Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/36—Couplers containing compounds with active methylene groups
  • G03C7/38—Couplers containing compounds with active methylene groups in rings
  • G03C7/381—Heterocyclic compounds
  • G03C7/382—Heterocyclic compounds with two heterocyclic rings
  • G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms

Definitions

• the present invention relates to a silver halide color photosensitive material containing a novel coupler.
• cyan dye forming couplers with a novel skeleton having a nitrogen-containing heterocyclic ring have been actively studied, and various heterocyclic compounds have been proposed: for example, a diphenylimidazole coupler disclosed in Japanese Patent Application Laid-Open (KOKAI) No. 63-226653 (1988), and pyrazoloazole couplers disclosed in Japanese Patent Application Laid-Open (KOKAI) Nos. 63-199352 (1988), 63-250649 (1988), 63-250650 (1988), 64-554 (1989), 64-555 (1989), 1-105250 (1989), 1-105251 (1989), etc.
• These couplers are expressly improved in color reproducibility and are characterized by excellent absorption characteristics of the dyes formed therefrom.
• a first object of the present invention is to provide a silver halide color photosensitive material containing a novel cyan coupler and capable of forming a cyan dye having a high color density and excellent spectral extinction characteristics.
• a second object of the present invention is to provide a silver halide color photosensitive material capable of forming cyan dye images which are superior in heat resistance and which will not readily fade in a reducing atmosphere.
• formula (I) wherein R1 represents hydrogen atom or a substituent; R2 represents a substituent; X represents hydrogen atom or a group releasable on a coupling reaction with an oxidation product of a color developing agent; Z1 represents a nonmetallic atom
• Cyan dye images obtained from the coupler of the present invention are superior in both resistance to light and stability to heat.
• the silver halide color photosensitive material of the present invention which contains the novel coupler, provides dye images that are stable to light, heat and moisture and exhibit a high dye forming speed and a high maximum color density in a color developer.
• the dye forming speed and the maximum color density are satisfactorily high even in a color developer with benzyl alcohol removed therefrom.
• the silver halide color photosensitive material of the present invention makes it possible to attain a silver halide color photosensitive material processing method wherein there is substantially no lowering in the density when the photosensitive material is processed with a processing solution having a bleaching agent of weak oxidizing power (e.g., a processing solution having a bleaching agent containing EDTA iron (III) Na salt or EDTA iron (III) NH4 salt) or a processing solution having bleaching power which has become exhausted.
• a processing solution having a bleaching agent of weak oxidizing power e.g., a processing solution having a bleaching agent containing EDTA iron (III) Na salt or EDTA iron (III) NH4 salt
• R1 represents hydrogen atom or a substituent
• R and R2 each represent a substituent.
• substituents represented by R, R1 and R2 include an aryl group, an alkyl group, cyano group, an acyl group, formyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, formylamino group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a ureido group, a sulfamoylamino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, a heteryloxy group, an alkylthio group, an arylthio group, a heterylthio group, a heterocyclic group, a halogen atom,
• substituents represented by R, R1 and R2 include an aryl group (preferably having from 6 to 30 carbon atoms, e.g., phenyl, naphthyl, m-acetylaminophenyl, p-methoxyphenyl, etc.), an alkyl group (preferably having from 1 to 30 carbon atoms, e.g., methyl, trifluoromethyl, ethyl, isopropyl, heptafluoropropyl, t-butyl, n-octyl, n-dodecyl, etc.), cyano group, an alkyl, aryl or heteryl acyl group (preferably having from 1 to 30 carbon atoms, e.g., acetyl, pivaloyl, benzoyl, furoyl, 2-pyridylcarbonyl, etc.), formyl group, a carbamoyl group (preferably having from 1 to 30 carbon
• At least either one of R1 and R2, preferably R1, more preferably both R1 and R2, is an electron withdrawing group having a Hammett's ⁇ p value of 0.35 or higher. More preferably, at least either one of R1 and R2, preferably R1, is an electron withdrawing group having a Hammett's ⁇ p value of 0.60 or higher. Particularly preferably, at least either one of R1 and R2, preferably R1, is cyano group.
• Hammett's substituent constant that is employed in this specification will be explained below briefly.
• Hammett's rule is an empirical rule proposed by L.P. Hammett in 1935 to discuss quantitatively the effect of substituents on the reaction or equilibrium of benzene derivatives. At present, this rule is generally accepted as valid.
• electron withdrawing groups having a Hammett's o p value of 0.60 or higher include cyano group, nitro group, and a sulfonyl group.
• X represents hydrogen atom or a group releasable on a coupling reaction with an oxidation product of a color developing agent, for example, an aromatic primary amine developing agent, (hereinafter referred to as "releasable group").
• the releasable group include a halogen atom (e.g., fluorine, chlorine, bromine, etc.), an alkoxy group (e.g., ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, etc.), an aryloxy group (e.g., 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, etc.), an alkyl, aryl or heteryl acyloxy group (e.g., acetoxy, tetradecanoyloxy, benzoyloxy, etc.), an alkyl, aryl or heteryl sulfonyloxy group (e.g., a methanesulfonyloxy, toluenesulfonyloxy, etc.), an acylamino group (e.g., dichloroph
• Releasable groups bonded via a carbon atom further include bis-form couplers which are obtained by condensation of a four-equivalent coupler by an aldehyde or a ketone.
• the releasable groups which are usable in the present invention may contain a photographically useful group such as a residue of a development inhibitor or a development accelerator.
• X are a hydrogen atom, a halogen atom, an aryloxy group and an arylthio group, more preferable examples of X are a hydrogen atom and a chlorine atom.
• Z1 represents a nonmetallic atom group necessary for forming a nitrogen-containing, six-membered, heterocyclic ring which has at least one dissociative group.
• dissociative group examples are groups having an acid proton, e.g., -NH-, -CH(R)-, etc., preferably those having a pKa value of from 3 to 12 in water.
• the dye forming couplers of formula (I) are preferably those which are represented by formulae (II) to (XIX):
• R1 and R2 are the same as those in formula (I).
• R3, R5, R6, R7 and R8 each represent hydrogen atom or a substituent, and R4 represents a substituent.
• EWG represents an electron withdrawing group having a Hammett's ⁇ p value of 0.35 or higher.
• R3, R4, R5, R6, R7 and R8 are the same as those mentioned for R1.
• the couplers represented by formula (I) may form dimers or other polymers having a coupler residue of formula (I) in the groups represented by R1 to R8.
• the couplers may form monopolymers or copolymers in which the groups of R1 to R8 have polymer chains.
• Typical examples of such mono or copolymers are those of addition polymer ethylene type unsaturated compounds having a coupler residue of formula (I).
• the polymers may contain one or more color developing repeating units having a coupler residue of formula (I).
• the polymers may be copolymers containing as a copolymerization component one or more non-color developing ethylene type monomers such as acrylic esters, methacrylic esters and maleates.
• the couplers of the present invention are effectively used as cyan couplers.
• the releasable group may be introduced by the following four different methods depending upon the kind of releasable group.
• halogen atom is chlorine atom
• a releasable group can be obtained by chlorinating a four-equivalent coupler containing a hydrogen atom as X with sulfuryl chloride, N-chlorosuccinimide, etc. in a halogeno hydrocarbon solution (e.g., chloroform, methylene chloride, etc.).
• a halogeno hydrocarbon solution e.g., chloroform, methylene chloride, etc.
• the other compounds can also be synthesized by a similar method.
• the photosensitive material of the present invention has at least one layer containing the coupler of the present invention on a support. Any hydrophilic colloidal layer on the support can contain the coupler of the present invention.
• General color photosensitive materials can be formed by coating a support with at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer in the mentioned order or any order different therefrom.
• An infrared-sensitive silver halide emulsion layer may be used in place of at least one of the above-described photosensitive emulsion layers.
• Each of these photosensitive emulsion layers contains a silver halide emulsion having sensitivity to the corresponding wavelength region and a color coupler capable of forming a dye of a color complementary to the light to which it is sensitive, thereby enabling color reproduction by the subtractive color process.
• the arrangement may also be such that the photosensitive layers and the developed hues of the couplers do not have the above-described relationship.
• the coupler of the present invention When the coupler of the present invention is applied to a color photosensitive material, it is particularly preferable to use it in a red-sensitive silver halide emulsion layer.
• the coupler of the present invention is added to a photosensitive material in an amount of from 1 x 10 ⁇ 3 to 1 mol, preferably from 2 x 10 ⁇ 3 to 3 x 10 ⁇ 1 mol, per mol of silver halide.
• the coupler of the present invention can be introduced into a photosensitive material by various known dispersion methods. It is preferable to employ an oil-in-water dispersion method wherein the coupler is dissolved in a high-boiling organic solvent (together with a low-boiling organic solvent, if necessary), dispersed in an aqueous gelatin solution, and added to a silver halide emulsion.
• Examples of high-boiling solvents which are usable in the oil-in-water dispersion method are described, for example, in U.S. Patent No. 2,322,027.
• the steps and effects of a latex dispersion method, as one polymer dispersion method, and specific examples of latices for impregnation are described in U.S. Patent No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230, Japanese Patent Application Post-Exam. Publication No. 53-41091 (1978), and European Patent Publication No. 029104.
• a dispersion method using an organic solvent-soluble polymer is described in PCT No. W088/00723.
• high-boiling organic solvents which are usable in the oil-in-water dispersion method are phthalic esters (e.g., dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-tert-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric or phosphonic esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, dioctylbutyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexylpheny
• Organic solvents having a boiling point of from 30 o C to about 160 o C may be used in combination as an auxiliary solvent.
• Typical examples of such an auxiliary solvent are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
• the high-boiling organic solvent is used in an amount of from 0 to 10.0 times, preferably from 0 to 4.0 time, the weight of the coupler.
• a typical example of the photosensitive material has on a support at least one photosensitive layer comprising a plurality of silver halide emulsion layers which are substantially the same in color sensitivity but different in photosensitivity.
• the photosensitive layer is a unit photosensitive layer having color sensitivity to one of blue light, green light and red light.
• unit photosensitive layers are generally arranged in the following order from the support side: a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer.
• the order in which the unit photosensitive layers are arranged may be reversed according to each particular purpose. It is also possible to arrange the unit photosensitive layers such that a photosensitive layer of one color is sandwiched between a pair of photosensitive layers of another color.
• non-photosensitive layer for example, an interlayer, in between a pair of silver halide photosensitive layers and on the top and bottom of the photosensitive material as uppermost and lowermost layers.
• the interlayer may contain a coupler, a DIR compound, etc. such as those described in the specifications of Japanese Patent Application Laid-Open (KOKAI) Nos. 61-43748 (1986), 59-113438 (1984), 59-113440 (1984), 61-20037 (1986) and 61-20038 (1986).
• the interlayer may also contain a color amalgamation preventing agent as in the common practice.
• a plurality of silver halide emulsion layers that constitute each unit photosensitive layer can preferably employ a double-layer configuration comprising a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, as described in West German Patent No. 1,121,470 and British Patent No. 923,045.
• a non-photosensitive layer may be provided between each pair of halide emulsion layers.
• a plurality of silver halide emulsion layers may be installed in the following order from the side remote from the support: a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / a high-sensitivity red-sensitive layer (RH) / a low-sensitivity red-sensitive layer (RL); or BH / BL / GL / GH / RH / RL; or BH / BL / GH / GL / RL / RH.
• BL low-sensitivity blue-sensitive layer
• BH high-sensitivity blue-sensitive layer
• GH high-sensitivity green-sensitive layer
• GL low-sensitivity green-sensitive layer
• RH high-sensitivity red-sensitive layer
• RL low-sensitivity red-sensitive layer
• a plurality of silver halide emulsion layers in the following order from the side remote from the support: a blue-sensitive layer / GH / RH / GL / RL, as described in Japanese Patent Application Post-Exam Publication No. 55-34932 (1980). It is also possible to arrange a plurality of silver halide emulsion layers in the following order from the side remote from the support: a blue-sensitive layer / GL / RL / GH / RH, as described in Japanese Patent Application Laid-Open (KOKAI) Nos. 56-25738 (1981) and 62-63936 (1987).
• KOKKAI Japanese Patent Application Laid-Open
• a layer configuration in which a silver halide emulsion layer having the highest sensitivity forms an upper layer, a silver halide emulsion layer having a lower sensitivity than that of the upper layer forms a middle layer, and a silver halide emulsion layer having a lower sensitivity than that of the middle layer forms a lower layer, thereby constituting a layer configuration comprising three layers having different sensitivities so that the sensitivity gradually lowers toward the support, as described in Japanese Patent Application Post-Exam Publication No. 49-15495 (1974).
• the three layers may be disposed in the same color sensitive layer in the following order from the side remote from the support: a medium-sensitivity emulsion layer / a high-sensitivity emulsion layer / a low-sensitivity emulsion layer, as described in Japanese Patent Application Laid-Open (KOKAI) No. 59-202464 (1984).
• a medium-sensitivity emulsion layer / a high-sensitivity emulsion layer / a low-sensitivity emulsion layer as described in Japanese Patent Application Laid-Open (KOKAI) No. 59-202464 (1984).
• the three layers may also be arranged in the order: a high-sensitivity emulsion layer / a low-sensitivity emulsion layer / a medium-sensitivity emulsion layer, or a low-sensitivity emulsion layer / a medium-sensitivity emulsion layer / a high-sensitivity emulsion layer.
• a layer configuration comprising four or more layers also, the arrangement of the layers may be changed as described above.
• an interlayer effect donor layer which is different in spectral sensitivity distribution from the main photosensitive layer, e.g., BL, GL, RL, etc. as described in U.S. Patent Nos. 4,663,271, 4,705,744 and 4,707,436, and Japanese Patent Application Laid-Open (KOKAI) Nos. 62-160448 (1987) and 63-89850 (1988).
• Silver halides which are usable in the present invention are silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide, silver iodochloride, etc.
• a preferred halogen composition depends on the desired type of photosensitive material.
• a silver chlorobromide emulsion is preferred for use in color papers; a silver iodobromide emulsion having a silver iodide content of from 0.5 to 30 mol% (preferably from 2 to 25 mol%) is preferred in photosensitive materials for photography, such as color negative films and color reversal films; and a silver bromide emulsion or a silver chlorobromide emulsion is preferred in direct positive color photosensitive materials.
• an emulsion having a high silver chloride content hereinafter referred to as "high silver chloride emulsion) is preferably used.
• Such a high silver chloride emulsion preferably has a silver chloride content of 90 mol% or more, more preferably 95 mol% or more.
• Silver halide grain in the high silver chloride emulsion preferably has localized silver bromide phases in the inside and/or on the surface of the individual grains in layer or non-layer form, as described above.
• the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%.
• These localized phases may be present in the inside of the grains or on the surface (e.g., edges, corners, or planes) of the grains.
• One preferred example of such localized phases is an epitaxially grown portion on the corner(s) of grains.
• a silver chlorobromide or silver chloride emulsion containing substantially no silver iodide is preferably employed.
• the expression "containing substantially no silver iodide” as used herein means that the silver iodide content is not more than 1 mol%, more preferably not more than 0.2 mol%.
• halogen composition of a silver halide emulsion may be either the same or different among individual grains
• use of an emulsion having the same halogen composition among grains makes it easy to obtain grains having uniform properties.
• the halogen composition may be uniformly distributed throughout the individual grains (homogeneous grains), or the individual grains may have a non-uniformly distributed halogen composition to form a laminate structure comprising a core and a single-layered or multi-layered outer shell or may have a non-layered portion differing in halogen composition in the inside or on the surface thereof (when such a portion is on the surface, it is fused on the edge, corner or plane of the grain).
• Either of the latter two types of grain is preferred to the homogeneous grains in order to obtain high sensitivity and also from the standpoint of preventing pressure marks.
• layers or portions differing in halogen composition may have a clear boundary therebetween or may form a mixed crystal to have a vague boundary therebetween.
• the structure may be so designed as to have a continuously varying halogen composition.
• the silver halide grains in the silver halide emulsions used in the present invention have a mean grain size preferably of from 0.1 to 2 ⁇ m, more preferably of from 0.15 to 1.5 ⁇ m (the mean grain size is a number average of a diameter of a circle equivalent to a projected area of a grain) with a size distribution having a coefficient of variation (a quotient obtained by dividing a standard deviation by a mean grain size) of not more than 20%, preferably not more than 15% (so-called monodispersed grains).
• a mean grain size preferably of from 0.1 to 2 ⁇ m, more preferably of from 0.15 to 1.5 ⁇ m
• the mean grain size is a number average of a diameter of a circle equivalent to a projected area of a grain
• Silver halide grains contained in photographic emulsions may have a regular crystal form such as a cubic form, an octahedral form or a tetradecahedral form, an irregular crystal form such as a spherical form or a tabular form, a crystal form having a crystal defect, e.g., a twinning plane, or a composite crystal form of these crystal forms.
• Silver halide grains usable in the present invention range from fine grains having a grain size not larger than about 0.2 ⁇ m to large-sized grains having a projected area diameter of about 10 ⁇ m.
• the silver halide photographic emulsion may be either a monodisperse emulsion or a polydisperse emulsion.
• Silver halide photographic emulsions which are usable in the present invention can be prepared by processes described, for example, in Research Disclosure (RD) No. 17643 (Dec. 1978), pp. 22-23, "I. Emulsion Preparation and Types", and ibid., No. 18716 (Nov. 1979), p. 648, P. Glafkides, Chemie et Phisique Photographique, Paul Montel (1967), G.F. Duffin, Photographic Emulsion Chemistry, Focal Press (1966), and V.L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press (1964).
• Monodisperse emulsions described, for example, in U.S. Patent Nos. 3,574,628 and 3,655,394 and British Patent No. 1,413,748 are also preferably used.
• Tabular grains having an aspect ratio of about 3 or more are also usable in the present invention. Such tabular grains can be readily prepared by processes described, for example, in Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248-257 (1970), U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048 and 4,439,520, and British Patent No. 2,112,157.
• the silver halide grains may be homogeneous grains having a uniform crystal structure throughout the individual grains or heterogeneous grains including those in which the inside and the outer shell have different halogen compositions, those in which the halogen composition differs among layers, and those having silver halides of different halogen composition epitaxially joined together.
• Silver halide grains joined to compounds other than silver halides, for example, silver rhodanide or lead oxide may also be used. It is also possible to employ a mixture of grains of various crystal forms.
• the above-described emulsions may be either a surface latent image type which forms a latent image predominantly on the grain surface or an internal latent image type which forms a latent image predominantly in the inside of the grains, but they must be negative emulsions.
• a core/shell type internal latent image type emulsion described in Japanese Patent Application Laid-Open (KOKAI) No. 63-264740 (1988) may also be employed.
• a method of preparing this core/shell type internal latent image type emulsion is described in Japanese Patent Application Laid-Open (KOKAI) No. 59-133542 (1984).
• the thickness of the shell of this emulsion is preferably in the range of 3 nm to 40 nm, particularly preferably in the range of 5 nm to 20 nm, although it depends on the developing process employed.
• the silver halide emulsions are usually used after physical ripening, chemical ripening and spectral sensitization.
• Additives which are usable in physical ripening, chemical ripening and spectral sensitization of the silver halide emulsion and other known photographic additives which can be used in the present invention are described in Research Disclosure Nos. 17643, 18716 and 30710, as tabulated below.
• the photosensitive material of the present invention it is possible to use in the same layer a mixture of two or more different kinds of emulsion which are different in at least one of the properties, that is, the grain size of the photosensitive silver halide emulsion, the grain size distribution, the halogen composition, the grain shape, and sensitivity.
• silver halide grains fogged at the surface thereof as described in U.S. Patent No. 4,082,553, silver halide grains fogged at the inside thereof, as described in U.S. Patent No. 4,626,498 and Japanese Patent Application Laid-Open (KOKAI) No. 59-214852 (1984), or colloidal silver for a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloidal layer.
• the silver halide grains fogged at the inside or surface thereof enable uniform (non-imagewise) development whether the exposed or unexposed regions of the photosensitive material.
• a method of preparing silver halide grains fogged at the inside or surface thereof is described in U.S. Patent No. 4,626,498 and Japanese Patent Application Laid-Open (KOKAI) No. 59-214852 (1984).
• the halogen composition of a silver halide which forms the internal nuclei of core/shell type silver halide grains fogged at the inside thereof, may be the same as or different from that of the silver halide grains.
• any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide may be employed.
• the grain shape of these fogged silver halide grains is preferably in the range of 0.01 ⁇ m to 0.75 ⁇ m, particularly preferably in the range of 0.05 ⁇ m to 0.6 ⁇ m.
• the grain shape either.
• the silver halide grains may have a regular crystal form. Further, the silver halide grains may form a polydisperse emulsion, but it is preferable for them to form a monodisperse emulsion (in which at least 95% of the overall weight of the silver halide grains or of the total number of grains have a grain size within ⁇ 40% of the mean grain size).
• the non-photosensitive fine-grain silver halide comprises silver halide fine grains which are not sensitive to imagewise exposure light for obtaining a dye image and which are not substantially developed in the developing process. It is preferable that the silver halide fine grains should not to be fogged in advance.
• the fine-grain silver halide preferably has a silver bromide content in the range of 0 to 100 mol% and may contain silver chloride and/ or silver iodide according to need.
• the fine-grain silver halide has a silver iodide content in the range of 0.5 mol% to 10 mol%.
• the fine-grain silver halide in the present invention preferably has a mean grain size in the range of 0.01 ⁇ m to 0.5 ⁇ m, more preferably in the range of 0.02 ⁇ m to 0.2 ⁇ m (the mean grain size is an average of diameters of circles equivalent to the projected areas of grains).
• the fine-grain silver halide can be prepared in the same method as in the case of the ordinary photosensitive silver halide. In this case, the surfaces of the silver halide grains need not be chemically sensitized. No spectral sensitization is needed, either. However, it is preferable to add thereto a known stabilizer, e.g., a triazole, azaindene, benzothiazole or mercapto compound, or a zinc compound, in advance of addition of the silver halide grains to the coating solution.
• the fine-grain silver halide containing layer can preferably contain colloidal silver.
• Additives RD 17643 RD 18716 RD 307105 1. Chemical sensitizer p.23 p.648, right column (RC) p.866 2. Sensitivity increasing agent p.648, RC 3. Spectral sensitizer supersensitizer pp.23-24 p.648, RC to p.649, RC pp.866-868 4. Brightening agent p.24 p.647, RC p.868 5. Antifoggant and stabilizer pp.24-25 p.649, RC pp.868-870 6.
• Light absorber, filter dye, ultra-violet absorber pp.25-26 p.649, RC to p.650, left column (LC) p.873 7.
• Stain inhibitor p.25, RC p.650, LC to RC p.872 8.
• Dye image stabilizer p.25 p.650, LC p.872 9.
• Hardening agent p.26 p.651, LC pp.874-875 10.
• Binder p.26 p.651, LC pp.873-874 11.
• Plasticizer, lubricant p.27 p.650, RC p.876 12.
• Coating aid surface active agent pp.26-27 p.650, RC pp.875-876 13.
• the photosensitive material of the present invention preferably contains a compound capable of reacting with formaldehyde to fix it, as described in U.S. Patent Nos. 4,411,987 and 4,435,503.
• the photosensitive material of the present invention prefferably contains a mercapto compound as described in U.S. Patent Nos. 4,740,454 and 4,788,132, and Japanese Patent Application Laid-Open (KOKAI) Nos. 62-18539 (1987) and 1-283551 (1989).
• a mercapto compound as described in U.S. Patent Nos. 4,740,454 and 4,788,132, and Japanese Patent Application Laid-Open (KOKAI) Nos. 62-18539 (1987) and 1-283551 (1989).
• the photosensitive material of the present invention it is preferable for the photosensitive material of the present invention to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or precursors thereof irrespective of the amount of developed silver, resulting from the developing process, as described in Japanese Patent Application Laid-Open (KOKAI) No. 1-106052 (1989).
• the photosensitive material of the present invention it is preferable for the photosensitive material of the present invention to contain a dye dispersed by a method as described in International Publication No. W088/04794 and Japanese Patent Application Laid-Open (KOKAI) No. 1-502912, or a dye as described in EP No. 317,308A, U.S. Patent No. 4,420555 and Japanese Patent Application Laid-Open (KOKAI) No. 1-259358 (1989).
• color couplers can be used in the photosensitive material of the present invention in combination with the coupler of the present invention. Specific examples of usable color couplers are described in patents cited in Research Disclosure No. 17643, supra, VII-C to G and ibid., No. 307105, VII-C to G.
• magenta couplers examples include 5-pyrazolone couplers and pyrazoloazole couplers.
• suitable magenta couplers include 5-pyrazolone couplers and pyrazoloazole couplers.
• particularly preferred magenta couplers are described in U.S. Patent Nos. 4,310,619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (Jun. 1984), Japanese Patent Application Laid-Open (KOKAI) No. 60-33552 (1985), Research Disclosure No. 24230 (Jun. 1984), Japanese Patent Application Laid-Open (KOKAI) Nos.
• cyan coupler phenol and naphthol couplers may be used jointly.
• suitable cyan couplers are described in U.S. Patent Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos.
• Couplers for correcting unnecessary absorption of a developed dye.
• Preferred examples of such couplers are described in Research Disclosure No. 17643, VII-G, ibid., No. 307105, VII-G, U.S. Patent No. 4,163,670, Japanese Patent Application Post-Exam Publication No. 57-39413 (1982), U.S. Patent Nos. 4,004,929 and 4,138,258, and British Patent No. 1,146,368.
• coupler capable of releasing a fluorescent dye upon coupling by which unnecessary absorption of a developed dye is corrected as described in U.S. Patent No. 4,774,181, and couplers having a dye precursor group as a releasable group which is capable of reacting with a developing agent to form a dye, as described in U.S. Patent No. 4,777,120.
• Couplers capable of releasing a photographically useful residue on coupling are also usable in the present invention.
• Examples of preferred DIR couplers which release a development inhibitor are described in patents cited in Research Disclosure No. 17643, VII-F, ibid., No. 307105, VII-F, Japanese Patent Application Laid-Open (KOKAI) Nos. 57-151944 (1982), 57-154234 (1982), 60-184248 (1985), 63-37346 (1988) and 63-37350 (1988), and U.S. Patent Nos. 4,248,962 and 4,782,012.
• Couplers capable of releasing a bleaching accelerator as described in Research Disclosure Nos. 11449 and 24241, and Japanese Patent Application Laid-Open (KOKAI) No. 61-201247 (1986) are effective in shortening the time required for the processing step having bleaching power, particularly when added to a photosensitive material that employs the above-described tabular silver halide grains.
• Examples of preferred couplers which imagewise release a nucleating agent or a development accelerator at the time of development are described in British Patent Nos. 2,097,140 and 2,131,188, and Japanese Patent Application Laid-Open (KOKAI) Nos. 59-157638 (1984) and 59-170840 (1984).
• Other compounds preferably used in the present invention include compounds which release a fogging agent, a development accelerator, a silver halide solvent, etc. on a reduction-oxidation reaction with an oxidation product of a color developing agent, as described in Japanese Patent Application Laid-Open (KOKAI) Nos. 60-107029 (1985), 60-252340 (1985), 1-44940 (1989) and 1-45687 (1989).
• KOKAI Japanese Patent Application Laid-Open
• KOKAI Japanese Patent Application Laid-Open
• couplers capable of releasing a ligand as described in U.S. Patent No. 4,553,477 couplers capable of releasing a leuco dye as described in Japanese Patent Application Laid-Open (KOKAI) No. 63-75747 (1988); and couplers capable of releasing a fluorescent dye as described in U.S. Patent No. 4,774,181.
• the coupler of the present invention can be introduced into a photosensitive material by various known dispersion methods as described above.
• the standard amount of color couplers usable in combination with the couplers of the present invention ranges from 0.001 to 1 mol per mol of photosensitive silver halide.
• yellow couplers are used in an amount of from 0.01 to 0.5 mol; magenta couplers from 0.003 to 0.3 mol; and cyan couplers from 0.002 to 0.3 mol.
• the photosensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color fog inhibitor.
• the photosensitive material of the present invention may also contain various discoloration inhibitors.
• suitable organic discoloration inhibitors for cyan, magenta and/or yellow images include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols chiefly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives of these phenol compounds obtained by silylating or alkylating the phenolic hydroxyl group thereof.
• Metal complexes such as bissalicylaldoximatonickel complexes and bis-N,N-dialkyldithiocarbamatonickel complexes are also usable.
• organic discoloration inhibitors include hydroquinones as described in U.S. Patent Nos. 2,360,290, 2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944 and 4,430,425, British Patent No. 1,363,921, and U.S. Patent Nos. 2,710,801 and 2,816,028; 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans, as described in U.S. Patent Nos. 3,432,300, 3,573,050, 3,574,627, 3,698,909 and 3,764,337, and Japanese Patent Application Laid-Open (KOKAI) No.
• Suitable ultraviolet absorbents include benzotriazole compounds having an aryl substituent as described, for example, in U.S. Patent No. 3,533,794; 4-thiazolidone compounds as described, for example, in U.S. Patent Nos. 3,314,794 and 3,352,681; benzophenone compounds as described, for example, in Japanese Patent Application Laid-Open (KOKAI) No. 46-2784 (1971); cinnamic ester compounds as described, for example, in U.S. Patent Nos. 3,705,805 and 3,707,395; butadiene compounds as described, for example, in U.S. Patent No. 4,045,229; and benzoxazol compounds as described, for example, in U.S.
• Ultraviolet absorbing couplers e.g., -naphthol type cyan-forming couplers
• ultraviolet absorbing polymers are also usable. These ultraviolet absorbents may be mordanted in a specific layer.
• benzotriazole compounds having an aryl substituent are preferred.
• Binders or protective colloids which are usable in the emulsion layers of the photosensitive material of the present invention include gelatin to an advantage.
• Other hydrophilic colloids may also be used alone or in combination with gelatin.
• Gelatin usable in the present invention may be either lime-processed gelatin or acid-processed gelatin.
• the details of the preparation of gelatin are described in Arthor Vice, The Macromolecular Chemistry of Gelatin, Academic Press (1964).
• the photosensitive material of the present invention preferably contains various antiseptics or antifungal agents, e.g., phenethyl alcohol and those described in Japanese Patent Application Laid-Open (KOKAI) Nos. 63-257747 (1988), 62-272248 (1987) and 1-80941 (1989), such as 1,2-benzisothiazoline-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)-benzimidazole.
• various antiseptics or antifungal agents e.g., phenethyl alcohol and those described in Japanese Patent Application Laid-Open (KOKAI) Nos. 63-257747 (1988), 62-272248 (1987) and 1-80941 (1989), such as 1,2-benzisothiazoline-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5
• Direct positive color photosensitive materials according to the present invention can also contain a nucleating agent, such as hydrazine compounds and quaternary heterocyclic compounds, and a nucleation accelerator for enhancing the effect of the nucleating agent as described in Research Discloure No. 22534 (Jan. 1983).
• a nucleating agent such as hydrazine compounds and quaternary heterocyclic compounds
• a nucleation accelerator for enhancing the effect of the nucleating agent as described in Research Discloure No. 22534 (Jan. 1983).
• the present invention is applicable to various color photosensitive materials. Typical examples include ordinary color negative films, color negative films for movies, color reversal films for slides or television, color print papers, color positive films, and color reversal print papers.
• Supports which can be generally used in the present invention include a transparent film commonly employed in photographic photosensitive materials, for example, a cellulose nitrate film and a polyethylene terephthalate film, and a reflective support.
• a reflective support is preferred for accomplishing the object of the present invention.
• reflective support means a support having increased reflecting properties to make a dye image formed in the silver halide emulsion layers more distinct.
• a reflective support includes a support coated with a hydrophobic resin having dispersed therein a light-reflecting substance, e.g., titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc.; and a support made from a hydrophobic resin having the above-mentioned light-reflecting substance dispersed therein.
• Suitable reflective supports include baryta paper, polyethylene-coated paper, polypropylene synthetic paper; and a transparent support, e.g., a glass plate, a polyester film (e.g., polyethylene terephthalate, cellulose triacetate, cellulose nitrate), a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin film, having thereon a reflective layer or containing therein a reflective substance.
• a transparent support e.g., a glass plate, a polyester film (e.g., polyethylene terephthalate, cellulose triacetate, cellulose nitrate), a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin film, having thereon a reflective layer or containing therein a reflective substance.
• a transparent support e.g., a glass plate, a polyester film (e.g., polyethylene terephthalate,
• the sum total of the film thicknesses of all hydrophilic colloidal layers on the side where an emulsion layer is provided is preferably not larger than 28 ⁇ m, more preferably not larger than 23 ⁇ m, even more preferably not larger than 18 ⁇ m, and particularly preferably not larger than 16 ⁇ m.
• the film swelling speed T 1/2 is preferably not more than 30 seconds, more preferably not more than 20 seconds.
• film thickness as used herein means a film thickness measured at 25 o C and a relative humidity of 55% under moisture-conditioned circumstances (2 days).
• the film swelling speed T 1/2 can be measured by a means known in the technical field concerned.
• T 1/2 is defined as a length of time required to reach 1/2 of the saturated film thickness, which is defined as 90% of the maximum swell film thickness reached when processing is carried out for 3 minutes and 15 seconds at 30 o C with a color developing solution.
• the film swelling speed T 1/2 can be controlled by adding a hardening agent to gelatin used as a binder, or changing aging conditions after the coating process.
• the degree of swelling is preferably in the range of 150% to 400%.
• the degree of swelling can be calculated from the maximum swell film thickness under the above-described conditions according to the expression: (maximum swell film thickness - film thickness) / film thickness.
• a hydrophilic colloidal layer in which the sum total of dry film thicknesses is in the range of 2 ⁇ m to 20 ⁇ m is preferably provided on the side reverse to the side where the emulsion layer is provided.
• the backing layer it is preferable for the backing layer to contain the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardening agent, binder, plasticizer, lubricant, coating aid, surface active agent, etc.
• the degree of swelling of the backing layer is preferably in the range of 150% to 500%.
• the color photosensitive material according to the present invention can be developed by any of the conventional methods described in the above-mentioned RD No. 17643, pp. 28-29, RD No. 18716, from the left-hand column to the right-hand column, p. 651, and RD No. 307105, pp. 880-881.
• color development processing consists of color development, desilvering, and washing.
• Reversal development processing consists of black-and-white development, washing or rinsing, reversing, and color development.
• Desilvering consists of bleach with a bleaching bath and fixing with a fixing bath or, alternatively, bleach-fix with a bleach-fix bath.
• Bleach, fixing, and bleach-fix may be combined in an arbitrary order. Washing may be replaced with stabilization, or washing may be followed by stabilization.
• Color development, bleach, and fixing may be carried out in a development-bleach-fix monobath.
• processing systems may further be combined with pre-hardening, neutralization after pre-hardening, stop-fixing, after-hardening, compensation, intensification, or a like step. Between two of these steps, an intermediate washing step may be inserted. Color development may be replaced with so-called activator treatment.
• a color developing solution which is usable for development processing of the photosensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent.
• Useful color developing agents include aminophenol compounds and preferably p-phenylenediamine compounds.
• Typical examples of p-phenylenediamine compounds are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl- ⁇ -methoxyethylaniline, 4-amino-3-methyl-N-methyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-ethyl-N-(2-hydroxypropyl)aniline, 4-amino-3-ethyl-N-ethyl-N-(3-hydroxypropyl)aniline, 4-amino-3-ethyl-N-ethyl-N
• These developing agents may be used either individually or in combination of two or more of them according to the desired purpose.
• the color developing solution usually contains pH buffering agents, e.g., carbonates, borates or phosphates of alkali metals, and development inhibitors or antifoggants, e.g., chlorides, bromides, iodides, benzimidazoles, benzothiazoles, and mercapto compounds.
• pH buffering agents e.g., carbonates, borates or phosphates of alkali metals
• development inhibitors or antifoggants e.g., chlorides, bromides, iodides, benzimidazoles, benzothiazoles, and mercapto compounds.
• the color developing solution further contains various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines (e.g., N,N-bis-carboxymethylhydrazine), phenyl semicarbazides, triethanolamine, and catecholsulfonic acids; organic solvents, e.g., ethylene glycol and diethylene glycol; development accelerators, e.g., benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines; dye forming couplers; competing couplers; auxiliary developing agents (e.g., 1-phenyl-3-pyrazolidone); viscosity-imparting agents; and various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylenetri
• B/W developing solution When reversal development is to be carried out, color development is generally effected after black-and-white (hereinafter abbreviated as B/W) development.
• B/W developing solution it is possible to use known B/W developing agents solely or in combination, for example, dihydroxybenzenes, e.g., hydroquinone, 3-pyrazolidones, e.g., 1-phenyl-3-pyrazolidone, and aminophenols, e.g., N-methyl-p-aminophenol.
• dihydroxybenzenes e.g., hydroquinone
• 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone
• aminophenols e.g., N-methyl-p-aminophenol.
• These color and B/W developing solutions generally have a pH value in the range of 9 to 12.
• the rate of replenishment of these developing solutions is generally not more than 3 liters per square meter of the photosensitive material, although it depends on the color photographic material to be processed.
• the rate of replenishment can be reduced to 500 ml or less by lowering the bromide ion concentration in the replenisher.
• the above-described opening ratio is preferably not higher than 0.1 (cm ⁇ 1), more preferably in the range of 0.01 to 0.05.
• the opening ratio can be reduced by, for example, putting a barrier, such as a floating cover, on the surface of the photographic processing solution in the processing tank. Reduction of the opening ratio may also be achieved by a method that employs a movable cover, as described in Japanese Patent Application Laid-Open (KOKAI) No.
• the technique of reducing the opening ratio is preferably applied not only to color development and B/W development but also to all of the subsequent steps, e.g., bleach, bleach-fix, fixing, washing, and stabilization. Reduction of the replenishment rate may also be achieved by using a means for suppressing the accumulation of bromide ions in the developing solution.
• the color development processing time is usually from 2 to 5 minutes.
• the processing time may be shortened by conducting development processing at an elevated temperature and with an increased pH, using a color developing agent at an increased concentration.
• bleaching The photographic emulsion layers after color development are usually subjected to bleaching.
• Bleaching and fixing may be carried out either simultaneously (bleach-fix) or separately.
• bleaching may be followed by bleach-fix.
• the mode of bleaching can be arbitrarily selected according to the end use.
• bleach-fix may be effected using two tanks connected in series, or fixing may be followed by bleach-fix, or bleach-fix may be followed by bleach.
• Bleaching agents used in a bleaching bath or bleach-fix bath include compounds of polyvalent metals, e.g., iron (III), peracids, quinones, and nitro compounds.
• Typical bleaching agents include organic complex salts of iron (III), e.g., aminopolycarboxylic acid iron (III) complex salts, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc., and complex salts of citric acid, tartaric acid, malic acid, etc.
• iron (III) e.g., aminopolycarboxylic acid iron (III) complex salts, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc.
• aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt are preferred from the viewpoint of speeding up the processing and preventing environmental pollution.
• Aminopolycarboxylic acid iron (III) complex salts are particularly useful either in a bleaching bath or in a bleach-fix bath.
• a bleaching bath or bleach-fix bath containing these aminopolycarboxylic acid iron (III) complex salts usually has a pH between 4.0 and 8.0. However, for rapid processing, the pH value may be lowered.
• the bleaching or bleach-fix bath or a prebath therefor may contain known bleaching accelerators.
• useful bleaching accelerators include compounds having a mercapto group or a disulfide group as described in U.S. Patent No. 3,893,858, West German Patent Nos. 1,290,812 and 2,059,988, Japanese Patent Application Laid-Open (KOKAI) Nos. 53-32736 (1978), 53-57831 (1978), 53-37418 (1978), 53-72623 (1978), 53-95630 (1978), 53-95631 (1978), 53-104232 (1978), 53-124424 (1978), 53-141623 (1978) and 53-28426 (1978), and Research Disclosure No. 17129 (Jul.
• the bleaching or bleach-fix bath preferably contains organic acids.
• organic acids used for this purpose are those having an acid dissociation constant (pKa) of from 2 to 5, e.g., acetic acid, propionic acid, hydroxyacetic acid, etc.
• Fixing agents which can be used in a fixing or bleach-fix bath include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large quantity of iodide. Among them, thiosulfates are commonly used. In particular, ammonium thiosulfate is usable most widely. It is also preferable to use a thiosulfate in combination with a thiocyanate, a thioether compound, a thiourea, etc.
• Preferred preservatives for the fixing or bleach-fix bath include sulfites, bisulfites, carbonyl-bisulfite adducts, and sulfinic acid compounds described in European Patent No. 294769A.
• the fixing or bleach-fix bath preferably contains various aminopolycarboxylic acids or organo-phosphonic acids.
• the fixing or bleach-fix bath it is preferable for the fixing or bleach-fix bath to contain a compound whose pKa is in the range of from 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, etc., in an amount of from 0.1 mol to 10 mol per liter.
• a compound whose pKa is in the range of from 6.0 to 9.0 preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, etc., in an amount of from 0.1 mol to 10 mol per liter.
• the total time of desilvering is preferably as short as possible as long as sufficient desilvering results.
• the preferred desilvering time is from 1 to 3 minutes.
• the desilvering temperature is from 25 o C to 50 o C, preferably from 35 o C to 45 o C. In the preferable temperature range, the desilvering speed increases, and staining after the processing is effectively prevented.
• Methods or means for achieving enhanced stirring include a method in which a jet stream of a processing solution is made to strike against the surface of the emulsion layer of the photosensitive material as described in Japanese Patent Application Laid-Open (KOKAI) No. 62-183460 (1987), a method in which the stirring effect is enhanced by using a rotating means as described in Japanese Patent Application Laid-Open (KOKAI) No.
• An automatic processor that is employed for the photosensitive material of the present invention preferably has a photosensitive material transport means as described in Japanese Patent Application Laid-Open (KOKAI) Nos. 60-191257 (1985), 60-191258 (1985) and 60-191259 (1985).
• a transport means enables a marked reduction in the amount of processing solution carried from one bath to the subsequent bath and is therefore highly effective in preventing deterioration in the performance of the processing solution.
• Such effectiveness is particularly useful to shorten the processing time in each step of the processing and to reduce the amount of processing solution replenished.
• the silver halide color photosensitive material of the present invention generally undergoes washing and/or stabilizing step after the delivering process.
• the amount of washing water used in the washing step is selected from a broad range depending on the characteristics of the photosensitive material (e.g., the kind of photosensitive material such as couplers), the end use of the photosensitive material, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishing system (e.g., counter-flow system or direct-flow system), and other various conditions.
• a relation between the number of washing tanks and the quantity of water in a multi-stage counter-flow system can be decided by the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pp. 248-253 (May 1955).
• the amount of water needed for washing can be reduced by a large margin.
• an increase in the residence time of water in the tank causes propagation of bacteria, and the resulting suspended matter may adhere to the photosensitive material.
• a method of reducing calcium and magnesium ions in the washing water as described in Japanese Patent Application Laid-Open (KOKAI) No. 62-288838 (1987), can be employed extremely effectively for the processing of the color photosensitive material of the present invention.
• chlorine germicides for example, isothiazolone compounds as described in Japanese Patent Application Laid-Open (KOKAI) No.
• Washing water used in the processing of the photosensitive material of the present invention has a pH between 4 and 9, preferably between 5 and 8. Washing conditions, although varying depending on the characteristics or the end use of the photosensitive material and the like, are usually from 15 o C to 45 o C in temperature and from 20 seconds to 10 minutes in time, preferably from 25 o C to 40 o C in temperature and from 30 seconds to 5 minutes in time.
• the photosensitive material of the present invention may also be processed directly with a stabilizing bath without carrying out the above-described washing. In such a stabilizing process, any of the known methods described in Japanese Patent Application Laid-Open (KOKAI) Nos. 57-8543 (1982), 58-14834 (1983) and 60-220345 (1985) can be used.
• the above-described washing may be followed by stabilization using, for example, a stabilizing bath containing a dye stabilizer and a surface active agent as a final bath, which is usually used for color photosensitive materials for photography.
• a stabilizing bath containing a dye stabilizer and a surface active agent as a final bath, which is usually used for color photosensitive materials for photography.
• usable dye stabilizers include aldehydes such as formalin, glutaraldehyde, etc., N-methylol compounds such as dimethylol urea, N-methylolpyrazole, N-methylol-1,2,4-triazole, etc., azolylmethylamines such as hexamethylenetetramine, 1,4-bis(1,2,4-triazole-1-ylmethyl)piperazine, and aldehyde sulfurous acid additives.
• This stabilizing bath may contain various chelate and antifungal agents.
• Overflow accompanying replenishment for washing and /or stabilization may be reused in other processing steps, for example, in a desilvering step.
• the photosensitive material of the present invention may contain a color developing agent, preferably in the form of a precursor thereof.
• color developing agent precursors include iodoaniline compounds described in U.S. Patent No. 3,342,597, Schiff base compounds described in U.S. Patent No. 3,342,599 and Research Disclosure Nos. 14,850 and 15,159, aldol compounds described in Research Disclosure No. 13,924, metal complex salts described in U.S. Patent No. 3,719,492, and urethane compounds described in Japanese Patent Application Laid-Open (KOKAI) No. 53-135628 (1978).
• the photosensitive material of the present invention may further contain various 1-phenyl-3-pyrazolidone compounds for the purpose of accelerating color development.
• Typical examples of these accelerators are described in Japanese Patent Application Laid-Open (KOKAI) Nos. 56-64339 (1981), 57-144547 (1982) and 58-115438 (1983).
• processing solution employed in the present invention are used at a temperature of from 10 o C to 50 o C; in a standard manner, from 33 o C to 38 o C. Higher processing temperatures may be employed for reducing the processing time, or lower temperatures may be employed for improving the image quality or stability of the processing solution.
• the silver halide color photosensitive material of the present invention manifests its effectiveness even more advantageously when it is applied to a film unit with a lens as described, for example, in Japanese Patent Application Post-Exam Publication No. 2-32615 (1990) and Japanese Utility Model Application Post-Exam Publication No. 3-39784 (1991).
• Cyan dyes (A), (B), (C) and (E) were synthesized by using couplers (III)-1 and (II)-1 of the present invention, a comparative coupler (C-1) and (C-2), and a developing agent (D), and reduction potential was measured.
• a THF solution of each dye and Britton-Robinson buffer solution were mixed in a volume ratio of 3:2 to prepare a solution having a dye concentration of 1 x 10 ⁇ 4 mol/liter and a pH of 7.0. With this solution, the reduction potential was measured (voltammetric analyzer P-1000: manufactured by Yanagimoto Seisakusho; dropping mercury electrode). The smaller the reduction potential value, the higher the resistance to reduction.
• Table 6 Dye Potential E 1/2 (V vs S.C.E) Remarks (A) -0.33 Present invention (B) -0.35 Present invention (C) -0.11 Comp.
• Emulsion dispersion 1 of coupler (I)-1 was prepared by the method described below.
• a coating solution having the following composition was prepared and then applied to a cellulose triacetate film base provided with an undercoat layer so that the amount of coupler applied was 1 mmol/m2. Further, 1.5 g/m2 of gelatin was coated on the resulting emulsion layer as a protective layer, thereby preparing sample 101.
• Emulsion (silver chlorobromide (Br: 30 mol%)) 13 g 10% gelatin 28 g Emulsion dispersion 1 22 g Water 37 cc Aqueous solution of 4% 1-oxy-3,5-dichloro-s-triazine sodium salt 5 cc
• Samples 102 to 117 were prepared in the same manner as for sample 101 except that coupler (I)-1 was replaced with an equimolar amount of each of the couplers shown in Table 7 below.
• Each processing solution had the following composition.
• Formalin (37%) 0.1 g Formalin-sulfurous acid additive 0.7 g 5-chloro-2-methyl-4-isothiazoline-3-one 0.02 g 2-methyl-4-isothiazoline-3-one 0.01 g Copper sulfate 0.005 g Water to make 1000 ml pH (25 o C) 4.0 Table 7 Sample Coupler No.
• sample 301 On a cellulose triacetate film base provided with an undercoat layer, various layers having the following compositions were stacked up by coating to prepare sample 301 in the form of a multilayer color photosensitive material.
• composition of photosensitive layers is a composition of photosensitive layers
• ExC cyan coupler UV: ultraviolet absorbing agent
• ExM magenta coupler
• HBS high-boiling organic solvent
• ExY yellow coupler
• ExS sensitizing dye
• the numeral corresponding to each component represents the coating weight expressed in the unit of g/m2.
• the coating weight in terms of silver is shown.
• sensitizing dyes the coating weight per mol of silver halide in the same layer is shown in units of mol.
• the layers contained proper additives, e.g., W-1 to W-3, B-4 to B-6, F-1 to F-17, iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt for the purpose of improving storage properties, processability, pressure resistance, antifungal and antibacterial properties, antistatic properties and coating properties.
• proper additives e.g., W-1 to W-3, B-4 to B-6, F-1 to F-17, iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt for the purpose of improving storage properties, processability, pressure resistance, antifungal and antibacterial properties, antistatic properties and coating properties.
• samples 302 to 310 were prepared in the same manner as for sample 301 except that cyan couplers ExC-1 and ExC-4 in the 3rd, 4th and 5th layers were replaced with an equimolar amount of each of the couplers shown in Table 9.
• Each of samples 301 to 310 was gradationally exposed to red light and then processed by using an automatic processor according to the following processing schedule (II).
• Processing Schedule (II) Step Time Temperature Replenishment rate* Tank capacity Color development 3'05" 38 o C 600 ml 17 lit. Bleach 50" 38 o C 140 ml 5 lit. Bleach-fix 50" 38 o C -- 5 lit. Fixing 50" 38 o C 420 ml 5 lit.
• Stabilization was effected in a 2-tank counter-flow system: from tank (2) toward tank (1). Overflow of washing water was all introduced into the fixing bath. Replenishment to the bleach-fix bath was effected by providing cut portions in the respective upper parts of the bleaching and fixing tanks of the automatic processor so that all the overflow resulting from the supply of the replenisher into the bleaching and fixing tanks was allowed to flow into the bleach-fix bath.
• the amount of developing bath carried to the bleach step, the amount of bleaching bath carried to the bleach-fix step, the amount of bleach-fix bath carried to the fixing step, and the amount of fixing bath carried to the washing step were respectively 65 ml, 50 ml, 50 ml, and 50 ml per m2 of the photosensitive material.
• the crossover time was 6 sec. each, which was included in the processing time in the preceding step.
• Each processing solution had the following composition.
• Tap water was passed through a mixed bed column packed with an H-type strongly acidic cation exchange resin Amberlite IR-120B (manufactured by Rohm & Haas Co.) and an OH-type strongly basic anion exchange resin Amberlite IR-400 (manufactured by Rohm & Haas Co.) to reduce calcium and magnesium ions to 3 mg/lit. or less, respectively.
• Amberlite IR-120B manufactured by Rohm & Haas Co.
• Amberlite IR-400 manufactured by Rohm & Haas Co.
• Samples 301 to 310 that developed color were measured for the red density with a Fuji-type densitometer.
• evaluation was made in the same way as in Example 1 except that the value measured at a point of cyan density 1.5 was used as a measure of image storage characteristics. The results are shown in Table 9 below. Table 9 Sample No.
• a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was provided thereon, and further various photographic constituent layers were coated thereon, thereby preparing a multilayer color photographic paper (sample 401) having the following layer configuration.
• the coating solutions were prepared as follows.
• a silver chlorobromide emulsion A was prepared (a mixture in the silver molar ratio of 3:7 of a large-sized emulsion A of cubic grains having a mean grain size of 0.88 ⁇ m and a small-sized emulsion A having a mean grain size of 0.70 ⁇ m; the coefficients of variation in the grain size distribution were 0.08 and 0.10, respectively; and each of the large- and small-sized emulsions had 0.3 mol% silver bromide localized in a part of the grain surface).
• the emulsion had the following blue-sensitive sensitizing dyes A and B each added thereto in an amount of 2.0 x 10 ⁇ 4 mol per mol of silver for the large-sized emulsion A and 2.5 x 10 ⁇ 4 mol per mol of silver for the small-sized emulsion A.
• Chemical ripening for this emulsion was effected by adding sulfur and gold sensitizing agents.
• the above-described emulsion dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a 1st layer coating solution having the composition described later.
• a silver chlorobromide emulsion C was prepared (a mixture in the Ag molar ratio of 1:4 of a large-sized emulsion C of cubic grains having a mean grain size of 0.50 ⁇ m and a small-sized emulsion C having a mean grain size of 0.41 ⁇ m; the coefficients of variation in the grain size distribution were 0.09 and 0.11, respectively; and each of the large- and small-sized emulsions had 0.8 mol% AgBr localized in a part of the grain surface).
• the emulsion C had red-sensitive sensitizing dye E added thereto in an amount of 0.9 x 10 ⁇ 4 mol per mol of silver for the large-sized emulsion C and 1.1 x 10 ⁇ 4 mol per mol of silver for the small-sized emulsion C. Further, compound F was added thereto in an amount of 2.6 x 10 ⁇ 3 mol per mol of silver halide. Chemical ripening for this emulsion C was effected by adding sulfur and gold sensitizing agents. The above-described emulsion dispersion and the red-sensitive silver chlorobromide emulsion C were mixed and dissolved to prepare a 5th layer coating solution having the composition described later.
• Coating solutions for the 2nd to 4th layers and 6th and 7th layers were prepared in the same manner as in the case of the 1st layer coating solution.
• As a gelatin hardening agent for each layer 1-oxy-3,5-dichloro-s-triazine sodium salt was employed.
• Cpd-14 and Cpd-15 were added to each layer so that the total amounts of Cpd-14 and Cpd-15 were 25.0 mg/m2 and 50 mg/m2, respectively.
• the spectral sensitizing dyes employed in the silver chlorobromide emulsions for the photosensitive emulsion layers are shown below:
• 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-, green- and red-sensitive emulsion layers in amounts of 8.5 x 10 ⁇ 5 mol, 7.7 x 10 ⁇ 4 mol and 2.5 x 10 ⁇ 4, respectively, per mol of silver halide.
• each layer will be shown below.
• the numerals represent coating weight (g/m2).
• the numerals represent coating weight in terms of silver.
• Table 16 7th layer (protective layer) Gelatin 1.13 Acryl modified copolymer of polyvinyl alcohol (degree of modification: 17%) 0.05 Liquid paraffin 0.02
• Dye image stabilizing agent (Cpd-5) 0.01
• UV-1 Ultraviolet absorbing agent: mixture in the weight ratio of 10:5:1:5 of
• UV-2 Ultraviolet absorbing agent: mixture in the weight ratio of 1:2:2 of
• Samples 402 to 407 were prepared in the same manner as for sample 401 except that cyan coupler ExC of sample 401 was replaced with an equimolar amount of each of the cyan couplers shown in Table 20 below.
• samples 401 to 407 were exposed according to the method described in Example 1 (exposure was carried out with red light). After the completion of the exposure, sample 401 was continuously processed (running test) in the subsequent processing step (III) by using a paper processor until the amount of replenisher supplied became double the capacity of the tank for color development,
• each processing solution was as follows: Table 18 Color Developing Solution Tank solution Replenisher Water 800 ml 800 ml Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g Potassium carbonate 25 g 25 g N-ethyl-N-( ⁇ -methanesulfon amidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N,N-bis(carboxymethyl)hydrazine 4.0 g 5.0 g N,N-di(sulfoethyl)hydroxyamine 1Na 4.0 g 5.0 g Fluorescent brightening agent (WHITEX 4B, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g Water to make 1000 ml 1000 ml pH (25
• the photosensitive materials employing the couplers of the present invention exhibit superior leuco dye reciprocity characteristics even when a processing solution having bleaching power having declined in oxidizing power is used.
• samples 502 to 507 were prepared in the same way except that cyan couplers C-1, C-2 and C-3 in the 4th, 5th and 6th layers of sample 501 were replaced with the couplers shown in Table 22 below, and evaluation was made in the same way as in Example 1.

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• 1992
  • 1992-02-19 JP JP4069854A patent/JP2779728B2/ja not_active Expired - Fee Related
• 1993
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