antimold (ADI-1).
• surfactant ASU-1, ASU-2 and ASU-3
• layer hardeners AH-1, AH-2 and AH-3
• anti-irradiation dyes AAI-1, AAI-2, AAI-3 and AAI-4
• ADI-1 antimold
• Samples 102 through 105 were each prepared in the same manner as in Sample 101, except that yellow coupler AY-1 contained in Layers 8 and 9 of Sample 101 were replaced by the yellow couplers shown in Table 6 in the same mols as that of AY-1.
• Table 6 Sample No. Yellow couplers of Layers 8 & 9 101 AY-1 102 Exemplified compound 57 103 Exemplified compound 14 104 Exemplified compound 60 105 Exemplified compound 3
• compositions of the processing solutions used in the above-mentioned processing steps were as follows. ⁇ First developper> Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone ⁇ monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (an aqueous 0.1% solution) 2 ml Add water to make 1000 ml ⁇ Reversing solution> Hexasodium nitrilotrimethylene phosphate 3 g Stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Add water to make 1000 ml ⁇ Adjusting solution> Sodium sulfite 12 g Sodium ethylenediamine tetraacetate
• the color-rendition chart and portrait were photographed on a color positive film and were then developed.
• the charts and portraits were printed thereon and the printed Samples 101 through 105 were each developed, so that the color prints were obtained.
• Each of the resulting color prints was so printed again as to make the gray of the MacBeth Chart be constant.
• a maximum value of S Y ( ⁇ ) of each sample was in a wavelength region of 430 to 450nm, and a wavelength ⁇ Y 50 giving 50% of the maximum value of S Y ( ⁇ ) of each sample was within the range of 485 to 495nm on the longer wavelength side.
• print A came out of the color reversal paper and film each unsatisfied the constitutional requirements of the invention, the resulting color reproducibilities of both yellow and skin colors were not preferable.
• prints B and C even when either one of a color light sensitive material for picture-taking use and a color light sensitive material for printing use contains a yellow coupler relating to the invention, any preferable color reproducibility could not be obtained.
• prints D through H satisfying the constitutional requirements of the invention were tinted with a healthy pink on the resulting skin color and excellent in yellow color reproducibility.

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• 1992
  • 1992-04-09 JP JP11528692A patent/JPH05289266A/ja active Pending
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