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
  • 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
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
• • 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
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
• • 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
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
  • G03C1/83—Organic dyestuffs therefor
  • G03C1/832—Methine or polymethine dyes
• • 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
  • G03C7/396—Macromolecular additives

Definitions

• the present invention relates to a silver halide photo­graphic light-sensitive element which enables rapid processing and is characterized by sharpness of the dye images produced.
• the developing speed etc. is greatly influenced by the configuration, size, and composition of the silver halide grains which constitute the emulsion of a photographic light-sensitive element.
• the halogen composition has a significant influence and the use of a silver halide with a high content of chloride is known to show remarkable increasing in the developing speed.
• the dyes used for such purposes must satisfy various requirements, for example: the dye is required to have a satisfactory spectral absorption characteristic according to the intended purpose; the dye must be completely decolorized in the processing bath, readily eludes out of the photographic element so that no residual staining by the dye occurs after the developing process; the dye should not cause the emulsions to undergo fogging, desensitization, or the like adverse influences; the dye is required to have good shelf life while it is in solution as well as when it is in the photographic element, and does not undergo fading or discoloration.
• dyes which satisfy such requirements, and, as a result, a large number of dyes have been proposed for use.
• Some of such dyes are, for example, oxonol dyes disclosed in U.S. Patent Nos. 506,385 and 3,247,127, Japanese Patent Examined Publication Nos. 22069/1964 and 13168/1978; styryl dyes disclosed, for example, in U.S. Patent No. 1,845,404; merocyanine dyes disclosed, for example, in U.S. Patent Nos. 2,493,747, 3,148,187 and 3,282,699; cyanine dyes etc. disclosed, for example, in U.S. Patent No. 2,843,486; and anthraquinone dyes disclosed, for example, in U.S. Patent No. 2,865,725.
• the inventors through their studies on dyes especially in pursuit of their satisfactory decolorization property even in rapid processing, discovered that dyes of some specific structure satisfy the requirements when used in combination with a silver halide with a high content of chloride which, as mentioned before, has a high developing speed and suits rapid processing.
• the object of the present invention is to provide a silver halide photographic light-sensitive element which is excellent in adaptability to rapid processing and in decolorization property of the dye and finally produces a picture image with a distinct improvement in sharpness.
• the object of the present invention can be accomplished by a silver halide photographic light-sensitive element comprising a support having thereon photographic component layers including at least one silver halide emulsion layer which contains silver halide grains comprising not less than 90 mol% of silver chloride, and at least one layer among said photographic component layers contains a compound presented by the following formula [I] and a capturing material for fluorescent whitening agent: wherein R1 and R2 independently represent a -CN group, a -CFR5R6 group, a -COR7 group, a -COOR7 group or a -CONHR5 group, in which R5 and R6 represent a hydrogen atom, a fluorinated alkyl group having one to four carbon atoms, respectively, and R7 represents an alkyl group or an aryl group which may have a substituent; R3 and R4 independently represent a hydrogen atom, an aliphatic group, an alicyclic group, an automatic group or a heterocyclic group, which may have
• At least one of the silver halide emulsion layers contain silver halide grains comprising not less than 90 mol% of silver chloride grains.
• the silver halide grains according to the invention comprise not less than 90 mol%, preferably, not less than 95 mol% of silver chloride grains.
• the content of silver bromide grains is preferably 5 mol% or less and that of silver iodide is preferably 0.5 mol% or less.
• the silver halide grains prepared according to this invention can be used alone or in a mixture with another type of silver halide grains having a different composition.
• the silver halide grains according to the invention may be used also by mixing with another type of silver halide grains comprising a silver chloride content of less than 10 mol%.
• the proportion of the silver halide grains comprising not less than 90 mol% of silver chloride grains per total silver halide grains in said emulsion layer is not less than 60 wt%, or, preferably, not less than 80 wt%.
• composition of the individual silver halide grains according to the present invention may be uniform from the inside to the surface, or different between the inner portion and the surface. Where the composition differs between the inner and outer portions, the composition may vary in some sequential order or in no sequence.
• This invention does not restrict the grain size of the silver halide grains to any particular range.
• the preferred grain size is within the range from 0.2 to 1.6 ⁇ m, or in particular, within the range from 0.25 to 1.2 ⁇ m, with the adaptability to rapid processing, sensitivity, and other photographic properties taken into consideration.
• the grain size can be measured by an ordinary method in general use in the technical fields concerned. Methods most generally applicable are described in "Grain Size Analysis” by Labrand (A.S.T.M. Symposium on light Microscopy, 1955, pp. 94-122) and "Theory of Photographic Process” by Meas & James (3rd Ed. Mcmillan, 1966, Chapter 2).
• the grain size can be measured by using the projected area of the grain or by using an approximate value of the diameter. When the grains are virtually uniform in shape, the grain size distribution can be determined fairly accurately in terms of diameter or projected area.
• the grain size distribution of the silver halide grains according to this invention may assume a multi-dispersed system or a monodispersed system. It is preferable for the silver halide grains to be a monodispersed system with a variation coefficient of 0.22 or less, or more favorably 0.15 or less, in the grain size distribution of silver halide grains.
• This variation coefficient is a coefficient which indicates the extent of the grain size distribution, and can be defined by the following formulas: wherein ri represents the grain size of the individual grains and ni their quantity.
• grain size herein used means the diameter when the silver halide grains are spherical; when the grains are cubic or of a shape other than spherical, the term means the diameter obtained by converting the projected image into a corresponding circular area.
• the present invention permits the silver halide grains to be formed in any desired configurations.
• One preferable configuration is a cube having ⁇ 100 ⁇ face as crystalline faces. It is also possible to produce the grains having octahedral, tetradecahedral or dodecahedral configuration or the like by a method described, for example, in U.S. Patent Nos. 4,183,756 and 4,225,666, and Japanese Patent O.P.I. Publication No. 26589/1980 and Japanese Patent Examined Publication No. 42737/1980 and in the literature such as The Journal of Photographic Science 21 , 39 (1973).
• a metal ion can be added and incorporated into the interior and/or the surface of the grains by using a cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or iridium complex salt, rhodium salt or rhodium complex salt, and iron salt or iron complex salt, and then by palcing the grains in a suitable reducing environment, reduction-­sensitizing nuclei can be imparted to the grain at the interior and/or the surface.
• the silver halide grains used for the emulsion according to this invention are preferably to be grains wherein a latent image is primarily formed on the grains surfaces.
• the emulsion according to the invention is chemically sensitized by a conventional method.
• Some of such methods are sulfur-sensitizing method using a sulfur compound reactive with silver ion or using active gelatin; selenium-sensitizing method using a selenium compound; reduction-sensitizing method using a reducing substance; and noble metal-sensitizing method using a noble metal compound such as of gold.
• Such methods can be used singly or in combination.
• Chalcogen sensitizers are useful for chemical sensitization in the practice of this invention.
• sulfur sensitizers and selenium sensitizers are advantageous.
• the sulfur sensitizers useful for this purpose are, for example, thiosulfate, alkyl thiocarbazide, thiourea, aryl isothiocyanate, cystine, p-toluene thiosulfonate, and rhodanine.
• Sulfur sensitizers useful for this purpose are also found in the specifications of U.S. Patent Nos.
• the quantity of the sulfur sensitizer added varies widely depending on various conditions such as pH, temperature, and size of the silver halide grains. Roughly, sulfur sensitizer is used in a quantity in a range of 10 ⁇ 7 mol to 10 ⁇ 1 mol per mol silver halide.
• the selenium sensitizers useful for the purpose are selenides such as aliphatic isoselenocyanates such as alkyl isoselenocyanate; selenoureas, selenoketones, selenoamides, selenocarboxylates and esters; selenophosphates; selenides such as diethylselenide, and diethyldiselenide. Examples of such sensitizers are described in U.S. Patent Nos. 1,574,944, 1,602,592, and 1,623,499.
• Reduction sensitization can be used in combination with other sensitizing processes.
• the reducing agents useful for this purpose are stannous chloride, thiourea dioxide, hydrazine, polyamide, and the like.
• Noble metal compounds other than gold such as palladium compound, can also be used in combination.
• the silver halide grains embodying this invention may contain a gold compound.
• a gold compound suitable for the use in the practice of the present invention may have a gold oxidation number of +1 or +3, whereby a wide variety of gold compounds are applicable.
• Some examples of such gold compounds are chloraurate, potassium chloraurate, auric trichloride, potassium auric thiocyanate, potassium iodine aurate, tetracyanoauric azide, ammonium aurothio­cyanate, pyridyl trichlorogold, gold sulfide, and gold selenide.
• a gold compound can be used either in such a way as to sensitize the silver halide grains or in such a way not to contribute to sensitization virtually.
• the quantity of a gold compound used varies depending on various conditions. Roughly, a gold compound is used in a quantity of a range of 10 ⁇ 8 mol to 10 ⁇ 10 mol, or, preferably, 10 ⁇ 7 mol to 10 ⁇ 2 mol per mol silver halide. Such a gold compound can be added at any of the stages of formation of the silver halide grains, physical ripening, chemical ripening, and after the chemical ripening.
• the emulsion produced according to the present invention can be spectrally sensitized at a desired wavelength range by using a sensitizing dye.
• the sensitizing dyes can be used singly or in combination of two or more kinds.
• a supersensitizing dye which is a dye or compound not having the spectral sensitization function or not actually absorbing visible light, though such a dye or compound is capable of enhancing the sensitizing action of the sensitizing dye.
• silver halide grains used for an emulsion layer other than that of the present invention are used for an emulsion layer other than that of the present invention. But, it is preferable for such silver halide grains to comprise not less than 90 mol% of silver chloride grains, that is, such silver halide grains should, like those of the invention, comprise not less than 90 mol% of silver chloride grains.
• the photographic light-sensitive element according to the present invention has a compound expressed by formula [I] and a capturing material for fluorescent whitening agent in at least one layer selected from among the photographic structural light-sensitive layers, that is, the silver halide emulsion layers according to the invention, and other silver halide emulsion layers, or among the non-light-sensitive layers, that is, intermediate layer, protective layer, filter layer, anti-halation layer and the like.
• R1 and R2 individually represent -CN, -CFR5R6, -COR7, or -CONHR5, wherein the fluorinated alkyl groups with 1 to 4 carbon atoms represented by R5 or R6 -CFR5R6 and -CONHR5 above are, for example, difluoromethyl group, trifluoromethyl group, 1,1,2,2-tetrafluoroethyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, and 1,1,2,2,3,3-­hexafluoropropyl group.
• R7 in -COR7 or -COOR7 represented by R1 or R2 represents an alkyl group or aryl group, wherein such an alkyl group or aryl group may have a substituent group.
• R3 and R4 individually represent a hydrogen atom, aliphatic group, alicyclic group, aromatic group, or hetero­cyclic group, of which the aliphatic group is, for example, an alkyl group or alkenyl group; the alicyclic group is, for example, a cycloalkyl group; the alicyclic group is, for example, a cycloalkyl group; the aromatic group is, for example, an aryl group such as phenyl group or naphthyl group; the heterocyclic group is, for example, benzothiazolyl group or benzoxazolyl group.
• R3 and R4 represent, as above, an aliphatic group, alicyclic group, aromatic group or heterocyclic group, including those having a substituent.
• the methine group represented by each of L1, L2, L3, L4, and L5 may be a group substituted by an alkyl or aryl group with 1 to 4 carbon atoms.
• R1 and R2 are -CN group, -CF3 group, -CONH2 group, or -COR7 group, and for R7 to be an alkyl group. It is preferable for R3 and R4 to be an aromatic group, especially preferably to be 4-sulfophenyl group, 2,5-di-sulfophenyl group, or their salts.
• such a dye it is preferable for such a dye to contain at least one water soluble group (such as sulfo group, carboxyl group, or their salts) in its molecular structure.
• dyes applicable effectively to the practice of the present invention are shown in the specification of Japanese Application No. 8796/1986, pp. 179-199, which are Examples (2), (3), (7), (9), (15), (16), (18), (19), (21), (22), (24), (25), (27), (33), (34), (35), (40), (42), (43), (44), (45), (46), (47), (48), (49), (50), (51), (52), (53), (54), (55), (58), (59), (60), and (62).
• Said dyes according to the present invention can be synthesized by the method described in the above-mentioned specification of Japanese Patent Application No. 8796/1986.
• the dyes according to the invention expressed by formula [I] can also be used, in a silver halide photographic light-­sensitive element embodying the invention, as an anti-­irradiation dye by introducing it into a silver halide emulsion layer according to the invention or other silver halide emulsion layer, or as a filter dye or an anti-halation dye by introducing it into a non-light-sensitive hydrophilic colloidal layer.
• a dye embodying the invention is incorporated into a silver halide emulsion layer
• a dye embodying the invention can be used in combination with another kind or more of the embodiments or in combination with a dye other than the embodiments, depending on the purpose of the use.
• a dye embodying the invention can be incorporated into a silver halide light-sensitive emulsion or other hydrophilic colloidal layer, usually by dissolving the dye or an organic/inorganic alkali salt of the dye in an aqueous solution or an organic solvent, such as alcohol, glycol, cellosolve, dimethylformaldehyde, dibutyl phthalate, and tricresylphosphate, dispersing it, if necessary, by emulsifying, adding it to a coating solution, and then by applying to and drying over the support.
• an organic solvent such as alcohol, glycol, cellosolve, dimethylformaldehyde, dibutyl phthalate, and tricresylphosphate
• the dye can be added to a coating solution for a different layer rather than that of the dye so that the dye, once the solution is applied, is allowed to diffuse and eventually be incorporated, before the solution completely dries, into a layer which contains the capturing material for fluorescent whitening agent.
• the dye according to the invention is present in the layer containing a capturing material for fluorescent whitening agent.
• the quantities of the dyes being used vary depending on the purpose of application and are not restricted to any specific amounts. But, generally, it is preferable for the dye applied at a rate of 0.1 - 1.0 mg/dm2, or, preferably, 0.03 - 0.4 mg/dm2.
• the fluorescent whitening agents include, for example, the compounds of a diaminostilbene, a benzidine, an imidazole, a triazole or an imidazolone, each having a hydrophilic group, as described in Japanese Patent O.P.I. No. 71049-1984.
• a fluorescent whitening agent having been added into the hydrophilic colloidal layer of a light-sensitive element is eluted from the hydrophilic colloidal layer into a processing solution in the course of processing the light-sensitive element.
• there is some kind of compounds capable of capturing a fluorescent whitening agent so as to prevent the fluorescent whitening agent from eluting out of the hydrophilic colloidal layer so that the compounds have been widely used with the purpose of enhancing the effects of fluorescent whitening agents used in light-sensitive elements, as described in Japanese Patent O.P.I. Publication No. 71045-­1984.
• a substance having such an effect of capturing a fluorescent whitening agent as mentioned above are called a capturing material for fluorescent whitening agents or simply a capturing agent of the invention.
• Any compound may be used as a capturing material of the invention, provided that it may be able to capture a fluorescent whitening agent. It is, however, preferred that it is a non-color-developable hydrophilic synthetic macro­molecular polymer.
• hydrophilic polymers include polyvinyl pyrrolidone or copolymers having vinyl pyrrolidone as repeating units, wherein the examples of monomers being capable forming repeating units together with vinyl pyrrolidone include acrylic acid, methacrylate acid, amide compounds of acrylic acid and methacrylic acid, such as acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-­diethylacrylamide, N-methyloylacrylamide, N-hydroxyethyl­ acrylamide, N-tert-butylacrylamide, N-cyclohexylacrylamide, diacetoneacrylamide, N-(1,1-dimethyl-3-hydroxybutyl)­acrylamide, N-( ⁇ -morpholino)ethylacrylamide, N-benzylacryl­amide, N-acryloymorpholine, N-methacryloylmorpholine, N-methyl-N-acryloylpiperazine, N-acryloylpiperazine, N-
• polymer of N-vinylamide compound expressed by a formula CH2 CHNR1COR2, in which R1 represents an alkyl group and R2 represents a hydrogen atom or an alkyl group; hydrophilic polymer including a cationic nitrogen-­containing active group described in Japanese Patent O.P.I. Publication No. 42732/1973; polymers of monopholino alkyl­alkenoylamide described in Japanese Patent Examined Publication No. 2522/1969; copolymers of vinyl alcohol and vinyl-pyrrolidone described in Japanese Patent Examined Publication No. 20738/1972; polymers described in Japanese Patent Examined Publication No.
• hydrophilic polymers it is preferable for said hydrophilic polymers to have a molecular weight of not less than 1,000, in particular, a molecular weight of not less than 10,000, in terms of weight-­average molecular weight in the practice of the invention. Still more advantageous is a molecular weight in the range of 50,000-1,000,000.
• the capturing material of the invention can be incorporated into any desirable layer in the photographic structural layers, that is, in a light-sensitive layer including the silver halide emulsion layer according to the invention as well as in a non-light-sensitive layer. It is preferable for the capturing material of the invention to be contained in a non-light-sensitive layer.
• the capturing material of the invention is preferable for the capturing material of the invention to be used ordinarily at a rate of 0.05 to 3.0 mg/dm2, more preferably 0.1 to 20 mg/dm2. It is also preferable for the capturing material of the invention to be used at a rate of 0.1 to 50 wt%, or, more favorably, at a rate of 1 to 30 wt% per amount of gelatin which is used as a binder in the photographic structural layer where the capturing material is contained.
• a sensitizing dye used in the green-sensitive silver halide emulsion layer according to the invention is one expressed by the following formula [B]: wherein Z11 and Z12 individually represent a group of atoms required to form a benzene ring or naphthalene ring condensed into an oxazole.
• the rings formed include those having substituents and the preferable substituents are halogen atoms, aryl group, alkyl group, or alkoxy group. Halogen atoms, phenyl group, and methoxy group are more advantageous as substituents, and phenyl group is most favorable as a substituent.
• both Z11 and Z12 represent a benzene ring condensed into an oxazole ring, wherein at least one of these benzene rings has a substituent phenyl group in the 5-position, or one of these benzene ring has a substituent phenyl group in the 5-position, and the other benzene ring has in the 5-position a halogen atom as a substituent group.
• R21 hand R22 individually represent an alkyl group, alkenyl group, or aryl group, preferably an alkyl group. It is more advantageous for R21 and R22 individually to be an alkyl group having a carboxyl or sulfo group as a substituent group.
• the more favorable example of R21 and R22 is a sulfoalkyl group having 1 to 4 carbon atoms, where the most favorable is a sulfoethyl group.
• R23 represents a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms, or, preferably, a hydrogen atom or ethyl group.
• X1 ⁇ represents an anion, such as a halogen ion of chloride, bromine, or iodine, or an anion such as CH3SO4, or C2H5SO4.
• n represents 1 or 0. When a compound forms an inner salt, however, n represents 0.
• sensitizing dyes preferable in the practice of the present invention expressed by the formula [B], will now be shown hereunder.
• a sensitizing dye incorporated into the red-sensitive silver halide emulsion layer according to the invention is one expressed by the following formula [C] or another expressed by the following formula [D].
• R represents a hydrogen atom, or an alkyl group
• R11 through R14 individually represent an alkyl group or aryl group
• Z1, Z2, Z4, and Z5 individually represent a group of atoms required to form a benzene or naphthalene ring condensed into a thiazole or selenazole ring
• Z3 represents a group hydrocarbon atoms required to form a six-membered ring
• l represents 1 or 2
• Z represents a sulfur atom or selenium atom
• X ⁇ represents an anion.
• R in the formulas above represents preferably an hydrogen atom, methyl group or ethyl group. It is especially preferable from R to be a hydrogen atom or ethyl group.
• R11, R12, R13, and R14 individually represent a straight-chained or branched alkyl or aryl group, wherein an alkyl group or aryl group may have a substituent.
• the rings formed by Z1, Z2, Z4, and Z5 include those having substituents, wherein preferred substituents are halogen atoms, aryl group, alkyl group, and alkoxy group. Particularly preferred substituents are halogen atoms such as chlorine atoms, phenyl group, and methoxy group.
• the ring formed by Z3 may have a substituent such as alkyl group.
• X represents an anion (such as Cl, Br, I, CH3SO4, and C2H5SO4); and l represents 1 or 2.
• any of these sensitizing dyes is dissolved in water soluble solvent such as pyridine, methyl alcohol ethyl alcohol, methyl Cellosolve and acetone (or the mixture of any of these solvents), whereby the solution is diluted with water to form a solution being added into a coating solution, or, otherwise, any of these sensitizing dyes is dissolved in water to prepare a solution being added into a coating solution.
• water soluble solvent such as pyridine, methyl alcohol ethyl alcohol, methyl Cellosolve and acetone
• the amount of sensitizing dye being added is not specifically limited.
• a preferred range of addition is 2 ⁇ 10 ⁇ 6 to 1 ⁇ 10 ⁇ 3 mol, in particular, 5 ⁇ 10 ⁇ 6 to 5 ⁇ 10 ⁇ 4 mol per mol silver halide.
• the silver halide photographic light-sensitive element of the invention having the constitution described above may be, for example, a color negative film, color positive film, or color photographic paper.
• the effect of the invention is best demonstrated when the material takes the form of a color photographic paper, which will be directly appreciated by human vision.
• the silver halide photographic light-sensitive elements of the invention may be of monochromatic application or multi-color application.
• the multi-color silver halide photographic light-sensitive element usually comprises a support having thereon, in an appropriate order and number, silver halide emulsion layers containing as photographic couplers each of magenta, yellow and cyan couplers, as well as non-light-sensitive layers. The order and number of these layers may be deliverately changed in accordance with the target performance and intended application.
• silver halide photographic light-sensitive element used in embodying the invention is the multi-color light-­sensitive element
• the preferred layer configuration comprises a support provided sequentially thereon in the order of a yellow dye-image forming layer, intermediate layer, magenta dye-image forming layer, intermediate layer, cyan dye-image forming layer, intermediate layer, and protective layer.
• These dye-forming couplers preferably contains within the molecular structure a group known as a "ballast group" which has not less than 8 carbon atoms and is capable of making the coupler non-diffusible.
• the preferred yellow dye-forming couplers are acyl­acetanilide couplers.
• benzoyl­acetanilide compounds and pyvaloylacetanilide compounds are particularly advantageous.
• the preferred compounds are those represented by the following formula [Y].
• R y1 represents a halogen atom, or alkoxy group.
• R y2 represents a hydrogen atom, halogen atom, or alkoxy group.
• R y3 represents an acylamino group, alkoxy­carbonyl group, alkylsulfamoyl group, arylsulfamoyl group, alkylureide group, arylureide group, succinimide group, alkoxy group or aryloxy group.
• Z y1 represents a group being capable of split off by the reaction with an oxidation product of the color developing agent.
• useful yellow coupler are those described, for example, in British Patent No. 1,077,874, Japanese Patent Examined Publication No. 40757/1970, Japanese Patent O.P.I. Publication Nos. 1031/1972, 26133/1972, 94432/1973, 87650/1975, 3631/1976, 115219/1977, 99433/1979, 133329/1979, and 30127/1981, U.S. Patent Nos.
• the preferred magenta dye-forming couplers are 5-­pyrazolone couplers and pyrazoloazole couplers.
• the particularly preferred couplers are those represented by the following formula [P] or [a].
• Ar represents an aryl group.
• R p1 represents a hydrogen atom or a substituent group.
• R p2 represents a substituent group.
• Y represents a group being capable of split off by the reaction with an oxidation product of the color developing agent.
• W represents -NH-, -NHCO- (N atom being bonded to a carbon atom on the pyrazolone nuclei), or -NHCONH-.
• m represents an integer, 1 or 2.
• Z a represents a group of non-metal atoms required for forming a nitrogen-heterocycle.
• the heterocycle formed by this Z a may have a substituent.
• X represents a hydrogen atom, or a group being capable of split off by the reaction with an oxidation product of the color developing agent.
• R a represents a hydrogen atom, or a substituent group.
• the examples of a substituent group represented by this R a include a halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkinyl group, aryl group, heterocyclic group, acyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue group, bridged hydrocarbon compound residue group, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureide group, sulfamoylamino group, alkoxycarbonylamino group, aryloxy­carbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group
• magenta coupler examples are described, for example, in U.S. Patent Nos. 2,600,788, 3,061,432, 3,062,653, 3,127,269, 3,311,476, 3,152,896, 3,419,391, 3,519,429, 3,555,318, 3,684,514, 3,888,680, 3,907,571, 3,928,044 3,930,861, 3,930,866, and 3,933,500, Japanese Patent O.P.I. Publication Nos. 29639/1974, 111631/1974, 129538/1974, 58922/1977, 62454/1980, 118034/1980, 38043/1981, 35858/1982, and 23855/1985, British Patent No.
• the cyan dye-forming couplers used are phenol and naphthol cyan dye forming couplers.
• the particularly preferred couplers are those represented by the following formula [E] or [F].
• R e1 represents an alkyl group, cycloalkyl group or heterocyclic group.
• R e2 represents an alkyl group or phenyl group.
• R e3 represents a hydrogen atom, halogen atom, alkyl group or alkoxy group.
• Z e1 represents a hydrogen atom, or a group being capable of split off by the reaction with an oxidation product of the color developing agent.
• R e1 through R e3 may have a substituent group.
• R f1 represents an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, and nonyl group.
• R f2 represents an alkyl group such as a methyl group and ethyl group.
• R f3 represents a hydrogen atom, halogen atom such as fluorine, chlorine and bromide, or alkyl group.
• Z f1 represents a hydrogen atom, or a group being capable of split off by the reaction with an oxidation product of the color developing agent.
• R f1 through R f3 may have a substituent group.
• the dye forming coupler used in embodying the invention is incorporated into each silver halide emulsion layer, usually, at a rate of 1 ⁇ 10 ⁇ 3 to 1 mol, or, preferably, 1 ⁇ 10 ⁇ 2 to 8 ⁇ 10 ⁇ 1 mol per mol silver halide.
• the advantageous binder, or protective colloid, incorporated into the silver halide photographic light-­sensitive element according to the invention is gelatin.
• Other useful binders include a gelatin derivative, graft polymer of gelatin and another high-molecular compound, protein, sugar derivative, cellulose derivative, and hydrophilic colloid of synthesized high-molecular compound such as monomer or polymer.
• the photographic emulsion layers and other hydrophilic colloid layers of the silver halide photographic light-­sensitive element of the invention are hardened by singly or combinedly using hardeners which enhance layer strength by bridging between binder, or protective colloid, molecules.
• the hardeners are preferably incorporated at a rate enough to eliminate hardeners added to processing solutions. However, the hardeners may be added to processing solutions.
• a chlorotriazine hardener represented by the following formula [HDA] or [HDB], is preferably used to harden the silver halide emulsion layers.
• R d1 represents a chlorine atom, hydroxy group, alkyl group, alkoxy group, alkylthio group, -OM group (M represents a monovalent metal atom), -NR ⁇ R ⁇ group (R ⁇ and R ⁇ independently represent a hydrogen atom, alkyl group or aryl group), or -NHCOR′′′ group (R′′′ represents an alkyl group or aryl group).
• R d2 is synonymous with R d1 above, except for a chlorine atom.
• R d3 and R d4 independently represent a chlorine atom, hydroxy group, alkyl group, alkoxy group, or -OM group in which M represents a monovalent metal atom.
• Q and Q ⁇ independently a connecting group i.e. -O-, -S- or -NH-.
• L represents an alkylene group or arylene group.
• p and q independently represent 0 or 1.
• the hardener represented by formula either [HDA] or [HDB] can be incorporated into silver halide emulsion layers and other structural layers by dissolving the hardener in water, or a solvent compatible with water such as methanol and ethanol, thereby adding the resultant solution to a coating solution for these structural layers.
• the method of addition can be either batch process or in-line process.
• the timing of addition is not specifically limited. However, the preferred timing of addition is immediately before the application of coating solutions.
• hardeners are added at a rate of 0.5 to 100 mg, or, preferably, at a rate of 2.0 to 50 mg per 1 gram gelatin being applied.
• silver halide photographic light-sensitive element of the invention may be further added various additives such as an anti-stain agent, image-stabilizing agent, ultraviolet absorbent, plasticizer, latex, surface active agent, matting agent, lubricant, and anti-static agent.
• various additives such as an anti-stain agent, image-stabilizing agent, ultraviolet absorbent, plasticizer, latex, surface active agent, matting agent, lubricant, and anti-static agent.
• the silver halide photographic light-sensitive element according to the invention can form an image by color developing known in the art.
• the color developing agents incorporated into the color developers, according to the invention include aminophenol derivatives and p-phenylenediamine derivatives widely used in various color photographic processes.
• the pH value of a color developer solution is normally higher than 7, or, most usually, approx. 10 to 13.
• the color developing temperature is usually higher than 15°C, or, generally, within a range of 20 to 50°C.
• the preferred temperature is higher than 30°C.
• a conventional color developing requires 3 to 4 minutes, while the preferred color developing time intended for rapid processing is usually within a range of 20 to 60 seconds, in particular, 30 to 50 seconds.
• the silver halide photographic light-sensitive element of the invention is subjected to bleaching and fixing.
• the bleaching and the fixing may be performed simultaneously.
• the similar element is usually subjected to rinsing with water. Stabilizing may substitute the rinsing, or these two steps may combinedly used.
• the silver halide photographic light-sensitive element of the invention excels in rapid processability, as well as in decolorization of the dyes, wherein the resultant photographic image provides improves sharpness.
• Em-A through Em-E above were, using a conventional method, subjected to sulfur sensitization by adding sodium thiosulfate, and further subjected to optical sensitization using exemplified sensitizing dye No. C-9.
• red-­sensitive silver halide emulsions Em-R Nos. A through E were prepared.
• mono-color light-sensitive element sample No. 1 was prepared.
• the amounts added for each coating solution are indicated by amounts applied per each independent coat formed.
• red-sensitive silver halide emulsion listed in Table-1 at a rate, as converted into metal silver, of 3 mg/dm2; example cyan coupler CI-5, at a rate of 2 mg/dm2; example cyan coupler CI-7, at a rate of 2 mg/dm2; dioctylphthalate as a high boiling organic solvent, at a rate of 3 mg/dm2; hydroquinone derivative HQ-1 mentioned later, at rate of 0.15 mg/dm2; gelatin, at a rate of 14 mg/dm2; and HD-2 as a hardener at a rate of 0.05 mg/dm2.
• Light-sensitive element sample Nos. 2 through 44 were prepared in manner identical with that of sample No. 1 above, except that the combination of EM, type of compound represented by formula [I], type of fluorescent whitening agent, and coating solution dissolving them, was modified as listed in Table-1, like substances were used in a same weight.
• sample No. 45 was prepared in a manner identical with that of sample No. 10, except that the following sensitizing dye A was used instead of exemplified sensitizing dye No. C-9 in Em-E.
• Sample Nos. 46 and 47 were prepared in a manner identical with sample No. 10, except that polyvinyl pyrrolidone in the second layer of sample No. 10 was replaced for No. 46 with a like weight of polyvinyl alcohol, polymerization degree, approx. 500; saponification degree, 88%, or for No. 47 with a copolymer (1 : 1, by molecular ratio) of polyvinyl alcohol of vinyl pyrrolidone and metha­crylic acid.
• sample No. 48, 49 and 50 were prepared in a manner identical with sample No. 10, except that polyvinyl pyrrolidone added was at a rate of 0.275 mg/dm2 (No. 48), 0.11 mg/dm2 No. 49), or 0.055 mg/dm2 (No. 50).
• Sample No. 51 was prepared in a manner identical with that of sample No. 10, except that a hardener, examplified compound No. HD-2, in the first and second layers was replaced with the same weight of the following hardener H-1.
• Ferric ammonium ethylenediaminetertraacetate dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml
• the pH level was adjusted to 7.1 using potassium carbonate or glacial acetic acid, thereby water was added to prepare one liter solution.
• a resolution test chart was printed on each sample using red exposure light, thereby each sample was treated by the previously specified processing, and then, the resultant cyan dye image was measured for density using a microphotometer, wherein the sharpness value was determined by the following expression.
• Each unexposed sample was treated by the previously specified treatment, then using a color analyzer (Model 607, Hitachi, Ltd.), measured for the reflective density at a maximum absorption wavelength described below.
• sample Nos. 1 and 2 which used an emulsion, not in compliance with the invention, of a lower silver chloride content and containing comparative dye and a capturing material of the invention for fluorescent whitening agent, respectively showed insufficient sensitivity and maximum density, and, especially, greater stain, and also failed to attain satisfactory level of sharpness.
• Sample Nos. 3 through 5 having an emulsion of the invention of a higher silver chloride content unlike sample Nos. 1 and 2, showed still insufficient improvement in stain and sharpness, in spite of improved sensitivity and maximum density.
• Sample No. 6 and sample Nos. 8 through 51 respectively incorporating a dye represented by formula [I] according to the invention respectively showed improvement to nearly satisfactory level in terms of stain.
• HD-5, HD-13, or HD-15 instead of HD-2, achieved the same effects above.
• the effects of the invention were achieved by a sample prepared by simultaneously applying and drying not only a coating solution for the first layer, which was a coating solution, unlike the original coating solution, prepared by incorporating dye of the invention No. 2, 4, 6 or 7 into the coating solution for the first layer on Example-3, but a coating solution for the second layer, protective layer, containing polyvinyl pyrrolidone, weight average molecular weight, 360,000, at a rate of 0.55 mg/dm2, gelatin at a rate of 20 mg/dm2, and a hardener at a rate of 0.05 mg/dm2.
• Em-A through Em-E To Em-A through Em-E was added sodium thiosulfate by a conventional method, whereby each emulsion was subjected to sulfur sensitization, and then, to spectral sensitization using sensitizing dye, exemplified compound No. B-11.
• Green-sensitive silver halide emulsions Em-G Nos. A through E were prepared.
• mono-color light-sensitive element sample No. 2-1 was prepared.
• the amounts added for each coating solution are indicated by amounts applied per each independent coat formed.
• Light-sensitive element sample Nos. 2-2 through 2-17 were prepared in a manner identical with that of sample No. 2 above, except that the combination of type of compound represented by formula [I], and coating solution dissolving it, was modified as listed in Table-2, like substances were used in a same weight.
• Em-D sensitized by gold and sulfur as mentioned above was subjected to spectral sensitization using a sensitizing dye, exemplified compound No. D-3, so as to prepare red-sensitive silver halide emulsion Em-R No. D2.
• Em-E was spectrally sensitized using sensitizing dye, exemplified compound No.
• Em-F was spectrally sensitized using the following sensitizing dye SD-A, so as to prepare blue-sensitive silver halide emulsion Em-B No. F.
• the amounts added for each coating solution are indicated by amounts applied per each independent coat formed.
• magenta coupler m-3 at a rate of 4 mg/dm2; a dye listed in Table-3 at a rate of 0.1 mg/dm2; green-sensitive silver chloro-bromide emulsion Em-G No. E2 at a rate, as converted into metal silver, of 3 mg/dm2; high boiling organic solvent S-2 at a rate of 4 mg/dm2; and gelatin at a rate of 16 mg/dm2.
• UV-1 at a rate of 3 mg/dm2 and UV-2 at a rate of 3 mg/dm2; high boiling organic solvent S-1 at a rate of 4 mg/dm2; hydroquinone derivative HQ-1 at a rate of 0.45 mg/dm2; and gelatin at a rate of 14 mg/dm2.
• UV-1 ultraviolet absorbents
• UV-2 at a rate of mg/dm2
• high boiling organic solvent S-1 at a rate of 2 mg/dm2
• gelatin at a rate of 6 mg/dm2.
• Sample Nos. 3-1 through 3-26 were prepared by variously changing type and amount added of a compound represented by formula [I] and being added into the third and fifth layers, and also by changing type and amount added by a compound as a capturing material of the invention being added into the sixth layer. Additionally, sample Nos. 3-27 through 3-32 were prepared by incorporating a dye of the invention into a coating solution for the second, fourth, sixth or seventh layer.
• Those dyes added into the third and fifth layers as listed in Table-3 were as follows: comparative dye No. 1 was same as that in example-1, comparative dye No. 2 was same as that in example-2.
• the structural formulas of high boiling organic solvents S-1 and S-2, ultraviolet absorbents UV-1 and UV-2, and sensitizing dye SD-A are as follows.
• Table-3 lists the test results.
• Sample Nos. 4-1 through 4-16 were prepared in a manner identical with sample No. 3-25 in Example-3, except that the combination of a yellow coupler in the first layer, a magenta coupler in the third layer, and a cyan coupler in the fifth layer was changed, while maintaining same mol ratios, as listed in Table-4 below.

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• 1987
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