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
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
• • 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
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
• • 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
  • G03C1/0051—Tabular grain emulsions

Definitions

• the present invention relates to a silver halide photographic light-sensitive material and a method of processing the same, and more particularly to a silver halide photographic light-sensitive material which has high sensitivity and improved sharpness, and a method of processing the same.
• tabular silver halide grains methods of forming these grains, and methods of using these grains are disclosed in, for example, U.S. Patents 4,434,226, 4,439,520, 4,414,310, 4,433,048, 4,414,306 and 4,459,353, JP-A-59-99433, and JP-A-62-209445.
• JP-A means Published Unexamined Japanese Patent Application.
• tabular silver halide grains increase a sensitivity including an increase in color sensitizing efficiency by a sensitizing dye, improve the sensitivity-graininess relationship, and enhance sharpness and covering power because of the optical properties specific to the tabular grains.
• a tabular silver halide grain emulsion is developed in the initial phase of a developing process at a higher rate than an emulsion of silver halide grains of any other shape, such as cubic grains, octahedral grains, tetradecahedral grains, or spherical grains. Due to the difference in rate of development, it is hard to use the tabular silver halide emulsion together with an emulsion of silver halide grains of any other shape.
• JP-A-63-220238 discloses the technique of introducing dislocations into tabular grains, and teaches that the use of tabular grains having dislocations serves to improve the sensitivity, pressure resistance, exposure illuminance and storage stability of a silver halide emulsion.
• the emulsion of tabular grains having dislocations is developed at a higher rate than an emulsion of ordinary tabular grains.
• the tabular grains are used, thus reducing optical scattering thereby to improve the sharpness of any layer closer to a support than a layer containing the tabular grains, the layer containing the tabular grains fails to exhibit sufficient sharpness. In other words, good use cannot be made of the desirable characteristic of the tabular grains. Therefore it has been demanded that inter-image effect and edge effect be increased, even by using tabular grains containing dislocations.
• DIR compound Used commonly as a DIR compound is a DIR coupler which imagewisely releases an development inhibitor, and forms a coloring dye, upon coupling reaction with an oxidized form of a color developing agent.
• a DIR coupler When a DIR coupler is used, however, there is the possibility that the dye obtained from the main coupler presents a turbid hue. Hence, a DIR coupler should not better be used, and a DIR compound which forms a colorless compound is requested for.
• DIR compounds which form a colorless compound are classified into two types, i.e., coupling type and redox type, in accordance with the mode in which they react with an oxidized form of a color developing agent.
• Examples of DIR compounds of the coupling type are disclosed in, for example, JP-B-51-16141, JP-B-51-16142, U.S. Patent 4,226,943 and U.S. Patent 4,171,223.
• JP-B means Published Examined Japanese Patent Application.
• DIR compounds of the redox type are DIR hydroquinone compounds disclosed in, for example, U.S. Patents 3,379,529, U.S.
• first development black/white development
• second development color development
• an inhibitor be released from a DIR compound in the first development.
• all silver halide left undeveloped is developed, and the silver development speed is extremely high.
• a development inhibition is to be applied imagewisely in the second development, the silver development speed must be decreased, inevitably making the color development unstable.
• a DIR compound be reacted in the first development.
• This DIR compound should be a redox type one which can also react with an oxidized form of a black/white developing agent, too.
• Examples of a DIR compound which is very active and greatly serves to improve inter-image effect and edge effect are disclosed in, for example, JP-A-3-226744, JP-A-3-226745 and JP-A-3-226746. These references, however, make no mention of the problem inherent in tabular gains containing dislocations, generally describing only the improvement of inter-image effect and edge effect.
• a DIR compound increases sharpness to one value when applied to tabular grains, and to another value when applied to grains of any other type.
• a DIR compound cannot sufficiently increase the sharpness of tabular grains in some cases, though it can greatly increases the sharpness of grains of any other type. Therefore, it has been demanded that a DIR compound be developed which is effective even if use is made of tabular grains containing dislocations.
• An object of the present invention is to provide a color photographic light-sensitive material which excels in sharpness.
• Another object of the invention is to provide a method of processing the light-sensitive material.
• R11 is R14-N(R16)CON(R15)-, R14OCON(R15)-, R14SO2N(R15)-, R14-N(R16)SO2N(R15)- or R17CONH-.
• R14 is a substituted or unsubstituted alkyl group (one having 1 to 30 carbon atoms, e.g., methyl, ethyl, isopropyl, decyl, hexadecyl, t-butyl, cyclohexyl, or benzyl), a substituted or unsubstituted alkenyl group (one having 2 to 30 carbon atoms, e.g., 1-butenyl or 1-octadecenyl), a substituted or unsubstituted alkynyl group (one having 2 to 30 carbon atoms, e.g., ethynyl or 1-octynyl), a substituted
• Examples of the substituent groups which R14 has are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxylic acid amido group, a sulfonic acid amido group, an alkoxycarbonylamino group, a ureido group, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group, a sulfonyl group, cyano, a halogen atom, an acyl group, hydroxyl group, a carboxyl group, a sulfo group, a nitro group, and a heterocyclic group.
• R15 and R16 may be either identical or different, and can be hydrogen atoms or those exemplified as R14. Preferable as R15 is a hydrogen atom.
• R17 is a substituted or unsubstituted alkyl group having two or more carbon atoms, in which a hetero atom is not substituted on the carbon atom adjacent to the carbonyl group (preferably, one having 2 to 30 carbon atoms, e.g., ethyl, nonyl, pentadecyl, isopropyl, t-butyl, 1-hexylnonyl, 3-(2,5-di-t-pentylphenoxy)propyl, cyclohexyl, or benzyl), a substituted or unsubstituted alkenyl group (one having 2 to 30 carbon atoms, e.g., vinyl, 1-octenyl, or 2-phenylvinyl), a substituted or unsubstituted alkynyl group (one having 2 to 30 carbon atoms, e.g., ethynyl or phenylethynyl), a substituted or un
• Examples of the substituent group which R17 has are those exemplified as the substitutent groups which R14 has.
• R12 and R13 shown in the formula (I) are hydrogen atoms or substituent groups having a Hammett's substituent constant ⁇ p of 0.3 or less.
• substituent groups are: an alkyl group (one having 1 to 30 carbon atoms, e.g., methyl, ethyl, isopropyl, t-butyl, decyl, hexadecyl, cyclohexyl, benzyl, or t-octyl), an aryl group (one having 6 to 30 carbon atoms, e.g., phenyl or naphthyl), an alkoxy group (one having 1 to 30 carbon atoms, e.g., methoxy, hexyloxy, hexadecyloxy, 2-dodecyloxy, or benzyloxy), an aryloxy group (one having 6 to 30 carbon atoms, e.g., phenoxy or naphthoxy),
• R12 and R13 may have a substituent group.
• Q1 in the formula (II) is a divalent group having at least one hetero atom.
• the divalent group are: an amide bond, a divalent amino group, an ether bond, a thioether bond, an imino bond, a sulfonyl group, a carbonyl group, an alkylene group, and an alkenylene group.
• the divalent group may be a combination of two or more of these.
• the examples of the divalent group, which are specified above, may have a substituent group. If Q1 contains an ether bond, it does not form a 5-membered ring.
• R21 in the formula (II) is a group which can be substituted on the hydroquinone nucleus. More specifically, examples of R21 are those specified above as examples of R13.
• R21 are a substituted or unsubstituted acyl group (preferably, one having 1 to 30 carbon atoms, e.g., acetyl, octanoyl, benzoyl, chloroacetyl, 3-carboxypropionyl, or actadecanoyl), a substituted or unsubstituted alkoxycarbonyl group (preferably, one having 2 to 30 carbon atoms, e.g., methoxycarbonyl, octyloxycarbonyl, phenoxycarbonyl, octadecyloxycarbonyl, or methoxyethoxycarbonyl), a substituted or unsubstituted carbamoyl group (preferably, one having 1 to 30 carbon atoms, e.g., carbamoyl, N-propylcarbamoyl, N-hexadecylcarbamoyl, N-(3-(2,4-di-ter
• a and A' in the formulas (I) and (II) are groups which can be removed by alkali (hereinafter called “precursor groups”), each of them is, preferably, a group which can be hydrolyzed, such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxalyl group, or a sulfonyl group; a precursor group of the type utilizing anti-Michael reaction, disclosed in U.S.
• Patent 4,009,029 a precursor group of the type using an anion generated after ring cleavage, as an intramolecular nucleophilic group, disclosed in U.S. Patent 4,310,612; a precursor group wherein an anion undergoes electron transfer along a conjugate system, causing cleavage reaction, which is disclosed in U.S. Patents 3,674,478; 3,932,480 and 3,993,661; a precursor group wherein an anion reacted after ring cleavage undergoes electron transfer, causing cleavage reaction, which is disclosed in U.S. Patent 4,335,200; or a precursor group utilizing an imidomethyl group, disclosed in U.S. Patents 4,363,865 and 4,410,618.
• the group represented by B is a divalent group which can release -(B) k -X first and X then, after the hydroquinone nucleus has been oxidized into a quinone form by an oxdized form of a developing agent during development. It may have timing-adjusting function, or may be a group which becomes a coupler or a redox group releasing X upon reaction with another molecule of an oxidized form of a developing agent. If k is 0, X is bonded directly to the hydroquinone nucleus. If k is 2 or more, there are two or more groups B which are the same or different.
• B which is a group having timing-adjusting function
• B is disclosed in, for example, U.S. Patents 4,248,962 and 4,409,323, British Patent 2,096,783, U.S Patent 4,146,396, JP-A-51-146,828, and JP-A-57-56837. Two or groups, selected from these, may be used as Bs in combination.
• timing-adjusting group Preferred examples of the timing-adjusting group are as follows:
• Example of this group are disclosed in, for example, U.S. Patent 4,146,396, JP-A-60-249148, and JP-A-60-249149.
• Example of this group are disclosed in, for example, U.S. Patents 4,409,323 and 4,421,845.
• This group is the linking group disclosed in, for example, West German Laid-Open Patent Application 2,626,315.
• Examples of the group prepresented by B which is a coupler or a redox group, are as follows:
• An example of the coupler is a phenol type one which is bonded to the hydroquinone nucleus at the oxygen atom of the hydroxy group removed of the hydrogen atom thereof.
• Another example of the coupler is a 5-pyrazoline type coupler which is bonded to the hydroquinone nucleus at the oxygen atom of the hydroxy group of the tautomeried 5-hydroxypyrazole, removed of the hydrogen atom thereof.
• couplers Only after these couplers have been released from hydroquinone nuclei, they act as couplers, reacting with an oxidized form of a developing agent to release X from the coupling position.
• B which is a coupler are those represented by the following formulas (C-1) to (C-4):
• V1 and V2 are substituent groups
• V3, V4, V5, and V6 are nitrogen atoms or substituted or unsubstituted methine groups.
• V7 is a substituent group
• x is an integer ranging from 0 to 4. When x is 2 or more, plural groups V7 may be the same or different. Two groups V7 may combine together to form a ring structure.
• V8 is -CO- group, -SO2-group, an oxygen atom, or a substituted imino group
• V10 is a hydrogen atom or a substituent group.
• the mark * indicates a position where the coupler bonds to the hydroquinone nucleus
• the mark ** indicates a position where the coupler bonds to X.
• P and Q are independently an oxygen atom or a substituted or unsubstituted imino group
• at least one of n X's and n Y's is a methine group having -X as a substituent group, and the remaining X's and Y's are substituted or unsubstituted methine groups or nitrogen atoms
• n is an integer ranging from 1 to 3 (n X's are identical or different, and n Y's are likewise identical or different)
• A'' is a hydrogen atom or a group which can be removed by an alkali, and is of the same meaning as A in the formula (I).
• substituent groups P, X', Y', Q, and A'' may be a divalent groups, combining together to form a ring structure.
• R64 is a substituent group, and q is 0, 1, 2 or 3. If q is 2 or 3, the groups R64 may be the same or different. If two substituent groups R64 are on adjacent carbon atoms, they may be divalent groups, bonding together to form a ring structure.
• R64 R21 in the formula (II) can be cited.
• X represents a development inhibitor.
• Preferable examples of X are a compound having a mercapto group which bonds to the heterocyclic ring and represented by the following formula (X-1), and a heterocyclic compound which can form imino silver and represented by the following formula (X-2).
• Z1 is a non-metallic atomic group required to form a monocyclic or fused heterocyclic ring
• Z2 is a non-metallic atomic group required to form, together with N, a monocyclic or fused heterocyclic ring.
• the heterocyclic ring may have a substituent group.
• the mark * indicates the position where the inhibitor X bonds to B.
• a heterocyclic ring formed by Z1 or Z2 are 5- to 8-membered heterocyclic rings, each having at least one heteroatom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom. Of these, the most preferred is a 5- or 6-membered heterocyclic ring.
• heterocyclic ring represented by Z1 examples include: azoles (tetrazole, 1,2,4-triazole, 1,2,3-triazole, 1,3,4-thiadiazole, 1,3,4-oxadiazole, 1,3-thiazole, 1,3-oxazole, imidazole, benzothiazole, benzoxazole, benzimidazole, pyrrole, pyrazole, and indazole), azaindenes (tetraazaindene, pentaazaindene, and triazaindene), and azines (pyrimidine, triazine, pyrazine, and pyridazine).
• azoles tetrazole, 1,2,4-triazole, 1,2,3-triazole, 1,3,4-thiadiazole, 1,3,4-oxadiazole, 1,3-thiazole, 1,3-oxazole, imidazole, benzothiazole, benzoxazole, benzimidazo
• heterocyclic ring represented by Z2 examples include triazoles (1,2,4-triazole, benzotriazole, and 1,2,3-triazole), indazole, benzimidazole, azaindenes (tetraazaindene and pentaazaindene), and tetrazole.
• R77 is an aliphatic group, an aromatic group, or a heterocyclic group.
• R78, R79, and R80 are each an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. If there are two or more R77 groups, two or more R78 groups, and two or more R80 groups, these may bond together, forming a ring (e.g., a benzene ring).
• Examples of the compound represented by the formula (X-1) are: substituted or unsubstituted mercaptoazoles (e.g., 1-phenyl-5-mercaptotetrazole, 1-propyl-5-mercaptotetrazole, 1-butyl-5-mercaptotetrazole, 2-methylthio-5-mercapto-1,3,4-thiadiazole, 3-methyl-4-phenyl-5-mercapto-1,3,4-triazole, 1-(4-ethylcarbamoylphenyl)-2-mercaptoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-phenyl-5-mercapto-1,3,4-oxadiazole, 1- ⁇ 3-(3-methylureido)phenyl ⁇ -5-mercaptotetrazole, 1-(4-nitrophenyl)-5-mercaptotetrazol
• heterocyclic compound which can form imino silver examples include: substituted or unsubstituted triazoles (e.g., 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-bromobenzotriazole, 5-n-butylbenzotriazole, and 5,6-dimethylbenzotriazole), substituted or unsubstituted indazoles (e.g., indazole, 5-nitroindazole, 3-nitroindazole, and 3-chloro-5-nitroindazole), and substituted or unsubstituted benzimidazoles (e.g., 5-nitrobenzimidazole and 5,6-dichlorobenzimidazole).
• triazoles e.g., 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-bromobenzotriazole, 5-n-butylbenzotriazole,
• X may be a compound becoming a development-inhibiting compound upon releasing from B, which in turn undergoes a certain reaction with a developer component, turning into to a compound which substantially does not have a development-inhibiting property or of which development-inhibiting property is remarkably reduced.
• a functional group which undergo such chemical reaction is, for example, an ester group, a carbonyl group, an imino group, an immonium group, a Mickael-addition receptor group, or imido group.
• Examples of such a deactivating type development inhibitor are the development-inhibiting residual groups described in, for example, U.S. Patents 4,477,563, JP-A-60-218644, JP-A-60-221750, JP-A-60-233650, and JP-A-61-11743.
• Examples of such a compound are: 1-(3-phenoxycarbonylphenyl)-5-mercaptotetrazole, 1-(4-phenoxycarbonylphenyl)-5-mercaptotetrazole, 1-(3-maleinimidophenyl)-5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5-(4-cyanophenoxycarbonyl)benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3, 4-thiadiol, 5-nitro-3-phenoxycarbonylimidazole, 5-(2,3-dichloropropyloxycarbonyl)benzotriazole, 1-(4-benzoyloxyphenyl)-5-mercaptotetrazole, 5-(2-methanesulfonylethoxycarbonyl)-2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1-
• X are mercaptoazoles and benzotriazoles.
• mercaptoazoles mercaptotetrazoles, 5-mercapto-1,3,4-thiadiazoles, and 5-mercapto-1,3,4-oxadiazoles are particularly preferred.
• X 5-mercapto-1,3,4-thiadiazoles.
• k is preferably 0, 1 or 2.
• R11 preferable as R11 are: R14-N(R16)CON(R15)- and R14OCON(R15)-.
• R14, R15, and R16 are of the meanings which have been explained.
• k is preferably 0 or 1.
• a and A' are prefer ably hydrogen atoms.
• Q1 is preferably -N(R28)-CO-Q2-, where Q2 is, for example, a divalent amino group, an ether bond, a thioether bond, an alkylene group, an ethylene bond, an imino bond, a sulfonyl group, a carbonyl group, an arylene group, or a divalent heterocyclic group, or a group consisting of two or more of these.
• R28 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and may have a substituent group. Preferable as R28 is a hydrogen atom.
• R21 is preferably a hydrogen atom or or a substituent group having a Hammett substituent group constant ⁇ p of 0 or more.
• the heterocyclic ring containing Q1 is preferably 5- to 7-membered.
• the compound represented by the following formula (IIA) is preferable.
• Q2 is of the same meaning as has been explained in conjunction with Q1.
• R21, A, A', B, X, and k are identical in meaning to those in the formula (II).
• R11 in the formula (IA) is R17CONH-
• the compounds represented by the following formulas (IB) and (IC) are preferable:
• R34 and R35 are substituent groups, n' is an integer of 2 or more, and m is an integer ranging from 1 to 5. If m is 2 or more, groups R35 may be identical or different.
• A, A', B, X, and k are identical in meaning to those in the formula (I).
• R34 and R35 are those exemplified above as substituent groups which R14 has. These substituent groups may further be substituted.
• R34 is preferably a substituent group having 5 to 30 carbon atoms, and n' is preferably 2 to 5.
• R35 has preferably 5 to 30 carbon atoms.
• the compound represented by the formulas (I) and (II) can be synthesized by the methods disclosed in, for example, JP-A-49-129536, JP-A-52-57828, JP-A-60-21044, JP-A-60-233642, JP-A-60-233648, JP-A-61-18946, JP-A-61-156043, JP-A-61-213847, JP-A-61-230135, JP-A-61-236549, JP-A-62-62352, JP-A-62-103639, and U.S. Patents 3,379,529; 3,620,746; 4,332,828; 4,377,634 and 4,684,604.
• the compounds of the formulas (I) and (II) according to the invention are used in a multilayered color photographic light-sensitive material, they are contained in a silver halide emulsion layer or at least one of the layers adjacent to the silver halide emulsion layer, such as a yellow filter layer, an antihalation layer, an interlayer and a protective layer. It is desirable that the compounds be contained in a silver halide emulsion or the interlayer located adjacent thereto.
• the amounts in which to use the compounds of the formula (I) and (II) in any layer of the silver halide photographic light-sensitive material depends on the features of the material, the application of the material, and the method of developing the material. Generally, the compound is used in an amount of 1 to 10 ⁇ 7 mol, preferably 3 ⁇ 10 ⁇ 2 to 3 ⁇ 10 ⁇ 5 mol, per mol of silver halide contained in the same layer or in an adjacent layer.
• tabular silver halide grain in the present invention is a grain having two opposed major surfaces parallel to each other, each having an equivalent-circle diameter (a diameter of a circle having the same area as the projected area of the major surface) which is two or more times greater than the distance between the major surfaces (i.e., the thickness of the grain).
• the tabular grains have an average diameter/thickness ratio of 2 to 12, preferably 2 to 8.
• the diameter/thickness ratio can be obtained by dividing the sum of the diameter/thickness ratios of the individual tabular grains by the number of the individual grains. It can, nonetheless, be determined by a more simple method, that is, by dividing the average diameter of the tabular grains by the average thickness thereof.
• the tabular grains of the invention have a (equivalent-circle) diameter of 0.3 ⁇ m or more, usually 0.3 to 0.5 ⁇ m, preferably 0.3 to 4.0 ⁇ m, and more preferably 0.3 to 3.0 ⁇ m. They have a thickness of less than 0.5 ⁇ m, preferably 0.05 to less than 0.5 ⁇ m, more preferably 0.08 to 0.3 ⁇ m.
• the diameter and thickness of a grain can be determined from an electron micrograph, as is described in U.S. Patent 4,434,226.
• the halogen composition of the tabular grains is preferably silver bromoiodide or silver bromochloroiodide.
• silver bromoiodide containing 0.1 to 20 mol% of silver iodide is preferred. More preferable is silver bromoiodide containing 1 to 10 mol% of silver iodide. Still more preferable is silver bromoiodide containing 1 to 5 mol% of silver iodide.
• tabular grains those may be used which have each (111) planes, (100) planes, or both of (111) and (100) planes.
• the dislocations in tabular silver halide grains can be observed by a direct method disclosed in J.F. Hamilton, Phot. Sci. Eng., 11 , 57 (1967) and T. Shiozawa, J. Soc. Phot. Sci. Japan, 35 , 213 (1972), in which use is made of a transmission electron microscope at low temperatures. More specifically, silver halide grains are extracted from the emulsion, not applying so high a pressure as to cause dislocation in the grains, are placed on a mesh designed for use in electron microscope observation, and are observed by a transmission method while being cooled not to have damages (e.g., printouts) due to electron beams. The thicker the grains, the more hard it is for electron beams to pass through the grains.
• a high-voltage (200 KV or more for grains having a thickness of 0.25 ⁇ m) electron microscope should better be employed to obtain clear photos of the grains.
• the dislocations in each grain as viewed in the direction perpendicular to the major surface, can be counted and located.
• Each of the dislocations in each tabular grain of the invention can be described as extending, to an edge of the grains, from a position (start position of the dislocation) which is away from the center of the long axis of the grain by a distance corresponding to x% of the length from the center to the edge.
• the value for x is preferably 10 ⁇ x ⁇ 100, more preferably 30 ⁇ x ⁇ 98, still more preferably 50 ⁇ x ⁇ 95.
• the closed line figure formed by connecting the start positions of the dislocation is substantially similar to the shape of the grain, but may not be perfectly similar.
• the line of dislocation substantially linearly extends from the start position to the edge, but often meanders.
• 50% (in number) or more of the tabular grains contained in the silver halide emulsion of the invention have 10 or more dislocation lines each. More preferably, 80% or more of the tabular grains have 10 or more dislocation lines each. Still more preferably, 80% or more of the tabular grains have 20 or more dislocation lines each.
• the tabular grains used in this invention have as small a relative standard deviation of halogen composition of an individual grain as is possible.
• the relative standard deviation is preferably 30% or less, more preferably 20% or less.
• the halogen composition of individual emulsion grains can be measured by analyzing the composition of each gain by means of, for example, an X-ray micro-analyzer.
• the term "relative standard deviation of halogen composition of an individual grain” means the value obtained by measuring the contents of a specified halogen in at least 100 grains by the X-ray micro-analyzer, calculating the average content of the specified halogen in these grains, and obtaining the quotient of the standard deviation of the contents of the specified halogen divided by the average content, and then multiplying the quotient by 100.
• a method of measuring the halogen composition of each grain is described in, for example, in European Patent 147,848A.
• a structure as to the halogen composition of the tabular grains can be determined by using various methods in combination. Among these methods are: X-ray diffraction; EPMA method (also known as “XMA method; ESCA analysis (also known as "EPS method”).
• EPMA method X-ray diffraction
• ESCA analysis also known as "EPS method”
• XMA method silver halide grains are scanned with electron beams, thereby to detect the composition of the grains.
• ESCA method X rays are applied onto grains, and the photoelectrons emanating from the grains are analyzed by a spectroscope.
• the words "surface of a grain” means the surface region of the grain which is about 50 angstroms deep from the surface.
• the halogen composition of this region can be determined by means of the ESCA method.
• the words “inner portion of a grain” means the region of the grain other than the "surface” thereof.
• the tabular grains can be obtained by, for example, forming seed crystals, 40% or more by weight of which are tabular grains, in a relatively high-pAg atmosphere having a pBr value of 1.3, and then growing the seed crystals while adding a silver solution and a halogen solution while maintaining the pBr value at a similar value or a greater value.
• the silver and the halogen solutions be added during the growth of grains by the addition of the silver and halogen, so that no new crystal seeds are formed.
• the size of the tabular grains can be adjusted by, for example, changing the temperature, selecting the type and amount of the solvent, and the type of a silver salt, and controlling the speed of adding the halide.
• the emulsion of the present invention can be principally prepared by the method disclosed in JP-A-63-220238.
• the silver halide emulsion of the present invention has a narrow grain-size distribution and a narrow diameter and/or thickness distribution. It can be manufactured, preferably by the method described in JP-A-63-151618, in which the grains are formed through unclei formation, Ostwald ripening and grain growth.
• the sizes and shapes of the Ostwald-ripened grains should be as uniform as possible.
• a silver nitrate aqueous solution and an alkali halide aqueous solution should better be added by double jet method, while maintaining the pAg value constant at 6.0 to 10.0, during growth stage.
• the solutions being added should have as much over-saturated as is possible.
• the method disclosed in U.S. Patent 4,242,445 can be employed, in which the solutions are added which are so over-saturated that grains grow at 30 to 100% of the critical crystal-growing speed.
• the dislocations in the tabular grains of the invention can be introduced under control by forming a phase within each grain, which phase has a largely different halogen composition.
• the dislocations can be introduced preferably by forming an iodine-rich phase within the grain. More specifically, substrate grains are first prepared, then, an inner iodine-rich phase is formed, covering each substrate grain, and finally a phase containing less iodine than the iodine-rich phase is formed, covering the iodine-rich phase. In this case, it is important to suitably select conditions for forming the iodine-rich phase.
• inner iodine-rich phase means a silver halide solid-solution containing iodine.
• silver halide Preferable as silver halide for the iodine-rich phase is silver iodide, silver bromoiodide, or silver bromochloroiodide. Of these, more preferable are silver iodide and silver bromoiodide (iodine content: 10 to 40 mol%). The most preferable is silver iodide.
• the inner iodine-rich phase may be either one uniformly precipitated on the- substrate grain, or one locally present on a major surface, a side, a ridge, or an apex of the substrate grain.
• the inner iodine-rich phase can be epitaxially orientated at such a position.
• a pAg value before the addition of the iodide salt is preferably 8.5 to 10.5, more preferably 9.0 to 10.5; the temperature is maintained preferably at 30°C to 60°C; and the iodide salt is preferably added in an amount of 1 mol% or less of the total silver, over 30 second to 5 minutes, while the solution is being sufficiently stirred.
• the outer phase covering the iodine-rich phase has a lower iodine content than the iodine-rich phase. Its iodine content is preferably 0 to 12 mol%, more preferably 0 to 10 mol%, and most preferably 0 to 3 mol%.
• the iodine-rich phase exists within an annular region with its center coinciding with the center of the long axis of the grains, in which region 5 mol% to 80 mol%, preferably 10 mol% to 70 mol%, more preferably 20 mol% to 70 mol% of the total silver content of the grain are present, measured along the long-axis direction of the grain.
• long-axis direction means the diameter direction of each tabular grain, in contrast to the short-axis direction which is the direction of the thickness of the gain.
• the iodine content of the inner iodine-rich phase is higher than the average iodine content of the silver bromide, silver bromoiodide or silver bromochloroiodide existing in the surface of the grain; it is preferably 5 or more times higher, more preferably 20 times or more higher.
• a method is preferably employed in which a silver salt solution (e.g., AgNO3 aqueous solution) and a silver halide solution (e.g., KBr aqueous solution) are added at a relatively high speed, in a comparatively great amount, and in a relatively high concentration, in order to increase the speed of growing the grains.
• a silver salt solution e.g., AgNO3 aqueous solution
• a silver halide solution e.g., KBr aqueous solution
• Solvents for silver halide are useful in accelerating ripening.
• halogen ions is introduced in an excessive amount into the reaction vessel, in order to accelerate ripening.
• ripening can be accelerated merely by introducing an excessive amount of a halide solution into the reaction vessel.
• Other ripening agents can be used.
• a ripening agent can be contained, in its entirety, in the dispersion medium placed in the reaction vessel, before silver and halide salts are added. It can also be introduced in the reaction vessel together with the addition of one or more halide salts, silver salts, or deflocculants.
• a ripening agent can be independently introduced at the stage of adding halide salt and silver salt.
• ripening agents other than halogen ions ammonia, amine compound, and thiocyanate, such as alkali metal thiocyanate, particularly sodium thiocyanate, potassium thiocyanate or ammonium thiocyanate, can be used.
• alkali metal thiocyanate particularly sodium thiocyanate, potassium thiocyanate or ammonium thiocyanate
• thiocyanate as a ripening agent is taught in U.S. Patents 2,222,264; 2,448,534 and 3,320,069.
• thioether ordinarly used, such as as those disclosed in U.S. Patents 3,271,157, 3,574,628 and 3,737,313 can be used as ripening agents.
• thion compounds of the type disclosed in JP-A-53-82408 and JP-A-53-144319 can be used.
• the nature of silver halide grains can be controlled in the presence of various compounds during the precipitation of silver halide. These compounds may be introduced into the reaction vessel from the beginning. Alternatively, they may be added, together with one or more salts, by the ordinary method.
• the nature of silver halide can be controlled during the precipitation of silver halide, in the presence of a compound of copper, iridium, lead, bismuth, cadmium or zinc, a chalcogen compound such as a compound of sulfur, selenium or tellurium, or a compound of gold or a Group VIII noble metal, as is described in U.S. Patents 2,448,060; 2,628,167; 3,737,313 and 3,772,031, and Research Disclosure Vol. 134, No.
• silver halides having different compositions may be joined by an epitaxial junction, or compounds other than silver halide, such as silver rhodanide or lead oxide, may be joined.
• These emulsion grains are disclosed in, for example, U.S. Patents 4,094,684; 4,142,900 and 4,459,353, British Patent 2,038,792, U.S. Patents 4,349,622; 4,395,478; 4,433,501; 4,463,087; 3,656,962 and 3,852,067, and JP-A-59-162540.
• the tabular grains for use in the present invention are, usually, chemically sensitized.
• Chemical sensitization can be carried out by using active gelatin as is described in T.H. James, "The Theory of the Photographic Process, 4th Ed.,” Macmillan, 1977, pp. 67-76.
• chemical sensitization can be effected by using a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, a gold sensitizer, a platinum sensitizer, an iridium sensitizer, or a combination of two or more of these sensitizers, at a pAg of 5 to 10 and a pH of 5 to 8 and at a temperature of 30 to 80°C, as is described in Research Disclosure No. 12008, Vol. 120, April 1974, Research Disclosure No. 13452, Vol.
• chemical sensitization can be performed in the presence of a chemical sensitization aid.
• a chemical sensitization aid used as chemical sensitization aid is a compound known to suppress fog and increase sensitivity during the chemical sensitization, such as azaindene, azapyridadine or azapyrimidine.
• Various instances of a modifier of chemical sensitization aid are described in U.S. Patents 2,131,038, 3,411,914 and 3,554,757, JP-A-58-126526, and G.F. Duffin, "Photographic Emulsion Chemistry," Focal Press, 1966, pp. 138-143.
• reduction sensitization using, for example, hydrogen can be carried out, as is described in U.S.
• a reducing agent such as stannous chloride, thiourea dioxide or polyamine
• JP-A-61-3134 or JP-A-61-3136 wherein an oxidizing agent is used, can be applied to the present invention.
• the tabular grains of the invention occupy preferably 50% or more of the projected area of all silver halide grains contained in the emulsion, more preferably 70% or more thereof, and most preferably 90% or more thereof.
• the tabular grain emulsion of this invention can be used in the same silver halide emulsion layer, together with an emulsion of ordinary, chemically sensitized silver halide grains (hereinafter referred to as "non-tabular grains".) Particularly, in the case of a color photographic light-sensitive material, the tabular grain emulsion and the non-tabular grain emulsion can be used in the same emulsion layer and/or different emulsion layers.
• the non-tabular grains are: regular grains having regular crystal shapes, such as cubic grains, octahedral grains and tetradecahedral grains, and irregular grains having irregular crystal shapes, such as spherical grains and potato-shaped grains.
• non-tabular grains may be made of any silver halide such as silver bromide, silver bromoiodide, silver bromochloroiodide, silver bromochloride, or silver chloride.
• silver halides preferable are silver bromoiodide and silver bromochloroiodide, each containing 30 mol% or less of silver iodide, and particularly preferable is silver bromoiodide containing 2 mol% to 25 mol% of silver iodide.
• the non-tabular grains may be fine grains having a grain size of 0.1 ⁇ m or less, or large grains having a projected area diameter of up to 10 ⁇ m, and the emulsion may be a monodisperse emulsion having a narrow distribution, or a polydisperse emulsion having a broad distribution.
• the non-tabular grains used in the present invention can be formed by the methods described in, for example, P. Glafkides, "Chemie et Phisi que 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.
• the grains can be formed by acid method, neutral method, or ammonia method.
• a sheme for reacting a soluble silver salt and a soluble halogen salt a single-ject method, or a double-ject method, or a combination thereof may be employed.
• the so-called reverse mixing method can be used, in which grains are formed in the presence of an excessive amount of silver ions.
• One type of the double-jet method is so-called "controlled double jet method" in which the liquid phase in which silver halide is formed is maintained at a constant pAg value. By this method there can be prepared a silver halide emulsion of grains having a regular crystal shape and an almost uniform grain size.
• Two or more silver halide emulsions, prepared independently, may be used in the form of a mixture.
• a silver halide emulsion comprising the regular grains described above can be prepared by controlling the pAg value and the pH value during the forming of the grains. This is detailed in, for example, Photographic Science and Engineering, Vol. 6, pp. 159-165 (1962), Journal of Photographic Science, Vol. 12, pp. 242-251 (1964), U.S. Patent 3,655,394, and British Patent 1,413,748.
• Monodispers emulsions are described in JP-A-48-8600, JP-A-51-39027, JP-A-51-83097, JP-A-53-137133, JP-A-54-48521, JP-A-54-99419, JP-A-58-37635, JP-A-58-49938, JP-B-47-11386, U.S. Patent 3,655,394, and British Patent 1,413,748.
• the crystal structure of the non-tabular grain may be uniform, may have different halogen compositions in the inner and outer portions thereof, or may be a layered structure.
• Emulsion grains of such types are disclosed in, for example, British Patent 1,027,146, U.S. Patents 3,505,068 and 4,444,877, and JP-A-60-143331.
• an emulsion of non-light-sensitive fine grains having a grain size of 0.6 ⁇ m or less, preferably 0.2 ⁇ m or less may be added to a silver halide emulsion layer, an interlayer, or a protective layer, for the purpose of, for example, accelerating development, improving storage stability, and making good use of reflected light.
• the tabular grain emulsions and the non-tabular grain emulsions are usually those which have been subjected to physical ripening, chemical ripening and spectral sensitization.
• the additives used in these processes are described in Research Disclosure No. 17643 and Research Disclosure No. 18716, as will be specified in the following Table A.
• Various color couplers can be used in the present invention, and specific examples of these couplers are described in patents described in above-mentioned Research Disclosure (RD), No. 17643, VII-C to VII-G.
• Important as dye-forming couplers are those which present, by color development, the three primary colors of subtractive color process (i.e., yellow, magenta, and cyan).
• the examples of non-diffusing, 4-equivalent or 2-equivalent couplers, specified below, can preferably used in this invention, in addition to the couplers described in RD No. 17643, VII-C and VII-D.
• a typical examples of a yellow coupler which can be used in the light-sensitive material according to the present invention is the hydrophobic acylacetamide-based coupler having ballast groups.
• Specific examples of the yellow coupler are disclosed in, for example, U.S. Patents 2,407,210, 2,875,057, and 3,265,506.
• a two-equialent yellow coupler is preferably used.
• Typical examples of the two-equivalent yellow coupler are: oxygen-releasing yellow couplers disclosed in, for example, U.S. Patents 3,408,194; 3,447,928; 3,933,501 and 4,022,620, and nitrogen-releasing yellow couplers disclosed in, for example, JP-B-58-10739, U.S.
• Patents 4,401,752 and 4,326,024, RD No. 18035 (April 1979), British Patent 1,425,020, and West German Laid-Open Applications 2,219,917, 2,261,361, 2,329,587 and 2,433,812.
• An ⁇ -pivaloylacetanilide-based coupler excels in fastness, particularly light fastness, of the formed dye, and an ⁇ -benzoylacetoanilide-based coupler can present high color-forming density.
• magenta coupler which can be used in the light-sensitive material according to this invention are an indazolone-based coupler or a cyanoacetyl-based coupler, each being hydrophobic and having ballast groups.
• the magenta coupler is preferably 5-pyrazolone-based or pyrazoloazole-based coupler.
• 5-pyrazolone-based couplers one wherein 3-position is substituted with an arylamino group or an acylamino group is preferable in view of the formed dye hue and color-forming density.
• Typical examples of such a 5-pyrazolone-based coupler are described in, for example, U.S.
• Particularly preferable as the leaving group of the two-equivalent 5-pyrazolone-based coupler are the nitrogen atom-releasing group disclosed in U.S. Patent 4,310,619 and the arylthio group disclosed in U.S. Patent 4,351,897.
• the 5-pyrazolone-based coupler described in European Patent 73,636, which has ballast groups, can achieve high color-forming density.
• Examples of pyrazoloazole-based couplers are pyrazolobenzimidazoles described in U.S. Patent 3,061,432.
• pyrazoloazole-based couplers are pyrazolone[5,1-c] [1,2,4]triazoles disclosed in U.S. Patent 3,715,067, pyrazolotetrazoles disclosed in Research Disclosure 24220 (June 1984) and JP-A-60-33552, and pyrazolopyrazoles disclosed in Research Disclosure 24230 (June 1984) and JP-A-60-43659.
• Imidazo[1,2-b]pyrazoles disclosed in U.S. Patent 4,500,630 are desirable because of its excellence in light fastness and smallness in auxiliary yellow absorption, of the formed dye.
• Pyrazolo[1,5-b][1,2,4]triazoles disclosed in U.S. Patent 4,540,654 are particularly preferred.
• Examples of a cyan coupler which can be used in the light-sensitive material according to the present invention are hydrophobic and non-diffusing naphthol-based and phenol-based couplers.
• Typical examples of a naphthol-based coupler are the naphthol-based coupler disclosed in U.S. Patent 2,474,293 and, preferably the two-equivalent naphthol-based couplers releasing an oxygen atom, which are disclosed in U.S. Patents 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
• Specific examples of a phenol-based coupler are described in, for example, U.S. Patents 2,369,929; 2,801,171; 2,772,162 and 2,895,826.
• a coupler which can form a cyan dye resistant to temperature and humidity is preferably used in the present invention.
• Typical examples of this coupler are: the phenol-based cyan coupler disclosed in U.S. Patent 3,772,002, which has ethyl or a higer alkyl group at the metha position of the phenol nucleus; the 2,5-diacylamino-substituted phenol-based coupler disclosed in, for example, U.S.
• the cyan coupler in which a sulfonamido group or an amido group is substituted at 5-position of naththol disclosed in European Patent 161,626A, can be preferably used in the present invention since it excels in color-image fastness.
• a colored coupler it is desirable that masking be carried out, by using a colored coupler, together with other couplers, in a color light-sensitive material for photographic use, in order to correct undesirable absorption of the formed dye.
• this colored coupler are: the yellow-colored magenta couplers disclosed in, for example, U.S. Patent 4,163,670 and JP-B-57-39413; and the magenta-colored cyan couplers disclosed in, for example, U.S. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368.
• Other colored couplers are described in RD No. 17643, VII-G, mentioned above.
• a coupler capable of forming colored dyes having proper diffusibility can be used, along with other couplers, in order to improve graininess.
• Examples of such a coupler are the magenta couplers described in U.S. Patent 4,366,237 and British Patent 2,125,570, and the yellow, magenta and cyan couplers described in European Patent 96,570 and West German Laid-Open Application 3,234,533.
• the dye-forming coupler and the special coupler, both described above, may form a dimer or a higher polymer.
• Typical examples of a polymerized dye-forming coupler are described in, for example, U.S. Patents 3,451,820 and 4,080,221.
• Specific examples of a polymerized magenta coupler are disclosed in British Patent 2,102,173 and U.S. Patent 4,367,282.
• a coupler releasing a photographically useful residue upon coupling can also preferably be used in the present invention.
• DIR couplers i.e., couplers releasing a development inhibitor, are those described in the patents cited in the above-described RD No. 17643, VII-F.
• DIR couplers which are preferable for use in combination with the DIR couplers of the present invention are: a developer-deactivating type one, typical examples of which are disclosed in JP-A-57-151944; a timing type one, typical examples of which are disclosed in U.S. Patent 4,248,963 and JP-A-57-154234; and a reaction type one, typical examples of which are disclosed in JP-A-60-184248.
• a coupler which imagewise releases a nucleating agent, a development accelerator, or a precursor of either.
• this compound are described in British Patents 2,097,140 and 2,131,188. Particularly preferable as such is, for example, a coupler which releases a nucleating agent capable of absorbing to silver halide.
• Typical example of this coupler is described in, for example, JP-A-59-157638, and JP-A-59-170840.
• the couplers for use in this invention can be introduced into the light-sensitive material by various known dispersion methods.
• Steps and effects of a latex dispersion method and examples of a loading latex are described in, for example, U.S. Patent 4,199,363 and German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
• a support which can be suitably used in the present invention is described in, for example, RD. No. 17643, page 28, and RD. No. 18716, from the right column, page 647 to the left column, page 648.
• the color photographic light-sensitive material according to the present invention can be developed by the conventional methods described in RD. No. 17643, pp. 28 and 29, RD. No. 18716, the left to right columns, page 651, and RD. No. 307105, pp. 880 and 881.
• a color developer used in development of the light-sensitive material of the present invention is an aqueous alkaline solution containing as a main component, preferably, an aromatic primary amine-based color developing agent.
• an aromatic primary amine-based color developing agent preferably, an aminophenol-based compound is effective, a p-phenylenediamine-based compound is preferably used.
• Typical examples of the p-phenylenediamine-based compound 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-N- ⁇ -methoxyethylaniline, and sulfates, hydrochlorides and p-toluene sulfonates thereof.
• 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline or a sulfate thereof is particularly preferable.
• These compounds can be used in a combination of two or more thereof in accordance with the application.
• the color developer contains a pH buffering agent such as a carbonate, a borate or a phosphate of an alkali metal, and a development restrainer or an antifoggant such as a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound.
• a pH buffering agent such as a carbonate, a borate or a phosphate of an alkali metal
• an antifoggant such as a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound.
• the color developer may also contain a preservative such as hydroxylamine, diethylhydroxylamine, a sulfite, a hydrazine such as N,N-biscarboxymethylhydrazine, a phenylsemicarbazide, triethanolamine, or a catechol sulfonic acid; an organic solvent such as ethyleneglycol or diethyleneglycol; a development accelerator such as benzylalcohol, polyethyleneglycol, a quaternary ammonium salt or an amine; a dye-forming coupler; a competing coupler; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity-imparting agent; and a chelating agent such as aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid, or a phosphonocarboxylic acid.
• a preservative such as hydroxylamine, diethylhydroxylamine, a s
• Typical examples of the chelating agent are ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, and ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.
• black-and-white development is performed and then color development is performed.
• black-and-white developer well-known black-and-white developing agents, e.g., a dihydroxybenzene such as hydroquinone, a 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, and an aminophenol such as N-methyl-p-aminophenol can be used singly or in a combination of two or more thereof.
• the pH of the color and black-and-white developers is generally 9 to 12.
• a replenishment amount of the developer depends on a color photographic light-sensitive material to be processed, it is generally 3 liters or less per m2 of the light-sensitive material.
• the replenishment amount can be decreased to be 500 ml or less by decreasing a bromide ion concentration in a replenishing solution.
• a contact area of a processing tank with air is preferably decreased to prevent evaporation and oxidation of the solution upon contact with air.
• Aperture [contact area (cm2) of processing solution with air]/[volume (cm3) of the solution]
• the above aperture is preferably 0.1 or less, and more preferably, 0.001 to 0.05.
• a shielding member such as a floating cover may be provided on the surface of the photographic processing solution in the processing tank.
• a method of using a movable cover described in JP-A-1-82033 or a slit developing method descried in JP-A-63-216050 may be used.
• the aperture is preferably reduced not only in color and black-and-white development steps but also in all subsequent steps, e.g., bleaching, bleach-fixing, fixing, washing, and stabilizing steps.
• the quantity of replenisher can be reduced by using a means of suppressing accumulation of bromide ions in the developing solution.
• a color development time is normally 2 to 5 minutes.
• the processing time can be shortened by setting a high temperature and a high pH and using the color developing agent at a high concentration.
• the photographic emulsion layer is generally subjected to bleaching after color development.
• the bleaching may be performed either simultaneously with fixing (bleach-fixing) or independently thereof.
• bleach-fixing may be performed after bleaching.
• processing may be performed in a bleach-fixing bath having two continuous tanks, fixing may be performed before bleach-fixing, or bleaching may be performed after bleach-fixing, in accordance with the application.
• the bleaching agent are a compound of a multivalent metal, e.g., iron (III); peroxides; quinones; and a nitro compound.
• Typical examples of the bleaching agent are: an organic complex salt of iron (III), e.g., a complex salt thereof with an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycoletherdiamine tetraacetic acid, and a complex salt thereof with an organic acid such as citric acid, tartaric acid, or malic acid.
• an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycoletherdiamine tetraacetic acid
• an organic acid such as citric acid, tartaric acid,
• iron (III) complex salts of aminopolycarboxylic acid such as an iron (III) complex salt of ethylenediamine tetraacetic acid and a iron (III) complex salt of 2,3-diaminopropanetetraacetic acid, are preferred because they can increase a processing speed and prevent an environmental contamination.
• the iron (III) complex salt of aminopolycarboxylic acid is particularly useful in both the bleaching and bleach-fixing solutions.
• the pH of the bleaching or bleach-fixing solution using the iron (III) complex salt of aminopolycarboxylic acid is normally 4.0 to 8. In order to increase the processing speed, however, processing can be performed at a lower pH.
• a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their prebath, if necessary.
• Useful examples of the bleaching accelerator are: compounds having a mercapto group or a disulfide group described in, for example, U.S.
• Patent 3,893,858 West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, and JP-A-53-141623, and JP-A-53-28426, and Research Disclosure No.
• 17129 July, 1978; a thiazolidine derivative described in JP-A-50-140129; thiourea derivatives disclosed in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S.
• a compound having a mercapto group or a disulfide group is preferable since the compound has a large accelerating effect.
• Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are preferred.
• a compound described in U.S. Patent 4,552,834 is also preferable.
• These bleaching accelerators may be added in the light-sensitive material. These bleaching accelerators are useful especially in bleach-fixing of a photographic color light-sensitive material.
• an organic acid be contained in the bleaching solution or the bleach-fixing solution for the purpose of preventing bleach stain.
• an organic acid is a compound having an acid-dissociation constant (pKa) of 2 to 5.
• pKa acid-dissociation constant
• Specific examples of this organic acid are acetic acid, propionic acid, and hydroxyacetic acid.
• Examples of the fixing agent used in the fixing solution or the bleach-fixing solution are a thiosulfate, a thiocyanate, a thioether-based compound, a thiourea and a large amount of an iodide.
• a thiosulfate is used.
• ammonium thiosulfate can be used in the widest range of applications.
• a thiosulfate and, for example, a thiocyanate, a thioether-based compound, or a thiourea can preferably be used in combination.
• Preferable as preservative of the bleach-fixing solution are: a sulfite, a bisulfite, a carbonyl bisulfite adduct, or the sulfinic acid compound disclosed in European Patent 294,769A. It is desirable that various aminopolycarbonic acids or organic sulfonic acids be added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.
• a compound having a pKa of 6.0 to 9.0 should better be added to the fixing solution or the bleach-fixing solution, in an amount of 0.1 to 10 mol per liter.
• imidazoles especially imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
• the total desilverization time should better be as short as possible, as long as desilvering defect does not occur.
• the time is preferably 1 to 3 minutes, more preferably 1 to 2 minutes.
• the desilverization temperature is 5°C to 50°C, preferably 35°C to 45°C. Within the preferable desilverization temperature, the desilverization proceeds at high speed, and stain formation after the processing is effectively prevented.
• stirring is preferably as strong as possible.
• a method of intensifying the stirring are a method of colliding a jet stream of the processing solution against the emulsion surface of the light-sensitive material described in JP-A-62-183460, a method of increasing the stirring effect using rotating means described in JP-A-62-183461, a method of moving the light-sensitive material while the emulsion surface is brought into contact with a wiper blade provided in the solution to cause disturbance on the emulsion surface, thereby improving the stirring effect, and a method of increasing the circulating flow amount in the overall processing solution.
• Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution.
• the above stirring improving means is more effective when the bleaching accelerator is used, i.e., significantly increases the accelerating speed or eliminates fixing interference caused by the bleaching accelerator.
• An automatic developing machine for processing the light-sensitive material of the present invention preferably has a light-sensitive material conveyer means described in JP-A-60-191257, JP-A-60-191258, or JP-A-60-191259.
• this conveyer means can significantly reduce carry-over of a processing solution from a pre-bath to a post-bath, thereby effectively preventing degradation in performance of the processing solution. This effect significantly shortens especially a processing time in each processing step and reduces the quantity of replenisher of a processing solution.
• the silver halide color photographic light-sensitive material of the present invention is normally subjected to washing and/or stabilizing steps after desilvering.
• An amount of water used in the washing step can be arbitrarily determined over a broad range in accordance with the properties (e.g., a property determined by used material such as a coupler) of the light-sensitive material, the application of the material, the temperature of the washing water, the number of water tanks (the number of stages), a replenishing scheme representing a counter or forward current, and other conditions.
• the relationship between the amount of water and the number of water tanks in a multi-stage counter-current scheme can be obtained by a method described in "Journal of the Society of Motion Picture and Television Engineers", Vol. 64, PP.
• a germicide such as an isothiazolone compound and cyabendazole described in JP-A-57-8542, a chlorine-based germicide such as chlorinated sodium isocyanurate, and germicides such as benzotriazole described in Hiroshi Horiguchi et al., "Chemistry of Antibacterial and Antifungal Agents", (1986), Sankyo Shuppan, Eiseigijutsu-Kai ed., “Sterilization, Antibacterial, and Antifungal Techniques for Microorganisms", (1982), Kogyogijutsu-Kai, and Nippon Bokin Bokabi Gakkai ed., “Dictionary of Antibacterial and Antifungal Agents", (1986), can be used.
• the pH of the water for washing the photographic light-sensitive material of the present invention is 4 to 9, and preferably, 5 to 8.
• the water temperature and the washing time can vary in accordance with the properties and applications of the light-sensitive material. Normally, the washing time is 20 seconds to 10 minutes at a temperature of 15°C to 45°C, and preferably, 30 seconds to 5 minutes at 25°C to 40°C.
• the light-sensitive material of the present invention can be processed directly by a stabilizing agent in place of washing. All known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used in such stabilizing processing.
• stabilizing is performed subsequently to washing.
• An example is a stabilizing bath containing a dye stabilizing agent and a surface-active agent to be used as a final bath of the photographic color light-sensitive material.
• Suitable as the dye stabilizing agent are: aldehydes such as formalin and glutaraldehyde, n-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
• aldehydes such as formalin and glutaraldehyde, n-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
• Various chelating agents and various antifungal agents can be added to this stabilizing bath.
• An overflow solution produced upon washing and/or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.
• the silver halide color light-sensitive material of the present invention may contain a color developing agent in order to simplify processing and increases a processing speed.
• a color developing agent for this purpose, various types of precursors of a color developing agent can be preferably used.
• the precursor are an indoaniline-based compound described in U.S. Patent 3,342,597, Schiff base compounds described in U.S. Patent 3,342,599 and Research Disclosure (RD) Nos. 14850 and 15159, an aldol compound described in RD No. 13924, a metal salt complex described in U.S. Patent 3,719,492, and an urethane-based compound described in JP-A-53-135628.
• the silver halide color light-sensitive material of the present invention may -contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
• Typical examples of the compound are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
• Each processing solution in the present invention is used at a temperature of 10°C to 50°C. Although a normal processing temperature is 33°C to 38°C, processing may be accelerated at a higher temperature to shorten a processing time, or image quality or stability of a processing solution may be improved at a lower temperature.
• the silver halide light-sensitive material of the present invention can be applied to thermal development light-sensitive materials described in, for example, U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and European Patent 210,660A2.
• the present invention can be applied to various color light-sensitive materials, especially well applied to color reversal light-sensitive material.
• aqueous solution was prepared by dissolving 10 g of potassium bromide and 20 g of inactive gelatin in 3.7 liters of distilled water. To this aqueous solution a 14% potassium bromide aqueous solution and a 20% silver nitrate aqueous solution were added by the double jet method at a constant flow rate over one minute, while thoroughly stirring the aqueous solution. This addition was performed at 40°C. (During this addition (I), 10.00% of all silver was consumed.) Then, a gelatin aqueous solution (17%, 300 cc) was added to the resultant solution, and the resultant mixture was heated to 75°C.
• Emulsion A thus prepared, contained the tabular grains which occupied 98% of all grains contained. These tabular grains had an equivalent-spherical diameter of 0.50 ⁇ m and an average diameter/thickness ratio of 5.0.
• Emulsion A Direct observation was performed on Emulsion A to detect dislocations, by the method described in Example I-(2) of JP-A-63-220238, by means of a transmission electron microscope. No dislocations were found in Emulsion A.
• Emulsions B to F were prepared in the same way as Emulsion A, except that the silver amount ratios in the additions (I) and (III) were changed, and the amount of potassium iodide added at the time of the addition (III) was adjusted, and the pAg value during the addition (III) was adjusted.
• Emulsion B had been spectrally sensitized with sensitizing dyes S-5 and S-6. It contained tabular grains which occupied 94% of all grains contained. The tabular grains had an equivalent-sphere diameter of 0.45 ⁇ m, an average diameter/thickness ratio of 3.0 and an average AgI content of 4.0 mol%.
• Emulsion C had been spectrally sensitized with sensitizing dyes S-5 and S-6. It contained tabular grains which occupied 97% of all grains contained.
• the babular grains had an equivalent-sphere diameter of 0.55 ⁇ m, an average diameter/thickness ratio of 6, and an average AgI content of 2.5 mol%.
• Emulsion D had been spectrally sensitized with sensitizing dyes S-5 and S-6. It contained tabular grains which occupied 98% of all grains contained. The tabular grains had an equivalent-sphere diameter of 0.95 ⁇ m, an average diameter/thickness ratio of 12 and an average AgI content of 1.5 mol%.
• Emulsion E had been spectrally sensitized with sensitizing dyes S-1 and S-2. It contained tabular grains which occupied 96% of all grains contained. The tabular grains had an equivalent-sphere diameter of 0.7 ⁇ m, an average diameter/thickness ratio of 4, and an average AgI content of 2.5 mol%.
• Emulsion F had been spectrally sensitized with sensitizing dyes S-3 and S-4. It contained tabular grains which occupied 98% of all grains contained. The tabular grains had an equivalent-sphere diameter of 0.8 ⁇ m, an average diameter/thickness ratio of 8.5, and an average AgI content of 2.5 mol%.
• Emulsions B to F were examined for dislocations, in the same way as Emulsion A. No dislocations were found in Emulsions B to F.
• Emulsion G was prepared in the same way as Emulsion A, except for the following points. Potassium iodide was removed from the halogen solution used in the addition (III), and the addition (III) was effected, with the pAg value maintained at 8.4. Addition of silver nitrate and potassium bromide was interrupted during the addition (III), at the time 45% of all silver was consumed. The temperature was lowered to 55°C, and potassium bromide was added, thereby adjusting the pAg value to 9.4. Then, 1250 ml of 1% potassium iodide aqueous solution were added over 120 seconds. Thereafter, the remaining part of the addition (III) were performed over 50 minutes.
• Emulsions H to L were prepared in the same way as Emulsion G, except for those points except for which Emulsion B to F were prepared in the same way as Emulsion A.
• Emulsions G to L were identical to Emulsions A to F, respectively, in terms of the content of tabular grains, the equivalent-sphere diameter, average diameter/thickness ratio and AgI content of the tabular grains. Emulsions G to L were examined for dislocations, in the same way as Emulsion A. It was found that 50% or more (in number) of the grains contained in each of Emulsions G to L had 10 or more dislocation lines each.
• the density of dislocation lines is, by definition, the number of dislocation lines existing in one grain. It is determined by preparing a series of photographs of each grain, taken at different angles to the path of incident electrons, detecting the dislocation lines in each of these photographs, and counting the dislocation lines detected in each grain. Many dislocation lines are assumed to exist in a grain if they are arranged too densely to count.
• the dislocation density distribution among grains is obtained by measuring the dislocation-line densities of 200 or more grains, preferably 300 or more grains, and determining the frequency distribution of these densities.
• a multilayered color light-sensitive material constituted by layers having the following compositions was formed on an undercoated 127 ⁇ m thick triacetylcellulose film support, thereby preparing Sample 101.
• Numerals below indicate an addition amount per m2. Note that the effects of the added compounds are not limited to those described here.
• Layer 1 Antihalation layer Black colloidal silver silver 0.20 g Gelatin 1.9 g Ultraviolet absorbent U-1 0.04 g Ultraviolet absorbent U-2 0.1 g Ultraviolet absorbent U-3 0.1 g Ultraviolet absorbent U-4 0.1 g Ultraviolet absorbent U-6 0.1 g High-boiling organic solvent Oil-1 0.1 g Solid dispersion of fine crystals of dye E-1 0.1 g
• Layer 2 Interlayer Gelatin 0.40 g High-boiling organic solvent Oil-3 0.1 g Dye D-4 0.4 mg
• Layer 3 Interlayer Surface-fogged and internally fogged fine grain silver bromoiodiede emulsion (average grain size: 0.06 ⁇ m, variation coefficient: 18%, AgI content: 1 mol%) silver 0.05 g Gelatin 0.4 g
• Layer 4 Low-speed red-sensitive emulsion layer Silver bromoiodide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (spher
• additives F-1 to F-8 were added to all of the emulsion layers. Furthermore, in addition to the above compositions, gelatin hardener H-1 and surfactants W-3, W-4, W-5, W-6, and W-7 for coating and emulsification were added to each layer.
• Samples 102 to 124 were prepared in the same way as Sample 101, except that tabular grains were used in stead of spherical grains as is shown in Table 1 to 3 (presented later), and that DIR compounds were added as is specified in Tables 1 to 3.
• the DIR compound Cpd-D used in some of Samples 102 to 124 will be specified in Table A (presented later).
• Samples 101 to 124 were tested by the method described below, to determine their sensitivities and sharpnesses.
• Samples 101 to 124 were exposed for 1/100 second to white light applied through a wedge from a light source whose color temperature had been adjusted to 4800°K, and were subjected to the developing process which will be specified below. They were evaluated for their sensitivities in terms of yellow density, magenta density and cyan density.
• Samples 101 to 124 were also subjected to the following sharpness test.
• the samples were exposed to gray light applied through a wedge designed to measure black/white rectangular-wave MTF value, by means of a photometer whose color temperature had been adjusted to 4800°K. Then, they were subjected to the developing process which will be specified below. They were evaluated for their MTF values, i.e., the MTF values of the color-sensitive layers at 30 cycles/mm.
• Samples 101 to 109 were identical to Sample 101, except in that comparative DIR compound Cpd-D or DIR compound I-(1) of this invention was added to layer 9, and that tabular grain emulsions A, C, and D, each having no dislocations, or the tabular grains of the invention which contains dislocations was used in layers 15, 16 and 17 (i.e., blue-sensitive layers).
• the yellow sharpness of the blue-sensitive layers using the tabular grain emulsion was insufficient unless a DIR compound was used.
• the sharpness of any sample using the comparative DIR compound was greater than that of any sample using spherical grains or tabular grains having no dislocations, but was less than that of any sample using tabular grains having dislocations.
• Samples 101 to 124 were as follows: Steps Time Temperature- First development 6 min. 38°C Washing 2 min. 38°C Reversing 2 min. 38°C Color Development 6 min. 38°C Control 2 min. 38°C Bleaching 6 min. 38°C Fixing 4 min. 38°C Washing 4 min. 38°C Stabilization Drying 1 min. Normal temp.
• compositions of the respective processing solutions used in processing Samples 101 to 124 were as follows.
• (First development solution) Water 700 ml Pentasodium nitrilo-N N,N-trimethylenephosphonate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Potassium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2.0 mg Water to make 1000 ml (Reversing solution) Water 700 ml Pentasodium nitrilo-N,N,N-trimethylenephosphonate 3 g Stannous chloride dihydrate 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water to make 1000 ml (Color developing solution) Water 700 ml Pen
• DIR Compound Emulsion 122 (Invention) I-(52) 10 mg/m2 in layers 2 and 7 The same as in Sample 118 123 (Invention) II-(1) 10 mg/m2 in layers 2 and 7 The same as in Sample 118 124 (Invention) II-(28) 10 mg/m2 in layers 2 and 7 The same as in Sample 118 Table 4 Sample No.
• Relative yellow sensitivity density 1.0 Sharpness; MTF value R G B 101 (Comparative 100 0.28 0.43 0.74 102 ( “ ) 97 0.31 0.50 0.78 103 ( “ ) 95 0.35 0.56 0.81 104 ( “ ) 103 0.36 0.52 0.75 105 ( “ ) 100 0.39 0.58 0.84 106 ( “ ) 98 0.44 0.65 0.87 107 ( “ ) 128 0.36 0.52 0.73 108 ( “ ) 127 0.40 0.58 0.78 109 (Invention) 124 0.44 0.65 0.88 Table 5 Sample No.
• Relative yellow sensitivity density 1.0) Sharpness; MTF value R G B 110 (Comparative) 100 0.30 0.49 0.78 111 ( “ ) 97 0.34 0.55 0.81 112 ( “ ) 105 0.33 0.54 0.78 113 ( “ ) 103 0.37 0.57 0.81 114 ( “ ) 132 0.34 0.47 0.78 115 (Invention) 130 0.38 0.59 0.81

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