EP0323215A2 - Photoempfindliches photographisches Silberhalogenidmaterial - Google Patents

Photoempfindliches photographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0323215A2
EP0323215A2 EP88312348A EP88312348A EP0323215A2 EP 0323215 A2 EP0323215 A2 EP 0323215A2 EP 88312348 A EP88312348 A EP 88312348A EP 88312348 A EP88312348 A EP 88312348A EP 0323215 A2 EP0323215 A2 EP 0323215A2
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EP
European Patent Office
Prior art keywords
group
silver halide
sample
ring
silver
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EP88312348A
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English (en)
French (fr)
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EP0323215A3 (de
Inventor
Yukio Ohya
Syoji Matsuzaka
Yasushi Irie
Shuji Murakami
Satomi Asano
Hiroshi Okusa
Hirofumi Ohtani
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Konica Minolta Inc
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Konica Minolta Inc
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    • 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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes

Definitions

  • the present invention relates to a photosensitive silver halide photographic material, more specifically to the photosensitive silver halide photographic material which comprises high sensitivity and can provide an image comprising high optical density and execellent graininess.
  • silver halide grains are prepared by a method comprising preparation process of silver halide seed grains followed by process of growing the seed grains, wherein water soluble silver salt solution and water soluble halide solution are supplied using jet method (for example, single jet method, double jet method). Said preparation of silver halide grains is described in USP4610958, USP2996287, USP3785777 and USP90386.
  • the photosensitive silver halide photographic material containing silver halide grains mentioned above can't meet the above mentioned demands sufficiently.
  • the object of the present invention is to provide a photosensitive silver halide photographic material comprising high sensitivity, and capable of providing an image having excellent graininess and sufficiently high optical density.
  • the photosensitive silver the halide photographic material of the invention comprises at least one silver halide emulsion layer containign silver halide grains (1) having at least two kinds of halogens, wherein said silver halide grains (1) are grown to in a system in the presence of silver halide grains (2) coexisting with silver halide grains which are growing to the silver halide grains (1), for at least some portion of period that the silver halide grains are growing in the system, and comprising solubility product less than that of said growing silver halide grains.
  • the at least two kinds of halogens may distribute uniformly or ununiformly in the AgX(1).
  • AgX(1) is the grains in which distribution of said halogens is not uniform, such as core/shell type or epitaxitial type silver halide grains, and core/shell type grains are more preferable.
  • Preferable composition of Agx(1) is AgBrCI, AgBrl or AgBrCII, and more preferably AgBrl.
  • the AgX(1) is contained in a ratio of not less than 30 mol%, more preferably not less than 60 mol% as the amount of AgX, in at least one of the emulsion layers constituting the photosensitive material.
  • the photosensitive material is of multilayer structure, at least one emulsion layer for which the AgX(1) should be contained is chosen, but it is preferable that AgX(1) is contained in all emulsion layers.
  • the characteristic of the present invention is to consume AgX(2) grains as an alternative for at least one portion of water soluble silver salt solution and water soluble halide solution (hereinafter referred to as the grain growth compositions) to form the AgX(1) grains.
  • One preparation process is that AgX seed grains are grown to AgX(1) by supply of water soluble silver salt solution and water soluble halide solution.
  • Another preparation process is that without said seed grains, AgX nucleus is formed followed by growth of said nucleus to AgX(1) by supply of said two solution.
  • the former process is preferable because reproduction of size of AgX grains formed is better.
  • AgX(2) is necessary to exist at latest by completion of growth to AgX(1) in the grain growth suspension (hereinafter referred to as mother suspension.).
  • said seed grains may be added to AgX(2), and AgX(2) may be added to said seed grains prior to and/or in the middle of adding of grain growth compositions in mother suspension.
  • AgX(2) is added after AgX nucleation prior to and/or in the middle of adding of the grain growth compositions.
  • Each of AgX(2) and the grain growth composition may be added continuously, discontinuously or at a time.
  • AgX(2) and the grain growth compositions respectively are added to mother suspension by the multi jet method (for example, double jet method) at an adaptive rate to grain growth under the controlled pH, pAg and temperature etc.
  • the multi jet method for example, double jet method
  • Each of AgX(2) and AgX seed grains may be prepared out of the grain growth suspension followed by addition to said suspension or may be prepared in mother suspension.
  • Water sotuble silver solution used for forming AgX(2) is preferably an ammoniacal silver nitrate solution.
  • AgX(2) is preferably Agl or AgBrl of which iodide content is more than that of growing AgBrl and in case that AgX(1) is AgCIBr, AgX(2) is preferably AgBr or AgCIBr of which bromide content is more than that of growing AgBrl.
  • AgX(1) is AgBrl
  • AgX(2) is Agl
  • AgBrl or AgBrCII is preferably used in this invention, and in such case, it is preferable that an entire amount of iodide used in grain growth is provided by AgX(2), but a portion of iodide may be supplied by water soluble iodide solution.
  • AgX (2) be highly monodispersible. Although they may not necessarily be very fine, their average grain size is preferably 0.001 to 0.7 ⁇ m, more preferably, 0.3 to 0.005 ⁇ m, still more preferebly, 0.1 to 0.01 ⁇ m.
  • the seed emulsion particles can have any composition, various silver compounds can be used, e.g. silver chloride, silver bromide, silver chlorobromide, silver chloroiodide, silver bromoiodide, and silver bromochlo- roiodide.
  • mother suspension temperature is preferably 10 to 70°C, more preferably 20 to 60° C;
  • pAg is preferably 6 to 11, more preferably 7.5 to 10.5; and pH is preferably 5 to 11, more preferably 7 to 11.
  • the substances other than gelatin, adsorptive to AgX grains may be added in preparation of an AgX grains (including preparation of an AgX seed grains).
  • the examples of the adsorptive substances which serve well for this purpose include sensitizing dyes and compounds or heavy metal ions used in the relevant industry as anti-fogging agents or stabilizers.
  • the preceding adsorptive substances are described in the examples of Japanese Patent Publication Open to Public Inspection No. 7040/1987.
  • At least one anti-fogging agent or stabilizer chosen from the preceding adsorptive substances be added in preparation of an Agx seed grains emulsion.
  • heterocyclic mercapto compounds and/or azaindene compounds are particularly preferable.
  • the examples of more preferable heterocyclic mercapto compounds and azaindene compounds are described in detail in Japanese Patent Publication O.P.I. No. 41848/1988; those substances can be used for the present invention.
  • an addition amount of the above-mentioned heterocyclic mercapto compounds and azaindene compounds is preferably 1 x 10- 5 to 3 x 10- 2 , more preferably, 5 x 10- 5 to 3 x 10- 3 per mole of AgX. This amount depends on production conditions of AgX grains, AgX average grain size and a type of the preceding compounds.
  • a finished emulsion containing the AgX(1) grains with the needed properties is then desalinated by a known method after AgX grain formation.
  • gelatin coagulating agents used for desalination of AgX grains as AgX seed grains described in Japanese Patent Application Nos. 81373/1987 and 9047/1988 may be used. It is also possible to use a noodle washing method in which gelatin is gelated, or a coagulation method which utilizes inorganic salts comprising multivalent anions such as sodium sulfate, anionic surfactants or anionic polymers (e.g. polystyrene sulfate).
  • the AgX grains thus desalinated are then redispersed in gelatin to prepare an AgX emulsion.
  • AgX(1) may be of uniform composition or of shell-layer type core/shell composition; AgX(1) of the present invention is efficient for a core-shell composition.
  • an average grain size of AgX(1) grain there is no particular limitation on an average grain size of AgX(1) grain, and it may vary by application, but it is preferably 0.1 to 3.0 ⁇ m.
  • the average grain size means the length of one side of an AgX grain if it is in a cube form, or the length of one side of a cube assumed to have the volume equal to that of an AgX grain if it is in a non-cube form.
  • the average grain size y can be expressed by the equation.
  • a large part of the AgX grains with high monodispersibility have an identical crystal phase, and thus have a narrow size distribution.
  • the value obtained by dividing a standard deviation in a grain size distribution by an average grain size (variation coefficient) is not more than 0.20.
  • the AgX emulsion of the present invention is desirable, since it broadens an exposure latitude of AgX photosensitive materials having at least one emulsion layer containing at least two AgX emulsions with substantially different sensitivities, as well as improves graininess and sharpness, when it is used as at least one of said two AgX emulsions.
  • two or more silver halide emulsions with different average grain sizes Two or more emulsions with different sensitivities prepared by varying an addition amount of chemical sensitizer or spectrally sensitizing dye may also be mixed. It is also possible to use the method in which two or more emulsions with different amounts of desensitizing agent are mixed, and the method in which two or more AgX seed grain emulsions with different amounts of desensitizing are mixed and grown.
  • the requirement of "substantially different sensitivities" in the present invention is satisfied by the condition that at least two emulsions have different sensitivities; it is preferable that at least two emulsions have difference of not less than 0.2 as expressed in logE value on a characteristic curve, and difference of 0.4 to 2.0 is more preferable.
  • Exposure latitude relating to the present invention is the range of light acceptance in which significantly different exposure effects are observed.
  • the possible desensitizing agents are arbitrarily selected from various agents such as metal ions, antifoggants, stabilizers and desensitizing dyes; however, for desensitizing, a method of metal ion doping is preferable.
  • metal ions used for the doping are metal ions such as Cd, Zn, Pb, Fe, T-R, Ru, Rh, Bi, lr, Au, Os, Os, and Pd. These types of metal ions are preferably used, for example, in the form of halogen complex salt; the preferred pH level in the Agx suspension system in the course of doping is not higher than 5.
  • the preferred amount of metal ions used for doping varies depending upon the type of metal ions, size of silver halide grains, position of doping with metal ions, and intended sensitivity. However the preferred amount is 10- 17 to 10- 2 , or, in particular, 10- 16 to 10- 4 mol per mol Agx. If such metal ions are rhodium ions, the preferred amount is 10- 14 to 10- 2 mol, in particular, 10- 11 to 10- 4 mol per mol Agx.
  • each Agx grain is endowed with different sensitivity potential.
  • An amount of metal ions used for doping not more than 10- 2 mol/Agx mol does not significantly affect the growth of silver halide grains. Accordingly, it is possible under identical conditions for growing grains, to prepare Agx grains exhibiting a narrow size distribution.
  • Each of the respective Agx grain respectively undergone doping under different conditions can be subjected to treatment that allows these grains to be industrially applicable, thereby these grains are mixed together at a specific mixing ratio into a same batch, that is chemically sensitized.
  • the respective Agx grains are sensitized depending on their unique sensitivity potential, whereby a resultant emulsion is endowed with intended latitude based on the sensitivities of the grains and on a mixing ratio between the grains.
  • a compound known in the art as antifoggant, stabilizer or desensitizing dye may be used in order to prepare the Agx grains of different sensitivity potentials.
  • Such Agx grains are mixed at a specific mixing ratio in compliance with the intended exposure latitude.
  • the examples of the preceding anti-fogging agents and stabilizers include azoles such as benzthiazolium salts, indazoles, triazoles, benztriazoles, benzimidazoles, heterocyclic mercapto compounds such as mercaptotetrazoles, mercaptothiazoles, mercaptothiadiazoles, mercaptobenzthiazols mercaptobenzimidazoles, mercaptopyrimidine, azaindenes such as tetrazaindenes, pentazaindenes, nucleic acid decomposition products such as adenine, guanine, benzenethiosulfonic acids, and thioke to compounds.
  • azoles such as benzthiazolium salts, indazoles, triazoles, benztriazoles, benzimidazoles, heterocyclic mercapto compounds such as mercaptotetrazoles, mercaptothiazoles,
  • spectral desensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxol dyes.
  • the emulsion of the present invention is chemically sensitized by a conventional method. It is possible to use singly or in combination a sulfur sensitization method using a sulfur compound capable of reacting with silver ions or using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, and a noble metal sensitization method using a compound of gold or another noble metal.
  • chalcogen sensitizers for instance, can be used as a chemical sensitizer; sulfur sensitizers and selenium sensitizers are particularly preferable.
  • sulfur sensitizers include thiosulfates, allyl thiocarbazide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. It is also possible to use the sulfur sensitizers described in U.S. Patent Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, and 3,656,955; West German OLS Patent No. 1,422,869; Japanese Patent Publication Open to Public Inspection Nos. 24937/1981 and 45016/1980, for instance.
  • the amount of the sulfur sensitizer added may vary over a fairly wide range depending on various conditions such as pH, temperature and silver halide grain size, but, as a standard, it is preferably about 10- 7 to 10- 1 mole per mole of silver halide.
  • selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate; selenoureas; selenoketones; selenoamides; salts and esters of selenocarboxylic acids; selenophosphates; and selenides such as diethyl selenide and diethyl diselenide.
  • aliphatic isoselenocyanates such as allyl isoselenocyanate; selenoureas; selenoketones; selenoamides; salts and esters of selenocarboxylic acids; selenophosphates; and selenides such as diethyl selenide and diethyl diselenide.
  • Reduction sensitization can also be applied in combination.
  • Reducing agents include stannous chloride, thiourea dioxide, hydrazine and polyamine.
  • the AgX grains of the present invention contain a gold compound.
  • Gold compounds which can be preferably used for the present invention include a wide variety of compounds of monovalent or trivalent gold. The typical examples include potassium chloroaurate, auric trichloride, potassium iodoaurate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyltrichlorogold, gold sulfide, and gold selenide.
  • the gold compounds may be used in such manner that the AgX grains are sensitized, or in such manner that it does not substantially contribute to sensitization.
  • the amount of the gold compound added varies depending on various conditions, but, as a standard, it is 10- 8 to 10- 1 mole, preferably 10- 7 to 10- 2 mole per mole of silver halide. These compounds can be added in any of the processes of AgX grain formation, physical aging and chemical aging, or after completion of chemical aging.
  • An emulsion of the present invention can be spectrally sensitized for a desired wavelength range by means of sensitizing dyes, which may be used singly or in combination of two or more sensitizers.
  • the dyes which have no spectral sensitizing function or the supersensitizers, which virtually do not absorb visible light, and can strengthen a sensitizing function of a sensitizing dye may be incorporated into an emulsion together with the sensitizing dyes.
  • the emulsion of the present invention spectrally sensitized with at least one sensitizing dye selected from the group of the sensitizing dyes represented by Formula [A] shown below, improves a photosensitive AgX photographic material in sensitizing dye adsorption, sensitivity and provides an image with excellent graininess.
  • the cyanine dyes represented by Formula [I] or [II] are preferable for the present invention.
  • Z 1 , Z 2 , Z 3 , and Z 4 independently represent the group of the atoms necessary to form a 5- or 6-membered nitrogen containing heterocyclic ring;
  • L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , Ls, Lg, and Lio independently represent a methine group;
  • Y represents an oxygen atom, a sulfur atom, a selenium atom, or -N-R 7 group;
  • R 1 , R 2 , R 3 , and R 5 independently represents an alkyl group;
  • R 4 and R 7 independently represent an alkyl group, an alicyclic group, a heterocyclic group, or an aryl group;
  • X and X independently represent an acid anion;
  • ki, k 2 , l 1 , £ 2 , B3, and £ 4 independently represent the integer of 0 or 1;
  • m 1 , m2, n 1 , and n 2 independently
  • a heterocyclic ring formed by Zi, Z 2 , Z 3 or Z 4 is a 5- or 6-membered heterocyclic ring usually composing cyanine dyes and includes a condensed ring with an aromatic ring such as a benzene ring or a naphthalene ring.
  • said heterocyclic ring includes cyanine heterocycle nuclei which comprises, for example, a thiazole ring, a selenazole ring, an oxazole ring, a tetrazole ring, a pyridine ring, a pyrroline ring an imidazole ring, an oxazoline ring, a thiazoline ring, an isoxazole ring, a 1, 3, 4 -thiadizole ring, a thienothiazole ring, an imidazoquinoxaline ring, an imidazoquinoline ring, a pyrrolopyridine ring, a pyrrolopyrazine ring, a pyridopyridine ring or condensed ring thereof, each substituted or not substituted.
  • cyanine heterocycle nuclei which comprises, for example, a thiazole ring, a selenazole ring, an oxazole ring,
  • the examples include a thiazole series such as thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, benzothiazole, 5-fluorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 5-carbox- ybenzothiazole, 5-ethoxycarbonylbenxothiazole, 5-hydroxybenzothiazole, 5-phenylbenzothiazole, 6-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-ethoxybenzo- thiazole, tetrahydrobenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dime
  • the preceding 1-(cyclo)alkyl-groups are preferably the alkyl groups or cycloalkyl growp with a carbon number of 1 to 10 (not including the carbon atoms of the substituents), and also include the alkyl groups or cycloalkyl groups substituted with an alkoxy group having a carbon number of 1 to 6, an alkoxycarbonyl group having an alkoxy group with a carbon number of 1 to 4, a carboxy group, a carbamoyl group, a cyano group, a halogen atom, a hydroxy group, a sulfo group, a phenyl group, including substituted phenyl group, a vinyl group, etc.; the examples of the 1-(cyclo)alkyl include methyl group, ethyl group, cyclohexyl group, butyl group, decyl group, 2-methoxyethyl group, 3-butoxypropyl group, 2-hydroxy-ethoxyethyl group,
  • the methine group represented by L i , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L s , Lg, and Lio include substituted methine group.
  • the examples of the substituents include a lower alkyl groups having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group, isobutyl group), an aryl group (e.g. phenyl group, p-tolyl group, p-chlorophenyl group), an alkoxy group having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group), an aryloxy group (e.g.
  • phenoxy group an aralkyl group (e.g. benzyl group, phenetyl group), a heterocyclic group (e.g. thienyl group, furyl group), a substituted amino group (e.g. dimethyl amino group, tetramethylenamino group, anilino group), an alkylthio group (e.g. methylthio group), and an acid nuclei groups (e.g.
  • the substituents of the methine groups may be combined to form a 4- to 6-membered ring (e.g. 2-hydroxy-4- oxocyclobutene ring, cyclopentene ring, 3,3- dimethylcyclohexene).
  • the alkyl groups for each of R 1 , R 2 , R 3 and R 5 include substituted alkyl groups.
  • the preferred alkyl group is an alkyl groups having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, butyl group, isobuty! group), and the examples of the substituent include an alkoxy group, an alkoxycarbonyl group, an aryl group, a hydroxy group, a cyano group, a vinyl group, a halogen atom, a carbamoyl group, a sulfamoyl group, a carboxy group, a sulfo group, and a sulfato group.
  • the alkyl groups for each of R 4 and R 7 include substituted alkyl groups and the preferred alkyl groups is an alkyl group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group).
  • the examples of the substituent include an alkoxy group, an alkylthio group, an aryloxy group, an aryl group, a hydroxy group, a cyano group, a vinyl group, a halogen atom, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, and a carboxy group.
  • the alicyclic groups for each of R 4 and R 7 are preferably 5- or 6-membered alicyclic groups (e.g. cyclopentyl group, cyclohexyl group) and include substituted alicyclic group.
  • the heterocyclic group and the aryl group represented by R4 and R 7 respectively include the substituted heterocyclic group and the substituted aryl group.
  • heterocyclic group examples include a pyridyl group (e.g. a 2-pyridyl group, 3-pyridyl group, 4-pyridyl group) and a 2-thiazolyl group;
  • the examples of the aryl group include a phenyl group, a 2-naphthyl group (e.g. p-tolyl group, p-chlorophenyl group, p-carboxyphenyl group).
  • the acid anion represented by X9, and X? may be any acid residue; the examples include ethyl sulfate, methyl sulfate, p-toluenesulfonate, benzenesulfonate, thiocyanate, chloride, bromide, iodide, perchlorate, and perfluoroborate.
  • ki and k 2 each is zero.
  • Z 1 , Z 2 , Z 3 , Y, R 1 , R 2 , R 3 , R 4 , Rs, R 7 Xi, X 2 , l 1 , £2, l 3 , ki, and k 2 represent the same groups and numbers as those defined in Formulae [I] and [II].
  • Y 1 and Y 2 independently represent an oxygen atom, a sulfur atom, a selenium atom, tellurium atom, or -N-R 7 group;
  • Ys and Y 4 independently represent an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom.
  • V 1 V 2 , V 3 , V 4 , Vs and Vs independently represent a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, trifluoromethyl group), an alkoxy group (e.g. methoxy group, ethoxy group), a halogen atom (e.g. fluorine, chlorine, bromine), a phenyl group, a hydroxy group, a cyano group, an alkoxycarbonyl group (e.g. methoxycarbonyl group, butoxycarbonyl group), a carbamoyl group (e.g.
  • V 1 and V 2 , V 2 and V 3 , V 4 and Vs, and Vs and V 6 may be combined each other to form, e.g.
  • W 1 , W 2 , Ws, and W 4 independently represent a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group), or a phenyl group and W1 and W2, and/or W3 and W4 can be combined each other to form a ring which includes substituted ring.
  • the ring formed by combining W i and W 2 and/or W 3 and W 4 each other is a benzene ring, a cyclohexene ring, a thiophene ring, or a naphthalene ring, which may be substituted by, for example, a halogen atom (e.g. fluorine, chlorine, bromine), an alkyl group (e.g. methyl group, a trilfuoromethyl group,ethyl group), an alkoxy group (e.g. methoxy group, ethoxy group), a phenyl group, a cyano group, an alkoxycarbonyl group (e.g.
  • a halogen atom e.g. fluorine, chlorine, bromine
  • an alkyl group e.g. methyl group, a trilfuoromethyl group,ethyl group
  • an alkoxy group e.g. methoxy group, ethoxy group
  • methoxycarbonyl group, butoxycarbonyl group a carbamoyl group (e.g. carbamoyl group, N,N-dimethylaminocarbamoyl group), a sulfonyl group (e.g. methanesulfonyl group, benzenesulfonyl group), and a sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylaminosulfonyl group);
  • a carbamoyl group e.g. carbamoyl group, N,N-dimethylaminocarbamoyl group
  • a sulfonyl group e.g. methanesulfonyl group, benzenesulfonyl group
  • a sulfamoyl group e.g. sulfamoyl group, N,N-dimethylaminosulfonyl group
  • the sensitizing dyes represented by Formula [A] of the present invention can easily be synthesized by the methods described in, for example, the Journal of the American Chemical Society, 67, 1875-1899 (1945), "Heterocyclic Compounds - Cyanine Dyes and Related Compounds", F.M. Hamer, published by Inter Science Publishers (1964), U.S. Patent Nos. 3,483,196, 3,541,089, 3,598,595, 3,598,596, 3,632,808, 3,757,663, and Japanese Patent Publication Open to Public Inspection No. 78445/1985.
  • the preceding spectral sensitizing dye is preferably used at a ratio of 1 x 10- 6 to 1 x 10- 2 mole, more preferably 5 x 10- 6 to 1 x 10- 3 mole per mole of silver halide.
  • the spectral sensitizing dyes described above can be added to a silver halide emulsion by various methods. The methods include a protonization dissolution method described in Japanese Patent Publication Open to Public Inspection Nos. 80826/1975 and 80827/1975, a method in which a dye is dispersed in the presence of a surfactant, described in Japanese Patent Publication Open to Public Inspection Nos.
  • a dye is dissolved in at least one water-soluble solvent capable of dissolving the dye, selected from the group comprising of water, methanol, ethanol, propylalcohol, acetone, fluorinated alcohol, and dimethylformamide, and then added to an emulsion. It may be added at any stage of emulsion preparation, but it is Preferable to add in chemical aging or after that.
  • the sensitizing dye described above can be used in combination of various dyes having a supersensitizing function.
  • the sensitizing dye can be used in combination with other dyes such as hemicyanine dyes, styryl dyes and benzilidene dyes.
  • the AgX emulsion of the present invention can be applied to black-and-white photoseseitive silver halide photographic material (e.g. X-ray film, lith type photo-sensitive material, baick-and-white negative film) and color photographic material (e.g. color negative film, color reversal film, color paper). It can also be applied to diffusion transfer photosensitive material (e.g. color diffusion transfer component, silver salt diffusion transfer component) and heat development photosensitive material (black-and-white, color).
  • black-and-white photoseseitive silver halide photographic material e.g. X-ray film, lith type photo-sensitive material, baick-and-white negative film
  • color photographic material e.g. color negative film, color reversal film, color paper
  • diffusion transfer photosensitive material e.g. color diffusion transfer component, silver salt diffusion transfer component
  • heat development photosensitive material black-and-white, color
  • multicolor photosensitive AgX photographic material it usually comprises a support provided thereon the blue-sensitive, green-sensitive and red-sensitive AgX emulsion layers respectively containing yellow, magenta and cyan couplers, and a non-photosensitive layer as needed, each having a prescribed number of layers in prescribed layering order, but the number of layers and the layering order are changeable according to key performance and application.
  • At least one, or preferably all, of the blue-sensitive, gree-sensitive and red sensitive layer is composed of a single layer comprising an AgX emulsion of the present invention, whereby it can provide a color image with a higher maximum density and excellent graininess and sharpness.
  • a non-photosensitive hydrophilic colloid layer (e.g. interlayer) may be or may not be present between the blue-sensitive, green-sensitive and red-sensitive emulsion layers.
  • a non-photosensitive hydrophilic colloid layer (e.g. protective layer) may be or may not be present; between the lowest emulsion layer and a support, a non-photosensitive hydrophilic colloid layer may be or may not be present.
  • dry thickness of the entire photographic component layers of the multicolor photosensitive material is preferably not more than 20 ⁇ m, more preferably, 8 to 18 ⁇ m. For much higher graininess and sharpness, the dry thickness is further preferably 10 to 15 ⁇ m.
  • the photographic component layers include all of the emulsion layers and the non-photosensitive layers prepared as needed, excluding a support.
  • coating layer thickness as the difference of dry thickness including a film base and thickness of a film base itself separately measured. Another method is to measure directly by observing visually or taking photograph with a microscope a thin section of a photosensitive material cut by a microtome.
  • the couplers used for a multicolor photosensitive material is added in a solution of a high boiling point organic solvent.
  • the yellow couplers preferably used for multicolor photosensitive silver halide photographic materials are benzoylacetanilide yellow couplers and pivaloylacetanilide yellow couplers.
  • the compounds represented by Formulae [III] and [IV] can be preferably used.
  • R 1 through R 7 and W independently represent a hydrogen atom or a substituent; preferably R 1 , R 2 and R 3 represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acylamino group, a carbamoyl group, an alkoxycarbonyl group, a sulfonamide group, or a sulfamoyl group.
  • R 4 , Rs, Rs, and R 7 preferably represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, or a sulfonamide group.
  • W preferably represents a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or a dialkylamino group.
  • X 1 represents a hydrogen atom or a group capable of splitting off by reaction with an oxidized product of a color developing agent.
  • the examples of such splitting off groups include a monovalent group such as a halogen atom, a group bonded via an oxygen atom (e.g. an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group), a group bonded via a sulfur atom (e.g. an alkylthio group, an arylthio group, a heterocyclic thio group), a group bonded with a nitrogen atom (e.g.
  • Xi represents the group of the atoms necessary to form a 5- or 6-membered ring with the nitrogen atom in the formula and at least one atom selected from carbon, oxygen, nitrogen and sulfur atoms; an acylamino group; a sulfonamide group) and a divalent group such as an alkylene group.
  • Formula [III] involves the cases where a dimer or higher polymer is formed at R 1 through R 7 , W, or Xi.
  • R 8 through R 1 independently represent a hydrogen atom or a substituent;
  • R 8 preferably represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is more preferable;
  • Rg, Rio, and R 11 independently preferably represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfone group, a sulfamoyl group, an alkylsulfonamide group, an acylamide group, an ureido group, or an amino group; more preferably R 9 and R 10 is a hydrogen atom, respectively
  • Formula [IV] involves the cases where a dimer or higher polymer is formed at R 8 through R 11 or X.
  • a diequivalent benzoyl type yellow coupler is particularly preferable.
  • magenta couplers preferably used are represented by Formula [V], [VI], [VII] or [VIII];.
  • R 3 represents a substituent
  • R i and R 2 independently represent a hydrogen atom or a substituent
  • X represents the same groups as Xi in Formula [III]; represents the integer of 0 through 5; each R 2 may be identical or not, provided that is 2 or more.
  • the examples of the substituent represented by Ri or R 2 include a halogen atom and a group bonded directly or via a divalent group or atom such as alkyl, cycloalkyl, aryl or heterocyclic groups, which include substituted ones.
  • the examples of the substituent represented by R 3 include a group such as alkyl, cycloalkyl, aryl, and heterocyclic groups, which include substituted ones.
  • the splitting off group represented by X is exemplified by the same examples as those of X i in Formula [III].
  • those bonded via a nitrogen atom or a sulfur atom are preferred for X in Formulae [V] and [VI] and halogen atom is preferred for X in Formula [VII] and [VIII].
  • Formulae [V] and [VI] involve the cases where a dimer or higher polymer is formed at R 2 , R 3 or X; Formulae [VII] and [VIII] involve the cases where a dimer or higher polymer is formed at R 1 , R 2 or X.
  • the cyan couplers preferably used are represented by Formula [IX], [X], or [XI];
  • R 2 and R 3 represent the same groups as R 2 and R 3 in Formula [V];
  • X represents the same groups as X 1 in Formula [III];
  • R 4 represents a substituent; m is the integer of 1, or 3; n is the integer of 1 or 2; p is the integer 1 through 5; each R 2 may be identical or not, provided that m, n, and p are independently 2 or more.
  • R 2 and R 3 are exemplified by the same examples as those of R 2 and R 3 in Formula [V];
  • R 4 is exemplified by the same examples as those of R 3 in Formula [V].
  • the examples of the splitting off group represented by X are the same as those of Formula [III]; a halogen atom and a group bonded via an oxygen atom are preferred.
  • Formulae [IX] and [XI] involve the cases where a dimer or higher polymer is formed at R 2 , R 3 or X; Formula [X] involves the cases where a dimer or higher polymer is formed at R 2 , R 3 , R 4 or X..
  • the preceding yellow, magenta, and cyan couplers are normally used in an amount of 1 x 10- 4 to 10 moles per mole of silver halide.
  • coupler which releases a development inhibitor e. g. DIR coupler
  • a development inhibitor e.g. DIR coupler
  • a compound capable of scavenging an oxidized product of a color developer e.g. DSR coupler
  • masking coupler capable of correcting color
  • DIR couplers are diffusible DIR couplers.
  • the diffusible DIR couplers should meet the requirement that a development inhibitor or a compound capable of releasing a development inhibitor, which splits off by reaction with an oxidized product of a color developer has a diffusibility of not less than 0.34, as determined by the evaluation method described below, preferably not less than 0.40.
  • Photosensitive material samples (I) and (li) each having a layer of the following composition is prepared on a transparent support.
  • Sample (I) Sample having a green-sensitive silver halide emulsion layer.
  • Sample (II) the same sample as sample (I), besides that silver bromoiodide is removed from a protective layer.
  • Each layer contains a gelatin hardener and surfactant.
  • compositions of the processing solutions used in respective processes are as follows: [Color developer]
  • Any diffusible DIR coupler can be used irrespective of its chemical structure, as long as a diffusibility of groups released therefrom is at the preceding range.
  • Y is represented by Formulae (D-1) through (D-19).
  • Rd 1 represents a hydrogen atom, a halogen atom, alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolidinilideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocyclic, cyano, alkylsulfonyl or aryloxycarbonylamino group; n represents the integer of 0, 1, or 2; Rd 1 may be identical or not when n is 2. The total number of carbon atoms contained in n Rd 1 units is 0 to 10. The number of carbon atoms contained in n Rd 1 units is
  • Rd 2 represents an alkyl group, an aryl group, or a heterocyclic group.
  • Rd 3 represents a hydrogen atom, alkyl, cycloalkyl, aryl, or heterocyclic group
  • Rd 4 represents a hydrogen atom, halogen atom, alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamide, cyano, heterocyclic, alkylthio, or amino group.
  • Rdi, Rd 2 , Rd 3 , or Rd 4 represents an alkyl group, the alkyl group includes a substituted alkyl, a linear alkyl and a branched alkeyl.
  • Rd 1 , Rd 2 , Rd 3 , or Rd 4 represents a heterocyclic group
  • the heterocyclic group is preferably a 5- or 6-membered monocyclic ring or a condensed ring containing at least one atom selected from nitrogen, oxygen, and sulfur atoms as a hetero atom
  • the examples of such heterocyclic rings include groups such as pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide, and oxazine.
  • the preceding group represented by Rdi - Rd 4 includes substituted one.
  • the preferred substituents include a halogen atom, a nitro group, a cyano group, a sulfonamide group, a hydroxyl group, a carboxyl group, an alkyl group, an alkoxy group, a carbonyloxy group, an acylamino group, and an aryl group.
  • Rd 2 contains 0 to 15 carbon atoms.
  • the TIME group is a group combining a coupling site of A in Formula (D-1), which can split off by reaction with an oxidized product of a color developer and control the INHIBIT group for releasing after separating from the coupler.
  • the INHIBIT group is a group which becomes a development inhibitor [e.g. groups represented by Formulae (D-2) through (D-9)] after releasing.
  • the -TIME-INHIBIT group is preferably represented by Formulae (D-11) through (D-19) shown below.
  • Rd s represents a hydrogen atom, a halogen atom, alkyl, cycloalkyl, alkenyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxy, sulfo, hydroxy, alkanesulfonyl group.
  • Rds may be combined each other to form a condensed ring.
  • Rd 6 represents alkyl, alkenyl, cycloalkyl, heterocyclic, or aryl group.
  • Rd 7 represents a hydrogen atom, alkyl, alkenyl, cycloalkyl, heterocyclic, or aryl group.
  • Rd 8 and Rd 9 in Formula (D-19) independently represent a hydrogen atom or an alkyl group (preferably an alkyl group with a carbon number of 1 to 4).
  • k in Formulae (D-11) and (D-15) through (D-18) represents the integer of 0, 1 or 2; in Formulae (D-11) through (D-13), (D-15), and (D-18) represents the integer of 1 through 4;
  • m in Formula (D-16) represents the integer of 1 or 2;
  • Rd 7 may be identical or not, when m is 2;
  • n in Formula (D-19) represents the integer of 2, 3 or 4;
  • n groups of Rda and Rd9 may be identical or not;
  • B in Formulae (D-16) through (D-18) represents an oxygen atom or (Rd 6 represents the same group as defined above); in General (D-16) represents a single bond or a double bond; in a single bond, m is 2, and in a double bond, m is and the INHIBIT group represents the same groups as those defined in Formulae (D-2) through (D-9) except the number of carbon atoms.
  • the number of carbon atoms contained in Rdi per molecule of Formulae (D-2) through (D-7) is 0 to 32;
  • R d2 in Formula (D-8) contains 1 to 32 carbon atoms;
  • Rd 3 and Rd 4 in Formula (D-9) contain 0 to 32 carbon atoms in total.
  • Rds to Rd 7 includes a substituted one.
  • DIR compounds those represented by Formula (D-2), (D-3) or (D-10) are preferred.
  • compounds represented by Formula (D-10) are preferred those having an INHIBIT group represented by Formula (D-2), (D-6) [particularly when X in Formula (D-6) is an oxygen atom], or (D-8) [particularly when Rd 2 in Formula (D-8) is a hydroxyaryl group or an alkyl group with a carbon number of 1 through 3].
  • the coupler components represented by A in Formula (D-1) are yellow, magenta and cyan color image forming coupler residues, and non-color-forming coupler residue.
  • diffusible DIR couplers including these couplers, which can be used for the present invention, are described in U.S. Patent Nos. 4,234,678, 3,227,554, 3,617,291, 3,958,993, 4,149,886, and 3,933,500, Japanese Patent Publication Open to Public Inspection Nos. 56837/1982 and 13239/1976, U.S. Patent Nos. 2,072,363 and 2,070,266 and Research Disclosure No. 21228/December, 1981, for instance.
  • the diffusible DIR compounds are used preferably in amounts of 0.0001 to 0.1 mole, more preferably 0.001 to 0.05 mole per mole of silver halide.
  • a DSR coupler is defined as a coupler capable of releasing a compound capable of scavenging an oxidized product of a color developer, or its precursor by reaction with an oxidized product of a color developer, and preferably is represented by Formula [S];
  • Coup represents a coupler residue capable of releasing (Time) ⁇ l-Sc by reaction with an oxidized product of a color developer
  • Time represents a timing group capable of releasing Sc after release of Time-Sc from Coup
  • Sc represents a scavenger capable of scavenging an oxidized product of a color developer by oxidation-reduction reaction or coupling reaction
  • .e represents the integer of 0 or 1.
  • the coupler residue represented by Coup is generally a yellow coupler residue, magenta coupler residue, cyan coupler residue, or a coupler residue which forms substantially no image forming coupling dye, or preferably a coupler residue represented by Formulae [Sa] through [Sh].
  • R 1 presents an alkyl group, an aryl group, or an arylamino group
  • R 2 represents an aryl group or an alkyl group.
  • R 3 represents an alkyl group or an aryl group
  • R 4 represents an alkyl group, an acylamino group, an arylamino group, an arylureido group, or an alkylureido group.
  • R 4 represents the same groups as those defined in Formula [Sb]; Rs represents an acylamino group, a sulfonamide group, an alkyl group, an alkoxy group, or a halogen atom.
  • R 7 represents an alkyl group, an aryl group, an acylamino group, an arylamino group, an alkoxy group, an arylureido group, or an alkylureido group;
  • R 6 represents an alkyl group or an aryl group.
  • R 9 represents an acylamino group, a carbamoyl group, or an arylureido group; Rs represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or a sulfonamide group.
  • R 9 represents the same groups as defined in Formula [Sf]; Rio represents an amino group, a acylamide group, a sulfonamide group, or a hydroxyl group.
  • R 11 represents a nitro group, an acylamino group, a succinimide group, a sulfonamide group, an alkoxy group, an alkyl group, a halogen atom, or a cyano group.
  • [Sc] represents the integers of 0 through 3; n in [Sf] and [Sh] represents the integer of 0, 1, or 2; m in [Sg] represents the integer of 0 or 1; when and/or n is 2 or more, R s R s and R 11 may independently be identical or not.
  • the preceding groups may have substituents; the preferred substituents include a halogen atom, a nitro group, a cyano group, a sulfonamide group, a hydroxyl group, a carboxyl group, an alkyl group, an alkoxy group, a carbonyloxy group, an acylamino group, and an aryl group, and also include groups having a coupler moiety which constitutes what is called bis type coupler or polymer coupler.
  • R 1 through R 11 in the above Formulae can be arbitrarily selected by purpose.
  • the total number of carbon atoms of R 1 through Rio is preferably 10 to 60, more preferably 15 to 30.
  • the total number of carbon atoms of R 1 through R 10 is preferably not more than 15.
  • the couplers which virtually do not form dyes for forming an image represent the couplers which leave no color image after development, including couplers which form no colored dye, what is called effluent dye-forming couplers, where colored dyes flow out from a photosensitive material into a processing solution, and what is called bleaching dye-forming couplers, where colored dyes are bleached by reaction with components in a processing solution.
  • effluent dye-forming couplers the total number of carbon atoms of R 1 through Rio is preferably not more than 15, and preferably contains at least one carboxyl group, arylsulfonamide group or alkylsulfonamide group as a substituent for R 1 through Rio.
  • the timing group represented by Time in the above Formula [S] is preferably represented by Formula [Si], [Sj] or [Sk]; wherein B represents an atomic group necessary to form a benzene ring or a naphthalene ring; Y represents -O-, -S-, or and combines an active site of Coup (coupling component) in the above Formula [S]; R 12 , R 13 , and R 14 independently represent a hydrogen atom, an alkyl group or an aryl group. is positioned at ortho or para to Y in Bring, and the other end is combined to Sc in the above Formula [S].
  • Y, R 12 , and R 13 independently represent the same atoms and groups as those defined in Formula [Si];
  • R 15 represents a hydrogen atom, an alkyl. group, an aryl group, an acyl group, a sulfone group, an alkoxycarbonyl group, or a heterocyclic residue;
  • R 16 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amino group, an acid amide group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, or a cyano group.
  • Y is combined to an active site of Coup (coupling component) and to Sc in the above Formula [S].
  • Time group which releases Sc by intramolecular nucleophilic substitution include the group represented by the following Formula [Sk].
  • Nu represents a nucleophilic group having oxygen, sulfur, nitrogen, or other atoms, and is combined to an active site of Coup (coupling component) in Formula [S];
  • E represents an electrophilic group having a carbonyl group, a thiocarbonyl group, a phosphinyl group, a thiophosphinyl group, or other groups. This electrophilic group E is combined to a hetero atom of Sc;
  • D represents a linkage group which sterically links Nu and E and is capable of initialing an intramolecular nucleophilic substitution followed by a reaction to form a 3-to 7-membered ring after Nu is released from Coup (coupling component), and thereby releasing Sc.
  • a scavenger which scavenges an oxidized product of a color developer and is represented by Sc includes two types, namely an oxidation-reduction type and a coupling type.
  • Sc in Formula [S] is a group which scavenges an oxidized product of a color developer by oxidation-reduction reaction, it is capable of reducing the oxidized product of the color developing agent; for example, the reducing agents described in Angew. Chem. lnt. Ed., 17, 875-886 (1978), "The Theory of the Photographic Process", 4th edition (Macmillan, 1977), Chapter 11, Japanese Patent Publication Open to Public Inspection No. 5247/1984, etc. are preferred for Sc, and in addition, Sc may be a precursor capable of releasing any one of these reducing agents.
  • the preferred groups are an aryl group and a heterocyclic group, each having at least two of -OH group, -NHS0 2 R 1 group, and (wherein R and R' independently represent a hydrogen atom, an alkyl, a cycloalkyl, an alkenyl, or an aryl group); of these groups, aryl groups are particularly preferable, and a phenyl group is more preferable.
  • An oleophilicity of Sc can be arbitrarily selected by purpose, as is the case in the couplers represented by the above Formulae [Sa] through [Sh]; however, for maximizing the effect of the present invention, the total number of carbon atoms of Sc is 6 to 50, preferably 6 to 30, more preferably 6 to 20.
  • Sc When Sc scavenges an oxidized product of a color developer by coupling reaction, it may be any one of various coupler residues. However, Sc is preferably a coupler residue which forms substantially no image forming coupling dye; couplers used for this purpose include the preceding effluent dye-forming couplers, bleaching dye-forming couplers, and Weiss couplers which have a non-leaving substituent at a reactive point and forms no dye.
  • the examples of the compound represented by Formula [S] include the compounds described in British Patent No. 1,546,837, Japanese Patent Publication Open to Public Inspection Nos. 150631/1977,111536/1982, 111537/1982, 138636/1982, 185950/1985, 203943/1985, 213944/1985, 214358/1985, 53643/1986, 84646/1986, 86751/1986, 102646/1986, 102647/1986, 107245/1986, 113060/1986, 231553/1986, 233741/1986, 236550/1986, 236551/1986, 238057/1986, 240240/1986, 249052/1986, 81638/1987, 205346/1987, and 287249/1987.
  • Oxidation-reduction type scavengers can be preferably used for Sc; in this case, an oxidized color developer can be reduced for reuse.
  • a DSR coupler can be added to a photosensitive silver halide emulsion layer and/or a non-photosensitive layer, but the DSR coupler is preferably added to the photosensitive silver halide emulsion layer.
  • Two or more DSR couplers may be added to a single layer and the same DSR coupler may be added to two or more layers.
  • these DSR couplers are preferably used in amounts of 2 x 10- 4 to 5 x 10- 1 mote, more preferably, 1 x 10- 2 to 2 x 10- 1 mole per mole of silver in an emulsion layer.
  • the amount of the DSR coupler used is preferably 0.01 to 100 moles, more preferably 0.03 to 10 moles per mole of yellow, magenta, or cyan coupler.
  • colored couplers used for the invention include those described in U.S. Patent Nos. 3,476,560, 2,521,908, and 3,034,892, Japanese Patent Examined Publication Nos. 2016/1969, 22335/1963, 11304/1967, and 32461/1969, Japanese Patent Publication Open to Public Inspection Nos. 26034/1976 and 42121/1977, and West German OLS Patent No. 2,418,959.
  • the preceding various couplers can be added in any manner, as long as they are dissolved in a high-boiling-point organic solvent to be eventually contained in a photosensitive material; usually, after dissolved in a water-immiscible high-boiling-point organic solvent with a boiling point of over 150°C, in combination with a low-boiling-point and/or water-soluble organic solvent as needed, a coupler is mixed with an aqueous gelatin solution containing a surfactant to emulsify by a high-speed rotary mixer, colloid mill or other means, and then is added to a hydrophilic colloid such as silver halide emulsion.
  • High-boiling-point organic solvents used for the invention include organic solvents with a boiling point of over 150°C, which do not react with an oxidized product of a developer, such as phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters, and trimesates; particularly, those with a boiling point of over 170°C are preferred.
  • Low-boiling-point and/or water-soluble organic solvents which can be used in combination with high-boiling-point solvents include those described in U.S. Patent Nos. 2,801,171 and 2,949,360, for instance.
  • the examples of low-boiling-point, substantially water-insoluble organic solvents include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene;
  • the examples of water-soluble organic solvents include acetone, methyl isobutyl ketone, ⁇ -ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, and phenoxyethanol.
  • the preceding photosensitive halide photographic material after imagewise exposing, is subjected to at least color development and a treatment including bleaching and/or fixing; from the viewpoint of sensitivity and image graininess and sharpness, a photosensitive material is developed preferably in not more than 120 seconds, more preferably in 20 to 120 seconds, further more preferably 40 to 100 seconds.
  • Aromatic primary amine-based color developers are preferably used, including known ones widely used for various color photographic processes. These color developers include aminophenol derivatives and p-phenylenediamine derivatives. These compounds are normally used in the form of salts, e.g. hydrochlorides or sulfates, since they are more stable than free forms.
  • aminophenols include o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethylbenzene, and their salts.
  • p-phenylenediamine-based color developers include p-phenylenediamine, N,N-diethyl- p-phenylenediamine, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, and their salts.
  • the preferable aromatic primary amine-based color developers include the various compounds described in Japanese Patent Publication Open to Public Inspection No. 162885/1986, pp. 79-86.
  • the preceding color developer is preferably contained in a developing solution in amounts of not less than 2 x 10- 2 mole, more preferably 2.5 x 10- 2 to 2 x 10- 1 mole, further more preferably 3 x 10- 2 to 1 x 10- 1 mole per liter of developing solution.
  • the other preferred compounds which can be used for a color developing solution are sulfites, hydroxylmaines and development inhibitors.
  • the sulfites include sodium sulfite, sodium hydrogen sulfite, potassium sulfite, and potassium hydrogen sulfite. They are used preferably at the range of 0.1 to 40 g/i, more preferably 0.5 to 10 gle.
  • the hydroxylamines are used as counter salts against hydrochlorides, sulfates, etc.; they are used preferably at the range of 0.1 to 40 g/i, more preferably 0.5 to 10 gle.
  • the inhibitors include halides such as sodium bromide, potassium bromide, sodium iodide, and potassium iodide; the organic inhibitors include the following compounds, which are added in amounts of 0.005 to 20 g/l, preferably 0.01 to 5 g/l.
  • Organic inhibitors used for the invention include the compounds described in Japanese Patent Publication Open to Public Inspection No. 162885/1986, pp. 88-105.
  • a color developing solution contains a compound represented by the following Formula [IS].
  • R S 1 represents -OH, -ORs 4 or Rs 4 and Rs 5 independently represent an alkyl group; the alkyl groups represented by each of Rs 4 and Rs 5 include substituted ones, and the examples of substituents are a hydroxyl group and an aryl group such as a phenyl group and the alkyl groups include methyl, ethyl, propyl, butyl, benzy, ⁇ -hydroxyethyl, and dodecyl groups;
  • R S 2 and Rs 3 independently represent -H or Rs 6 represents an alkyl group or an aryl group; the alkyl group represented by R S 6 include long-chained alkyl groups such as undecyl group;
  • Xs and Ys are respectively carbon atoms and hydrogen atoms, which are combined with other atomic groups to form a 6-membered ring;
  • the compound represented by Formula [IS] is preferably used in an amount of 0.1 to 50 g, more preferably 0.2 to 20 g per liter of color developing solution.
  • the color developing solution may be further supplemented with various conventional additives, e.g. alkali agents such as sodium hydroxide and sodium carbonate; alkali metal thiocyanates; alkali metal halides; benzyl alcohol; water softening agents; thickening agents; and development accelerators.
  • the other additives used for a developing solution include anti-stain agents, anti-sludge agents, preservatives, interlayer effect accelerators, and chelating agents.
  • a color developing solution is used preferably at pH not less than 9, more preferably at pH 9 to 13.
  • Color developing temperature is normally over 15° C, usually at the range of 20 to 50° C, and preferably over 30° C for quick development.
  • the representative methods include a method in which bleach-fixing is conducted after color developing and, if needed, followed by washing or stabilization for substituting washing; a method in which bleaching and fixing are separately conducted after color developing, and, if needed, followed by washing or stabilization for substituting washing; a method in which pre-hardening neutralization, color developing, stop-fixing, washing (or stabilization for substituting washing), bleaching, fixing, washing (or stabilization for substituting washing), post-hardening, and washing (or stabilization for substituting washing) are conducted in this order; a method in which color developing, washing (or stabilization for substituting washing), secondary color developing, stop, bleaching, fixing, washing (or stabilization for substituting washing), and stabilization are conducted in this order; and a method in which developed silver resulting from color developing is again subjected to color developing after subjected to halogenation bleaching, to increase the amount of dye formed
  • Bleaching agents generally known to be usable in the bleaching bath or bleach-fix bath include aminopolycarboxylic acids and other organic acids such as oxalic acid and citric acid as coordinated with metal ions such as iron, cobalt, and silver ions.
  • aminopolycarboxylic acids include:
  • Bleaching and bleach-fixing solutions generally can be used at the pH range of 0.2 to 9.5, preferably over 4.0, more preferably over 5.0. Processing temperature is normally 20 to 80° C, preferably over 30° C.
  • Bleaching solution may be supplemented with various additives as well as the preceding bleaching agents (ferric complex salts of organic acids are preferred).
  • the particularly preferable additives are alkali halides and ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, and ammonium iodide.
  • pH buffers such as borates, oxalates, acetates, carbonates, and phosphates
  • stabilizing agents such as triethanolamine
  • other additives known to be usually added to bleaching bath such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, alkylamine, and polyethylene oxide.
  • Bleach-fix solution includes bleach-fix solution with a composition supplemented with small amounts of halides such as potassium bromide, bleach-fix solution with a composition suppiemented with large amounts of halides such as potassium bromide and ammonium bromide, and bleach-fix solution specially comprising a bleaching agent of the present invention and large amounts of halides such as potassium bromide.
  • halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide, and ammonium iodide, as well as potassium bromide.
  • the representative examples of a silver halide fixer contained in bleach-fix solution include compounds which react with silver halides to form water-soluble complex salts and is used for ordinary fixing, e.g. thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate; thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate; thioureas; thioethers; high concentration bromides and iodides.
  • thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate
  • thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate
  • thioureas thioethers
  • high concentration bromides and iodides are used at the amount range where they are dissolved at ratio of
  • Bleach-fixing solution like bleaching solution, can be supplemented with two or more pH buffers containg boric acid, acetic acid, and various salts such as borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, and ammonium hydroxide. Furthermore, various brightening agents, defoaming agents, surfactants, and fungicides can also be added.
  • preservatives as hydroxylamine, hydrazine, sulfites, metabisulfites, and metabisulfite adducts of aldehyde or ketone compounds; organic chelating agents such as acetylacetones, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, dicarboxylic acids, and aminopolycarboxylic acids; stabilizers such as nitroalcohol and nitrates; anti-stain agents such as organic amines; other additives; and organic solvents such as methanol, dimethylformamide, and dimethylsulfoxide.
  • organic chelating agents such as acetylacetones, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, dicarboxylic acids, and aminopolycarboxylic acids
  • stabilizers such as nitroalcohol
  • bleaching or bleach-fix processing may be conducted after washing or other processes such as rinsing and stopping, following color developing, and a pre-bath supplemented with bleaching accelerator may also be used as a processing solution prior to bleaching or bleach-fixing.
  • processing temperature in various processes other than developing e.g. bleaching-fixing (or bleaching and fixing), and washing or stabilization for substituting washing conducted as needed, is preferably 20 to 80°C, more preferably over 30°C.
  • Aqueous gelatin solution containing the AgX grains of a total amount of silver added was adjusted to pH 5.5, and then, 364 ml of 5% aqueous solution of Demol N (produced by Kao Atlas), as well as 244 ml of 20% aqueous solution containing magnesium sulfate as multivalent ion were added to come into coagulation. The resultant precipitant was allowed to settle down, and then, the supernatant was decanted, and redispersed after 1400 ml of distilled water was added. To the dispersion was added 36.4 ml of 200/o aqueous magnesium sulfate to allow re-coagulation, and then the supernatant was decanted. An aqueous solution containing 28 g of ossein gelatin was added to make total quantity 425 ml, which was dispersed for 40 minutes at 40° C to prepare AgX emulsion.
  • N-1 This emulsion was designated N-1. Electromicroscopic observation revealed that N-1 was a monodispersed emulsion with an average grain size of 0.093 ⁇ m.
  • AgX seed emulsions N-4, and N-5 were prepared, at the conditions identical to those of emulsion N-1, wherein an additive was added to the preceding 4M aqueous KBr/KI solution in an amount as specified in Table below. Electromicroscopic observation revealed that each and N-4 and N-5 was a monodispersed emulsion with an average grain size of 0.093 ⁇ m.
  • the silver halide grains of the invention were prepared.
  • the grains were the core/shell type silver bromoiodide grains having an average size of 0.38 * m, and an average Agl content of 8.46 mol%.
  • FIG. 1 is an electron micrograph of EM-1.
  • the AgX (core/shell type AgBrl) grains of the invention were prepared, wherein the average size was 0.27 ⁇ m, and the average content was 8.46 mol%.
  • FIG. 2 is an electron micrograph of EM-2.
  • the AgX (core/shell type AgBrl) grains of the invention were prepared, wherein an average size was 0.65 ⁇ m, and an average I content was 7.16 mol%.
  • This emulsion was designated EM-3.
  • FIG. 3 is an electron micrograph of EM-3.
  • the AgX (core/shell type AgBrl) grains of the invention were prepared, wherein an average size was 2.0 ⁇ m, and an average I content was 6.54 mol%.
  • This emulsion was designated EM-4.
  • Fig. 4 is an electron micrograph of EM-4.
  • a silver bromoiodide emulsion (comparative) was prepared, wherein the emulsion comprised core/shell grains having an average size of 0.38 ⁇ m and an average I content of 8.46 mol%, and an individual grain had the I contents of 15 mol%, 5 mol%, and 3 mol% in an order from core
  • Solutions E-5 and B-5 were simultaneously added to Solution A-5 by a double jet method, and upon termination of adding B-5, C-5 was added. Then, upon termination of adding C-5, D-5 was added. During adding, pAg, pH and the rates of adding Solutions E-5, B-5, C-5 and D-5were controlled as specified in Table 5.
  • PAg and pH were controlled by changing the flow rates of Solutions F-5 and G-5 by a variable flow rate roller tube pump.
  • This emulsion was designated EM-5.
  • a silver bromoiodide emulsion (comparative) was prepared, wherein the emulsion comprised core/shell grains having an average size of 2.0 ⁇ m and an average I content of 6.54 mol O fo, an individual grain had the I contents of 15 mol%, 5 mol% and 0 mol% in an order from a core.
  • An emulsion was prepared at 50 0 C in the same conditions as those of Manufacturing Example 5, besides the grain growth conditions shown in Table 6.
  • This emulsion was designated EM-6.
  • a silver bromoiodide emulsion (comparative) was prepared in the same manner as manufacturing Example 5, wherein the emulsion comprised the core/shell grains with an average size of 0.65 ⁇ m, and an average I content of 7.16 mol%, and an individual grain had the I contents of 15 mol%, 5 mol% and 3 mol% in an order from a core.
  • This emulsion was designated EM-7.
  • the seed emulsion used was N-2.
  • Solution A-8 was poured into a reaction vessel and heated to 40°C, stirring by a propeller agitator, solutions B-8 and C-8 were added in 30 minutes to form the Agl grains having an average grain of approx. 0.045 ⁇ m.
  • Solution D-8 was added to adjust pAg at 13. This emulsion was designated EM-8.
  • the suspension containing the Agl grains contained 0.709 mole of silver halide per liter.
  • the core/shell type silver halide grains of the invention were prepared.
  • the grains had an average grain size of 0.38 ⁇ m, and an average I content of 8.46 mol%.
  • Solution B-9 was stirred at 50°C for 60 minutes, it was added to Solution A-9 maintained at 40°C stirring by the same stirrer as used in Manufacturing Example 1.
  • 97 m£ of 28% aqueous ammonium solution and 72.6 ml of 56% aqueous acetic acid Solution were added, and then, using Solutions F-9 and G-9, pH and pAg were adjusted to 9.0 and 8.55, respectively.
  • Solutions C-9 and D-9 were added by a double-jet method, while controlling pAg, pH, and the flow rate of C-9 and D-9 as specified in Table 7.
  • Em-9 This emulsion was designated Em-9.
  • FIG. 5 is an electron micrograph of EM-9.
  • This emulsion was designated EM-10.
  • the core/shell type silver halide grains of the invention were prepared.
  • the grains had an average size of 2.0 ⁇ m and an average I content of 6.54 mol%.
  • Solution E-11 and G-11 were added to Solution A-11 maintained at 50° C stirring by the same stirrer as used in Manufacturing Example 1 to adjust pH and pAg to 9.0 and 8.9, respectively.
  • Solutions B-11 and C-11 were added by a double jet method, while controlling pH, pAg, and the flow rates of B-11 and C-11 as specified in Table 8.
  • Solution D-11 was added while controlling the flow rate as shown in Table 8 and pH and pAg was controlled by E-11 and G-11 in the same manner as in Manufacturing Example 1.
  • EM-11 This emulsion was designated EM-11.
  • Fig. 6 is an electron micrograph of EM-11.
  • a silver bromoiodide emulsion was prepared, wherein the emulsion comprised the core/shell grains with an average size of 0.27 ⁇ m, and an average I content of 8.46 mol%.
  • An individual grain had I contents of 3 mol%, 5 mol% and 15 mol% in an orders from an outermost shell.
  • the seed emulsion was N-1. This emulsion was designated EM-12.
  • a silver bromoiodide emulsion (comparative) was prepared, wherein the emulsion comprised the grains with an average size of 0.38 ⁇ m and an average I content of 2 mol%, and an I content was uniformly distributed in the individual silver halide grains.
  • Solution B-13 and C-13 were simultaneously added to Solution A-13 by a double jet method at 40°C.
  • pAg, pH and the flow rates of Solutions B-13 and C-13 were controlled as shown in Table 9.
  • pAg and pH were controlled by changing the flow rates of Solutions D-13 and E-13 by a variable flow rate roller tube pump.
  • a monodispersed AgBrl emulsion was prepared in the same manner as manufacturing Example 13, wherein the emulsion comprised the grains with an average size of 0.27 ⁇ m and an average I content of 8.46 mol%, and an I content was uniformly distributed in the individual silver halide grains.
  • the seed emulsion was N-1. This emulsion was designated EM-14.
  • a monodispersed AgBrl emulsion was prepared in same manner as Manufacturing Example 13, wherein the emulsion comprised the grains with an average size of 0.65 ⁇ m, and an average I content of 2 mol%, and an I content was uniformly distributed in the individual silver halide grains.
  • the seed emulsion used was N-1. This emulsion was designated EM-15.
  • a silver bromoiodide emulsion (comparative) was prepared in the same manner as Manufacturing Example 12 , wherein the emulsion comprised the core/shell grains with an average size of 0.65 ⁇ m, and an average I content of 7.16 mol%, and the individual grains had the I contents of 15 mol%, 5 mol%, and 3 mol% in an order from a core.
  • This emulsion was designated EM-16.
  • the seed emulsion was N-1.
  • a monodispersed AgBrl emulsion was prepared in the same manner as Manufacturing Example 13, wherein an average Agl content was 2 mol% and an average grain size was 0.27 ⁇ m. An I content was uniformly distributed in the individual grains.
  • the seed emulsion was N-1.
  • This emulsion was designated EM-17.
  • a AgBrl emulsion was prepared in the same manner as Manufacturing Example 13, wherein an average I content was 2 mol% and an average grain size was 0.65 ⁇ m. An I content was uniformly distributed in the individual grains. This was designated EM-18.
  • the seed emulsion was N-2
  • a monodispersed AgBrl emulsion was prepared in the same manner as Manufacturing Example 17, wherein an average I content ws 2 mol%, an average grain size was 2.0 ⁇ m. An I content was uniformly distributed in the individual grains. This emulsion was designated EM-19.
  • Emulsions EM-20 and 21 were prepared in the manner oidentical to that of Manufacturing Example 1, except that the seed emulsion N-1 used for Manufacturing Example 1 was replaced with N-4 and N-5.
  • a silver iodobromide emulsion EM-22 was prepared in the same manner as Manufacturing Example 13, wherein an average I content was 2 mol% and an average grain size was 0.48 ⁇ m.
  • the seed emulsion was N-1.
  • Emulsion EM-23 was prepared in the manner identical to that of Preparation Example 1, except that the seed emulsion used for Manufacturing Example 1 was replaced with an emulsion of N-1 and N-4 blended at a mole
  • Table 10 summarizes the data of EM-1 through EM-23.
  • each of EM-1, EM-5 and EM-13 was subjected to gold/sulfur sensitization, and, then to spectral sensitization by adding the sensitizing dyes as specified in Table 11.
  • each emulsion was stabilized by addition of TAI and 1-phenyl-5-mercaptotetrazole.
  • the conventional photographic additives such as a spreading, agent, a hardener etc. to prepare a coating solution.
  • the coating solution was coated and dried on a subbed film base to prepare the respective samples.
  • Each sample was divided into two pieces, one of which was allowed to stand in a refrigerator and the other, at the conditions of 50°C and 80 0 /oRH, respectively for 2 days.
  • a transmission density of each sample was evaluated by a spectrophotometer, and an amount of a sensitizing dye desorbed at 50° C and 80%RH was determined.
  • the degree of desorbability (Q) of sensitizing dye was determined by the following equation:
  • a value of desorbability summarized in Table 11 is the relative value to those of Sample No.1-1 for Sample No. 1-2 and 1-3, Sample-No.1-4 for Sample No.1-5, Sample No.1-6, for Sample No.1-7 and Sample No.1-8 for Sample No.1-9.
  • the samples containig EM-1 of the invention are remarkably superior in desorbability of a sensitizing dye to those of the comparative emulsions (EM-5 and EM-13) containing the same sensitizing dyes as the samples of the invention, and, the samples containing the sensitizing dyes represented by the preceding Formula [A] were especially superior.
  • Each of EM-1 and EM-5 was subjected to gold/sulfur sensitization, and then to blue-spectral sensitization by adding 350 mg of each sensitizing dye (A-9) and sensitizing dye (A-3) per mol Ag. Nex, TAI and 1-phenyl-5-mercaptotetrazole were added the for stablization.
  • the conventional photographic additives such as a spreading agent a hardener etc. to prepare a coating solution.
  • each coating solution was coated and dried on a subbed film base to prepare sample Nos. 2-1 and 2-2.
  • the yellow coupler shown in Table 12 was dissolved in a mixture solvent comprising ethyl acetate and dioctyl phthalate (DOP) of weight equal to that of the coupler, and the mixture was emulsified in an aqueous gelatin solution. Then, the emulsion was added to each of EM-1 and EM-5, which were respectively coated and dried in the same manner as the preceding samples to obtain Sample Nos. 2-3 and 2-4.
  • DOP dioctyl phthalate
  • compositions of the processing solutions used in the respective processing steps are as follows;
  • compositions of the processing solutions used in the respective processing steps are as follows.
  • Sensitivity values in Table 12 are expressed by the inverses of exposure corresponding to fog densities +0.1 in the samples either containing or not containing a coupler, and are the relative sensitivity values (S I ) to those of sample Nos. 2-2 and 2-4, which are set at 100.
  • Dmax values are the relative Dmax values to those of samples Nos. 2-2 and 2-4, which are set at 100.
  • the samples containing the emulsion of the invention are superior to those containig comparative emulsion (EM-5) in sensitivity in either instant after-storage processing and in Dmax.
  • the sample containing a coupler was especially advantageous.
  • the effect of the invention was also observed in the samples containing Y-23 or Y 4 -14 instead of Y 4 -9.
  • Example 2 In the manner identical to that of Example 2, EM-3 and EM-7 were subjected to chemical and spectral sensitizations to prepare green-sensitive emulsions. To some of the emulsions were added magenta couplers dissolved in equivalent weight of DOP. Thus, sample Nos. 3-1 through 3-6 were prepared. Sensitizing dyes (A-18) and (A-34) were added by 300 mg and 30 mg per mol of Ag, respectively, for spectral sensitization.
  • Sample Nos. 3-1 and 3-2 were processed by Processing (I) in Example 2; Sample Nos. 3-3 through 3-6 by Processing (II) in Example 2.
  • the results are summarized in Table 13.
  • the sensitivities and Dmax of the samples containing no couplers are the relative values (Si) and Dmax to those of Sample No. 3-2, and the sensitivities and Dmax of the samples containing couplers to those of Sample Nos. 3-4 and 3-6, which are set at 100, respectively.
  • Example 2 In the manner identical to that of Example 2, EM-4 and EM-6 were subjected to chemical sensitization, and then to spectralred sensitization by adding sensitizing dyes (A-57) and (A-56) by 20 mg and 2mg, respectively. To some of these emulsions was added a cyan coupler specified in Table 14 (dissolved in an equivalent weight of DOP) to prepare the samples. Each sample was subjected to exposing and developing in the same manner as Example 3. Sample Nos. 4-1 to 4-4 were developed by Processing (I) shown in Example 2 and the photographic densities were evaluated. The sensitivities and Dmax of Sample Nos. 4-1 and 4-3 are the relative sensitivity values (S 1 ) and Dmax to those of Sample Nos. 4-2 and 4-4, which are set at 100, respectively.
  • EM-1, EM-5, EM-9 and EM-10 were subjected to gold/sulfur sensitization, and then, to spectral green-sensitization by adding sensitizing dye (A-22) and (A-34) by 550 mg and 340 mg per mol Ag, respectively.
  • sensitizing dye (A-22) and (A-34) by 550 mg and 340 mg per mol Ag, respectively.
  • each emulsion was stabilized with TAI and 1-phenyl-5-methylmercaptotetrazole.
  • Magenta Coupler (M 4 -4) dissolved in a mixture solvent of ethyl acetate and dinonyl phthalate (DNP), was dispersed in an aqueous gelatin solution. Then, the conventional photographic additives such as a spreading agent, a hardener etc. were added to each of the preceding emulsions to prepare the coating solutions. Each of the coating solutions was coated and dried on a subbed film base by a conventional method. Thus, Sample Nos. 5-1 through 5-4 were prepared.
  • the specific curve 1 in FIG. 7 is that of Sample No. 5-1 (EM-1, invention) and the curve 2 is that of Sample No. 5-2 (EM-5, comparative). Furthermore, Sample Nos. 5-3 and 5-4 exhibited the specific curves similar to
  • S 2 sensitivity is an inverse of an exposure that provides the density of fog density +0.3, and is the relative value to Sample No. 5-2, which is set at 100.
  • Example 6 Comparison of 2.0 ⁇ m grains
  • Example 5 The samples were prepared in the manner identical to that of Example 5, except that the emulsion in Example 5 was replaced with EM-4, EM-6 and EM-11, and that the sensitizing dye was substituted as below.
  • the amount of sensitizing dye is per mol of silver.
  • curve 3 in FIG. 8 is that of Sample No. 6-1 (EM-4, invention); curve 4 is that of Sample No. 6-2 (EM-6, comparative); and curve 5 is that of Sample No. 6-3 (EM-11, invention).
  • the samples of the invention showed less desorbability of sensitizing dyes, and, apparently, the silver halide emulsions of the invention are more prone to adsorb a sensitizing dye.
  • Sample Nos. 7-1 through 7-17 were prepared by replacing EM-1, A-9, A-3, Y 4 -9 and DOP in sample No. 2- 3 with emulsions, sensitizing dyes Y-5, and DNP as specified in Table 18.
  • the processed samples were evaluated for sensitivity (S 1 ), adsorbability of sensitizing dye and RMS granularity.
  • S 1 sensitivity
  • the results are summarized in Table 18.
  • the sensitivity of each sample is the relative value to those of Sample No. 7-2 for Sample Nos. 7-1 through 7-3, Sample No. 7-4 for Sample No. 7-5, Sample No. 7-6 for Sample Nos. 7-7 through 7-9, and Sample No. 7-11 for Sample Nos. 7-10 through 7-17, which are set at 100, respectively.
  • the RMS granularity of each sample is a value obtained by multiplying 1000 times the density variation observed by scanning an area of a density (fog density + 1.2) by a microdensitometer with spherical scanning diameter of 25 ⁇ m.
  • the samples were prepared in the manner identical to that of Sample No. 7-1 in Example 7, except that coupler Y-5 was replaced with M 4 -4, and emulsion and sensitizing dye were replaced as specified in Table 19, and that exposure was made by green light instead of blue light. Next, sensitivity, RMS granularity and adsorbability of sensitizing dye were evaluated.
  • the sensitivity of each sample is the relative value to those of Sample No. 8-2 for Sample Nos. 8-1 through 8-3.
  • Sample No. 8-4 for Sample No. 8-5
  • Sample No. 8-6 for Sample Nos. 8-7 and 8-8
  • Sample No. 8-10 for Sample Nos. 8-9 through 8-23, which are set at 100, respectively.
  • the silver halide emulsion of the invention contained in a green-sensitive emulsion layer is less prone to desorb a sensitizing dye, and has good granularity, and especially, the samples containing sensitizing dyes represented by Formula [A] are excellent in every criterion, i.e. sensitivity, adsorbability of sensitizing dye and granularity.
  • the effect of the invention was reserved in the other two samples which contain silver halide grains with an average size of 0.27 ⁇ m and an average I content of 8.46 mol. %, and prepared by the same method as EM-2, except that Agl grains with an average size of 0.05 ⁇ m with Agl grains with an average size of 0.2 ⁇ m and 0.5 ⁇ m, respectively, each prepared from Solution A-2 and C-2.
  • the samples were prepared in the manner identical to that of Example 8, except that Emulsion EM-2 with EM-4, EM-12 was replaced with EM-6, EM-17 with EM-19 and the amount of sensitizing dye was decreased to 50 wt.% of that of Sample Nos. 8-1 to 8-23. Each sample was evaluated as well for sensitivity, RMS granularity, and adsorbability of sensitizing dye.
  • the samples containing the silver halide emulsions of the invention were improved in sensitivity, adsorbability of sensitizing dye and granularity, and these results were comparable to those of the emulsions in Example 8 containing AgX grains with an average size of 0.27 ⁇ m.
  • Example 7 The samples were prepared in the manner identical to that of Example 7, except that coupler Y-5 was replaced with coupler C 4 -33, and emulsions and sensitizing dyes were replaced as specified in Table 20, and that exposure was performed with red light. The samples were evaluated as well.
  • the sensitivity of each sample is the relative value to those of Sample No. 10-2 for Sample No. 10-1 through 10-3.
  • the samples comprising the silver halide emulsions of the invention contained in a red-sensitive emulsion layer are improved in sensitivity, desorption of sensitizing dye and granularity.
  • the effect of the present invention was preserved in each of the samples, even when the amount of sensitizing dye (I) was decreased to 150 mg and that of sensitizing dye (II) was decreased to 80 mg in sample Nos. 10-1 to 10-19.
  • coated amounts of silver halide and colloidal silver are indicated by g/m 2 as converted to metal silver; those of the additives and gelatin are also by g/m 2 ; and sensitizing dye and coupler mol per mol of silver halide contained in the same layer.
  • the emulsions contained in the respective color-sensitive emulsion layers were subjected to optimum gold/sulfur sensitization.
  • Sample Nos. 11-2 through 11-7 were prepared in the manner identical to that of Sample No. 11-1, except that a coupler was replaced as specified in Table 21.
  • the coupler combinations in these multilayer samples were respectively designated Coupler Combination A, B, C, D, E, F, and G.
  • Multilayer Sample Nos. 11-8 through 11-14 were prepared in the manner identical to that of Sample Nos. 11-1 through 11-7, except that EM-1 was replaced with EM-5 (comparative emulsion) and that EM-3 with EM-7 (comparative emulsion).
  • the relative sensitivity was measured on the yellow, magenta, and cyan densities. A portion of each sample was allowed to stand for 2 days at 50° C and 80%RH, and then sensitivity was measured in order to evaluate stability for aging.
  • the samples comprising silver halide emulsions of the invention are superior to the comparative samples in sensitivity and granularity in the respective coupler combinations, and have much less desensitization attributable to desorption of sensitizing dye at a high temperature/high humidity also in the presence of a coupler.
  • the layers having the composition specified below were formed on a subbed cellulose acetate support to obtain a multilayer color photosensitive material No. 11-1.
  • the coated amounts are indicated by g/m 2 as converted to metal silver in silver halide and colloidal silver, by g/m 2 in the additives and gelatin; and bymol per mol of silver halide contained in the same layer in a sensitizing dye and a coupler.
  • the emulsions contained in the respective color-sensitive emulsion layers were subjected to optimum gold/sulfur sensitization in a sensitizing dye and a coupler .
  • a surfactant was added to each layer as a coating aid in addition to the preceding components.
  • Sample Nos. 12-2 through 12-6 were prepared in the same manner as Sample No. 12-1, except that a sensitizing dye and an emulsion were replaced as specified in Table 23.
  • Sensitivity is a relative value to that of Sample No. 12-6, which is set at 100.
  • the Sample Nos. 12-1 through 12-4 containing silver halide emulsions of the invention are superior to the comparative samples Nos. 12-5 and 12-6 in color sensitivity, granularity and desorbability of sensitizing dyes.
  • Sample No. 13-1 was prepared in the same manner as Sample No. 12-1, except that A-58 in Layers 3 and 4 with A-57, and A-59 with A-56, and M 4 -4 in Layer 7 with M-34.
  • This sample was prepared in the same manner as Sample No. 13-1, except that EM-1 in Layers 3, 6 and 9 was replaced with EM-5 (comparative emulsion), and EM-3 in Layers 4, 7 and 10 with EM-7 (comparative emulsion).
  • the processed samples were evaluated for sensitivity (S 1 ) in instant processing, and increased in fog ( Fog) at accelerated weathering conditions.
  • the sample containing silver halide emulsions (EM-1, EM-3 and EM-9) of the invention are superior to the comparative sample in sensitivity, and are improved in A fog caused by storage.
  • the layers of the following compositions were sequentially formed on a polyethylene terephthalate support to prepare a multi color photographic material.
  • the amounts of the additives in a photographic material are per square meter, unless otherwise specified.
  • the amounts of silver halide and colloidal silver are indicated as converted to metal silver.
  • Each emulsion was subjected to gold/sulfur sensitization.
  • the respective layers incorporated a gelatin hardener (H-1) and a surfactant, in addition to the above components.
  • the layer thickness of Layer 1 through Layer 12 was 22 ⁇ m, and the coated silver amount in Layer 1 through Layer 10 was 7.4 g/m 2 .
  • This sample was prepared in the same manner as Sample No. 14-1, except that the layer thickness of Layer 1 through Layer 12 was 17.6 ⁇ m and the coated silver amount in Layer 1 through Layer 10 was 5.9 g/m 2 . In other words, the coated silver amount in each layer of Sample No. 14-2 was 20% less than that of Sample No. 14-1.
  • Sample Nos. 14-3 and 14-4 corresponding to Coating modes A and B were prepared by replacing emulsions EM-12 and EM-7 in the green-sensitive layers with EM-13 and EM-15, respectively.
  • Sample Nos. 14-5 and 14-6 corresponding to Coating modes A and B were prepared by replacing emulsions EM-12 and EM-7 with EM-2 and EM-3, respectively.
  • the processed samples were evaluated for sensitivity (Si) of a green-sensitive layer, sharpness (MTF) and granularity (RMS). The evaluation results are summarized in Table 25.
  • MTF Modulation Transfer Function
  • the sensitivity (Si) is a relative value to that of Sample No. 14-1, which is set at 100.
  • the samples of the invention excel in general criteria, i.e. sensitivity, granularity and sharpness; as particularly indicated by Nos. 14-5 and 14-6, it was unexpected fact that the emulsion of the invention and thinner layer construction provided the samples with improved granularity.
  • the layers of the following compositions were formed on a support to prepare multicolor photosensitive materials Nos. 15-1 through 15-3.
  • the respective layers incorporated a gelatin hardener (H-1) and a surfactant, in addition to the above components.
  • the layer thickness of Layer 1 through Layer 11 was 22 ⁇ m, and the coated silver amount in Layer 1 through Layer 9 was 6.8 g/m 2 .
  • This sample was prepared in the same manner as Sample No. 15-1, except that EM-12 in Layer 6 was replaced with EM-17.
  • This sample was prepared in the same manner as Sample No. 15-1, except that EM-12 in Layer 6 was replaced with EM-2.
  • the processed samples were evaluated for sensitivity (S i ), maximum density Dmax, sharpness (MTF) and granularity (RMS).
  • S i sensitivity
  • MTF sharpness
  • RMS granularity
  • Sensitivity (S 1 ) and RMS are the relative values to those of Sample No. 15-1, which are set at 100.
  • the sample comprising EM-2 of the invention excels in general criteria, i.e. maximum density, sharpness, granularity and sensitivity.
  • Sample Nos. 16-1 through 16-3 were prepared in the same manner as Sample No. 15-1 in Example 15, except that EM-12 in Layer 6 was replaced as specified in Table 27.
  • the sample of the invention excels in general criteria, i.e. maximum density, sharpness, granularity and sensitiviy.
  • Sample Nos. 17-1 through 17-3 were prepared in the same manner as Sample No. 15-1 in Example 15, except that EM-12 in Layer 6 was replaced as specified in Table 28.
  • Sensitivity (S 1 ) and RMS are the relative values to those of Sample No. 17-1, which are set at 100.
  • the sample of the invention excels in general criteria, i.e. maximum density, sharpness, granularity and sensitivity.
  • Layers 1 through 7 were identical to those of Sample No. 16-3 of Example 16, except that the layers following Layer 7 were composed as follows;
  • Sample Nos. 18-2 through 18-5 were prepared as follows.
  • This sample was prepared by replacing yellow coupler Y-28 in Layer 8 of Sample No. 18-1 with an equivalent mole of Y-5.
  • Example 16 The respective samples and reference Sample No. 16-3 of Example 16 were processed in the same manner as in Example 15 and evaluated.
  • the sensitivity (S 1 ) and RMS are the relative values to those of Sample No. 16-3, which are set at 100.
  • every photosensitive layer is single layer in order to balance the properties of maximum density, granularity, sharpness and sensitivity.
  • a yellow coupler of a benzoyl acetoanilide family further improves the maximum density of a blue-sensitive layer.
  • the layers of the following compositions were formed on a polyethylene terephthalate support to prepare a a multilayer color photographic material.
  • Sample No. 19-2 was prepared in the same manner as Sample No. 19-1, except that the layer thickness in Layers 1 through 9 was 19 ⁇ m, and that the total coated silver amount in the three photosensitive layers was 6.4 g/m 2 . That is, the coated silver amount in each layer of Sample No. 19-2 was 13.50/ 0 less than that of Sample No. 19-1.
  • These thinner layers are hereunder identified by affixing two apostrophes (") to each layer described in Sample No. 19-1. For example, B" represents a layer 13.5% thinner than Layer B. This definition is applied hereinafter.
  • Sample No. 19-5 was prepared in the same manner as Sample No. 19-3, except that the layer thickness in Layers 1 through 9 was 16 ⁇ m, and that the total coated silver amount layers was 5.4 g/m 2. That is, the coated silver amount in each layer of Sample No. 19-5 was 27.0% less than that of Sample No. 19-3.
  • These thinner layers are hereunder identified by affixing three apostrophes ("') to each layer in Sample No. 19-1.
  • Sample No. 19-6 was prepared in the same manner as Sample No. 19-3, except that the layer thickness in Layers 1 through 9 was 14 ⁇ m, and that the total coated silver amount 4.7 g/m 2 . That is, the coated silver amount in each layer of Sample No. 19-6 was 36.5% less than that of Sample No. 19-3.
  • These thinner layers are hereunder identified by affixing an asterisk ( * ) to each layer in Sample No. 19-1.
  • Sample No. 19-7 was prepared in the same manner as Sample No. 19-3, except that the layer thickness in Layers 1 through 9 was 12.7 ⁇ m, and that the total coated silver amount was 4.3 g/m 2 . That is, the coated silver amount in each layer of Sample No. 19-7 was 42% less than that of Sample No. 19-3.
  • These thinner layers are hereunder identified by affixing two asterisks ( ** ) to each layer in Sample No. 19-1
  • the sensitivities of the samples of the invention are equal to or higher than those of Sample Nos. 19-1 and 19-2 containig conventional core/shell emulsions, and, the samples of the invention have been improved in granularity and sharpness to a large extent.
  • Such effects of the invention is particularly significant with the layer thickness of not more than 15 ⁇ m.
  • Example 19 The samples were prepared as per Table 32 and evaluated in the same manner as Example 19. The evaluation results are summarized in Table 32 together with the data of Sample Nos. 19-3 and 19-6 in Example 19.
  • Sample No. 21-1 was prepared in the same manner as Example 5, besides that EM-1 of Sample No. 5-1 in Example 5 was replaced with EM-13.
  • compositions of the processing solutions used in the processing steps were as follows;
  • Sensitivity (S 1 ), granularity (RMS value) and sharpness (MTF value) of each dye image were measured. The results are summarized in Table 33.
  • Sensitivity S 1 is a relative value to that of Sample No. 21-1 developed in 60 seconds, which is set at 100.
  • Sample No. 22-1 was prepared in the same manner as Sample No. 12-1, except that sensitizing dye A-58 in Layer 3 was replaced with A-57, and sensitixing dye A-59 with A-56.
  • This sample was prepared in the same manner as Sample No. 22-1, except that EM-1 in Layers 3, 6 and 9 in Sample No. 22-1 was replaced with EM-13 (comparative emulsion), and EM-3 in Layers 4, and 10 with EM-15 (comparative sample).
  • Sensitivity S 1 is a relative value to that of Sample No. 22-3 developed in 60 seconds, which is set at 100.
  • Sensitivity (S 1 ) is a relative value to that of Sample No. 23-2 (60 seconds), which is set at 100.
  • Each of EM-1 through -3, -7, -13, -17, and -20 through 23 was subjected to gold/sulfur sensitization, and then to spectral green-sensitization by sensitizing dyes (A-22) and (A-34) as per specified in Table 36. Next, each emulsion was stabilized by TAI and 1-phenyl-5-mercaptotetrazole.
  • M 4 -4 magenta coupler
  • DNP ethyl acetate and dinonylphthalate
  • coated amounts of the respective compounds per square meter of support are specified below.
  • Each sample was subjected to wedge exposing by a conventional method, and was processed by
  • the sensitivity values in the table are relative to the sensitivity 100 of a sample having EM-1 to which were added sensitizing dyes (A-22) and (A-34) in amounts, respectively, of 550 mg and 340 mg per mol of silver.
  • Sample No. 24-1 to 24-8, which contain the emulsions having various sensitivities, were prepared in the same manner as the samples specified in Table 36, except that the emulsions were combined as specified in Table 37.
  • the processed samples were evaluated for exposure latitude, sensitivity (S 1 ) and granularity (RMS). The evaluation results are summarized in Table 37.
  • Exposure latitude is indicated as follows, provided that AD is the difference between the minimum and maximum densities on a specific curve:
  • the samples of the invention have wide exposure latitude balanced with higher sensitivity and excellent granularity. Additionally, it is possible to perform chemical aging for the emulsion of Sample No. 24-4; and grain growth and chemical aging for the emulsion of Sample No. 24-5 in a single batch. This feature is advantageous in reducing manufacturing cost of sensitive material.
  • Sample Nos. 24-4 to 24-6 exhibit stable photographic performance even under a variable processing condition (e.g. pH, temperature). Effect mentioned above was observed about each of samples in which Rh ion in EM-20 and EM-23 was replaced to Ru ion or Os ion.
  • Sample Nos. 24-4 to 24-6 exhibit stable photographic performance even under a variable processing condition (e.g. pH, temperature). Effect mentioned above was observed about each of samples in which Rh ion in EM-20 and EM-23 was replaced to Ru ion or Os ion.
  • This sample was prepared in the same manner as Sample No. 25-1, except that EM-1 in Layers 3, 6 and 9 of Sample No. 25-1 was replaced with EM-5, and EM-3 in Layers 4, 7 and 10 with EM-7.
  • Example 24 The respective samples were subjected to wedge exposure, and developed as in Example 24. Latitude and granularity were evaluated. The evaluation results are summarized in Table 38.
  • the sample of the invention has a wide exposure latitude balanced with excellent granularity.
  • the layers specified below were formed on a subbed cellulose acetate support to obtain a multilayer color photosensitive material No. 26-1.
  • coated amounts are indicated by g/m 2 as converted to metal silver in silver halide and colloidal silver; by g/m 2 in additives and gelatin; and by mol per mol of silver halide contained in the same layer in sensitizing dye and coupler .
  • Example 24 The emulsions contained in the respective emulsion layers were subjected to optimum sensitization in the same manner as Example 24.
  • a surfactant was added to each layer as a coating aid.
  • This sample was prepared by replacing EM-5 and EM-17 in Layer 7 of Sample No. 26-1 with EM-1 and EM-20, respectively.
  • This sample was prepared by replacing EM-5 and EM-17 in Layers 3 and 7 of Sample No. 26-1 with EM-1 and EM-20, respectively.
  • the Sample Nos. 26-1 through 26-3 were subjected to wedge exposure by a conventional method, and were developed as in Example 24. Each of the processed samples were evaluated for latitude, sensitivity (S 1 ), granularity and sharpness. The evaluation results are summarized in Table 39.
  • Sensitivity was a relative value to that of Sample No. 26-1, which is set at 100.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP88312348A 1987-12-28 1988-12-28 Photoempfindliches photographisches Silberhalogenidmaterial Withdrawn EP0323215A3 (de)

Applications Claiming Priority (18)

Application Number Priority Date Filing Date Title
JP33393487 1987-12-28
JP333934/87 1987-12-28
JP6553288 1988-03-18
JP65534/88 1988-03-18
JP65532/88 1988-03-18
JP6553388 1988-03-18
JP65533/88 1988-03-18
JP6553488 1988-03-18
JP69123/88 1988-03-23
JP6912388 1988-03-23
JP7121788 1988-03-25
JP71217/88 1988-03-25
JP8360088 1988-04-05
JP83600/88 1988-04-05
JP96085/88 1988-04-19
JP9608588 1988-04-19
JP22400288 1988-09-07
JP224002/88 1988-09-07

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EP0323215A2 true EP0323215A2 (de) 1989-07-05
EP0323215A3 EP0323215A3 (de) 1990-08-22

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0405938A2 (de) * 1989-06-27 1991-01-02 Konica Corporation Hochempfindliches photographisches Silberhalogenidmaterial
EP0443475A2 (de) * 1990-02-19 1991-08-28 Konica Corporation Photographisches Silberhalogenidmaterial
EP0487228A1 (de) * 1990-11-13 1992-05-27 Konica Corporation Photographisches, lichtempfindliches Silberhalogenidmaterial
US5240824A (en) * 1990-02-15 1993-08-31 Konica Corporation Silver halide photographic light-sensitive material having a high sensitivity and improved preservability and a process for producing the same
US5262294A (en) * 1990-02-19 1993-11-16 Konica Corporation Silver halide photographic light sensitive material
US5362619A (en) * 1989-06-27 1994-11-08 Konica Corporation High-speed halide photographic light-sensitive material
US5674675A (en) * 1991-08-23 1997-10-07 Fuji Photo Film Co., Ltd. Silver halide photographic material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3342592A (en) * 1963-06-14 1967-09-19 Du Pont Photographic color films and processes
FR2079012A5 (de) * 1970-02-24 1971-11-05 Fuji Photo Film Co Ltd
FR2319920A1 (fr) * 1975-07-30 1977-02-25 Agfa Gevaert Ag Procede pour la preparation d'emulsions d'halogenure d'argent
EP0135883A2 (de) * 1983-09-21 1985-04-03 Konica Corporation Photographisches Silberhalogenidmaterial
EP0244184A2 (de) * 1986-04-26 1987-11-04 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial
JPS62278543A (ja) * 1986-05-27 1987-12-03 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3342592A (en) * 1963-06-14 1967-09-19 Du Pont Photographic color films and processes
FR2079012A5 (de) * 1970-02-24 1971-11-05 Fuji Photo Film Co Ltd
FR2319920A1 (fr) * 1975-07-30 1977-02-25 Agfa Gevaert Ag Procede pour la preparation d'emulsions d'halogenure d'argent
EP0135883A2 (de) * 1983-09-21 1985-04-03 Konica Corporation Photographisches Silberhalogenidmaterial
EP0244184A2 (de) * 1986-04-26 1987-11-04 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial
JPS62278543A (ja) * 1986-05-27 1987-12-03 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 12, no. 163 (P-703)[3010], 18th May 1988; & JP-A-62 278 543 (FUJI PHOTO FILM CO. LTD) 03-12-1987 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0405938A2 (de) * 1989-06-27 1991-01-02 Konica Corporation Hochempfindliches photographisches Silberhalogenidmaterial
EP0405938A3 (en) * 1989-06-27 1992-05-20 Konica Corporation High-speed silver halide phototographic light-sensitive material
US5362619A (en) * 1989-06-27 1994-11-08 Konica Corporation High-speed halide photographic light-sensitive material
US5240824A (en) * 1990-02-15 1993-08-31 Konica Corporation Silver halide photographic light-sensitive material having a high sensitivity and improved preservability and a process for producing the same
EP0443475A2 (de) * 1990-02-19 1991-08-28 Konica Corporation Photographisches Silberhalogenidmaterial
EP0443475A3 (en) * 1990-02-19 1992-05-20 Konica Corporation Silver-halide photographic light-sensitive material
US5262294A (en) * 1990-02-19 1993-11-16 Konica Corporation Silver halide photographic light sensitive material
EP0487228A1 (de) * 1990-11-13 1992-05-27 Konica Corporation Photographisches, lichtempfindliches Silberhalogenidmaterial
US5674675A (en) * 1991-08-23 1997-10-07 Fuji Photo Film Co., Ltd. Silver halide photographic material

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