EP0439069A2 - Lichtempfindliches photographisches Silberhalogenidmaterial - Google Patents

Lichtempfindliches photographisches Silberhalogenidmaterial Download PDF

Info

Publication number
EP0439069A2
EP0439069A2 EP91100578A EP91100578A EP0439069A2 EP 0439069 A2 EP0439069 A2 EP 0439069A2 EP 91100578 A EP91100578 A EP 91100578A EP 91100578 A EP91100578 A EP 91100578A EP 0439069 A2 EP0439069 A2 EP 0439069A2
Authority
EP
European Patent Office
Prior art keywords
group
sensitive material
silver halide
light
halide photographic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP91100578A
Other languages
English (en)
French (fr)
Other versions
EP0439069A3 (en
Inventor
Shinpei C/O Fuji Photo Film Co. Ltd. Ikenoue
Mamoru C/O Fuji Photo Film Co. Ltd. Tashiro
Junichi C/O Fuji Photo Film Co. Ltd. Yamanouchi
Keiichi C/O Fuji Photo Film Co. Ltd. Adachi
Toru C/O Fuji Photo Film Co. Ltd. Harada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0439069A2 publication Critical patent/EP0439069A2/de
Publication of EP0439069A3 publication Critical patent/EP0439069A3/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • 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
    • G03C3/00—Packages of films for inserting into cameras, e.g. roll-films, film-packs; Wrapping materials for light-sensitive plates, films or papers, e.g. materials characterised by the use of special dyes, printing inks, adhesives
    • 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
    • G03C3/00—Packages of films for inserting into cameras, e.g. roll-films, film-packs; Wrapping materials for light-sensitive plates, films or papers, e.g. materials characterised by the use of special dyes, printing inks, adhesives
    • G03C3/02—Photographic roll-films with paper strips

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material and, more particularly, to a silver halide photographic light-sensitive material in which photographic properties are not much degraded while the material is sealed in a closed vessel and stored.
  • a 135-formatted silver halide photographic light-sensitive material which is most often used by general users is normally sealed in a closed vessel and stored. In this manner, degradation in photographic properties caused by an external moisture or noxious gas can be reduced.
  • the above storage condition of a light-sensitive material is very effective in an extremely high humidity atmosphere or in the presence of a gas noxious to a light-sensitive material.
  • a degree of degradation in photographic properties is smaller when a light-sensitive material is stored outside a closed vessel under the same humidity as in the closed vessel than when it is stored in the closed vessel.
  • WO No. 12847/89 and U.S. Patents 3,900,323 and 4,211,837 disclose that degradation in photographic properties of a light-sensitive material can be reduced when a heavy metal compound capable of scavenging a noxious substance produced by a carbon black used in a shading paper is contained in a shading poper. Assuming that the same noxious substance is produced by a carbon black and a light-sensitive material, it is expected that degradation in photographic properties of a light-sensitive material during storage can be reduced if a heavy metal compound is contained in the light-sensitive material.
  • a serious problem of degradation in photographic properties arises when heavy metal compounds such as silver, copper, platinum, palladium, zinc, cadmium, lead, iron, bismuth, and mercury disclosed in the above patents are added to a light-sensitive material. Even if the same noxious substance is produced from a carbon black and a light-sensitive material, therefore, it is very difficult to apply the technique disclosed in the above patents to a 135-formatted silver halide photographic light-sensitive material.
  • JP-A-62-168143 JP-A-62-168143
  • JP-A means Published Unexamined Japanese Patent Application
  • JP-A discloses that degradation in photographic properties of a light-sensitive material during storage can be prevented by decreasing a humidity in a closed vessel.
  • This patent specification has no description which indicates that an influence of a noxious substance except for water produced from a light-sensitive material itself is reduced by means of decreasing a humidity.
  • the present inventors therefore, conducted experiments and found that degradation in photographic properties of a light-sensitive material during storage was reduced by decreasing the humidity in a closed vessel even in the case of the light-sensitive material which is assumed to release a noxious substance.
  • Fig. 1 is a schematic view showing a method of determining a released amount of cyan gas in the present invention.
  • 1 N-NaOH is filled in a washing bottles (I), (III), and (IV), and 1 m 2 of a light-sensitive material is finely cut and put in a washing bottle (II).
  • the bottles (I) and (II) are stored in a constant temperature bath at 75 C.
  • Hydrogen cyanide gas released from a sample is captured in the washing bottle (III) and therefore can be identified or quantitatively analysised by a colorimetry analysis method.
  • Haldrogen cyanide will be also referred to as “cyan gas” or “HCN gas” hereinafter.
  • cyan gas is produced in this order, the concentration of cyan gas in a patrone case housing a 24-frame light-sensitive material is in an order of 1 ppm. By way of parenthesis, a lethal dose of cyan gas is said to be 200 to 300 ppm.
  • the present invention is achieved by reducing an amount of cyan gas released from 1 m 2 of a silver halide photographic light-sensitive material, which is sealed in a closed vessel capable of maintaining a humidity constant and having at least one silver halide emulsion layer containing a silver halide emulsion subjected to sensitization by a gold compound and a chalcogenide compound on a support, to be 0.8 ⁇ g or less by a test method to be defined below.
  • WO No. 12847/89 discloses scavenging cyan gas released from a carbon black contained in a shading paper by a heavy metal compound. In the present invention, however, an amount of cyan gas released from a light-sensitive material is reduced. This is the difference between the reference and the present invention. In the manner of present invention, a change in photographic properties of a light-sensitive material stored in a closed vessel can be largely reduced without degrading photographic properties.
  • washing bottles (I) to (IV) are connected by glass tubes each having an inner diameter of 5 mm.
  • the volume of each of the bottles (I), (III), and (IV) is 250 cc.
  • the volume of the bottle (II) is 1 1.
  • the scrubbing bottles are available from Shibata Kagaku Kikai Kogyo K.K.
  • the glass tube to be dipped in a solution has a glass bulb with pores (G3) at its distal end in order to increase a cyan gas collection efficiency.
  • a sample to be measured is maintained at a relative humidity of about 75%, i.e., 75% ⁇ 15%.
  • An absorbance at 620 nm is read in accordance with the 38.2 pyridine-pyrazolone absorptiometric method in the item of a 38 cyan compound described in JIS K 0102 Factory Wastes Test Method, and an absorbance obtained by a blank operation is subtracted therefrom, thereby performing determination of the amount of cyanide ions in a collection solution.
  • an amount of cyan gas released from 1 m 2 of the light-sensitive material must be decreased to be 0.8 jig or less under the test conditions of the present invention.
  • a change in photographic properties can be reduced when the light-sensitive material is sealed in a closed vessel capable of maintaining a humidity constant.
  • Finding a source of cyan gas production and removing the cause is a most preferable means in order to suppress releasing of cyan gas from a light-sensitive material without changing its photographic properties.
  • a synthetic polymer, an ultraviolet absorbent containing a cyano group, or a dye containing a cyano group contained in a light-sensitive material can be a source of cyan gas releasing. More specifically, a polymer synthesized by a radical polymerization method can be a cyan gas source. The present inventors have made analysis in more detail and found that a polymer synthesized by using a polymerization initiator containing a cyano group can be a cyan gas source.
  • JP-A-59-42543 discloses that a polymer coupler synthesized by an azo-based polymerization initiator not containing a cyano group causes only a small amount of fog and a small change in photographic properties of a light-sensitive material at a high temperature and a high humidity.
  • This patent specification does not describe that cyan gas is produced from the polymer coupler, that a change in photographic properties is increased when the light-sensitive material is sealed in a patrone case and stored if a polymerization initiator containing a cyano group is used, and that the polymer coupler has a large influence on a silver halide emulsion sensitized by a gold compound and a chalcogenide compound. That is, the present invention cannot be expected from the above patent specification.
  • the means for decreasing an amount of cyan gas released from a light-sensitive material will be described in more detail below.
  • a polymerization initiator of the present invention will be described in detail below.
  • a polymerization initiator of the present invention is used as an initiator for a generally well-known radical polymerization reaction of an ethylenic unsaturated monomer and includes all initiators capable of generating a radical by, e.g., decomposition caused by heat, light, or radiation or a redox reaction, thereby starting a polymerization reaction of an ethylenic unsaturated monomer.
  • a compound which decomposes with, e.g., heat to generate a radical such as a peroxide (e.g., hydrogen peroxide, persulfate, hydroperoxide, dialkyl peroxide, diacyl peroxide, ester peroxide, and a metal peroxide), an azo compound, monosulfide, and disulfide, and a compound which generates a radical by a redox reaction between an oxidizing agent and a reducing agent. That is, various types of compounds and their combinations can be used.
  • a peroxide e.g., hydrogen peroxide, persulfate, hydroperoxide, dialkyl peroxide, diacyl peroxide, ester peroxide, and a metal peroxide
  • an azo compound e.g., monosulfide, and disulfide
  • a compound which generates a radical by a redox reaction between an oxidizing agent and a reducing agent e.g
  • a polymerization initiator not containing a cyano group is most preferable as a polymerization initiator for use in the present invention.
  • the initiator is not limited to these examples.
  • a polymerization initiator containing a cyano group is preferably not used at all since it can be a cyan gas source. Note that if no other cyan gas production source is present in a photographic light-sensitive material, the polymerization initiator of this type can be used as needed provided that a total amount of the initiator used in polymerization of a coated polymer is 5 ⁇ mol or less per 1 m 2 of the photographic material.
  • the usable total amount of the initiator containing a cyano group can be increased by purifying a produced polymer by, e.g., re-precipitation or column chromatography. Although this amount depends on a degree of purification, it falls within the range of about 5 ⁇ mol to about 40 ⁇ mol
  • the usable total amount of the polymerization initiator containing a cyano group is further limited. This amount naturally depends on the type or amount of the other cyano group-containing compound used.
  • a method of synthesizing a polymer derived from an ethylenic unsaturated monomer for use in the present invention will be described below.
  • Such a polymer can be synthesized by a generally well-known radical polymerization method (described in detail in, e.g., Takayuki Otsu and Masaetsu Kinoshita, "Experiment Method of Polymer Synthesis", Kagaku Dojin, 1972, pp.
  • solution polymerization suspension polymerization, bulk polymerization, emulsion polymerization, dispersion polymerization, and precipitation polymerization
  • various types of methods such as solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, dispersion polymerization, and precipitation polymerization
  • the type e.g., a solution, a dispersion, a powder, or a grain
  • physical properties e.g., a molecular weight, viscosity, or solubility
  • solution polymerization and emulsion polymerization can be preferably used.
  • a polymer can be obtained by dissolving an ethylenic unsaturated monomer into a suitable solvent (e.g., water, an organic solvent such as methanol, ethanol, propanol, ethyleneglycol, acetone, methylethylketone, acetonitrile, dioxane, N,N-dimethylformamide, N,N-dimethylacetoamide, ethyl acetate, or tetrahydrofuran or a solvent mixture thereof, or a solvent mixture of such an organic solvent and water) and performing solution polymerization.
  • a monomer or a monomer solution may be dropped into a polymerization vessel.
  • the solution polymerization is performed by using the polymerization initiator described above at a temperature of generally 30°C to about 100°C, and preferably 40 C to about 90 C.
  • an amount of the polymerization initiator variously changes in accordance with the type of ethylenic unsaturated monomer, the type of initiator, polymerization conditions (e.g., a temperature and a concentration), and various physical properties (e.g., a molecular weight, viscosity, and solubility) of a produced polymer, it is preferably 0.01 to 5 mol%, and most preferably, 0.03 to 3 mol% with respect to the ethylenic unsaturated monomer.
  • the type of polymerization initiator may be arbitrarily selected in accordance with, e.g., a polymerization temperature and a polymerization solvent, and two or more types of initiators can be simultaneously used.
  • an ethylenic unsaturated monomer is generally emulsion-dispersed in an aqueous medium by using at least one type of an emulsifying agent selected from the group consisting of an anionic surfactant (e.g., TRITON 770 available from Rohm & and House Co.), a cationic surfactant (e.
  • an anionic surfactant e.g., TRITON 770 available from Rohm & and House Co.
  • a cationic surfactant e.
  • cetyltrimethylammonium chloride and stearyltrimethylammonium chloride e.g., cetyltrimethylammonium chloride and stearyltrimethylammonium chloride
  • a nonionic surfactant e.g., EMALEX and NP-20 available from Japan Emulsion Co.
  • gelatin e.g., gelatin, and polyvinylalcohol
  • polymerization initiator most preferably a water-soluble initiator
  • the type and amount of polymerization initiator to be used in this emulsion polymerization can be similarly determined as in the case of solution polymerization described above.
  • a decomposition behavior of an initiator used changes in accordance with, e.g., the type of initiator and a polymerization temperature.
  • a polymerization initiator preferably 80% or more, and most preferably, 95% or more of a polymerization initiator are preferably completely decomposed.
  • Typical examples of a polymer which can be used in a silver halide photographic light-sensitive material of the present invention and is derived from an ethylenic unsaturated monomer will be described below.
  • the polymer is not limited to these examples.
  • a polymer coupler for use in the present invention is preferably a polymer, which is derived from a coupler monomer represented by formula (CI) below and having a repeating unit represented by formula (CII), or a copolymer of at least one type of a non-coloring monomer containing at least one ethylene group and not having oxidative coupling ability with an aromatic primary amine developing agent.
  • CI coupler monomer represented by formula (CI) below and having a repeating unit represented by formula (CII)
  • CII repeating unit represented by formula
  • two or more types of coupler monomers may be simultaneously polymerized.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom
  • L 1 represents (wherein R 2 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted alkyl group having 1 to 6 carbon atoms), -COO-, (wherein each of R 3 and R 4 independently represents a hydrogen, hydroxyl, or halogen atom or substituted or nonsubstituted alkyl, alkoxy, acyloxy, or aryloxy), (wherein R 2 , R 3 , and R 4 have the same meanings as described above), L 2 represents a bonding group for bonding L 1 to Q, i represents 0 or 1, j represents 0 or 1, and Q represents a coupler moiety capable of forming a dye upon coupling with an oxidized aromatic primary amine developing agent.
  • X 1 , X 2 , and X 3 may be the same or different and independently represent an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, an aralkylene group, or a substituted aralkylene group.
  • Each of g, r, and s independently represents 0 or 1.
  • X 1 , X 2 , and X 3 may be the same or different and independently represent a substituted or nonsubstituted alkylene group, aralkylene group, or phenylene group each having 1 to 10 carbon atoms, and the aralkylene group may be either straight-chain or branched.
  • alkylene group examples include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decylmethylene
  • an example of the aralkylene group is benzylidene
  • examples of the substituted and nonsubstituted phenylene group are p-phenylene, m-phenylene, and methylphenylene.
  • Examples of a substituting group of the alkylene group, the aralkylene group, or the phenylene group are a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, a group represented by -NHCOR 8 (wherein R 8 represents alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, or substituted aralkyl), -NHS0 2 R s (R 8 has the same meaning as defined above), -S0 2 R 8 (wherein R 8 has the same meaning as defined above), -SOR s (wherein R 8 has the same meaning as defined above), -COR s (wherein R 8 has the same meaning as defined above), a group represented by (wherein R 9 and R 10 may be the same or different and independently represent a hydrogen atom, alkyl, substituted alkyl, pheny
  • Examples of a substituting group of the substituted alkyl group, the substituted alkoxy group, the substituted phenyl group, and the substituted aralkyl group are a hydroxyl group, a nitro group, an alkoxy group having 1 to about 4 carbon atoms, -NHS0 2 R 8 (wherein R 8 have the same meanings as defined above), (wherein R 9 and R 10 have the same meanings as defined above), a group representedgroup represented by (wherein R 9 R 10 have the same meaning as defined above), -S0 2 R 8 (wherein R 8 has the same meaning as defined above), -COR 8 (wherein R 8 has the same meaning as defined above), a halogen atom, a cyano group, an amino group (which may be substituted by alkyl).
  • Q represents a group bonded to a compound represented by formula (CI) or (CII) at a portion of any of R 51 , to R 59 , Z 1 to Z 3 , and Y of formulas (Cp-1) to (Cp-a) below.
  • R 51 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group
  • each of Rs 2 and R 53 independentlyrepresents an aromatic group or a heterocyclic group.
  • an aliphatic group represented by R 51 may have 1 to 22 carbon atoms and may be substituted or nonsubstituted and chained or cyclic.
  • a substituting group of the aliphatic group are an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom. These substituting groups may have their substituting groups.
  • examples of an effective aliphatic group as R 51 are isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, 1,1-dimethylbutyl, 1,1-dimethylhexyl, 1,1-diethylhexyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, 2-methoxyisopropyl, 2-phenox- yisopropyl, 2-p-tert-butylphenoxyisopropyl, a-aminoisopropyl, a-(diethylkamino)isopropyl, a-(succinimido)-isopropyl, a-(phthalimido)isopropyl, and a-(benzenesulfonamido)isopropyl.
  • R 51 , R 52 , or R 53 represents an aromatic group (especially a phenyl group)
  • this aromatic group may be substituted.
  • An aromatic group such as a phenyl group may be substituted by, e.g., alkyl having 32 or less carbon atoms, alkenyl, alkoxy, alkoxycarbonyl, alkoxycarbonylamino, aliphatic amido, alkylsulfamoyl, alkylsulfonamido, alkylureido, or alkyl-substituted succinimido.
  • alkyl may have an aromatic group such as phenylene in its chain.
  • Phenyl may be substituted by, e.g., aryloxy, aryloxycarbonyl, arylcarbamoyl, arylamido, arylsulfamoyl, arylsulfonamido, or arylureido, and a portion of aryl of these substituting groups may be substituted by one or more alkyl groups having 1 to 22 carbon atoms in total.
  • Phenyl represented by R 51 , R s2 , or R sa may be substituted by amino which may be substituted by lower alkyl having 1 to 6 carbon atoms, hydroxyl, carboxyl, sulfo, nitro, cyano, thiocyano, or a halogen atom.
  • Rsi, R 52 , or Rs 3 may represent a substituting group, obtained when phenyl condenses another ring, such as naphthyl, quionlyl, isoquinolyl, chromanyl, coumaranyl, or tetrahydronaphthyl. These substituting groups may have their own substituting groups.
  • R 51 represents alkoxy
  • an alkyl portion of alkoxy may be substituted by straight-chain or branched alkyl having 1 to 32, and preferably, 1 to 22 carbon atoms, alkenyl, cyclic alkyl, or cyclic alkenyl, and they may be substituted by, e.g., a halogen atom, aryl, or alkoxy.
  • R 53 represents a heterocyclic group
  • this heterocyclic group is bonded to a carbon atom of a carbonyl group of an acyl group or a nitrogen atom of an amido group in a-acylacetoamido via one of carbon atoms forming the heterocyclic ring.
  • the heterocyclic ring are thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine, and they may have a substituting group on their rings.
  • R 55 represents a straight-chain or branch-chain alkyl having 1 to 32, and preferably, 1 to 22 carbon atoms (e.g., methyl, isopropyl, tert-butyl, hexyl, or dodecyl), alkenyl (e.g., aryl), cyclic alkyl (e.g., cyclopentyl, cyclohexyl, or nolbonyl), aralkyl (e.g., benzyl or ⁇ -phenylethyl), or cyclic alkenyl (e.g., cyclopentenyl or cyclohexenyl), and they may be substituted by a halogen atom, a nitro group, cyano, aryl, alkoxy, aryloxy, carboxyl, alkylthiocarbonyl, arylthiocarbonyl, alkoxycarbonyl, aryloxycarbonyl, s
  • R 55 may also represent aryl (e.g., phenyl or a- or 8-naphthyl).
  • Aryl may have one or more substituting groups such as alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl, a halogen atom, a nitro group, cyano, aryl, alkoxy, aryloxy, carboxyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, urethane, sulfonamido, a heterocyclic ring, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, dialkylamino, anilino, N-alkylanilino, N-arylanilino,
  • R 55 may represent a heterocyclic group (e.g., a 5- or 6-membered heterocyclic ring or condensation heterocyclic group, containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, such as pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, or naphthooxazolyl), a heterocyclic group, aliphatic or aromatic acyl, alkylsulfonyl, arylsulfonyl, alkylcarbamoyl, arylcarbamoyl, alkylthiocarbamoyl, or arylthiocarbamoyl, substituted by the substituting groups enumerated above with respect to the aryl group.
  • a heterocyclic group e.g., a 5- or 6-membered heterocyclic ring or condensation heterocyclic group, containing a nitrogen
  • R 54 represents straight-chain or branch-chain alkyl having 1 to 32, and preferably, 1 to 22 carbon atoms, alkenyl, cyclic alkyl, aralkyl, a cyclic alkenyl group (which may have the substituting groups enumerated above with respect to R ss ), an aryl group and a heterocyclic group (which may have the substituting groups enumerated above with respect to Rss), alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, or stearyloxycarbonyl), aryloxycarbonyl (e.g., phenoxycarbonyl or naphthoxycarbonyl), aralkyloxycarbonyl (e.g., benzyloxycarbonyl), alkoxy (e.g., methoxy, ethoxy, or heptadecyloxy), aryloxy (e.g., phenoxy or tolyl
  • R 56 represents a hydrogen atom, a straight-chain or branch-chain aralkyl having 1 to 32, and preferably, 1 to 22 carbon atoms, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl, and they may have the substituting groups enumerated above with respect to Rss.
  • Rss may also represent aryl or a heterocyclic group, and they may have the substituting groups enumerated above with respect to Rss.
  • R 56 may represent cyano, alkoxy, aryloxy, a halogen atom, carboxyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, sulfo, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, urethane, sulfonamido, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, dialkylamino, anilino, N-arylanilino, N-alkylanilino, N-acylanilino, or hydroxyl.
  • R 57 , Rss, and R 59 independently represents a group normally used in a 4-equivalent phenol or a-naphthol coupler. More specifically, examples of R 57 are a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon moiety, an N-arylureido group, an acylamino group, or -0-R 62 or -S-R 62 (wherein R 62 represents an aliphatic hydrocarbon moiety). If two or more R 57 s are present in one molecule, they may be the same or different. In addition, the aliphatic hydrocarbon moiety may have a substituting group. Furthermore, two R 57 s may form a nitrogen-containing heterocyclic ring.
  • substituting groups include an aryl group
  • this aryl group may have the substituting groups enumerated above with respect to Rss.
  • R 59 is a group selected from an aliphatic hydrocarbon moiety, an aryl group, and a heterocyclic moiety.
  • One of R 58 and R 59 may be a hydrogen atom, and the above groups may have a substituting group.
  • R 58 and Rss may together form a nitrogen-containing heterocyclic nucleus.
  • the aliphatic hydrocarbon moiety may be saturated or unsaturated or straight-chain, branched, or cyclic.
  • Preferable examples of the aliphatic hydrocarbon moiety are an alkyl group (e.g., groups of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, and cyclohexyl), and an alkenyl group (e.g., groups of allyl and octenyl).
  • aryl group examples are a phenyl group and a naphthyl group
  • heterocyclic moiety examples are groups of pyridinyl, quinolyl, thienyl, piperidyl, and imidazolyl.
  • Examples of a substituting group, to which the aliphatic hydrocarbon moiety, the aryl group, and the heterocyclic moiety are introduced, are a halogen atom, nitro, hydroxyl, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, a heterocyclic ring, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamido, sulfamoyl, sulfonyl, and morpholino.
  • l represents an integer of 1 to 4
  • m represents an integer of 1 to 3
  • p represents an integer of 1 to 5.
  • R 51 represents t-butyl or substituted or nonsubstituted aryl and R 52 represents substituted or nonsubsituted aryl in formula (Cp-1), and that R 52 and R 53 represent substituted or nonsubstituted aryl in formula (Cp-2).
  • R 54 represents acylamino, ureido, and arylamino and R 55 represents substituted aryl in formula (Cp-3), that R 54 represents acylamino, ureido, and arylamino and R 56 represents a hydrogen atom in formula (Cp-4), and that Rs4. and R 56 represent straight-chain or branch-chain alkyl, alkenyl, cyclic alkyl, aralkyl, and cyclic alkenyl in formulas (Cp-5) and (Cp-6).
  • R 57 represents acylamino or ureido at the 2-position, acylamino or alkyl at the 5-position, and hydrogen atom or chlorine atom at the 6-position in formula (Cp-7), and that R 57 represents hydrogen atom at the 5-position, acylamino, sulfonamido, and alkoxycarbonyl
  • R 58 represents a hydrogen atom
  • R 59 represents phenyl, aralkyl, alkenyl, cyclic alkyl, aralkyl, and cyclic alkenyl in formula (Cp-9).
  • Z 1 represents a hydrogen atom, a halogen atom, sulfo, acyloxy, alkoxy, aryloxy, heterocyclic oxy, alkylthio, arylthio, or heterocyclic thio, and these groups may be substituted by substituting groups such as aryl (e.g., phenyl), nitro, a hydroxyl group, cyano, sulfo, alkoxy (e.g., methoxy), aryloxy (e.g., phenoxy), acyloxy (e.g., acetoxy), acylamino (e.g., acetylamino), sulfonamido (e.g., methanesulfonamido), sulfamoyl (e.g., methylsulfamoyl), a halogen atom (e.g., fluorine, chlorine, and bromine), carboxyl, carbamoyl (e
  • Each of Z 2 and Y independently represents a hydrogen atom or a split-off group bonded to a coupling portion by an oxygen atom, a nitrogen atom, or a sulfur atom. If Z 2 and Y are bonded to a coupling position by an oxygen atom, a nitrogen atom, or a sulfur atom,. this atom is bonded to alkyl, aryl, alkylsulfonyl, arylsulfonyl, alkylcarbonyl, arylcarbonyl, or a heterocyclic group.
  • Z 2 and Y also mean a group which contains the nitrogen atom and can form a 5- or 6-membered ring to be an elimination group (e.g., imidazolyl, pyrazolyl, triazolyl, and tetrazolyl).
  • Alkyl, aryl, and the heterocyclic group described above may have substituting groups. More specifically, examples of the substituting group are alkyl (e.g., methyl and ethyl), alkoxy (e.g., methoxy and ethoxy), aryloxy (e.g., phenyloxy), alkoxycarbonyl (e.g., methoxycarbonyl), acylamino (e.g., acetylamino), carbamoyl, alkylcarbamoyl (e.g., methylcarbamoyl and ethylcarbamoyl), dialkylcarbamoyl (e.g., dimethylcarbamoyl), arylcarbamoyl (e.g., phenylcarbamoyl), alkylsulfonyl (e.g., methylsulfonyl), arylsulfonyl (e.g.,
  • substituting group are a halogen atom, alkyl, alkoxy, alkoxycarbonyl, and cyano.
  • a preferable group of Z 2 is a group bonded to a coupling position by a nitrogen atom or a sulfur atom
  • a preferable group of Y is a chlorine atom or a group bonded to a coupling position by an oxygen atom, a nitrogen atom, or a sulfur atom.
  • Z 3 is a hydrogen atom or represented by formula (R-1), (R-2), (R-3), or (R-4) below.
  • R ⁇ represents an aryl group or a heterocyclic group which may be substituted.
  • each of R64 and R 65 independently represents a hydrogen atom, a halogen atom, carboxylic ester, amino, alkyl, alkylthio, alkoxy, alkylsulfonyl, alkylsulfinyl, a carboxylic acid group, a sulfonic acid group, a substituted or nonsubstituted phenyl group, or a heterocyclic ring. These groups may be the same or diferent.
  • W 1 represents a nonmetal atom required to from a 4-, 5-, or 6-membered ring together with
  • formula (R-4) are represented by formulas (R-5) to (R-7) below.
  • each of R ss and R ⁇ z independently represents a hydrogen atom, alkyl, aryl, alkoxy, aryloxy, or hydroxyl
  • each of R ⁇ , R 69 , R 70 independently represents a hydrogen atom, alkyl, aryl, aralkyl, or acyl
  • W 2 represents an oxygen or sulfur atom.
  • non-color-forming ethylenic monomer which is not coupled to an oxidized product of an aromatic primary amine developing reagent
  • acrylic acid a-chloroacrylic acid
  • a-alkylacrylic acid e.g., acrylic acid and methacrylic acid
  • an ester or amide derived from these acrylic acids e.g., acrylamide, methacrylamide, t-butylacrylamide, 2-acrylamide-2-methylpropanesulfonic acid, methylacrylate, methylmethacrylate, ethylacrylate, n-propylacrylate, iso-propylacrylate, n-butylacrylate, t-butylacrylate, n-butylmethacrylate, 2-ethylhexylacrylate, n-hexylacrylate, n-octylacrylate, laurylacrylate, acetoacetoxyethylmethacrylate, glycidylmethacrylate
  • Most preferable examples are acrylic ester, methacrylic ester, acrylamide, methacrylamide, and styrene and its derivative.
  • n-butylacrylate and methylacrylate, n-butylacrylate and styrene, methylacrylate and t-butylacrylamide, ethylacrylate and methacrylic acid, and sodium 2-acrylamide-2-methylpropanesulfonate and potassium styrenesulfinate can be used.
  • a polymer coupler for use in the present invention may be either water soluble or insoluble.
  • a lipophilic polymer coupler or a telomer coupler formed by polymerization of a coupler monomer which is once extracted and then dissolved into an organic solvent may be emulsion-dispersed, or a polymer coupler latex formed by an emulsion polymerization method and a layered-structure polymer coupler latex may be added directly to a gelatin silver halide emulsion.
  • a hydrophilic polymer coupler once extracted and then dissolved in water or a water/water- miscible organic solvent may be added directly to a gelatin silver halide emulsion.
  • a ratio of a dye-forming portion in the polymer coupler is preferably 5 to 80 wt%, and most preferably, 20 to 70 wt% in consideration of color reproducibility, color forming properties, and stability.
  • an equimolecular weight grams of a polymer containing one mol of a coupler monomer is about 250 to 4,000, but it is not limited to this value.
  • An addition amount of the polymer coupler latex is 0.005 to 0.5 mol, and preferably, 0.01 to 0.05 mol per mol of silver on the basis of a coupler monomer.
  • Methods of synthesizing a polymer of a coupler are roughly classified into i) an emulsion polymerization method, ii) a seed polymerization method, and iii) a solution polymerization method, and i) a polymer coupler latex, ii) a layered-structure polymer coupler latex, and iii) a lipophilic polymer coupler, a telomer coupler, and a hydrophilic polymer coupler can be obtained, respectively.
  • Methods of manufacturing these polymers and methods of adding the polymers to an emulsion are described in i) U.S. Patent 4,080,211, ii) JP-A-58-42044, and iii) U.S. Patent 3,451,820, JP-A-62-276548, and JP-A-60-218646.
  • compositions of polymer couplers synthesized in accordance with these patents are listed in Table-I to Table-V.
  • a magenta coupler preferably a 2-equivalent magenta coupler, and most preferably, a pyrazole-split-off 5-pyrazolone type two-equivalent magenta polymer coupler are used.
  • the polymer coupler of the present invention may be added to any layer of photographic constituting layers, it is preferably added to a light-sensitive emulsion layer or its adjacent layer.
  • An addition amount of the polymer coupler is preferably 0.01 to 1.0 g, and more preferably, 0.05 to 0.5 g per m2.
  • a photographic light-sensitive material of the present invention can contain polymer beads (to be referred to as a polymer matting agent hereinafter) as long as image transparency and graininess are not degraded.
  • the polymer matting agent preferably has an average grain size of 0.3 to 5 pm, and two or more types of polymer matting agents having different average grain sizes can be mixed.
  • Examples of a monomer compound of the polymer matting agent are acrylic ester, methacrylic ester, itaconic diester, crotonic ester, maleic diester, and phthalic diester.
  • Examples of a vinylester are vinylacetate, vinylpropionate, vinylbutylate, vinylisobutylate, vinylcaproate, . vinylchloroacetate, vinylmethoxyacetate, vinylphenylacetate, vinyl benzoate, and vinyl salicylate.
  • Examples of an olefin are dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.
  • styrenes examples include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene, and vinyl methylester benzoate.
  • an acrylamide examples include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, ⁇ -cyanoethylacrylamide, and N-(2-acetoacetoxydiethyl)acrylamide;
  • acrylic acid methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, e.g., monomethyl itaconate, monoethyl itaconate, and monobutyl itaconate; monoalkyl maleate, e.g., monomethyl maleate, monoethyl maleate, and monobutyl maleate; citraconic acid, styrenesulfonic acid, vinylbenzylsul- fonic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acid, e.g., acryloyloxymethylsulfonic acid, acryloylox- yethylsulfonic acid, and acryloyloxypropylsulfonic acid;
  • These monomer compounds may be used in the form of grains of a polymer which is singly polymerized or a copolymer which is obtained by polymerizing a plurality of monomers.
  • a polymer matting agent which is soluble in an alkaline processing solution can be preferably used.
  • a solid of the above polymer may be milled and classified, spherical grains synthesized by a suspension polymerization method may be directly used, or grains may be formed to be spherical by a spray dry method or a dispersion method.
  • an addition amount of such a polymer matting agent depends on, e.g., the type of photographic light-sensitive material or the grain size of polymer matting agent grains, it is preferably 0.02 to 0.4 g/ m 2.
  • a polymer of an ultraviolet absorbent can also be used in the present invention.
  • Examples of the ultraviolet absorbent usable in the present invention are a benzylidene derivative, a benzophenone derivative, a benzotriazole derivative, and a butadiene derivative.
  • Examples of such absorbents are those described in, e.g., JP-A-47-560, JP-A-58-111942, JP-A-58-178351, JP-A-58-181041, JP-A-58-185677, JP-A-61-118749, JP-A-62-260152, JP-A-63-56651, U.S. Patents 4,178,303, 4,207,253, 4,464,463, 4,464,462, 4,645,735, and 4,551,420, and EP 27,259A and 189,059A.
  • a most preferable example in the present invention is an ultraviolet absorbent not containing a cyano group in an ethylenic unsaturated monomer or a copolymerized ethylenic unsaturated monomer is a copolymer is to be used, having an ultraviolet absorptive group.
  • the polymer ultraviolet absorbent used in the present invention may be either a homopolymer or a copolymer of the above ultraviolet absorptive monomers.
  • a monomer used in copolymerization are acrylic acid, a-alacrylic acid (e.g., an ester derived from an acrylic acids such as methacrylic acid, preferably, lower alkylester and an amide such as acrylamide, methacrylamide, t-butylacrylamide, methylacrylate, methylmethacrylate, ethylacrylate, ethylmethacrylate, n-propylacrylate, n-butylacrylate, 2-ethylhexylacrylate, n-hexylacrylate, octylmethacrylate, laurylmethacrylate, and methylenebisacrylamide), vinylester (e.g., vinylacetate, vinylpropionate, and vinyllaurate), an aromatic vinyl compound (e.g., styren
  • acrylic ester methacrylic ester
  • aromatic vinyl compound is most preferable.
  • Two or more types of the above comonomers can be simultaneously used.
  • n-butylacrylate and divinylbenzene, styrene and methylmethacrylate, and methylacrylate and methacrylic acid can be simultaneously used.
  • a ratio of an ultraviolet absorbent monomer component in an ultraviolet absorptive polymer is preferably 5 to 100 wt%, and most preferably, 50 to 100 wt%.
  • UV absorptive polymer Preferable examples of the ultraviolet absorptive polymer will be presented below, but the polymer is not limited to these examples.
  • the ultraviolet absorptive polymer used in the present invention may be prepared by an emulsion polymerization method as described above or stirring a material, obtained by dissolving lipophilic polymer prepared by polymerization of an ultraviolet absorptive monomer in an organic solvent (e.g., ethyl acetate), together with a surfactant in an aqueous gelatin solution to disperse the material in the form of a latex, and introducing the latex into a photographic light-sensitive material.
  • an organic solvent e.g., ethyl acetate
  • an amount of the ultraviolet absorbent polymer used in the present invention is particularly not limited, it is preferably 0.01 to 2.0 g/m 2 , and most preferably, 0.05 to 1.0 g/m 2.
  • these ultraviolet absorbent polymers may be used in a combination of two or more types thereof or in combination with one or more types of other low-molecular ultraviolet absorbent.
  • a polymer latex can be used in order to improve or adjust physical properties (e.g., flexibility and dimensional change) of a film.
  • Such a polymer latex used to improve physical properties of a film preferably has a glass transition temperature lower than room temperature.
  • the latex for this purpose can be used in any of light-sensitive layers and non-light-sensitive layers in a photographic material or in a plurality of layers.
  • an addition amount of the latex changes in accordance with an arrangement of a photographic light-sensitive material, it is preferably 0.05 to 2 g/m 2 , and most preferably, 0.1 to 1 g/m 2 .
  • the polymer latex is also used when additives are incorporated in a photographic layer.
  • the additive are a coupler, a UV absorbent, a brightener, a covering power imparting agent, an antioxidizing agent, a pigment, a developing agent, an antistatic agent, an antifoggant, an antitwisting agent, a redox dye- releasing compound, a matting agent, an absorbing dye, a development stopper, an antihalation dye, a filter dye, a sensitizing dye, a plasticizer, a slip agent, and a development inhibitor.
  • the glass transition temperature, for example, of the latex is not particularly limited, and various types of latexes can be used in accordance with, e.g., properties of an additive to be incorporated.
  • Methods of incorporating an additive in a polymer latex and examples of the polymer latex and additive are described in the following references.
  • a linear polymer derived from an ethylenic unsaturated monomer can be used singly or in the form of a mixture with gelatin as a binder.
  • a typical example of a synthetic polymer as a binder is represented by the following formula (V-1): wherein A represents a monomer unit obtained by copolymerizing a coplymerizable ethylenic unsaturated monomer.
  • Examples of the ethylenic unsaturated monomer in formula (V-I) are styrene, hydroxymethylstyrene, soda vinylbenzenesulfonate, N,N,N-trimethyl-N-vinylbenzylammoniumchloride, a-methylstyrene, 4-vinylpyridine, N-vinylpyrrolidone, a monoethylenic unsaturated ester of aliphatic acid (e.g., vinyl acetate), ethylenic unsaturated monocarboxylic acid or dicarboxylic acid and its salt (e.g., acrylic acid and methacrylic acid), maleic anhydride, an ester of ethylenic unsaturated monocarboxylic acid or dicarboxylic acid (e.g., n-butylacrylate, N,N-diethylaminoethylmethacrylate, and N,N-diethyl-N-methyl-N-me
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom
  • Q is a divalent bonding group and represents -0-, -COO-, or an arylene group having 6 to 10 carbon atoms.
  • R 2 represents -OH, -COOX, -SO ⁇ X (wherein X represents a hydrogen atom, an alkali metal, or an alkali earth metal), (wherein R4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m 2 represents an integer of 1 to 4).
  • R 3 represents -H or -COOX, and X has the same meaning as defined above.
  • Each of x and y represents a mole percentage, in which x represents 0 to 99 and y represents 1 to 100.
  • m 1 represents 0 or 1.
  • V-I Typical examples of a linear polymer as a binder represented by formula (V-I) will be presented below.
  • Effective compounds are the compounds enumerated above and compounds described in JP-A-49-135619, JP-A-51-14022, JP-A-54-1621, U.S. Patents 3,019,104, 3,003,873; 3,043,698, 3,165,412, 3,178,296, 3,271,158, 3,312,553, 3,173,790, and 3,316,097, and British Patents 867,899, 904,863, 861,985, 933,494, 1,010,917, 1,013,905, 976,222, 1,073,238, 1,048,016, 1,069,944, 1,078,335, 1,078,335, 1,076,378, 1,030,001, and 1,053,043.
  • a thickening agent is used in order to adjust the viscosity of a coating solution.
  • An anionic polymer having an interaction with gelatin can be used as the thickening agent.
  • Effective examples of the anionic polymer are compounds described in, e.g., JP-B-41-12835 ("JP-B" means Examined Published Japanese Patent Application), JP-B-57-33777, JP-B-59-7724, JP-A-57-105471, JP-A-51-81123, JP-A-53-39119, JP-A-52-67318, JP-A-55-98746, JP-A-56-5537, JP-A-53-13411, JP-A-53-98745, JP-A-53-18687, U.S. Patents 3,746,547 and 3,767,410, British Patent 1,421,930, and French Patent 21,178,157.
  • Preferable examples of the thickening agent used in the present invention are compounds represented by the following formulas (V-II) and (V-III): Formula (V-II) wherein A represents a monomer unit obtained by copolymerizing a copolymerizable ethylenic unsaturated monomer, and two or more types of monomer units may be contained.
  • Examples of an ethylenic unsaturated monomer represented by A in formula (V-II) are styrene, hydroxymethylstyrene, a-methylstyrene, 4-vinylpyridine, N-vinylpyrrolidone, 1-vinylimidazole, 2-methyl-1- vinylimidazole, a monoethylenic unsaturated ester of aliphatic acid (e.g., vinyl acetate), maleic anhydride, an ester of ethylenic unsaturated monocarboxylic acid or dicarboxylic acid (e.g, n-butylacrylate, N,N-diethylaminoethylmethacrylate, and methacrylate), an ethylenic unsaturated ether (e.g., methylvinylether), an amide of ethylenic unsaturated monocarboxylic acid or dicarboxylic acid (e.g., acrylamide, N-(
  • R 1 represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, and a butyl group), and most preferably, a hydrogen atom or a methyl group.
  • L represents a single bond or a divalent bonding group and may be substituted.
  • L is preferably an alkylene group, an arylene group, or a divalent group formed by combining these groups and one or a plurality of bonds represented by R 2 represents a hydrogen atom or an alkyl group or an aralkyl group each having 1 to 10 carbon atoms.
  • L represents -CONHC(CH 3 ) 2 CH 2 -, -COOCH 2 CH 2 0-, COOCH 2 CH 2 CCOCH 2 CH 2 -, -CONHCH 2 CH 2 0-, -C-ONHCH 2 CH 2 0COCH 2 CH 2 -, -COOCH 2 CH 2 , -CONHCH 2 CH 2 -, and a single bond.
  • Q" represents an anionic group, and preferably, a carboxylic group, a sulfo group, or a phosphonic acid group.
  • DMe represents a hydrogen ion, a monovalent metal ion, or an ammonium cation, and preferably, a hydrogen ion, sodium ion, potassium ion, or ammonium ion.
  • a monomer unit represented by may be a mixture of two or more types of different monomer units.
  • Each of x and y represents a mole percentage, in which x represents 0 to 99 and y represents 1 to 100. Preferably, x represents 0 to 75 and y represents 25 to 100.
  • A, x, and y have the same meanings as defined in formula (V-I), and the examples enumerated above in the item of formula (V-I) are also preferable in formula (V-III).
  • R 3 and R 4 have the same meanings as that of R 1 in formula (I) and may be the same or different.
  • Each of R 3 and R 4 is preferably a hydrogen atom.
  • X represents a hydrogen atom, a monovalent metal atom, or an ammonium salt, and preferably, a hydrogen atom, a sodium atom, or a potassium atom.
  • Y represents -0- or (wherein R 5 represents a hydrogen atom or an alkyl group, an aralkyl group, or an aryl group each having 1 to 10 carbon atoms), and preferably, -0-.
  • Z represents, in addition to those defined above as Rs, a monovalent metal atom or an ammonium salt, and preferably, a hydrogen atom, a sodium atom, or a potassium atom.
  • thickening agent for use in the present invention will be presented below, but the thickening agent is not limited to these examples.
  • a polymer in the present invention, can be used in, e.g., a undercoating layer, an interlayer, an emulsion layer, a protective layer, a back layer, an antistatic layer, an antihalation layer, and a scavenger layer, for various applications in addition to the applications described above. If a polymer for use in these layers is obtained by radial polymerization of an ethylenic unsaturated monomer, a total amount of an initiator containing a cyano group used in a coated polymer must be adjusted to be 5 ⁇ mol or less per m 2 of a photographic light-sensitive material, as described above.
  • a polymer not obtained by radical polymerization of an ethylenic unsaturated monomer can be preferably used.
  • a polymer examples include a natural substance such as a cellulose derivative, e.g., diacetylcellulose and triacetylcellulose, a saccharide such as dextran, prulane, and gum arabi, a synthetic polymer such as polyester, polyamide, polyurethane, polyurea, and polyether obtained by polycondensation, polyaddition, and ring opening polymerization, and polymers obtained by ion polymerization and coordination polymerization of an ethylenic unsaturated monomer.
  • a natural substance such as a cellulose derivative, e.g., diacetylcellulose and triacetylcellulose, a saccharide such as dextran, prulane, and gum arabi
  • a synthetic polymer such as polyester, polyamide, polyurethane, polyurea, and polyether obtained by polycondensation, polyaddition, and ring opening polymerization
  • Examples of an ultraviolet absorbent used in the present invention are ultraviolet absorbents represented by formulas described in JP-A-53-128333, JP-A-53-134431, JP-A-53-131837, JP-A-53-129633, JP-A-54-18727, and JP-A-53-133033 in which R 2 and R 3 are other than CN, an ultraviolet absorbent represented by a formula described in JP-A-53-97425 in which R s and R 7 are other than CN, an ultraviolet absorbent represented by a formula described in JP-A-56-27146 in which G is other than CN, an ultraviolet absorbent represented by a formula described in JP-A-54-111826 in which A and B are other than CN, ultraviolet absorbents represented by formulas described in British Patents 2,083,240A, 2,083,239A, and 2,083,241A in which P and Q are other than CN, an ultraviolet absorbent represented by formula (II) described in JP-B-56-21141
  • each of R 1 and R 2 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • R 1 and R 2 may be the same or different but are not simultaneously hydrogen atoms.
  • R 1 and R 2 may form a 5- or 6-membered ring together with N.
  • Each of X and Y independently represents -COR 3 , -COOR 3 , -S0 2 R 3 , or -COOH.
  • X and Y may be the same or different.
  • Each of R 3 and R4 independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 4 may be a hydrogen atom.
  • X and Y may be bonded to be integrated.
  • X and Y When X and Y are integrated, they represent an atom group required to form a nucleus of 1,3-dioxocyclohexane, varbituric acid, 1,2-diaza-3,5-diox- ocyclopentane, or 2,4-diaza-1-alkoxy-3,5-dioxocyclohexane.
  • n represents 1 or 2.
  • R i , R 2 , and R 3 may represent an alkylene group or an arylene group to form a dimer.
  • z represents an atom group required to form an oxazolidine ring, a pyrrolidine ring, or a thiazolidine ring.
  • R 5 represents an alkyl group or an aryl group.
  • Each of X and Y independently represents -COR s , -COOR 3 , -S0 2 R 3 , or -COOH.
  • X and Y may be the same or different.
  • R 3 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • X and Y may be bonded to be integrated.
  • X and Y When X and Y are integrated, they represent an atom group required to form a nucleus of 1,3-dioxocyclohexane, barbituric acid, 1,2-diaza-3,5-dioxocyclopentane, or 2,4-diaza-1-alkoxy-3,5-dioxocyclohexane.
  • n represents 1 or 2.
  • one of R 5 and R 3 may represent an alkylene group or an arylene group to form a dimer.
  • Z 1 represents 0, S, or R 5 represents an alkyl group or an aryl group
  • each of R 6 and R 7 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • R 6 and R 7 may be integrated to form a benzene ring or a naphthalene ring.
  • R 8 represents a hydrogen atom or an alkyl group
  • R g represents an alkyl group or an aryl group.
  • R 8 and R 9 may together form a nucleus of 1,3- indandione, barbituric acid, 2-thiobarbituric acid, 1,3-dioxocyclohexane, 2,4-diaza-1-alkoxy-3,5-dioxocyclohexane, 2,4-thiazolidinedione, 2-iminothiazolidine-4-one, hydantoin, 2,4-oxazolidinedione, 2- iminooxazolidine-4-one, or 2-thiooxazolidine-2,4-dione.
  • Each of R 10 and R 11 independently represents an alkyl group having 1 to 4 carbon atoms.
  • Z 2 represents an atom group required to.
  • R 12 represents an alkoxy group having 1 to 20 carbon atoms, -OCOR 17 , or a hydrogen atom.
  • R 17 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • Each of R 13 and R 14 independently represents a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms
  • each of R 15 or R 16 independently represents an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
  • R 28 , R 29 , R 30 , R 31 , and R 32 may be the same or different and may be a hydrogen atom or substituted by a substituting group allowed for an aromatic group.
  • R 31 and R 32 may be ring-closed to form a 5- or 6-membered aromatic ring consisting of carbon atoms. Of these substituting groups, those capable of having substituting groups may be further substituted by allowed substituting groups.
  • R 18 represents hydroxy, an alkoxy group, or an alkyl group.
  • R 19 and R 20 independently represents a hydrogen atom, hydroxy, an alkoxy group, or an alkyl group.
  • R 18 and R 19 or R 20 and R 18 may be at adjacent positions to form a 5- or 6-membered ring.
  • Each of X and Y independently represents -COR 3 , -COOR 3 , -S0 2 R 3 , or -COOH, and X and Y may be the same or different.
  • Each of R 3 and R 4 independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 4 may be a hydrogen atom.
  • X and Y may be bonded to be integrated. If X and Y are integrated, they represent an atom group required to form a nucleus of 1,3-dioxocyclohexane, barbituric acid, 1,2-diaza-3,5-dioxocyclopentane, or 2,4-diaza-1-alkoxy-3,5-dioxocyclohexane.
  • Examples of a dye used in the present invention are compounds described in, e.g., JP-A-1-179041 (except for those in which each of R 1 and R 2 represents a cyano group), JP-A-1-179042 (except for those in which each of X and Y represents a cyano group), JP-A-1-154149 (except for those in which each of X and Y represents a cyano group), DP 2,902,685, JP-A-1-102552, JP-A-64-90442, JP-A-64-40832, JP-A-64-42646, JP-A-63-27838, JP-A-59-154439 (except for those in which each of X and Y represents a cyano group), JP-A-63-64044 (except for those in which each of X and Y represents a cyano group), JP-B-62-41265, EP 29,412 (except for those in which each of A and B represents a cyano group), US 2,0
  • R 1 and R 2 may be the same or different and independently represent a hydrogen atom, an alkyl group or an aryl group. R 1 and R 2 may together form a 5- or 6-membered ring.
  • R 3 represents a halogen atom, alkyl, alkoxy, hydroxy, carboxy, substituted amino, carbamoyl, sulfamoyl, or alkoxycarbonyl.
  • n represents 0, 1, 2, 3, or 4. If a plurality of R 3 s are present, these groups may be the same or different.
  • R 1 and R 3 or R 2 and R 3 may be bonded to form a 5- or 6-membered ring.
  • Z represents a group selected from (wherein R 4 and R 5 may be the same or different and independently represent -COR 6 , -SO 2 R 6 , -CO 2 R 6 ,-CONR 6 •R 7 , -SO 2 NR 6 •R 7 , or -SO 2 R 6 wherein R 6 and R 7 may be the same or different and independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and Q represents a hydrogen group for forming a nitrogen-containing 5- or 6-membered heterocyclic ring).
  • L represents a methine group or a nitrogen atom.
  • R 8 represents an aryl group
  • Rg and n have the same meanings as those of R 3 and n in formula (DI), respectively.
  • R io and R 11 have the same meanings as those of R 1 and R 2 in formula ( D I), respectively.
  • Rs and R 10 or R 9 and R 11 may be bonded to form a 5- or 6-membered ring.
  • a dye compound used in the present invention can be easily synthesized by a method described in JP-A-63-64044.
  • a closed vessel means, e.g., a moistureproof bag, a moistureproof plastic case, and a metal case.
  • Examples of a material of the closed vessel are a metal and a metal foil such as an aluminum plate, a tin plate, and an aluminum foil, glass, a polymer such as polyethylene, polyvinylchloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, and polyamide, and a composite laminate member (called a "laminate material” in packaging technical terms) consisting of various types polymers and materials such as cellophane, paper, and an aluminum foil.
  • a metal and a metal foil such as an aluminum plate, a tin plate, and an aluminum foil, glass
  • a polymer such as polyethylene, polyvinylchloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, and polyamide
  • a composite laminate member called a "laminate material” in packaging technical terms
  • Examples of a sealing method are an adhesive method using various types of adhesives, a thermal fusing method such as heat sealing, and a method using a patrone which is generally used in this field of photography. These sealing methods are described in detail in "Food Packaging Technique Handbook", Japan Packaging Technique Association (ed.), pp. 573 to 609.
  • a patrone case consisting of a polymer such as polyethylene or polypropylene is preferably used for a roll type photographic light-sensitive material, and a package obtained by heat- sealing, e.g., polyethylene, is preferably used for a sheet type photographic light-sensitive material.
  • a humidity in a closed vessel is maintained constant means that when a humidity difference between the air and the interior of a case is 20%, a humidity change in the case is 10% or less after storage at 250 C for 12 months.
  • a decrease in humidity in a closed vessel is limited for the reasons described above.
  • An increase in humidity in the closed vessel is not preferred since photographic properties are degraded due to moisture.
  • the humidity in the closed vessel is preferably set around normal humidity. More specifically, at a temperature of 25 C, a relative humidity in the closed vessel is set to be 50% to 70%, and more preferably, 53% to 68%.
  • a relative humidity is a value measured at a temperature of 25 C by a conventional method (the relative humidity can be measured by a capacitance type humidity measuring machine such as a humicap humidity sensor available from VAISALA (K.K.)).
  • a significant effect of the present invention can be obtained when an internal volume of the closed vessel is 0.1 cm3 or less (where x is a surface area (cm 2 ) of a light-sensitive layer of a silver halide photographic light-sensitive material to be incorporated).
  • the effect of the present invention is further enhanced when the internal volume of the closed vessel is 0.07x cm 3.
  • a small size of a film cartridge is preferred because the size of a camera can be reduced.
  • a small size of the closed vessel is further preferred since portability of a light-sensitive material is improved.
  • a photographic light-sensitive material containing a silver halide emulsion subjected to chemical sensitization by a gold compound and a chalcogenide compound is particularly easily influenced by cyan gas.
  • a chemically sensitized silver halide emulsion contained in a light-sensitive material of the present invention will be described in detail below.
  • any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride can be used.
  • a preferable silver halide is silver iodobromide containing 30 mol% or less of silver iodide, silver bromide, or silver chlorobromide.
  • a silver halide grain to be used in the present invention can be selected from a regular crystal not including a twin crystal face and cryotals described in Japan Photographic Society ed., "Silver Salt Photographs, Basis of Photographic Industries", (Corona Co., p. 163) such as a single twined crystal including one twined crystal face, a parallel multiple twinned crystal including two or more parallel twin crystal faces, and a non-parallel multiple twinned crystal including two or more non-parallel twin crystal faces in accordance with its applications.
  • a cubic grain consisting of (100) faces, an octahedral grain consisting of (111) faces, and a dodecahedral grain consisting of (110) faces disclosed in JP-B-55-42737 and JP-A-60-222842 can be used.
  • a grain including two or more types of faces e.g., a tetradecahedral grain consisting of both (100) and (111) faces, a grain consisting of both (100) and (110) faces, and a grain consisting of both (111) and (110) faces can be selectively used in accordance with an application.
  • the grain of a silver halide may be a fine grain having a grain size of 0.1 microns or less or a large grain having a projected area diameter of 10 microns.
  • An emulsion may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.
  • a so-called monodisperse silver halide emulsion having a narrow size distribution i.e., in which 80% or more (the number or weight of grains) of all grains fall within the range of ⁇ 30% of an average grain size.
  • two or more types of monodisperse silver halide emulsions having different grain sizes can be coated in a single layer or overlapped in different layers, in emulsion layers having substantially the same color sensitivity.
  • two or more types of polydisperse silver halide emulsions or a combination of monodisperse and polydisperse emulsions can be mixed or overlapped.
  • the photographic emulsion for use in the present invention can be prepared by using methods described in, for example, P. Glafkides, "Chimie et Physique Photographique", Paul Montel, 1967; Duffin, “Photographic Emulsion Chemistry", Focal Press, 1966; and V.L. Zelikman et al., “Making and Coating Photographic Emulsion", Focal Press, 1964. That is, the photographic emulsion can be prepared by, e.g., an acid method, a neutralization method, and an ammonia method. Also, as a system for reacting a soluble silver salt and a soluble halide, a single mixing method, a double mixing method, or a combination thereof can be used.
  • a so-called back mixing method of forming silver halide grains in the presence of excessive silver ions can be used.
  • a so-called controlled double jet method wherein the pAg in the liquid phase generated by the silver halide is kept at a constant value can be used. According to this method, a silver halide emulsion having a regular crystal form and almost uniform grain sizes is obtained.
  • the silver halide emulsion containing the above-described regular silver halide grains can be obtained by controlling the pAg and pH during grain formation. More specifically, such a method is described in "Photographic Science and Engineering", Vol. 6, 159-165 (1962); “Journal of Photographic Science”, Vol. 12, 242-251 (1964); U.S. Patent 3,655,394, and British Patent 1,413,748.
  • a tabular grain having an aspect ratio of 3 or more can also be used in the present invention.
  • the tabular grain can be easily prepared by methods described in, for example, Cleve, "Photographic Science and Engineering", Vol. 14, pp. 248 to 257, (1970); and U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent 2,112,157.
  • covering power and a color sensitizing efficiency of a sensitizing dye can be advantageously improved as described in detail in U.S. Patent 4,434,226.
  • the tabular grains are preferably used in the emulsion of the present invention.
  • tabular grains in which grains having aspect ratios of 3 to 8 account for 50% or more of a total projected area, are preferable.
  • a crystal structure may be uniform, may have different halogen compositions inside and outside a crystal, or may be a layered structure.
  • These emulsion grains are disclosed in, e.g., British Patent 1,027,146, U.S. Patents 3,505,068 and 4,444,877, and Japanese Patent Application No. 58-248469.
  • the silver halide emulsion of the present invention preferably has a distribution or structure of a halogen composition in its grain.
  • a typical example is a core-shell type or double structured grain having different halogen compositions in the interior and surface layer of the grain as disclosed in, e.g., JP-B-43-13162, JP-A-61-215540, JP-A-60-222845, and JP-A-61-75337.
  • the shape of a core portion is sometimes different from that of the entire grain with the shell. More specifically, while the core portion is cubic, the grain with a shell is sometimes cubic or sometimes octahedral.
  • the grain with a shell is sometimes cubic or sometimes octahedral.
  • the core portion is a clear regular grain, the grain with a shell is sometimes slightly deformed or sometimes does not have any definite shape.
  • a simple double structure but a triple structure as disclosed in JP-A-60-222844 or a multilayered structure of more layers can be formed, or a thin layer of a silver halide having a different composition can be formed on the surface of a core-shell double structure grain.
  • the silver iodide content may be high at a core portion and low at a shell portion or vice versa.
  • the silver iodide content may be high in a host crystal and relatively low in a junction crystal or vice versa.
  • a boundary portion between different halogen compositions may be clear or unclear due to a crystal mixture formed by a composition difference.
  • a continuous structure change may be positively made.
  • the silver halide emulsion for use in the present invention can be subjected to a treatment for rounding a grain as disclosed in, e.g., EP-0096727B1 and EP-0064412B1 or a treatment of modifying the surface of a grain as disclosed in DE-2306447C2 and JP-A-60-221320.
  • the silver halide emulsion for use in the present invention is preferably of a surface latent image type.
  • a silver halide solvent can be effectively used to promote ripening.
  • an excessive amount of halide ions are supplied in a reactior vessel in order to promote ripening. Therefore, it is apparent that ripening can be promoted by only supplying a silver halide solution into a reactor vessel.
  • another ripening agent can be used. In this case, a total amount of these ripening agents can be mixed in a dispersion medium in the reactor vessel before a silver salt and a halide are added therein, or they can be added in the reactor vessel together with one or more halides, a silver salt or a deflocculant. Alternatively, the ripening agents can be added in separate steps together with a halide and a silver salt.
  • ripening agent other than the halide ion examples include ammonia, an amine compound and a thiocyanate such as an alkali metal thiocyanate, especially sodium or potassium thiocyanate and ammonium thiocyanate.
  • gold complex salt As a gold compound used in the present invention, especially gold complex salt (described in, e.g., U.S. Patent 2,399,083) can be preferably used.
  • gold complex salt potassium chloroaurate, potassium aurithiocyanate, aurictrichloride, sodium aurithiosulfate, and 2-aurosulfobenzothiazolemethochloride.
  • the content of the gold compound in the silver halide emulsion is preferably 10- 9 to 10- 3 mol, more preferably, 10- 8 to 10- 4 mol, and most preferably, 10- 7 to 10- 5 mol per mol of a silver halide.
  • the gold compound can be used together with another heavy metal compound.
  • a method of using a heavy metal compound is described in, e.g., U.S. Patent 2,448,060, 2,566,245, or 2,566,263.
  • the content of the heavy metal compound in the silver halide emulsion is 10- 9 to 10- 3 mol, and most preferably, 10- 8 to 10- 4 mol per mol of a silver halide.
  • a chalcogenide compound and a sensitization method used in the present invention will be described below.
  • Examples of the chalcogenide compound which can be used in the present invention are a sulfur compound, a selenium compound, and a tellurium compound.
  • examples are compounds containing various types of instable sulfurs, such as a thiosulfate (e.g., sodium thiosulfate and p-toluenethiosulfonate), a thiourea (e.g., arylthiourea, diphenyl- thiourea, triethylthiourea, acetylthiourea, N-ethyl-N'-(4-methylthiazolyl-2)thiourea, carboxymethyltrimethyl- thiourea, and N-aryl-N'-hydroxyethylthiourea), a thioamide (e.g., thioacetoamide), a rhodanine (e.g., rhodanine, N-ethylrhodanine, 5-benzylidene-N-ethylrhodanine, and diethylrhodanine), a disulfide
  • a selenium sensitizer and a selenium sensitization method are disclosed in, e.g., U.S. Patents 1,574,944, 1,602,592, 1,623,499, 3,297,446, 3,297,447, 3,320,069, 3,408,196, 3,408,197, 3,442,653, 3,420,670, and 3,591,385, French Patents 2,693,038 and 2,093,209, JP-B-52-34491, JP-B-52-34492, JP-B-53-295, JP-B-57-22090, JP-A-59-180536, JP-A-59-185330, JP-A-59-181337, JP-A-59-187338, JP-A-59-192241, JP-A-60-150046, JP-A-60-151637, and JP-A-61-246738, British Patents 255,846 and 861,984, and H.E. Spencer et al., "J
  • the selenium compounds disclosed in the above patents can be used as a selenium sensitizer used in the present invention.
  • an instable selenium compound which can react with silver nitrate in an aqueous solution to form precipitation of silver selenide can be preferably used.
  • Preferable examples of the selenium compound are described in U.S. Patents 1,574,944, 1,602,592, 1,623,499, and 3,297,446.
  • examples are colloidal metal selenium, isoselenocyanates (e.g., arylisoselenocyanate), selenoureas (e.g., selenourea; aliphatic selenourea such as N,N-dimethylselenourea and N,N-diethyl- selenourea; substituted selenourea having an aromatic group such as a phenyl group or a heterocyclic group such as a pyridyl group), selenoketones (e.g., selenoketone and selenoacetophenone), selenoamides (e.g., selenoacetoamide), selenocarboxylic acids and esters (e.g., 2-selenopropionic acid and methyl 3- selenobutylate), selenides (e.g., dimethylselenide, diethylselenide, and triphenylphosphirf
  • a tellurium sensitizer and a tellurium sensitization method are disclosed in, e.g., U.S. Patent 1,623,499, British Patents 1,295,462 and 1,396,696, and Canadian Patent 800,958.
  • Examples of the tellurium sensitizer used in the present invention are colloidal tellurium, a telluro urea (e.g., ethyltellurourea and allyltellurourea), isotellurocyanates (e.g., arylisotellurocyanate), telluroketones (e.g., telluroacetone), a telluride (e.g., potassium telluride, potassium tellurocyanide, and sodium telluropentathionate).
  • a telluro urea e.g., ethyltellurourea and allyltellurourea
  • isotellurocyanates e.g., arylisotellurocyanate
  • an amount of a chalcogenide compound changes in accordance with the type of compound, the type of silver halide grain, and conditions of chemical ripening, it is generally 10- 9 to 10 -4 mol, and preferably, 10- 8 to 10- 5 mol per mol of a silver halide.
  • the temperature, the pAg, and the pH of chemical sensitization can be arbitrarily selected within the ranges of 30 C to 90 C, 5 to 10, and 4 or more, respectively.
  • An emulsion preferably used in the present invention is an emulsion subjected to sensitization by a combination of gold and chalcogenide, and most preferably, a gold•sulfur-sensitized emulsion.
  • the gold sulfur sensitization is generally performed after grain formation.
  • a silver halide grain used in the present invention preferably contains a sulfur-containing silver halide solvent.
  • the sulfur-containing silver halide solvent used in the present invention can be added in any process from grain formation to coating of an emulsion, it is most preferably present during chemical sensitization for e center formation.
  • An addition amount of the sulfur-containing silver halide solvent used in the present invention is, preferably, 5.0 x 10 -4 to 5.0 x 10- 2 mol per mol of silver for a silver halide grain having a grain size of 0.5 ⁇ m, 2.5 x 10 -4 to 2.5 x 10- 2 mol per mol of silver for a silver halide grain having a grain size of 1.0 pm, and 1.25 x 10 -4 to 1.25 x 10 -3 mol per mol of silver for a silver halide grain having a grain size of 2.0 ⁇ m.
  • the sulfur-containing silver halide emulsion means a silver halide solvent which can be coordinated in a silver ion by a sulfur atom.
  • thiocyanate e.g., potassium rhodanate and ammonium rhodanate
  • an organic thioether compound e.g., U.S. Patents 3,574,628, 3,021,215, 3,057,724, 3,038,805, 4,276,374, 4,297,439, and 3,704,130, and JP-A-57-104926
  • a thione compound e.g., 4-substituted thiourea, thiocyanate
  • an organic thioether compound described in, e.g., JP-A-53-82408, JP-A-55-77737, and U.S. Patent 4,221,863 e.g., JP-A-53-82408, JP-A-55-77737, and U.S. Patent 4,221,863
  • a compound represented by formula (SIV) is preferable as organic thioether: wherein m represents 0 or an integer from 1 to 4.
  • Examples of a substituting group are -OH, -COOM, -SO 3 M, -NHR 19 , -NR 19 R 19 (wherein R 19 may be the same or different), -OR 19 , -CONHR 19 , -COOR 19 , and a heterocyclic ring.
  • R 19 may be a hydrogen atom, a lower alkyl group, or a substituted alkyl group obtained by being substituted by the above substituting group.
  • substituting groups may be substituted, and these substituting groups may be the same or different.
  • R 18 represents an alkylene group (preferably having 1 to 12 carbon atoms).
  • n R 18 S may be the same or different.
  • One or more groups of -0-, -CONH-, and -S0 2 NH- may be present in the middle of an alkylene chain, or the substituting groups described with reference to R 1 and R 17 , may be substituted therein.
  • R 1 and R 17 may be bonded to form cyclic thioether.
  • a compound represented by formula (SV) is preferable as a thione compound: wherein Z represents -OR 24 , or -SR 25 .
  • R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 may be the same or different and independently represent an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic moiety. These groups may be substituted (a total number of carbon atoms of each group is preferably 30 or less).
  • R 20 and R 21 , R 22 and R 23 , or R 20 and R 22 , R 20 and R 24 , and R 20 and R 25 may be bonded to form a 5- or 6-membered heterocyclic ring, and a substituting group may be bonded to the heterocyclic ring.
  • silver halide adsorptive substances When silver halide adsorptive substances are present in addition to a sensitizing dye, upon chemical ' sensitization of an emulsion of the present invention, a developing rate can be preferably increased.
  • These silver halide adsorptive substances other than the sensitizing dye can be added at any timing, e.g., during grain formation, immediately after grain formation, before or during after-ripening.
  • the substances can be added at different timings, they are preferably added before a chemical sensitizing agent (e.g., a gold or sulfur sensitizer) is added or simultaneously with the chemical sensitizer and must be present in at least a process in which chemical sensitization progresses.
  • a chemical sensitizing agent e.g., a gold or sulfur sensitizer
  • a temperature may be an arbitrary temperature from 30° C to 80° C and preferably falls within the range of 50° C to 80 C in order to enhance adsorptivity.
  • a pH and a pAg may be arbitrarily set, the pH is preferably 6 to 9 and the pAg is preferably 7 to 9, and most preferably, 7.6 to 8.4 upon chemical sensitization.
  • the silver halide absorptive substance other than the sensitizing dye means a kind of a photographic property stabilizing agent.
  • azoles ⁇ e.g., benzothiazolium salt, benzoimidazolium salt, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, and triazines ⁇ ; a mercapto compounds ⁇ e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptobenzimidazoles, mercaptobenzooxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, and mercaptotriazines); thioketo compounds such as ox- azolinethione;
  • purines, nucleic acids, and polymer compounds described in, e.g., JP-B-61-36213 and JP-A-59-90844 can be used as an absorptive substance.
  • azaindenes purines, nucleic acids, and mercapto compounds having a carboxyl group or a sulfonic acid group can be most preferably used in the present invention.
  • An addition amount of these compounds is 0.05 to 5.0 millimol, and preferably, 0.1 to 3.0 millimol per mol of a silver halide.
  • various color couplers can be used in the light-sensitive material. Specific examples of these couplers are described in above-described Research Disclosure, No. 17643, VII-C to VII-G as patent references.
  • a yellow coupler Preferred examples of a yellow coupler are described in, e.g., U.S. Patents 3,933,501, 4,022,620, 4,326,024, and 4,401,752, JP-B-58-10739, and British Patents 1,425,020 and 1,476,760.
  • magenta coupler examples are preferably 5-pyrazolone and pyrazoloazole compounds, and more preferably, compounds described in, e.g., U.S. Patents 4,310,619 and 4,351,897, EP 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, and U.S. Patents 4,500,630 and 4,540,654.
  • Examples of a cyan coupler are phenol and naphthol couplers, and preferably, those described in, e.g., U.S. Patents 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 Application (OLS) No. 3,329,729, EP 121,365A, U.S. Patents 3,446,622, 4,333,999, 4,451,559, and 4,427,767, and EP 161,626A.
  • OLS West German Patent Application
  • a colored coupler for correcting additional, undesirable absorption of a colored dye are those described in Research Disclosure No. 17643, VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368.
  • a coupler capable of forming colored dyes having proper diffusibility are those' described in U.S. Patent 4,366,237, British Patent 2,125,570, EP 96,570, and West German Patent Application (OLS) No. 3,234,533.
  • Couplers releasing a photographically useful residue upon coupling are preferably used in the present invention.
  • a DIR coupler releasing a development inhibitor are described in the patents cited in the above-described Research Disclosure No. 17643, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and U.S. Patent 4,248,962.
  • a coupler imagewise releasing a nucleating agent or a development accelerator upon development are those described in British Patent 2,097,140, 2,131,188, and JP-A-157638 and JP-A-59-170840.
  • Examples of a coupler which can be used in the light-sensitive material of the present invention are competing couplers described in, e.g., U.S. Patent 4,130,427; poly-equivalent couplers described in, e.g., U.S. Patents 4,283,472, 4,338,393, and 4,310,618; DIR redox compound or DIR coupler releasing couplers, or DIR coupler releasing couplers or redox described in, e.g., JP-A-60-185950 and JP-A-62-24252; couplers releasing a dye which turns to a colored form after being split off described in EP 173,302A; bleaching accelerator releasing couplers described in, e.g., RD. Nos. 11449 and 24241 and JP-A-61-201247; and a legand releasing coupler described in, e.g., U.S. Patent 4,553,477.
  • the couplers for use in this invention can be introduced in the light-sensitive material by various known dispersion methods.
  • a high-boiling organic solvent to be used in the oil-in-water dispersion method and having a boiling point of 175° C or more at normal pressure examples include phthalic esters (e.g., dibutylphthalate, dicyclohexyl- phthalate, and di-2-ethylhexylphthalate), phosphates or phosphonates (e.g., triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, and tri-2-ethylhexylphosphate), benzoates (e.g., 2-ethylhexylbenzoate, dodecylbenzoate, and 2-ehtylhexyl-p-hydrexybenzodate), amides (e.g., N, N-diethyldodecanemide, N,N-diethyl lauribamide, N-tetrade
  • An organic solvent having a boiling point of about 30 C or more, and preferably, 50 C to about 160 ⁇ C can be used as a co-solvent.
  • Typical examples of the co-solvent are ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexane, 2-ethoxyethylacetate, and dimethylformamied.
  • the present invention can be applied to various color light-sensitive materials.
  • the material are a color negative film for a general purpose or a movie, a color reversal film for a slide or a television, color paper, a color positive film, and color reversal paper.
  • the present invention When the present invention is used as a color photographic material for photographing, the present invention can be applied to light-sensitive materials having various structures and to light-sensitive materials having combinations of layer structures and special color materials.
  • Typical examples are: light-sensitive materials in which a special coupling speed of a color coupler or diffusibility is combined with a speacial layer structure, as disclosed in, e.g., JP-B-47-49031, JP-B-49-3843, JP-B-50-21248, JP-A-59-38147, JP-A-59-60437, JP-A-60-227256, JP-A-61-4043, JP-A-61-43743, and JP-A-61-42657; light-sensitive materials in which a single color-sensitive layer is divided into two or more layers, as disclosed in JP-B-49-15495 and U.S.
  • Patent 3,843,469 and light-sensitive materials in which an arrangement of high- and low-sensitivity layers or layers having different color sensitivities is defined, as disclosed in JP-B-53-37017, JP-B-53-37018, JP-A-51-49027, JP-A-52-143016, JP-A-53-97424, JP-A-53-97831, JP-A-62-200350, and JP-A-59-177551.
  • the color photographic light-sensitive materials of this invention can be developed by the conventional methods as described in, e.g., the above-described Research Disclosure, No. 17643, pages 28 to 29 and ibid., No. 18716, page 651, left to right columns.
  • a color developer used in developing of the light-sensitive material of the present invention is an aqueous alkaline solution mainly containing, as a main compornent, preferably, an aromatic primary amine- based color developing agent.
  • a color developing agent although 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- ⁇ 3-methoxyethylaniline, and sulfates, hydrochlorides, and p-toluenesulfonates thereof. These compounds can be used in a combination of two or more thereof in accordance with applications.
  • 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 antifoggant such as a bromide, an iodide, 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
  • a development restrainer or antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound.
  • the color developer may also contain a preservative such as hydroxylamine, diethylhydroxylamine, a hydrazine sulfite, a phenylsemicar-banide, triethanolamine, a catechol sulfonic acid or a triethylenediamine(1,4-diazabicyclo[2,2,2]octane); 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; a fogging agent such as sodium boron hydride; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity imparting agent; and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid, and alkylphosphonic acid or a phosphonocarboxylic acid.
  • Examples of the chelating agent are ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 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., dihydroxybenzenes such as hydroquinone, 3-pyrazolidones 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 m 2 of the light-sensitive material.
  • the replenishment amount can be decreased to be 500 m 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.
  • the replenishment amount can be decreased by using a means capable of suppressing an accumulation amount of bromide ions in the developer.
  • a color development time is normally set between 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 applications.
  • the bleaching agent are a compound of a multivalent metal such as iron (III), cobalt (III), chromium (VI) and copper (II); a peroxide; a quinone; and a nitro compound.
  • Typical examples of the bleaching agent are a ferricyanide; a dichromate; an organic complex salt of iron (III) or cobalt (III), e.g., a complex salt of an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid, or a complex salt of citric acid, tartaric acid or malic acid; a persulfate; a bromate; a permanganate; and a nitrobenzene.
  • an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-dia
  • an iron (III) complex salt of aminopolycarboxylic acid such as an iron (III) complex salt of ethylenediaminetetraacetic acid, and a persulfate are preferred because they can increase a processing speed and prevent an environmental contamination.
  • the iron (III) complex salt of aminopolycarboxylic acid is effective 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 5.5 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 pre- bath, if necessary. Effective examples of the bleaching accelerator are described in, e.g., U.S. Patent 3,893,858. 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 effective especially in bleach-fixing of a photographic color light-sensitive material for photographing.
  • the fixing agent examples include a thiosulfate, a thiocyanate, a thioether-based compound, a thiourea and a large amount of an iodide.
  • a thiosulfate, especially, ammonium thiosulfate can be used in a widest range of applications.
  • a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferred.
  • the 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 use of a coupler) of the light-sensitive material, the application of the material, the temperature of the 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. 248 - 253 (May, 1955).
  • the amount of water used for washing can be greatly decreased. Since washing water stays in the tanks for a long period of time, however, bacteria multiply and floating substances may be undesirably attached to the light-sensitive material In order to solve this problem, in the process of the color photographic light-sensitive material of the present invention, a method of decreasing calcium and magnesium ions can be effectively utilized, as described in JP-A-61-131632.
  • a germicide such as an isothiazolone compounds and cyaben- dazoles described in JP-A-57-8542, a chlorine-based germicide such as chlorinated sodium isocyanurate, and germicides such as benzotriazole described in Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents", Eiseigijutsukai ed., “Sterilization, Antibacterial, and Antifungal Techniques for Microorganisms", and Nippon Bokin Bokabi Gakkai ed., "Dictionary of Antibacterial and Antifungal Agents".
  • 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 sometimes performed subsequently to washing.
  • An example is a stabilizing bath containing formalin and a surfactant to be used as a final bath of the photographic color light-sensitive material.
  • Various chelating agents or antifungal agents can be added in the 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 increase a processing speed.
  • 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 high temperature to shorten a processing time, or image quality or stability of a processing solution may be improved at a lower temperature. In order to save silver for the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or U.S. Patent 3,674,499 may be performed.
  • the silver halide light-sensitive material of the present invention can also be applied to thermal development light-sensitive materials described in, e.g., U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and EP 210,660A2.
  • the light-sensitive material of the present invention is characterized in that an amount of released hydrogen cyanide is a small, (gold/silver) weight ratio is small, and photographic properties are not much degraded during storage. Therefore, photographic properities Brownie film or a 110 film, in which the light-sensitive material of the present invention and a light screen described in, e.g., WO No. 12847/89, or U.S. Patent 3,900,323 or 4,211,837 are conbined, are not much degraded during storage. In these points those photographic material is preferable.
  • an unsensitized silver iodobromide emulsion 2 having a silver iodide content of 10 mol% and a grain size of 0.87 ⁇ m.
  • the emulsion 2 comprised twined crystals having an aspect ratio of 2.3, and its (111) face ratio was 85%.
  • silver halide emulsions were coated on an undercoated triacetylcellulose film support so as to have the following compositions, thereby forming a sample 101.
  • a sample 102 was formed following the same procedures as for the sample 101 except that the emulsion A of the layer 1 was replaced by the emulsion B.
  • a sample 103 was formed following the same procedures as for the sample 101 except that an aqueous HAuCl 4 solution in an amount of 50 ppm of Au per Ag were added, to the layer 1 of sample 101.
  • compositions of the processing solutions will be described below.
  • the emulsion A used in the above comparative example was coated on an undercoated triacetylcellulose support so as to have the following compositions, thereby forming a sample 201.
  • a sample 202 was formed following the same procedures as for the sample 201 except that the emulsion A was replaced by an equal amount of the emulsion B.
  • a sample 203 was formed following the same procedures as for the sample 201 except that M-1 added to the layer 2 was changed to an equal amount of M-2, and a sample 204 was formed following the same procedures as for the sample 202 except that M-1 of the layer 2 was changed to M-2.
  • the obtained samples 201 to 204 were cut into strips having a width of 3.5 cm and a length of 117 cm and sufficiently moisture-conditioned at a temperature of 25 C and a relative humidity of 65%. Thereafter, each strip was sealed in a closed vessel (patrone case) having a volume of about 30 cm 3 and heated at 60° C for three days.
  • HAuCl 4 as a gold compound was used in an amount of 10- 6 to 10- 5 mol per mol of a silver halide and Na 2 S 2 0 3 as a chalcogenide compound was used in an amount of 10- 6 to 10- 5 mol per mol of a silver halide, upon chemical sensitization performed, after grain formation and desalting.
  • amounts of the compounds were changed in accordance with the grain size of an emulsion or the characteristics of a grain, the compounds were used in amounts falling within the above ranges so that most preferable properties were obtained. Note that neither gold nor chalcogenide was used in a fine silver iodobromide emulsion in a layer 13.
  • Coating amounts of a silver halide and a colloidal silver are represented in units of g/m 2 of silver, those of a coupler additive and gelatin are represented in units of g/m 2 , and that of a sensitizing dye is represented by the number of mols per mol of a silver halide in the same layer.
  • ExM-9 in the layers 7 and 8 of the sample 301 was replaced with an equal amount of ExM-16 to prepare a sample 302.
  • UV-2 and UV-3 were used instead of UV-5 used in the layer 13 of the sample 302, and ultraviolet absorption characteristics in a dry film were controlled by adjusting an amount, thereby forming a sample 303.
  • a sample 304 was formed following the same procedures as for the sample 303 except that the polymer matting agent M-1 (polymerization initiator X-3) in the layer 14 of the sample 303 was replaced by an equal amount of M-2 (polymerization initiator 1-1).
  • Each sample was cut into a strip having a width of 3.5 cm and a length of 117 cm and moisture-conditioned at a temperature of 25°C and a relative humidity of 60%. This moisture-conditioned strip was curled into a patrone and perfectly sealed in a patrone case. Thereafter, each sample was forcedly deteriorated at a temperature of 60 C for three days. These samples together with samples stored at room temperature were subjected to sensitmetry exposure and color development.
  • each of the samples 301 to 304 was similarly sealed in a patrone case and left to stand at a constant temperature of 25 C for 18 months. These samples together with samples stored in a freezer (-16 C) were exposed and developed.
  • Cyan, magenta, and yellow image densities of the developed samples were measured on the basis of status M density, thereby calculating a fog value, sensitivity, and gradation.
  • the sensitivity is represented by a logarithm of a reciprocal of a exposure amount for giving a density of fog density + 0.15 for each color image.
  • a point of exposure amount which was 100 times as greater as a exposure amount of photographic speed of each image was calculated on a curve, and the gradation was represented by an inclination angle (tangent) obtained when the two points were connected by a straight line.
  • An amount of HCN gas released from an area of 1 m 2 of each sample was obtained by a pyridine-pyrazolone absorptiometric method. The amount of HCN gas was determined in a dark room heated at 75 0 C for two hours.
  • Example 2 Each of the samples 301 and 304 formed in Example 2 was cut into eight strips having a width of 3.5 cm and a length of 117 cm and curled into general patrones.
  • One strip of each of the samples 301 and 304 was moisture-controled at temperature of 25 C, and relative humidity of 40%. Similarly, the strips were moisture-conditioned at a temperature of 25° C and relative humidities of 45%, 50%, 55%, 60%, 65%, 70%, and 75% and perfectly sealed in patrone cases at the respective humidities, thereby performing a forced deterioration test at 50° C for 14 days.
  • a static failure may be caused by the low humidity in a light-sensitive material manufacturing process, and the material gradually absorbs moisture in the air during storage of a long time period (in, e.g., shops) to increase the humidity in a patrone case to lead to degradation in storage stability. Therefore, it is not preferable to set the humidity to be less than 50%.
  • the humidity of 70% or more is also not preferable since deterioration caused by the humidity is large.
  • Example 2 Each of the samples 301 and 304 formed in Example 2 was cut into three strips having a width of 3.5 cm and lengths of 73 cm (corresponding to a 12-frame film), 117 cm (corresponding to a 24-frame film), and 328 cm (corresponding to a 72-frame film), and sufficiently moisture-conditioned at a temperature of 25° C and a relative humidity of 60%.
  • the moisture-conditioned samples were directly, perfectly sealed in patrone cases in the same place (dark room). These samples were left to stand in a constant temperature tank at a temperature of 60 C for three days and then extracted.
  • These samples together with the samples 301 and 304 stored at room temperature were exposed and developed to perform sensitmetry. Characteristic values are calculated following the same procedures as in Examples 2 and 3 and summarized as a difference with respect to the sample stored at room temperature in Table 5.
  • HAuC14 as a gold compound was used in an amount of 10- 6 to 10- 5 mol per mol of a silver halide and Na 2 S 2 0 3 as a chalcogenide compound was used in an amount of 10 -6 to 10- 5 mol per mol of a silver halide, upon chemical sensitization, after grain formation and desalting.
  • the amounts of the compounds were changed in accordance with the grain size of an emulsion or the characteristics of a grain, the compounds are used in amounts falling within the above ranges so that most preferable properties were obtained. Note that neither gold nor chalcogenide was used in a fine grain silver iodobromide emulsion in a layer 15.
  • Coating amounts of a silver halide and a colloidal silver are represented in units of g/m 2 of silver, those of a coupler, an additive, and gelatin are represented in units of g/m 2 and that of a sensitizing dye is represented by the number of mols per mol of a silver halide in the same layer.
  • Fine grain silver chloride (sphere-equivalent
  • B-1 (0.20 g/m 2 in total), 1,2-benzisothiazoline-3-one (about 200 ppm on the average with respect to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm on the average with respect to gelatin), and 2-phenoxyethanol (about 10,000 ppm on the average with respect to gelatin) were added to the layers.
  • Samples 402 and 403 were prepared by using Cpd-16 and Cpd-17, respectively, instead of the dye Cpd-11 added to the layer 1 of the sample 401.
  • samples 404 to 406 were formed by using Cpd-18, Cpd-19, and Cpd-20, respectively, instead of Cpd-11 of the sample 401.
  • each sample was cut into a strip having a width of 3.5 cm and a length of 117 cm and moisture-conditioned at a temperature of 25° C and a relative humidity of 60%. The moisture-conditioned sample was curled into a patrone and perfectly sealed in a patrone case.
EP19910100578 1990-01-19 1991-01-18 Silver halide photographic light-sensitive material Withdrawn EP0439069A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10423/90 1990-01-19
JP1042390A JPH03215844A (ja) 1990-01-19 1990-01-19 ハロゲン化銀写真感光材料

Publications (2)

Publication Number Publication Date
EP0439069A2 true EP0439069A2 (de) 1991-07-31
EP0439069A3 EP0439069A3 (en) 1991-10-16

Family

ID=11749744

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910100578 Withdrawn EP0439069A3 (en) 1990-01-19 1991-01-18 Silver halide photographic light-sensitive material

Country Status (2)

Country Link
EP (1) EP0439069A3 (de)
JP (1) JPH03215844A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0572022A2 (de) * 1992-05-27 1993-12-01 Fuji Photo Film Co., Ltd. In einer Filmkapsel verpacktes photographischen Material
EP0597312A1 (de) * 1992-11-12 1994-05-18 Minnesota Mining And Manufacturing Company Ein photographisches Silberhalogenidelement verschlossen in geschlossenem Behälter enthaltende photographische Zusammensetzung
EP0631177A1 (de) * 1993-06-23 1994-12-28 Fuji Photo Film Co., Ltd. Ein photographisches Silberhalogenidmaterial
US5578435A (en) * 1992-05-28 1996-11-26 Fuji Photo Film Co., Ltd. Encased photographic material
US5593818A (en) * 1993-06-22 1997-01-14 Fuji Photo Film Co., Ltd. Silver halide photographic material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2778853B2 (ja) * 1991-06-28 1998-07-23 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
EP0572662B1 (de) * 1991-12-18 1999-03-17 Fuji Photo Film Co., Ltd. Photographisches silberhalogenidmaterial

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023670A1 (de) * 1979-08-04 1981-02-11 Agfa-Gevaert AG Photographische Emulsion, Verfahren zur Herstellung sowie photographische Materialien
EP0053851A1 (de) * 1980-12-09 1982-06-16 Agfa-Gevaert N.V. Antischleierverbindungen und ihre Verwendung in der Silberhalogenidphotographie
EP0096561A2 (de) * 1982-06-04 1983-12-21 Minnesota Mining And Manufacturing Company Stabilisierung von Silberhalogenidemulsionen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023670A1 (de) * 1979-08-04 1981-02-11 Agfa-Gevaert AG Photographische Emulsion, Verfahren zur Herstellung sowie photographische Materialien
EP0053851A1 (de) * 1980-12-09 1982-06-16 Agfa-Gevaert N.V. Antischleierverbindungen und ihre Verwendung in der Silberhalogenidphotographie
EP0096561A2 (de) * 1982-06-04 1983-12-21 Minnesota Mining And Manufacturing Company Stabilisierung von Silberhalogenidemulsionen

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0572022A2 (de) * 1992-05-27 1993-12-01 Fuji Photo Film Co., Ltd. In einer Filmkapsel verpacktes photographischen Material
EP0572022A3 (de) * 1992-05-27 1994-12-14 Fuji Photo Film Co Ltd In einer Filmkapsel verpacktes photographischen Material.
US5578435A (en) * 1992-05-28 1996-11-26 Fuji Photo Film Co., Ltd. Encased photographic material
EP0597312A1 (de) * 1992-11-12 1994-05-18 Minnesota Mining And Manufacturing Company Ein photographisches Silberhalogenidelement verschlossen in geschlossenem Behälter enthaltende photographische Zusammensetzung
US6197485B1 (en) * 1992-11-12 2001-03-06 Minnesota Mining & Manufacturing Company Photographic assemblage comprising a silver halide photographic element sealed in a closed vessel
US5593818A (en) * 1993-06-22 1997-01-14 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0631177A1 (de) * 1993-06-23 1994-12-28 Fuji Photo Film Co., Ltd. Ein photographisches Silberhalogenidmaterial

Also Published As

Publication number Publication date
JPH03215844A (ja) 1991-09-20
EP0439069A3 (en) 1991-10-16

Similar Documents

Publication Publication Date Title
EP0439069A2 (de) Lichtempfindliches photographisches Silberhalogenidmaterial
US5370982A (en) Silver halide color photographic light-sensitive material
US5262274A (en) Silver halide photographic material
US5169746A (en) Silver halide color photographic photosensitive material
US4157917A (en) Color photographic light-sensitive material
US5286615A (en) Silver halide color photographic material
US5514527A (en) Silver halide color photographic material
US4165236A (en) Color photographic light-sensitive material
EP0369486B1 (de) Farbphotographisches lichtempfindliches Silberhalogenidnegativmaterial
US5429915A (en) Silver halide color photographic light-sensitive material comprising a red-sensitive silver halide emulsion layer unit having at least 3 sublayers of different sensitivity
EP0572022A2 (de) In einer Filmkapsel verpacktes photographischen Material
EP0438791B1 (de) Lichtempfindliches photographisches Silberhalogenidmaterial
US5478714A (en) Silver halide photographic emulsion and silver halide photographic light-sensitive material
US5804364A (en) Method for producing fine silver halide emulsion
US7531298B2 (en) Silver halide color photosensitive material
US5405737A (en) Silver halide color photographic light-sensitive material comprising blue sensitive emulsion layers containing acylacetoamide type yellow dye forming couplers and reduction sensitized silver halide emulsion
EP0558076B1 (de) Photographisches Silberhalogenidmaterial
JP2745365B2 (ja) ハロゲン化銀写真感光材料
JP2855030B2 (ja) ハロゲン化銀カラー写真感光材料
JP2699006B2 (ja) ハロゲン化銀カラー写真感光材料
US6815156B2 (en) Silver halide emulsion
JP2811252B2 (ja) ハロゲン化銀写真感光材料
JPH06208184A (ja) ハロゲン化銀写真感光材料
JP2691469B2 (ja) カラー画像形成法
JPH03236050A (ja) ハロゲン化銀カラー写真感光材料

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB NL

17P Request for examination filed

Effective date: 19920130

17Q First examination report despatched

Effective date: 19941221

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19970923