Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/34—Couplers containing phenols
  • G03C7/346—Phenolic couplers
• • 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
  • G03C1/485—Direct positive emulsions
  • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure

Definitions

• the present invention relates to a direct positive color photographic material, and more particularly to a direct positive silver halide photographic material containing a non-prefogged internal latent image silver halide emulsion.
• Photographic processes for obtaining a direct positive image without requiring a reversal process or a negative film are well known.
• a direct positive image is obtained by employing a previously fogged silver halide emulsion, and destroying a latent fog (a latent image) in the exposed areas by solarization, Herschel effect, etc., followed by development.
• a direct positive image is obtained by employing an unfogged internal latent image type silver halide emulsion, and carrying out imagewise exposure followed by surface development, either after a fogging treatment or along with a fogging treatment.
• internal latent image silver halide photographic emulsion refers to a silver halide photographic emulsion of the type in which photosensitive nuclei are mainly present in the interior of silver halide grains and a latent image is formed mainly in the interior of the grains by exposure.
• the second material is generally high in sensitivity and is suitable where high sensitivity is required.
• the present invention is directed to the latent type.
• latent fog is selectively formed only on the surface of silver halide grains in the unexposed areas by the surface desensitizing action due to the internal latent image produced in the inside of silver halide grains by the initial imagewise exposure, and a photographic image (a direct positive image) is formed in the unexposed areas by carrying out conventional surface development treatment.
• Techniques of selectively forming latent fog include a "light fogging method” in which a second exposure is effected throughout a photosensitive layer, for example, as described in British Patent 1,151,363; and a “chemical fogging method” that uses a nucleating agent. The latter method is described, for example, in Research Disclosure, Vol. 151, No. 15162 (November, 1976), pages 72 to 87.
• the light fogging method does not require high pH conditions in comparison with the chemical fogging method, and is relatively advantageous in practice, the light fogging method is also influenced by changes in the temperature and the pH of the developing solution, and it is difficult to obtain consistent performance.
• the minimum density areas of a direct positive emulsion photosensitive material which corresponds to the fogged part of a usual negative emulsion, is influenced, for example, by changes in the temperature and the pH of the developing solution and the wavelength and the amount of light used for light fogging, and it is difficult to obtain a constant low minimum density.
• the change in the liquid composition due to the processed amount of.the photosensitive material can be calculated to a certain extent in the case of continuous processing, and the liquid composition of the replenisher can be adjusted based thereon.
• air oxidation of the processing liquid is also caused when the processing liquid is allowed to stand with the automatic developing processing machine in operation, i.e., at an elevated temperature in contact with air.
• the oxidation resistance fo the liquid must be improved, by designing the photosensitive-material and the processing liquid in such a way that if a certain degree of oxidation occurs the photographic performance does not change.
• an automatic developing processing machine is left in operation, for example, one day to save the time required for warm-up for restarting the operation, in a lab where the frequency of use of the automatic developing processing machine is decreased.
• An object of the invention is to provide a nonprefogged internal latent image type silver halide photosensitive material that can form quickly and stably a direct positive color image with high maximum density, particularly of the cyan color image formed, and low minimum image density thereof, when processed with a low-pH color developing solution.
• Another object of the present invention is to provide a photosensitive material that can form a direct positive color image with consistent color reproduction, in which the minimum image density and the maximum image density, particularly of the cyan color formed, scarcely deviate from the optimum values even if the temperature and the pH of the color developing solution change.
• Still another object of the present invention is to provide a photosensitive material that can form a direct positive color image, in which the color reproduction scarcely changes and the minimum density and the maximum image density of the cyan color formed hardly deviate from the optimum values, even if the color development period deviates from the standard period.
• Still another object of the present invention is to provide a photosensitive material that can form a direct positive color image in which the minimum image density scarcely increases and the maximum image density scarcely decreases when the photosensitive material is stored for a long period of time.
• a still further object of the present invention is to provide a photosensitive material that can form a direct positive color image having reduced negative image rereversal in the case of high illumination exposure.
• a direct positive color photosensitive material composed of a support having thereon at least one photographic emulsion layer containing nonprefogged internal latent image silver halide grains and at least one non diffusible cyan coupler repersented by formula (C-1): in which R 1 represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group; R 2 represents an aliphatic group containing 2 to 20 carbon atoms; R 3 represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group; and Y represents a hydrogen atom or a. coupling off group.
• a plurality of such non-diffusible couplers may be linked through R 1 , R 2 , R 3 or Y 1 to form a dimer or higher polymer.
• the present cyan couplers are disclosed in Japanese Patent Application (OPI) No. 232550/85 (the term “OPI” as used herein refers to a "published unexamined Japanese pat ent "application”) and U.S. patenat 3,772,002, and are represented by the following general formula (C-1): in which R 1 represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group; R 2 represents an aliphatic group having 2 to 20 carbon atoms; R 3 represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group; and Y 1 represents a hydrogen atom or a coupling-off group.
• a dimer or higher polymer thereof may be formed through Ri, R 2 , R 3 or Yi.
• the coupling-off groups include halogen atoms (e.g., a fluorine atom, a chlorine atom and a bromine atom), alkoxy groups (e.g., an ethoxy group, a dodecyloxy group, a methoxyethylcar- bamoylmethoxy group, a carboxypropyloxy group and a methylsulfonylethoxy group), aryloxy groups (e.g., a 4-chlorophenoxy group, a 4-methoxyphenoxy group and a 4-carboxyphenoxy group), acyloxy groups (e.g., an acetoxy group, a tetradecanoyloxy group and a benzoyloxy group), aliphatic or aromatic sulfonyloxy groups (e.g., a methanesulfonyloxy group and a toluenesulfonyloxy group), acylamino groups (e.g
• Coupling off groups linked via the carbon atom include bis type couplers obtained by condensing four-equivalent couplers with aldehydes or ketones.
• the coupling off group may contain a photographically useful group such as a development inhibitor and a development accelerator.
• the aliphatic group represented by Ri, R 2 or R 3 includes linear, branched or cyclic alkyl, alkenyl or alkynyl groups that may be unsubstituted or substituted.
• R 1 represents an aliphatic group preferably having 1 to 36 carbon atoms, an aromatic group preferably having 6 to 36 carbon atoms (e.g., a phenyl group and a naphthyl group), a heterocyclic group (e.g, a 3-pyridyl group and a 2-furyl group), an aromatic or heterocyclic amino group (e.g., an anilino group, a naphthylamino group or a 2-benzothiazolylamino group and a 2-pyridylamino group), each of which may be substituted by substituents selected from an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., a methoxy group and a 2-methoxyethoxy group), an aryloxy group (e.g., a 2,4-di-tert-amylphenoxy group, a 2-chlorophenoxy group and a 4-cyan
• R 3 represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom and a bromine atom), an aliphatic group preferably having 1 to 20 carbon atoms, an aliphatic oxy group preferably having 1 to 20 carbon atoms or an acylamino group having 1 to 20 carbon atoms (e.g., an acetamido group, a benzamide group and a tetradecaneamide group), and these aliphatic groups, aliphatic oxy groups and acylamino groups may be substituted by the substituents for Ri.
• a halogen atom e.g., a fluorine atom, a chlorine atom and a bromine atom
• an aliphatic group preferably having 1 to 20 carbon atoms
• an aliphatic oxy group preferably having 1 to 20 carbon atoms
• an acylamino group having 1 to 20 carbon atoms e.
• One or two of Ri, R 2 , R 3 and Y in general formula (C-I) may be linked to form a dimer or higher polymer.
• these groups can represent a single bond or a divalent linking group (e.g., an alkylene group, an arylene group, an ether group, an ester group and an amide group and a combination of these), and if they form an oligomer or a polymer, it is preferable that these groups constitute the polymer main chain or link with the polymer main chain via such a divalent group as mentioned for a dimer.
• the polymer may be a homopolymer of a coupler derivative or a copolymer with one or more of other non-color forming ethylenic monomers (e.g., acrylic acid, methacrylic acid, methyl acrylate, n-butyl acrylamide, ⁇ -hydroxymethacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride and N-vinyl pyrrolidone).
• ethylenic monomers e.g., acrylic acid, methacrylic acid, methyl acrylate, n-butyl acrylamide, ⁇ -hydroxymethacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride and N-vinyl pyrrolidone.
• R 1 preferably represents a substituted or unsubstituted alkyl group or aryl group; the substituent for the alkyl group is particularly preferably an optionally substituted phenoxy group or a halogen atom (the substituent for the phenoxy group is preferably an alkyl group, an alkoxy group, a halogen atom, a sulfonamido group or a sulfamico group); and the aryl group is particularly preferably a phenyl group substituted with at least one of a halogen atom, an alkyl group, a sulfonamido group and an acylamino group.
• R 2 preferably represents an optionally substituted alkyl group having 2 to 20 carbon atoms.
• the substituent for R 2 is preferably an alkyloxy group, an aryloxy group, an acylamino group, an alkylthio group, an arylthio group, an imdo group, a ureido group, an -alkylsulfonyl group or an arylsulfonyl group.
• R 2 represents an alkyl group having 2 to 4 carbon atoms.
• R 3 preferably represents a hydrogen atom, a halogen atom (particularly preferably a fluorine atom or a chlorine atom) or an acylamino group, with a halogen atom more preferred.
• Y preferably represents a halogen atom, and moer preferably a chlorine atom.
• the couplers represented by general formula (C-I) may be used alone or in the form of a mixture thereof, and also may be used in combination with cyan couplers other than cyan couplers represented by general formula (C-I).
• the present cyan coupler is used in an amount of from about 0.01 to 1.0 mol, preferably of about 0.02 to 0.5 mol, more preferably 0.01 to 0.4 mol per mol of silver in the layer containing the coupler.
• the objects of the present invention in particular, the restraint of the increase in minimum image density of the formed cyan color due to deterioration by air oxidation of a developing solution, can be enhanced by including in the photosensitive material a hydroquinone compound having a sulfonic acid group.
• Hydroquinone compounds having a sulfonic acid group that can additionally be used effeectively in the present invention include compounds represented by formulae (HQ-1) and (HQ-II) and their ammonium and alkali metal salts: in which R 4 represents an alkyl group, an acylamino group, a hydrogen atom or a sulfonic acid group; R 5 represents an alkylene group or an acylamino group; and R 6 represents an alkyl group or an acylamino group.
• R 4 represents an alkyl group, an acylamino group, a hydrogen atom or a sulfonic acid group
• R 5 represents an alkylene group or an acylamino group
• R 6 represents an alkyl group or an acylamino group.
• the acylamino group represented by R 4 , R 5 and R 6 may be unsubstituted or substituted, and for example include wherein R 7 and R 8 each represents an aryl group (e.g., a phenyl group), an alkyl group, a hydrogen atom or a sulfonic acid group.
• R 7 and R 8 each represents an aryl group (e.g., a phenyl group), an alkyl group, a hydrogen atom or a sulfonic acid group.
• the alkyl group represented by R 4 and R 6 may be unsubstituted or substituted, and includes an aralkyl group.
• the length or the size of the alkyl group, the alkylene group and the acylamino group may be varied widely depending on the desired degree of diffusibility, and those skilled in the art can easily determine the amount of the required "ballast" according to the purpose.
• An alkyl group and an alkylene group having 1 to 22 carbon atoms are suitably used and preferably an alkyl group having 8 to 22 carbon atoms and an alkylene group having 1 to 8 carbon atoms are used, for this purpose.
• hydroquinone compounds having a sulfonic acid group that can be used in the present invention are given below, but the present invention is not to be construed as being limited thereto:
• the above sulfonated hydroquinones can be directly coated in a silver halide emulsion layer, an intermediate layer or a protective layer.
• a suitable concentration of the compound can be determined by those skilled in the art, generally the compound is used in an amount of about 1 to 100 mg, preferably about 10 to 200 mg, per m 2 of the photosensitive material. However an amount greater or smaller than that can be used.
• the nonprefogged internal latent image silver halide emulsion that is used in the present invention is an emul sion containing a silver halide wherein the surface of the silver halide grains has not been previously fogged in the manufacturing process, such that a latent image will be formed mainly in the inside of the grain.
• the maximum density measured by a conventional photographic density measuring method is preferably at least about 5 times, more preferably at least about 10 times, as high as the maximum density obtained when the silver halide emulsion is applied and exposed to light in the same amount as above, and is developed for a period of 6 minutes at 20°C in a developing solution B (a surface type developing solution) shown below.
• internal latent type emulsions include conversion type silver halide emulsions and emulsions having shells over a core of such conversion type silver halide emulsions described, for example, in U.S. Patent 2,592,250, Japanese Patent Publication Nos. 54379/83, 3536/83 and 5582/85, and Japanese Patent Application (OPI) Nos. 156614/77, 79940/82 and 70221/83; and core/shell type silver halide emulsions the core of which is doped with a metal described in U.S.
• OPI Japanese Patent Application
• the silver halide grains used in the present invention may be regular crystals such as cubic, octahedral, dodecahedral and tetradecahedral crystals or irregular crystals such as spherical crystals or tabular grains whose length/thickness ratio is 5 or more.
• regular crystals such as cubic, octahedral, dodecahedral and tetradecahedral crystals or irregular crystals such as spherical crystals or tabular grains whose length/thickness ratio is 5 or more.
• a composite form of these crystal forms may be used, and an emulsion made up of a mixture of these crystals may also be used.
• the composition of the silver halide includes silver chloride, silver bromide or a mixed silver halide, and the silver halide preferably used in the present invention is either free from silver iodide, or if it contains silver iodide, it is silver bromo(iodo)chloride, silver (iodo)chloride or silver (iodo)bromide containing about 3 mol% or less of silver iodide.
• the average grain size of the silver halide grains is preferably up to 2 um from about 0.1 urn, more preferably from about 0.15 l lm to 1 um.
• the distribution of the grain size may be wide or narrow, in order to improve graininess, sharpness, etc. it is preferred in the present invention to use a "monodisperse" silver halide emulsion having a narrow grain size distribution such that about 90% or more of all the grains fall within ⁇ about 40%, preferably ⁇ about 20%, of the average grain size, in terms of grain number or weight.
• two or more monodisperse silver halide emulsions different in grain size or a plurality of grains of the same size but different in sensitivity are mixed in the same layer or are applied as different layers that are superposed.
• Two or more polydisperse silver halide emulsions or a monodisperse silver halide emulsion and a polydisperse silver halide emulsion can be used in the form of a mixture or in superposed layers.
• the interior or the surface of the grains may be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization or noble metal sensitization, that can be used alone or in combination.
• sulfur sensitization selenium sensitization
• reduction sensitization reduction sensitization
• noble metal sensitization particularly examples of chemical sensitization are described, for example, in the patents cited in Research Disclosure, No. 17643-lll (December, 1978), page 23.
• the photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner.
• Particularly useful dyes are cyanine dyes, merocyanine dyes and compositie merocyanine dyes, which may be used alone or in combination, and also can be used in combination with supersensitizers. Particular examples are described, for example, in the patents cited in Reserach Disclosure , No. 17643-111 (December, 1978), pages 3 to 24.
• the photographic emulsion used in the present invention can contain an antifoggant or a stabilizer for the purpose of stabilizing the photographic performance, or of preventing fogging durig photographic treatment, storage or the production of the photographic material.
• antifoggants and stabilizers are described, for example, in Research Disclosure, No. 17643-VI (December, 1978), pages 24 to 25, and by E.J. Birr in Stabilization of Photographic Silver Halide Emulsions, 1974 (Focal Press).
• a magenta coupler and a yellow coupler can be used.
• Useful couplers are compounds that can couple with the oxidized product of an aromatic primary amine type color developer to produce or release a non-diffusible dye and that themselves are substantially non-diffusible.
• Typical examples of useful color couplers include pyrazolone or pyrazoloneazole compounds or open chain or heterocyclic ketomethylene compounds.
• Specific examples of these magenta and yellow couplers are compounds described in Research Disclosure, No. 17643 (December, 1978), page 25, section VII-D; No. 18717 (November, 1979); Japanese Patent Application (OPI) No. 215272/87 (pages 298 to 373); and compounds described in the patents cited in them.
• typical yellow couplers that can be used in the present invention include yellow two-equivalent couplers of oxygen atom releasing or nitrogen atom releasing type.
• a-pivaloylacetanilide type couplers are excellent in fastness, in particular light-fastness, of the colored dyes, while a-benzoylacetanilide type couplers are preferred because a high color density can be obtained.
• 5-Pyrazolone type magenta couplers preferably used in the present invention are 5-pyrazolone type couplers (particularly sulfur atom releasing two-equivalent couplers), substituted at the 3-position by an arylamino group or an acylamino group.
• Pyrazoloazole couplers are further preferred pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Patent 3,725,067 are particularly preferred, imidazo[1,2,-b]pyrazoles described in U.S. Patent 4,500,630 are more preferred in view of the fastness to light and the low yellow subsidary absorption of the colored dye, and pyrazoio[1,5-b][1,2,4]triazotes described in U.S. Patent 4,540,654 are most preferred.
• yellow and magenta couplers are compounds listed in Japanese Patent Application (OPI) No. 169523/86 (filed by Fuji Photo Film Co., Ltd. on June 8, 1986), and the compounds listed below are also preferred examples.
• Yellow Couplers are compounds listed in Japanese Patent Application (OPI) No. 169523/86 (filed by Fuji Photo Film Co., Ltd. on June 8, 1986), and the compounds listed below are also preferred examples.
• Couplers for correcting undesired absorption in the short wavelength range of produced dyes can also be used.
• couplers producing colored dyes with a suitable diffusibility can also be used.
• colorless couplers can also be used.
• DIR couplers that release a development restrainer as a result of the coupling reaction can also be used.
• couplers that can release a development accelerator can also be used.
• the amount of a color-dye forming coupler used is in the range of about 0.001 to 1 mol per mol of a photosensitive silver halide, and preferably in the case of a yellow coupler the amount is about 0.01 to 0.5 mol per mol of a photosensitive silver halide and in the case of a magenta coupler the amount is about 0.003 to 0.5 mol per mol of a photosensitive silver halide in silver halide layers containing these couplers.
• Cyan couplers that are outside the scope of the present invention and are generally used can be used in addition to the present cyan coupler.
• Photosensitive materials prepared in accordance with the present invention may contain, as a color fogging preventive agent or color mixing preventing agent, hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamidephenol derivatives, etc.
• Typical examples of color fogging preventive agents and color mixing preventive agents are described in Japanese Patent Application (OPI) No. 215272/87, pages 600 to 630.
• Organic discoloration preventing agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirch- romans, p-alkoxyphenols, hindered phenols including bisphenols, gallic -acid derivatives, methylenediox- ybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by the silylation or alkylation of the phenolic hydroxyl group of these compounds.
• metal complexes such as (bis- salicylaldoxymato)nickel complex and (bis-N,N-dialkyldithiocarbamato)nickel complexes can be used.
• Typical examples of these discoloration preventing agents are described in Japanese Patent Application (OPI) No. 215272/87, pages 401 to 440.
• the desired aim can be attained when these compounds are added to photosensitive layers generally in amounts of about 5 to 100 wt% based on the respective color couplers by co-emulsifying them with the couplers.
• an ultraviolet absorbing agent For the purpose of preventing cyan dye images from being deteriorated by heat and, particularly, light, it is effective to introduce an ultraviolet absorbing agent into both layers adjacent to a cyan color forming layer.
• An ultraviolet absorbing agent can also be added to a hydrophilic colloid layer such as protective layer.
• Typical examples of such compounds as desribed in Japanese Patent Application (OPI) No. 215272/87, pages 391-400.
• binding agents or protective colloids that can be used in emulsion layers and intermediate layers of the present photosensitive material, it is advantageous to use gelatin, but other hydrophilic colloids other than that can also be used.
• the present photosensitive materials can contain dyes for preventing irradiation or halation, ultraviolet absorbing agents, plasticizers, brightening agents, matting agents, air fogging preventing agents, coating assistants. hardening agents, antistatic agents, slipperiness improvers, etc. Typical examples of these additives are described in Research Disclosure, No. 17643. sections VIII to XIII (December, 1978), pages 25 to 27, and No. 18716 (November, 1979), pages 647 to 651.
• the present invention can be applied to multilayer multicolor photographic materials having at least two different spectral sensitivities on a base.
• a multilayer color photographic material has at least one red sensitive emulsion layer, at least one green sensitive emulsion layer and at least one blue sensitive emulsion layer on a base.
• the order of these layers is arbitrarily selected as desired.
• a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer are coated in that order on a support or a green-sensitive emulsion layer, a red-sensitive emulsion layer and a blue-sensitive emulsion layer are coated in that order on a support.
• Each of these emulsion layers may consist of two or more emulsion layers different in sensitivity, or may consist of two or more emulsion layers having the same sensitivity with a non-photosensitive layer between them.
• the red-sensitive emulsion layer contains a cyan forming coupler
• the green-sensitive emulsion layer contains a magenta forming coupler
• the blue-sensitive emulsion layer contains a yellow forming coupler, but in some cases the combination can be changed.
• the photosensitive material according to the invention is provided with suitable auxil iary layers such as a protective layer, an intermediate layer, a filter layer, a halation preventive layer, a backing layer and a white reflective layer.
• the photographic emulsion layers and other layers are applied on supports described in Research Disclosure, No. 17643, section XVII (December, 1978), page 28, European Patent No. 0,182.253, and Japanese Patent Application (OPI) No. 97655/86.
• the coating methods described in Research Disclosure, No. 17643, section XV, pages 28 to 29 can be employed.
• the present invention can be applied to various color photosensitive materials.
• color reversal papers and color reversal films for slides and television are typical examples.
• the present invention can also be applied to color hard copies for storing CRT images or full color copying machines.
• the present invention can be applied also to black and white photographic materials using a mixture of three color couplers described in Research Disclosure, No. 17123 (June, 1978).
• the present photosensitive material can provide a direct positive color image by exposing it to light imagewise, and then by subjecting it to a fogging process using light or a nucleating agent, either before or at the same time as developing it with a surface developing solution containing an aromatic primary amine type color developer, followed by bleaching and fixing.
• the fogging process in the present invention can use either a "light fogging method” mentioned above, by which the whole surface of the photosensitive layer is subjected to a second exposure, or the "chemical fogging method” in which development is carried out in the presence of a nucleating agent.
• the development may be carried out in the presence of a nucleating agent and fogging light.
• a photosensitive material containing a nucleating agent may be subjected to fogging exposure.
• the fogging exposure in the light fogging method in the present invention is carried out after the imagewise exposure, and before and/or during the development treatment.
• the photosensitive material that has been exposed to light imagewise is dipped in a developing solution or a bath prior to the developing solution, it is subjected to fogging exposure, or after the material is taken out from the solution or the bath, it is subjected to fogging exposure while it is still wet.
• the fogging exposure during immersion in the developing solution is preferred.
• any light source having wavelengths in the range of the photosensitive wavelength of the photosensitive material can be used.
• a fluorescent lamp, a tungsten lamp, a xenon lamp, sunlight, etc. can be used.
• Specific methods for the fogging exposure are described, for example, in British Patent 1,151,363, Japanese Patent Publication Nos. 12710/70, 12709/70 and 6936/83, and Japanese Patent Application (OPI) Nos. 9727/73, 137350/81, 129438/82, 62652/83, 60739/83, 70223/3 (corresponding to U.S. Patent 4,440,851) and 120248/83 (corresponding to European Patent 89101 A2).
• a light source high in color rendition (a light source nearer white) as described in Japanese Patent Application (OPI) Nos. 137350/81 and 70223/83 is preferred.
• the illumination of light be about 0.01 to 2000 lux, preferably about 0.05 to 30 lux, and more preferably abou 0.05 to 5 lux.
• the adjustment of the illumination may be effected by varying the intensity of the light source, reducing the amount of light by filters, or varying the distance or the angel between the photosensitive material and the light source.
• the exposure time can be shortened by using a weak light at the initial stage of the exposure and then a stronger light.
• fogging exposure be performed after the photosensitive material is dipped in a developing solution or a bath prior to the developing solution so that the solution thoroughly penetrates into the emulsion layer.
• the time between complete penetration of the solution and light fogging exposure is about 2 seconds to 2 minutes, preferably about 5 seconds to 1 minute, and more preferably about 10 seconds to 30 seconds.
• the exposure time for fogging is generally about 0.01 second to 2 minutes, preferably about 0.1 second to 1 minute, and more preferably about 1 second to 40 seconds.
• the nucleating agent that can be used in the present invention includes any compound that is capable of nucleating an internal latent type silver halide. Two or moer nucleating agents can be used in combination. Nucleating agents include those described, for example, in Research Disclosure, No. 22534 (January, 1983), pages 50 to 54; No. 15162 (November, 1976), pages 76 to 77; and No. 23510 (November, 1983), pages 346 to 352. These can be classified roughly into three types: quaternary heterocyclic compounds (compounds represented by general formula (N-I)), hydrazine type compounds (compounds represented by general formula (N-11)) and other compounds.
• N-I General formula (N-I): wherein Z represents a substituted or unsubstituted nonmetallic atomic group necessary for forming a 5- membered or 6-membered heterocyclic ring; R" represents a substituted or unsubstituted aliphatic group, R 12 represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group; provided that at least one of R 11 , R 12 and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R" and R 12 together form a 6-membered ring to complete a dihydropyridinium skeleton; Y represents a counter ion necessary for charge balance and n is 0 or 1. At least one of the substituents of R", R 12 and Z may contain the group in which X' represents a group capable of accelerating adsorption onto a silver halide
• the heterocyclic ring formed by Z includes a quinolinium nucleus, a benzothiazolium nucleus, a benzimidazolium nucleus, a pyridinium nucleus, a thiazolini um nucleus, a thiazolium nucleus, a naphthothiazolium nucleus, a selenazolium nucleus, a benzoselenazolium nucleus, an imidazolium nucleus, a tetrazolium nucleus, an indolenium nucleus, a pyrrolinium nucleus, an acridinium nucleus, a phenanthridinium nucleus, an isoquinolium nucleus, an oxazolium nucleus, a naphthooxazolium nucleus, a naphthopyridinium nucleus, and a benzoxazolium nucleus.
• the substituents for Z include an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylthio group, an arylthio group, an acyloxy group, an acylamino group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, a carboxyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, a ureido group, a urethane group, a carbonic acid ester group, a hydrazine group, a hydrazone group and an imino group.
• At least one of the above substituents is present as a substituent for Z, and if there are two or moe substituents on Z, they may be the same or different.
• the above substituents may be further substituted by the substituents mentioned above.
• the substituent for Z may have a heterocyclic ring quaternary ammonium group formed by Z via a suitable linking group L. In this case, it forms a dimer structure.
• the heterocyclic ring formed by Z is preferably a quinolium nucleus, a benzothiazolium nucleus, a benzimidazolium nucleus, a pyridinium nucleus, an acridinium nucleus, a phenanthridinium nucleus, a naphthopyridinium nucleus or an isoquinolinium nucleus, with a quinolinium nucleus, a benzothiazolium nucleus and a naphthopyridinium nucleus more preferred and a quinolium nucleus most preferred.
• the aliphatic group represented by R 11 and R 12 is an unsubstituted alkyl group having 1 to 18 carbon atoms or a substituted alkyl group having 1 to 18 carbon atoms in the alkyl moiety.
• the substituents may be the same as those for Z.
• the aromatic group represented by R 12 is one having 6 to 20 carbon atoms, such as a phenyl group and a naphthyl group.
• the substituents are the same as those for Z.
• R 12 represents an aliphatic group, most preferably a methyl group or a substituted methyl group.
• R 12 and Z at least one contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R" and R 12 are linked to form a 6-membered ring to complete a dihydropyridinium skeleton; and these groups may be substituted with the substituents for Z mentioned above.
• the hydrazine group is substituted, particularly with an acyl group or a sulfonyl group.
• a formyl group, an aliphatic group or an aromatic ketone is preferred as the acyl group.
• the hydrazone group is substituted with an aliphatic group or an aromatic group.
• R 12 and Z is an alkynyl group or an acyl-group, or that R 11 , R' 2 and Z is an alkynyl group or an acyl-group, or that R" and R 12 together form a dihydropyridinium skeleton, and it is most preferred that at least one alkynyl group is present.
• Preferred examples of a group capable of accelerating adsorption onto a silver halide represnets by X' include a thioamido group, a mercapto group and a 5-or 6-membered nitrogen-containing heterocyclic ring group. These groups may be substituted by the substituents for Z.
• the thioamido group is a non-cyclic thioamido group (e.g. a thiourethane group and a thioureide group).
• the mercapto group represented by X 1 is particularly preferably a heterocyclic mercapto group (e.g., 5-mercaptotetrazole, 3-mercapto-1.2,4-triazole, and 2-mercapto-1,3,4-thiadiazole).
• a heterocyclic mercapto group e.g., 5-mercaptotetrazole, 3-mercapto-1.2,4-triazole, and 2-mercapto-1,3,4-thiadiazole.
• the 5-or 6-membered nitrogen-containing heterocyclic ring represented by X' contain a combination of nitrogen, oxygen, sulfur and carbon and preferably is one that will form an imino silver such as benzotriazole.
• the 5-to 6-membered nitrogen-containing heterocyclic ring represented by X' includes a 5-to 6- membered nitrogen-containing heterocyclic ring made up of a combination of nitrogen, oxygen, sulfur and carbon.
• preferable ones are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine, etc., which may have a suitable substituent, for example, the substituents mentioned for Z.
• More preferably nitrogen-containing heterocyclic rings are benzotriazole, triazole, tetrazole, and indazole, with benzotriazole most preferable.
• the divalent linking group represented by L' is an atomic group containing at least one of C, N, S and O and more specifically contains, for example, one or a combination of an alkylene group, an alkenylene group, an alkynyl. ene group, an arylene group, -0-, -S-, -NH-, -N-, -CO-and -SOz-which may be substituted.
• the counter ion for charge balance represented by Y includes a bromide ion, a chloride ion, an iodine ion, a p-toluenesulfonate ion, an ethylsulfonate ion, a perchlorate ion, a trifluoromethanesulfonate ion and a thiocyanate ion.
• R 21 represents an aliphatic group, an aromatic group or a heterocyclic group
• R 22 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group
• G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group ( );
• R 23 and R 24 both represent a hydrogen atom, or one of R 23 and R 24 represents a hydrogen atom and the other represents an alkylsulfonyl group, an arylsulfonyl group or an acyl group.
• G, R 23 and R 24 together with the hydrazine nitrogens may form a hydrazone structure or These groups may, if possible, be substituted by a substituent.
• R 21 may be substituted by a substituent, which in turn may be further substituted, such as an alkyl group, an aralkyl group, an alkoxy group, an amino group substituted by an alkyl or aryl group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group and a carboxyl group, with a ureido group or sulfonamido group preferred, which groups may link together to form a ring if possible.
• a substituent such as an alkyl
• R 21 represents an aromatic group, an aromatic heterocyclic ring group or an aryl-substituted methyl group, with an aryl group (e.g., a phenyl group and a naphthyl group) more preferred.
• aryl group e.g., a phenyl group and a naphthyl group
• R 22 represents a hydrogen atom, an alkyl group (e.g., a methyl group) or an aralkyl group (e.g., an o-hydroxybenzyl group), with a hydrogen atom particularly preferred.
• an alkyl group e.g., a methyl group
• an aralkyl group e.g., an o-hydroxybenzyl group
• the substituents for R 22 include those for R 21 as well as an acyl group, an acyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkenyl group, an alkynyl group and a nitro group, which may be further substituted any of those substituents, and, if possible, may link together to form a ring.
• R2 1 or R 22 may contain a diffusion-resistant group such as a coupler, ballast group (preferably linked through a ureido gorup) and may contain a group 2 capable of accelerating adsorption onto the surface of silver halide grains, where X 2 has the same meaning as X' in general formula (N-I) and preferably represents a thioamide group (excluding a thiosemicarbazide and its substitution product), a mercapto group or a 5-or 6-membered nitrogen-containing heterocyclic ring group, L 2 represents a divalent linking group and has the same meaning as L' in general formula (N-I), and m 2 is 0 or 1.
• X 2 has the same meaning as X' in general formula (N-I) and preferably represents a thioamide group (excluding a thiosemicarbazide and its substitution product), a mercapto group or a 5-or 6-membered nitrogen-containing heterocyclic ring group
• L 2 represents
• X 2 represents a non-cyclic thioamido group (e.g., a thioureido group and a thiourethane group), a cyclic thioamido group (i.e., a mercapto-substituted nitrogen-containing heterocyclic ring, e.g., a 2-mercaptothiadiazole group, a 3-mercapto-1,2,4-triazole group, a 5-mercaptotetrazole group, a 2-mercapto-1,3,4-oxadiazole group and a 2-mercaptobenzoxazole group) or a nitrogen-containing heterocyclic ring group (e.g., a benzotriazole group, a benzimidazole group and an indazole group).
• a non-cyclic thioamido group e.g., a thioureido group and a thiourethane group
• X 2 is determined based on the photosensitive material.
• X 2 peferably represents a mercapto-substituted nitrogen-containing heterocyclic ring or a nitrogen-containing heterocyclic ring that will form an imino silver.
• X 2 preferably represents a non-cyclic thiamido group or a mercapto-substituted nitrogen-containing heterocyclic ring.
• X 2 preferably represents a mercapto-substituted nitrogen-containing heterocyclic ring or a nitrogen-containing heterocyclic ring that will form an imino silver.
• R 23 and R 24 represent a hydrogen atom.
• G in general formula (N-II) represents a carbonyl group.
• the compound represnets by general formula (N-II) contains a group capable of being adsorbed onto a silver halide or a group having a ureido group.
• hydrazine type nucleating agents having a group capable of being adsorbed onto a silver halide, and synthetic methods therefor are described, for example, in U.S. Patents 4,030,925, 4,080,207, 4,031,127, 3,718,470, 4,269,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,478,928 and 4,560,638, British Patent 2,011,391 B and Japanese Patent Application (OPI) Nos. 74729/79, 163533/80, 74536/80 and 179734/85.
• OPI Japanese Patent Application
• the nucleating agent used in the present invention can be contained in the photosensitive material or in a processing liquid for the photosensitive material, and preferably is contained in the photosensitive material.
• the nucleating agent used in the present invention is contained in the photosensitive material, although it is preferable that it is added to an internal latent image silver halide emulsion layer, it can be added to other layers such as an intermediate layer, an undercoat layer or a backing layer so long as the nucleating agent diffuses during application or processing to be adsorbed onto a silver halide.
• the nucleating agent is added to a processing liquid, it can be added to a developing solution or a prior bath having a low pH as described in Japanese Patent Application (OPI) No. 178350/83.
• the amount is about 10- 8 to 10- 2 mol, more preferably about 10- 7 to 10- 3 , per mol of silver halide contained in an emulsion layer.
• the amount of the nucleating agent is about 10- 5 to 10 -1 mol, more preferably about 10- 4 to 10- 2 mol, per liter thereof.
• hydroquinones e.g., compounds described in U.S. Patents 3,227,552 and 4,279,987
• chromans e.g., compounds described in U.S. Patent 4,268.621, Japanese Patent Application (OPI) No. 103031/79 and Research Dis closure, No. 18264 (June, 1979), pages 33 to 334
• quinones e.g., compounds described in Research Disclosure, No. 21206 (December, 1981 pages 433 to 434
• amines e.g., compounds described in U.S.
• Patent 4,150.993 and Japanese Patent Application (OPI) No. 174757/83 oxidizing agents
• oxidizing agents e.g., compounds described in Japanese Patent Application (OPI) No. 260039'85 and Research Disclosure, No. 16936 (May, 1978), pages 10 to 11
• catechols e.g., compounds described in Japanese Patent Application (OPI) Nos. 21013/80 and 65944/80
• compounds that will release a nucleating agent at the time of development e.g., compounds described in Japanese Patent Application (OPI) No. 107029/85
• thioureas e.g., compounds described in Japanese Patent Application (OPI) No. 95533/85
• spirobisindanes e.g., compounds described in Japanese Patent Application (OPI) No. 65944/80.
• Nucleation accelerators that can be used in the present invention include pentaazaindenes, triazain- denes and tetraazaindenes having at least one mercapto group that is optionally substituted by an alkali metal atom or ammonium group, and compounds described in Japanese Patent Application (OPI) No. 136948/86 (pages 2 to 6 and 16 to 43), Japanese Patent Application Nos. 136949/86 (pages 12 to 43) and 15348/86 (pages 10 to 29).
• OPI Japanese Patent Application
• nucleation accelerators are given below, but the present invention is not to be con strued as being limited to those compounds.
• the nucleation accelerator is added to a silver halide emulsion or a layer adjacent thereto.
• the amount of the nucleation accelerator added to the material is preferably about 10- 6 to 10- 2 mol, more preferably about 10- 5 to 10- 2 mol, per mol of a silver halide in the layer or adjacent layer.
• the amount of the nucleation accelerator is about 10- 8 to 10- 3 mol, preferably about 1 0- 7 to 10- 4 mol, per liter of the processing liquid.
• Two or more nucleation accelerators can be used in combination.
• the color developing solution used for developing the present photosensitive material is substantially free from a silver halide solvent and is preferably an alkaline solution whose major component is an aromatic primary amine color developing agent.
• the color developing agent aminophenol type compounds are useful, and p-phenylenediamine type compounds are preferred. Typical examples thereof are 3-methyl-4-amino-N-ethyl-N-( ⁇ -methanesulfonamidoethyl)-aniline, 3-methyl-4-amino-N-ethyl-N-( ⁇ -hydroxyethyl)-aniline and 3-methyl-4-amino-N-ethyl-N-methoxyethylaniline and their sulfates and hydrochlorides.
• color developing agent compounds described by L.F.A. Mason in Photographic Processing Chemistry, pages 226 to 229 (Focal Press, 1966); U.S. Patents 2,193,015 and 2,592,364; and Japanese Patent Application (OPI) No. 64933/73 can also be used. If desired, two or more color developing agents can be used in combination.
• the amount of the color developing agent is preferably about 0.1 to 20 g, more preferably about 0.5 to 15 g, per liter of the developing solution.
• the developer can contain preservatives including, for example, aromatic polyhydroxy compounds described in Japanese Patent Application (OPI) Nos. 49828/77, 47038/81, 32140181 and 160142/84 and U.S. Patent 3,746,544; hydroxyacetones described in U.S. Patent 3,615,503 and British Patent-1,306,176; ⁇ -aminocarbonyl compounds described in Japanese Patent Application (OPI) Nos. 143020/77 and 89425 / 78; metals described, for example, in Japanese Patent Application (OPI) Nos. 44148/82 and 53749/82; sugars described in Japanese Patent Application (OPI) No. 102727/77; hydroxamic acids described in Japanese Patent Application (OPI) No.
• preservatives including, for example, aromatic polyhydroxy compounds described in Japanese Patent Application (OPI) Nos. 49828/77, 47038/81, 32140181 and 160142/84 and U.S. Patent 3,746,544; hydroxyacetones described
• the amount of the preservative to be used is about 0.1 to 20 g, preferably about 0.5 to 10 g, per liter of the developing solution.
• the pH of the color developing solution in the present invention is preferably about 9.5 to 11.3, more preferably about 10.0 to 10.8.
• various buffers can be used, including carbonates such as potassium carbonate, phosphates such as potassium phosphate and compounds described in Japanese Patent Application (OPI) No. 215272/87, pages 11 to 22.
• the color developing solution can contain various chelating agents as agents for preventing calcium and magnesium from precipitating or for improving the stability of the color developing solution.
• Chelating agents include, for example, aminopolycarboxylic acids described in Japanese Patent Publication Nos. 30496/73 and 30232/69; organic phosphonic acids described in Japanese Patent Application (OPI) No. 97347/81, Japanese Patent Publication No. 39359/81 and West German Patent No. 2,227,639; phosphonocarboxylic acids described in Japanese Patent Application (OPI) Nos. 102726 1 77, 42730/78, 121127/79, 126241/80 and 65956/80; and other compounds de scribed in Japanese Patent Application (OPI) Nos. 195845/83 and 203440/83 and Japanese Patent Publication No. 40900178, which can be used in combination if required.
• the amount of the chelating agents to be added is that sufficient to form complexes with metal ions present in the color developing solution. For example, the amount is on the order of about 0.1 to 10 g per liter.
• any conventional development accelerator can be added to the color developing solution.
• Development accelerators include thioether type compounds described, for example, in Japanese Patent Publication Nos. 16088/62, 5987/62, 7826/63, 12380/69 and 9019/70, and U.S. Patent 3,813,247; p-phenylenediamine type compounds described in Japanese Patent Application (OPI) Nos. 49829/77 and 15554/75; quaternary ammonium salts described, for example, in Japanese Patent Application (OPI) No. 137726/75, Japanese Patent Publication No. 30074/69 and Japanese Patent Application (OPI) Nos. 156826/81 and 43429/77; p-aminophenols described in U.S.
• Patents 2,610,122 and 4,119,462 amine type compounds described, for example, in U.S. Patents 2,494,903, 3,128,182, 4,230,796 and 3,253,919, Japanese Patent Publication No. 11431/66, U.S. Patents 2,482,546, 2,596,926 and 3,582,346; and 1-phenyl-3-pyrazolidone, hydrazines, meso-ionic compounds, thionic compounds, imidazoles and polyalkylene oxides described, for example, in Japanese Patent Publication Nos. 16088/62 and 25201/67, U.S. Patent 3,128,183, Japanese Patent Publication Nos. 11431/66 and 23883/67 and U.S. Patent 3,532,501. Particularly, thioether type compounds and 1-phenyl-3-pyrazolidones are preferred.
• any conventional antifoggant can be added to the color developing solution in the present invention.
• antifoggants include an alkali metal halide such as potassium bromide, sodium chloride and potassium iodide or an organic antifoggant.
• an organic antifoggant can be used, for example, a nitrogen- containig heterocyclic ring-compound such benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethyl-benzimidazole and hydroxyazaindolizine; a mercapto-substituted heterocyclic compound such as 2-mercaptobenzimidazole and 2-mercaptobenzythiazole; and a mercapto-substituted aromatic compound such as thiosalicyclic acid and adenine.
• these antifoggants may dissolve out of the color photosensitive material during processing and may accumulate in the color developing solution, it is preferred that the amount of the accumulation be limited to reduce their discharge amount of the developer.
• the color developing solution in the present invention contain a brightening agent. It is preferred to use, as a brightening agent, a 4,4-diamino2,2'-disulfostilbene type compound.
• the amount of the brightening agent to be added is 0 to about 5 g/liter, preferably about 0.1 to 2 g/liter.
• surface active agents may be added, such as alkylhosphonic acids, arylphosphonic acids, aliphatic carboxylic acids and aromatic carboxylic acids.
• the photographic emulsion layer is bleached.
• the bleaching may be carried out simultaneously with fixing as a one-bath bleach-fixing or the bleaching and the fixing can be carried out separately.
• bleach-fixing can be performed either after the bleaching or after the fixing.
• the bleaching solution or the bleach-fix solution in the present invention uses, as a bleaching agent, an aminopolycarboxylic acid iron complex salt.
• the bleaching solution or the bleach-fix solution in the present invention can contain various additive compounds described in Japanese Patent Application (OPI) No. 21572/87, pages 22 to 30. After the desilvering (bleach-fix or bleaching), washing and/or stabilizing is carried out. It is preferred to use.
• a water softening treatment such as a method using an ion exchange resin or a reverse osmosis apparatus described in Japanese Patent Application No. 131632/86. More specifically, the method described in Japanese Patent Application No. 13132/86 is preferably used.
• additives that can be used in a washing step and a stabilizing step include various compounds described in Japanese Patent Application (OPI) No. 215272/87, pages 30 to 36.
• the amount of the replenishing solution in each step is small.
• the amount of the replenishing solution is about 0.1 to 50 times, more preferably about 3 to 30 times the amount of the solution carried over from the preceding bath per unit area of the photosensitive material.
• aqueous 10 wt% solution of potassium bromide and an aqueous 10 wt% solution of silver nitrate were simultaneously added at 65°C over a period of about 30 minutes with vigorous stirring to an aqueous 7 wt% gelatin solution containing 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thion per mol of Ag to obtain an octahedral monodispersed silver bromide emulsion having an average grain diameter of 0.45 urn.
• 16 mg each of sodium thiosulfate and chloroauric acid (tetrahydrate) were added to the emulsion per mol of silver and the emulsion was heated at 75°C for 80 minutes to be chemically sensitized.
• the thus prepared silver bromide grains were used as cores and were treated for a further 40 minutes while adding additional potassium bromide and silver nitrate under the same precipitation conditions described above to be further grown thereby producing an octahedral monodispersed (coefficient of variation: 11%) core/shell silver bromide emulsion having an average grain diameter of 0.8 ⁇ m.
• each color photographic paper having the layer structure shown in Table 1 was prepared using a paper base with opposite surfaces laminated with polyethylene.
• the coating liquids were prepared as follows.
• a first coating liquid 10 g of a cyan coupler (shown in Table 2) and 2.3 g of a dye image stabilizer (b) were dissolved in 10 ml of ethyl acetate and 4 ml of a solvent (c), and the solution was emulsified and dispersed in 90 ml of a 10% aqueous gelatin solution containing 5 ml of 10% of sodium dodecylbenzenesulfonate to prepare an emulsion dispersion.
• a red sensitizing dye shown below in an amount of 2.0 x 10- 4 mol per mol of the silver halide to produce 90 g of a red sensitive emulsion.
• the emulsified dispersion, the red-sensitive emulsion and a development accelerator were mixed and dissolved and the concentrations were adjusted using gelatin to have the composition shown in Table 1, and a nucleating agent (N-I-9) in an amount of 4.5 x 10- 6 mol per mol of Ag and a nucleation accelerator (A-15) in an amount of 1 x 10- 4 mol per mol of Ag were added thereto to prepare a coating liquid for a first layer.
• Coating liquids for the second to seventh layers were prepared in the same way as the coating liquid for the first layer.
• each layer contained 0.03 g/m 2 of 1-oxy-3,5-dichloro-s-triazine sodium salt.
• the spectral sensitizers for the emulsions are described below.
• the following dyes were used as irradiation preventive dyes.
• the replenishing method of the stabilizing bath was a countercurrent replenishing method, i.e., the replenishing solution was supplied to stabilizing bath (3), the overlfow from stabilizing bath (3) was fed to stabilizing bath (2), and the overflow from stabilizing bath (2) was fed to stabilizing bath (1).
• the pH was adjusted using potassium hydroxide or hydrochloric acid.
• the pH was adjusted using ammonia water or hydrochloric acid.
• the pH was adjusted using potassium hydroxide or hydrochloric acid.
• step (a) Using the same processing liquids used in step (a) without replenishing, an automatic developing processing machine was run one day and the step (a) was repeated.
• the color formation of the photosensitive materials containing a cyan coupler according to the invention was good in both steps (a) and (b).
• the values of the minimum density obtained using cyan couplers according to the invention and comparative cyan couplers in the step (a) were all the same, i.e., 0.21.
• Example 1 To prepare color photographic papers, Example 1 was repeated, except that an emulsion (B) given below was used; the nucleating agent and the nucleation accelerator were omitted; the cyan couplers shown in Table 3 were used in the first layer.
• B an emulsion given below
• the nucleating agent and the nucleation accelerator were omitted
• the cyan couplers shown in Table 3 were used in the first layer.
• Steps (c) and (d) steps (a) and (c) were repeated, except that light of 0.5 lux (5400 K) was used to expose the photosensitive material surface for 20 seconds, beginning 15 seconds after the start of the development.
• Example 1 was repeated, except that an emulsion (C) given below was used and the cyan couplers shown in Table 4 were used in the first layer.
• An aqueous 10 wt% solution of potassium bromide an aqueous 10 wt% solution of silver nitrate were simultaneously added to an aqueous 7 wt% gelatin solution containing 3,4-dimethyl-1,3-thiazoline-2-thione in an amount of 0.56 g per mol of Ag, at 75°C over a period of about 40 minutesto produce an octahedral monddispersed silver bromide emulsion having an average grain diameter of 0.5 ⁇ m.
• the processing liquids were the same as those used in step (a) in Example 1.
• the photosensitive materials were processed in steps (e) and (f) using an automatic developing processing machine after the automatic developing processing machine was run at 38°C for one day without replenishment.

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• 1986
  • 1986-10-27 JP JP61253716A patent/JPH0727184B2/ja not_active Expired - Lifetime
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