Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
• • 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
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/305—Additives other than developers

Definitions

• the present invention relates to a negative-type photographic silver halide photosensitive material. More specifically, the present invention is concerned with a method of developing a photosensitive material, which is extremely effective in ultra high-speed processing.
• the object of the present invention is to provide a method of developing a negative-type silver halide photographic light-sensitive material, which enables silver contained in said material to be developed effectively in a short period of time, thereby to obtain an image which is highly contrasty.
• the above object can be attained by a process comprising treating in a developer a negative-type silver halide photographic light-sensitive material having at least one photosensitive emulsion layer on a support, wherein one or more hydrophilic colloid layers provided on the same side of said support that said at least one photosensitive emulsion layer is provided contain a specific compound and the ratio of the silver content of said one or more colloid layers to the thickness of said one or more colloid layers is 0.7 or more, provided that the silver content is expressed in terms of mg/m2 and the thickness is expressed in terms of ⁇ m and wherein said developer contains a specific compound and the ratio of the content of said specific compound in said one or more colloid layers to the content of said specific compound in said developer is in the range of 0.01 to 1, provided that the content of said specific compound in said developer is expressed in terms of mg/ml.
• the present invention relates to a method of developing with a developer containing at least one compound selected from the group consisting of compounds represented by Formulae I, II and III negative-type silver halide photographic light-sensitive material having a support and provided thereon hydrophilic colloid layers comprising at least one light-sensitive silver halide emulsion layer, wherein at least one of said colloid layers on the emulsion layer side comprises at least one compound selected from the group consisting of compounds represented by Formulae I, II and III, the ratio of the silver content represented by g/m2 of at least one of said colloid layers to the thickness represented by ⁇ m of said colloid layers is not less than 0.7 and the ratio of the content of said compound represented by mg/m2 in at least one of said colloid layers to that of said compound represented by mg/l in said developer is from 0.01 to 1.
• R1 and R2 each represent a hydrogen atom, an alkyl group, -COOM, -SO3M, -OH, -CONHR3 or -NHCOR3, provided that at least one of R1 and R2 is -COOM, SO3M, -OH, -CONHR3 or -NHCOR3, wherein R3 represents an alkyl group; M represents a hydrogen atom, an alkali metal atom or -NH4; and Y represents an oxygen atom, a sulfur atom, a selenium atom or a - - group.
• Y1 and Y2 each represent a hydrogen atom or a mercapto group
• R4 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, each of which may either be substituted or unsubstituted, a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group, a hydroxycarbonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, a hydroxy group, a mercapto group or a sulfo group.
• A represents a nitrogen atom, a carbon atom or an oxygen atom.
• B represents a nitrogen atom or a carbon atom.
• M represents a hydrogen atom, alkali metal atom or -NH4.
• X represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an acylamino group or a sulfoamido group.
• the development time of a negative-type silver halide photosensitive material is normally 19 seconds or less, and "Dry to Dry” is usually 20 to 60 seconds.
• “Dry to Dry” means the total time taken from the time when a leading edge of a photosensitive material is introduced in an automatic developing machine having a developing step, a fixing step, a washing step and a drying step until the time when the leading edge comes out of the machine.
• “Dry to Dry” can be defined by the following equation: wherein the processing line includes the conjunction portion of each container. It is a distinctive feature of the present invention that Dry to Dry is merely 60 seconds or less.
• the "thickness” means the total thickness of one or more hydrophilic colloid layers which are provided on the same side of a support that a silver halide photosensitive layer is provided, and is not limited to the thickness of a silver halide photosensitive layer.
• the silver content as referred to herein is defined as the total amount of silver contained in hydrophilic colloid layers, when a plurality of said layers are provided on the same side of a support.
• photosensitive silver halide particles in one side of a support, photosensitive silver halide particles of 0.05 to 0.5 ⁇ m in average grain size are employed.
• the "grain size” as referred to herein means a diameter when silver halide particles are spherical.
• grain size means one obtained by converting the projected image of the particles to a circular image having the same area as that of the projected image. It is preferred that 60% or more of all silver halide particles have a grain size within the range of ⁇ 10% of the average grain size.
• silver halide there is no restriction as to the kind of silver halide to be employed.
• Use can be made of silver halides which are employed in an ordinary silver halide emulsion.
• examples of such silver halide include silver bromide, silver iodo-bromide, silver chloride, silver bromo chloride and silver iodo-bromo chloride. It is preferable to use silver bromo chloride containing 50 mol% of silver chloride.
• a silver halide particle may be obtained by acid process, neutral process or ammonia process.
• a silver halide particle may either be one having a uniform composition distribution or one being of a core/shell structure, in which the interior and the surface of the particle are different in composition distribution and also, one in which a latent image may be formed either on the surface of or inside, the particle.
• a silver halide particle there is no restriction as to the shape of a silver halide particle.
• One preferable example is a cubical silver halide particle having a (100) face as a crystalized face. It is also possible to employ octaheral, quadridecahedral, or dodecahedral silver halide particles obtained by processes described in U.S. Patent Nos. 4,183,756, 4,225,666, Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 26589/1980, Japanese Patent Examined Publication 42737/1980, the Journal of Photographic Science, 21, 39 (1973). A silver halide particle having a twin crystal face is also usable.
• silver halide particles may either be same or different in shape.
• Silver halide particles of any grain size distribution may be employed.
• Silver halide particles may either be monodispersed or polydispersed. It is also possible to employ a mixture of several kinds of monodispersed silver halide particles. A mixture of monodispersed particles and polydispersed particles is also usable.
• a monodispersed silver halide emulsion is preferable.
• the total weight of silver halide particles with their grain sizes being in the range of ⁇ 20% of the average grain size ( r ) may account for 60% or more, preferably 70% or more, more preferably 80% or more of the total weight of all silver halide particles.
• the "average grain size" as referred to herein is defined as a diameter (ri) which makes the value of ni x ri3 reach the maximum (wherein ni represents the frequency of a silver halide particle having a diameter of ri. Figures of three decimal places are significant figures. The smallest cipher is rounded).
• the "grain size” as referred to herein means a diameter of a particle when the particle is spherical. As to particles in other shapes than sphere, the grain size is obtained by converting its projected image into a circular image having the same area.
• the grain size can be obtained by measuring the diameter of an electron-microphotographed image of a particle (x10,000 to 50,000). Alternatively, the grain size can be obtained by measuring the area of the projected image of a particle. (measurement is done with respect to more than 1,000 particles selected arbitrarily.)
• the distribution size of a monodispersed emulsion may preferably be 20% or less, more preferably 15% or less.
• the distribution size is obtained by the following formula:
• the average grain size and the standard deviation of grain size can be obtained from the value of ri, which is defined before.
• a monodispersed emulsion can be prepared in accordance with methods described in Japanese O.P.I. Publication Nos. 48521/1979, 49938/1983 and 122935/1985.
• a photosensitive silver halide emulsion is subjected to chemical sensitization.
• Chemical sensitization can be performed according to methods described in books written by Glafkides and Zelikman, or a method described in Die Grundlagen der Photographischen mit Silberhaligeniden, Akademische Verlagsgesellschaft (edited by H. Frieser, 1968).
• sulfur sensitization an activated gelatin, or a compound containing sulfur which is reactive with a silver ion is used as a sensitizer
• reduction sensitization a reducing compound is used as a sensitizer
• noble metal sensitization a noble metal is used as a sensitizer
• These sensitization methods can be used either singly or in combination.
• the sulfur sensitizer include thiosulfates, thoureas, thiazoles, and rhodanines. The specific examples of these sensitizers are described in U.S. Patent Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668 and 3,656,955.
• stannous salts As a reducing compound for reduction sensitization, there can be employed stannous salts, amines, hidrazine derivatives, formamidine sulfinic acid, and silane compounds.
• stannous salts As a reducing compound for reduction sensitization, there can be employed stannous salts, amines, hidrazine derivatives, formamidine sulfinic acid, and silane compounds.
• the specific examples of these compounds are described in U.S. Patent Nos. 2,487,850, 2,419,974, 2,518,698, 2,983,609, 2,983,610 and 2,694,637.
• noble metal sensitization use can be made of a complex salt of gold, or a complex salt of a metal belonging to the Group VII of the periodic table, such as platinum, iridium, palladium and the like.
• the specific example of these complex salts are described in U.S. Patent Nos. 2,399,083, 2,448,060, and British Patent No.
• the pH may preferably be in the range of 4 to 9, more preferably 5 to 8.
• the pAg may preferably be in the range of 5 to 11, more preferably 8 to 10.
• the temperature may preferably be in the range of 40 to 90°C, more preferably 45 to 75°C.
• the reduction sensitization reducing compounds are employed
• the noble metal sensitization noble metal compounds are employed
• a silver halide photosensitive emulsion may be employed either singly or in mixture.
• various stabilizers can be added to a chemically sensitized emulsion.
• a chemically sensitized emulsion there may be mentioned 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 5-mercapto-1-phenyltetrazole, and 2-mercaptobenzothiazole.
• a solvent for a silver halide such as a thioether
• a crystal habit control agent such as a mercapto group-containing compound and a sensitization dye.
• a metal ion may be added to a silver halide particle during the course of formation and/or growth of the particle, so that the metal ion can be included inside and/or on the surface of the particle.
• a cadmium salt for this purpose, use can be made of a cadmium salt, a zinc salt, a lead salt, a thallium salt, a salt or a complex salt of iridium, a salt or a complex salt of rhodium, a salt or a complex salt of iron.
• a photosensitive silver halide emulsion may be spectrally sensitized by a sensitization dye so that it can be sensitive to blue light, green light, red light or infrared ray whose wavelength is relatively long.
• a sensitization dye there can be mentioned a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar-cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxonol dye.
• cyanine dyes, merocyanine dyes, and composite merocyanine dyes are especially effective.
• any nucleus which is normally used for cyanine dyes as the basic heterocyclic nucleus can be employed.
• the specific examples of such nucleus include a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazol nucleus, a thiazole nucleus, a selenazole nucleus, an imidazol nucleus, a tetrazole nucleus, and a pyridine nucleus.
• a nucleus obtained by the fusion of one of the above nuclei with an alicyclic or aromatic hydrocarbon ring are also usable.
• an indolenine nucleus there can be mentioned an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphtoxazole nucleus, a benzothiazole nucleus, a naphtothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus.
• These nuclei may be substituted on the carbon ring.
• a nucleus having a ketomethylene structure is usable.
• examples of such nucleus include a 5- or 6-membered heterocyclic nucleus such as a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbiturate nucleus.
• a sensitization dye may be employed in the same concentration as that in the case of ordinary negative type photosensitive emulsions. It is of advantage to employ a sensitization dye in such a concentration as will not have any adverse effect on the inherent sensitivity of a silver halide emulsion.
• a sensitization dye may preferably be employed in an amount of 1.0 x 10 ⁇ 5 to 5 x 10 ⁇ 4 mole, more preferably 4 x 10 ⁇ 5 to 2 x 10 ⁇ 4, per mole of a silver halide.
• sensitization dyes may either be employed singly or in combination.
• the specific examples of sensitization dyes which are advantageously employed in the present invention are given below.
• sensitization dye to be used for a blue-sensitive layer there can be mentioned those described in German Patent No. 929,080, U.S. Patent Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,956, 3,672,897, 3,694,217, 4,025,349, 4,046,572, British Patent No. 1,242,588, Japanese Patent Examined Publication No. 14030/1969, 24844/1977, Japanese Patent O.P.I. Publication Nos. 73137/1973 and 172140/1986.
• the representative examples of the sensitization dye for a green-sensitive layer include cyanine dyes, merocyanine dyes and composite cyanine dyes disclosed in U.S. Patent Nos. 1,939,201, 2,072,908, 2,739,149, 2,945,763, British Patent No. 505,979, and Japanese Patent Examined Publication No. 42172/1973.
• the sensitization dye to be used in a red-sensitive layer and an infrared ray-sensitive layer it is of advantage to use cyanine dyes, merocyanine dyes, and composite cyanine dyes disclosed in U.S. Patent Nos.
• sensitization dyes may be used either alone or in combination. Two or more sensitization dyes are often employed in combination for the purpose of supersensitization. Examples of the combined use of sensitization dyes are described in U.S. Patent Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent Nos. 1,344,281, 1,507,803, Japanese Patent Examined Publication Nos. 4936/1968, 12375/1978, Japanese Patent O.P.I. Publication Nos. 110618/1979 and 109925/1979.
• a water-soluble dye may be added to a hydrophilic colloid layer(s) as a filter dye, an anti-irradiation dye, an anti-halation dye, or for other various purposes.
• water-soluble dye include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.
• especially preferable dyes are oxonol dyes, hemioxonol dyes and merocyanine dyes.
• dyes, ultraviolet ray absorbents, or other materials when dyes, ultraviolet ray absorbents, or other materials are contained in a hydrophilic colloid layer(s), these materials may be mordanted by a cationic polymer.
• Various compounds may be added to the photosensitive silver halide emulsion so that occurrence of fogging and lowering in sensitivity of a photosensitive material, which may occur during the preparation, storage or at the time of processing, of a photosensitive material can be prevented.
• Many compounds known as a stabilizer are usable for these purposes.
• Examples of such compounds include azoles such as benzothiazolium salts, nitroindozoles, triazoles, benzotriazoles, benzimidazoles (especially, a nitro-, or halogen-substituted product), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially, 1-phenyl-5-­mercaptotetrazole), mercaptopyridines, the above-mentioned heterocyclic mercapto compounds may contain a water-soluble group such as a carboxyl group or a sulfone group, thioketo compounds such as exazolinethion, azaindenes such as tetrazaindenes (especially, 4-hydroxy-substituted-­1,3,3a,7-tetrazaindenes, benzenethios
• a preferable example of such stabilizer is a compound which is represented by the above-mentioned Formula [I], [II] or [III].
• these compounds are added to a hydrophilic colloid layer(s) which is provided on the same side of a support that a silver halide emulsion layer is located, and also to a developer to be used for processing a silver halide photosensitive material.
• the ratio of the content of this compound in the colloid layer(s) to that in a developer be in the range of 0.01 to 1, provided that the former content is indicated in terms of mg/m2 and the latter content is indicated in terms of mg/l.
• the content of the compound represented by Formula I, II or III in the hydrophilic colloid layer(s) is preferably in the range of 1 x 10 ⁇ 6 to 1 x 10 ⁇ 1 mole, more preferably 1 x 10 ⁇ 5 to 1 x 10 ⁇ 2 mole, per mole of silver halide contained in said layer.
• the content of this compound in a developer is preferably in the range of 1 x 10 ⁇ 6 mole to 1 x 10 ⁇ 1 mole, more preferably 1 x 10 ⁇ 5 mole to 1 x 10 ⁇ 2 mole, per liter of the developer.
• a silver halide photosensitive material may contain in its photographic structural layers an alkylacrylate-type latex described in U.S. Patent Nos. 3,411,911, 3,411,912 and Japanese Patent Examined Publication No. 5331/1970.
• Various additives may be added to a silver halide photosensitive material of the present invention.
• the thickner and the plasticizer use can be made of materials described in U.S. Patent No. 2,960,404, Japanese Patent Examined Publication Nos. 4939/1968, 15462/1970, German Patent No. 1,904,604, Japanese Patent O.P.I. Publication No. 63715/1973, Belgian Patent Nos. 762,833, 558,143, U.S. Patent No. 3,767,410.
• these materials include a copolymer of styrene and sodium maleate and dextran sulfate.
• a hardening agent use can be made of hardening agents of aldehyde-type, epoxy-type, ethylene imine-type, active halogen-type, vinyl sulfone-type, isocyanate-type, sulfonic acid ester-type, carbodiimido type, mucochloric acid-type, and acyloyl type.
• an ultraviolet ray absorbent compounds described in U.S. Patent No. 3,253,921 and in British Patent No. 1,309,349 are usable.
• Examples of such compounds include 2-(2′-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3′-tert-butyl-5′-butylphenyl)-5-­chlorobenzotriazole, 2-(2′-hydroxy-3′,5-di-tert-butylphenyl)-5-chlorobenzotriazole.
• a coating assisting agent for improving the permeability of a photosensitive material in a treatment liquid
• a defoaming agent for improving the permeability of a photosensitive material in a treatment liquid
• a surface-active agent for controlling the physical properties of a photosensitive material.
• the surface active agent there can be employed anion, cation, non-ion, or amphoteric compounds described in British Patent Nos. 548,532 and 1,216,389, U.S. Patent Nos. 2,026,202, 3,514,293, Japanese Patent Examined Publication Nos. 26580/1969, 17922/1968, 17926/1968, 13166/1968, 20785/1973, French Patent No. 202,588, Belgian Patent No.
• an anion surface active agent containing a sulfone group such as a sulfonated product of an ester of succinic acid, a sulfonated product of alkylnaphthalene, and a sulfonated product of alkylbenzene, is preferable.
• antistatic agent use can be made of compounds described in Japanese Patent Examined Publication Nos. 24159/1971, 39312/1971, 43809/1983, Japanese Patent O.P.I. Publication Nos. 89979/1973, 20785/1973, 43130/1973, 90391/1973, 33627/1972, U.S. Patent Nos. 2,882,157 and 2,972,535.
• the pH of a liquid to be coated on a support may preferably be in the range of 5.3 to 7.5.
• the pH of a mixture of individual coating liquids may preferably be in the range of 5.3 to 7.5. If the pH is smaller than 5.3, prompt hardening of coated layers is impeded. A pH value larger than 7.5 will have adverse effects on the photographic properties.
• a matting agent may be contained in photographic structural layers.
• the matting agent there can be employed iorganic particles, such as silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995; carbonates of alkali earth metals, cadmium and zinc described in British Patent No. 1,173,181; and organic particles, such as starch described in U.S. Patent No. 2,322,037, starch derivatives described in Belgian Patent No. 625,451 and British Patent No. 981,198, polyvinyl alcohol described in Japanese Patent Examined Publication No. 3643/1969, polystyrene and polymethyl methacrylate described in Swiss Patent No. 330,158, polyacrylonitrile described in U.S. Patent No. 3,079,257, and polycarbonate described in U.S. Patent No. 3,022,169.
• iorganic particles such as silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,
• the photographic structural layers of a photosensitive silver halide material may contain a lubricant.
• a lubricant there can be employed an ester of higher fatty alcohol described in U.S. Patent Nos. 2,558,756 and 3,121,060, casein described in U.S. Patent No. 3,295,979, a calcium salt of higher fatty acid described in British Patent No. 1,263,722, and a silicon compound described in British Patent No. 1,313,384, U.S. Patent Nos. 3,042,522 and 3,489,567.
• a dispersed product of fluid paraffin is also usable for this purpose.
• the dyes which are employable for various purposes e.g.
• filter dyes there can be mentioned oxonol dyes, hemioxonol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes.
• oxonol dyes, hemioxonol dyes and merocyanine dyes are effective.
• the specific examples of the employable dyes include those described in German Patent No. 616,007, British Patent Nos. 584,609 and 1,117,429, Japanese Patent Examined Publication No. 7777/1951, 22069/1964, 38129/1979, Japanese Patent O.P.I. Publication Nos.
• These compounds may either be soluble or insoluble in water.
• an acid group such as a carboxy group, a sulfo group, a phospho group, a sulfuric ester group, and a phosphoric ester group.
• the specific examples of these agents include a salt of alkylcarboxylic acid, a salt of alkylsulfonic acid, a salt of alkylbenzene sulfonic acid, a salt of alkylnapthalene sulfonic acid, an ester of alkylsulfuric acid, an ester of alkylphosphoric acid, an N-acyl-alkyltaurine, an ester of sulfosuccinic acid, an ether of sulfoalkylpolyoxyethylenealkylphenyl, and an ester of polyoxyethylenealkylphosphoric acid.
• amphoteric surface active agent there may preferably be employed amino acids, aminoalkylsulfonic acids, an ester of aminoalkylsulfuric acid or aminoalkylphophoric acid, alkylbetaines, and amineoxides.
• a salt of alkylamine an aliphatic or aromatic quaternary ammonium salt, a heterocyclic quaternary ammonium salt such as pyridium and imidazolium, a salt of alphatic or heterocyclic phosphonium or sulfonium.
• the ninion surface active agent there may preferably be employed saponin (steroid type), an alkyleneoxide derivative (e.g. polyethylene glycol, a condensation product of polyethylene glycol and polypropylene glycol, an alkylether of polyethylene glycol, an alkylarylether of polyethylene glycol, an ester of polyethylene glycol, an ester of polyethylene glycol sorbitan, an alkylamine or an alkylamide of polyalkyleneglycol, an addition product of a silicone and a polyethylene oxide), a glycide derivative (e.g. an alkenylsuccinic acid polyglyceride, an alkyphenol polyglyceride), an aliphatic acid ester of polyhydric alcohol, and an alkylester of sugar.
• an alkyleneoxide derivative e.g. polyethylene glycol, a condensation product of polyethylene glycol and polypropylene glycol, an alkylether of polyethylene glycol, an alkylarylether of polyethylene
• matting agent there can be mentioned organic matting agents described in British Patent No. 1,055,713, U.S. Patent Nos. 1,939,213, 2,221,873, 2,268,662, 2,332,037, 2,376,005, 2,391,181, 2,701,245, 2,992,101, 3,079,257, 3,262,782, 3,516,832, 3,539,344, 3,591,379, 3,754,924, 3,767,448, and inorganic matting agents described in German Patent No. 2,592,321, British Patent Nos. 760,775, 1,260,772, U.S. Patent Nos.
• antistatic agent there may preferably be employed compounds described in British Patent No. 1,466,600, Research Disclosure Nos. 15840, 16258, 16630, U.S. Patent Nos. 2,327,828, 2,861,056, 3,206,312, 3,245,833, 3,428,451, 3,775,126, 3,963,498, 4,025,342, 4,025,463, 4,025,691, and 4,025,704.
• a tetrazolium compound, a polyethylene oxide derivative, a quaternary microcosmic salt, and a hydrazine compound described in Japanese Patent O.P.I. Publication Nos. 210458/1987 and 139546/1987 are used as a contrast-controlling agent which helps an image to be more contrasty.
• gelatin is normally employed as a binder. It is also possible to use, in combination with gelatin, a hydrophilic colloid of a gelatin derivative, a cellulose derivative, a graft polymer of gelatin and other polymer than gelatin, other protein than gelatin, a derivative of sugar, or a synthesized high molecular compound such as homo- or copolymer.
• gelatin besides lime-treated gelatin, use can be made of acid-treated gelatin and oxygen-treated gelatin such as those described in Bulletin of Society of Japan, No. 16, p. 30 (1966). Also usable are a hydrolyzed product or an enzyme-decomposed product of gelatin.
• gelatin derivative there may be employed those obtained by allowing gelatin to react with various products including an acid halide, an acid anhydride, an isocyanate, a bromoacetic acid, an alkanesulton, a vinylsulfoneamido, a maleic imido compound, a polyalkylene oxide, an epoxy compound.
• the specific examples of these gelatin derivatives are described in U.S. Patent Nos. 2,614,928, 3,132,945, 3,186,846, 3,312,553, British Patent Nos. 861,414, 1,033,189, 1,005,784, and Japanese Patent Examined Publication No. 26845/1967.
• the protein use can be made of albumin, casein, or the like.
• the cellulose derivative use can be made of a hydroxyethylcellulose, a carboxymethylcellulose, a sufuric ester of cellulose, or the like.
• the derivative of sugar there can be employed soda alginate and starch derivatives. These compounds can be used in combination with gelatin.
• graft polymer of gelatin and other polymer there may be employed one obtained by graft polymerization of gelatin with an acrylic acid, a methacrylic acid, a derivative thereof including an ester and an amido, a homo- or copolymer of a vinyl monomer such as acrylonitrile and styrene.
• a graft polymer of gelatin with a polymer which shows mutual solubility with gelatin to some extent such as a polymer of acrylic acid, acrylamido, methacrylamide, hydroxyalkylmethacrylate, and the like. Examples of these polymers are described in U.S. Patent Nos. 2,763,625, 2,831,767, and 2,956,884.
• a paper obtained by laminating ⁇ -olefin polymers e.g. polyethylene, polypropylene, a ethylene/butene copolymer
• a flexible reflective support such as a synthetic paper
• a film of a semi-synthesized or synthesized polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, a polycarbonate, and a polyamide
• a flexible support obtained by providing a reflective layer on one of above films and a metalic film.
• a support of polyethylene terephthalate is especially preferred.
• undercoating layer imployable in the present invention there may be mentioned an undercoating layer obtained by using an organic solvent such as polyhydroxybenzenes, examples of which being described in Japanese Patent O.P.I. Publication No. 3972/1974 and an undercoating layer obtained by using a water-type latex, examples of which being described in Japanese Patent O.P.I. Publication Nos.
• the surface of an undercoating layer may be subjected to chemical or physical treatment.
• chemical treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet ray treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment.
• An undercoating layer should be distinguished from coating layers which fall in the scope of the present invention. There is, therefore, no restriction as to the time and conditions of providing this layer.
• dyes may be employed for various purposes.
• a filter dye an anti-halation dye
• employable dyes include triallyl dyes, oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes.
• oxanol dyes, hemioxanol dyes and merocyanine dyes are effective.
• the specific examples of these dyes are described in German Patent No. 616,007, British Patent Nos. 584,609 and 1,177,429, Japanese Patent Examined Publication Nos.
• dyes are advantageously employed especially in a photosensitive material for contact printing to be treated in a lighted room.
• a dye be employed in such an amount that the sensitivity of a photosensitive material to light of 400 nm becomes 30 times as large as that to light of 360 nm.
• an organic desensitizer described, for example, in Japanese Patent O.P.I. Publication No. 26041/1986.
• this desensitizer the sum of an anode potential and a cathode potential is positive in its polarogram.
• imagewise exposure may be performed by using an electromagnetic wave of a spectral region to which a photosensitive emulsion layer of a silver halide photosensitive material exhibits sensitivity.
• the light source any of conventional light sources may be employed. Examples of employable light sources include sunlight, tungsten lamps, fluorescent lamps, iodine quartz lamps, mercury lamps, microwave-emitting ultraviolet lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tubes, flying spots, various laser beams, ligth-emitting diodes, light emitted from a fluorescent substance exited by electron beam, X ray, ⁇ ray or ⁇ ray.
• a light source described in Japanese Patent O.P.I. Publication No. 210458/1987 which is obtained by attaching to an ultraviolet ray light source an absorption filter capable of absorbing light of not more than 370 nm in wavelength. Also possible is to use an ultraviolet ray light source emitting light of 370 to 420 nm in main wave length.
• Exposure time may be 1 millisecond to 1 second, as is employed in normal photographing by a camera. It is also possible that light exposure be effected for such a short time as less than 1 microsecond. For example, by using a cathode ray tube or a xenon flash tube, exposure can be effected for 100 nanosecond to 1 microsecond. On the other hand, it is also possible to perform exposure for 1 second or longer. Imagewise exposure may be performed either continuously or intermittently.
• the present invention can be applied to a variety of photosensitive materials.
• the present invention can be applied to films for printing, films for X-ray photography, a negative film for ordinary photographing, a reversal film for ordinary photographing, and a positive film for direct photographing.
• the fixing liquid may contain various substances such as thiosulfates, sulfites, various acids, salts, fixing acceleraters, wetting agents, surface active agents, chelating agents, hardening agents, and the like.
• thiosulfates and sulfites include potassium salts, sodium salts, and ammonium salts thereof
• the acids include sulfuric acid, hydrochloric acid, nitric acid, boric acid, formic acid, acetic acid, propinic acid, oxalic acid, tartaric acid, citric acid, malic acid, and phthalic acid.
• the salts include potassium salts, sodium salts, and ammonium salts of these acids.
• thiourea derivatives and an alcohol containing a triple bond in its molecule disclosed in Japanese Patent Examined Publication No. 35754/1970, Japanese Patent O.P.I. Publication Nos. 122535/1983 and 122536/1983, a thioether disclosed in U.S. Patent No. 4,126,459, an ether of cyclodextran which releases an anion, a crown ether, diazabicyclo undecene, and di(hydroxyethyl)butamine.
• the wetting agent use can be made of an alkanol amine and an alkylene glycol.
• chelating agent use can be made of a nitrilotriacetic acid and an aminoacetic acid such as a disodium salt of ethylenediamine tetraacetic acid.
• the hardening agent include chrome alum, pottasium alum, and Al compounds.
• the fixing liquid contain Al compounds so that a hardened layer of a photosensitive emulsion can be kept in a stable condition.
• the content of an Al compound in a fixing liquid may preferably be 0.1 to 3 g per liter of a fixing liquid (calculated in terms of Al in the fixing liquid).
• the concentration of sulfite in a fixing liquid may preferably be 0.03 to 0.4 mole, more preferably 0.04 to 0.3 mole per liter of a fixing liquid.
• the preferred pH value of a fixing liquid is 3.9 to 6.5. This pH value contributes to the improvement of photographic properties of an image. Moreover, when use is made of a fixing liquid having this pH value, a silver halide photosensitive material can produce remarkable effects. It is especially preferred that the pH of a fixing liquid be 4.2 to 5.3.
• aqueous silver nitrate, an aqueous sodium chloride and sodium bromide are mixed simultaneously in an aqueous gelatin solution, thereby forming silver halide granules.
• Desalting is performed by an ordinary method to obtain a photosensitive emulsion.
• the so-formed emulsion is chemically sensitized by known technique.
• 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene is added to the emulsion as a stabilizer.
• a compound represented by Formula I, II, or III nonylphenyloxy polyethylene glycol, and a latex of a copolymer of an acrylic acid and butyl methacrylate as described in Table 1.
• a tetrazolium compound (A) is added in an amount of 1.3 g per mole of silver.
• the resulting emulsion is then coated on a support of a polyethylene terephthalate film having a thickness of 100 ⁇ m, which is undercoated with a polymer latex.
• a protective layer is provided on the emulsion layer.
• the amount of silver and the thickness of a hydrophilic colloid layer(s) are varied as shown in Table 1.
• the so-formed photosensitive materials are subjected to imagewise exposure through a glass wedge, by using lighted room printer P627FM (manufactured by Dainippon Screen Co., Ltd.). Then, the photosensitive materials are subjected to development and fixing.
• the compositions of a developer and a fixing liquid, and the conditions under which development is performed are given below.
• the amount of silver is measured by using a fluorescent X-ray analyzer. In a photosensitive material after development, the amount of silver means the amount of silver in a portion which gives a maximum density.
• the thickness of a hydrophilic colloid layer(s) is measured by a swelling degree measuring machine (manufactured by Shinko Denshi Co., Ltd.).
• Photosensitive silver halide materials are prepared in substantially the same manner as in Example 1, except that chemical sensitization is performed by using the following sensitization dye (B). Imagewise exposure is carried out through a glass wedge by using a tungsten lamp as a light source. The results obtained are same as those obtained in Example 1.
• Table 1 Compound represented by Formula I, II or III Run No.
• the ⁇ value is obtained with respect to an image having a density of 0.3 to 3.0.
• An image having a ⁇ value of not more than 6 is poor in resolution, and therefore, can hardly be put to practical use.

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Cited By (4)

• 1988
  • 1988-09-05 JP JP22317988A patent/JPH0269736A/ja active Pending
• 1989
  • 1989-09-05 EP EP19890116367 patent/EP0358165A2/fr not_active Withdrawn

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