EP0267019A2 - Matériau photographique à l'halogénure d'argent sensible à la lumière capable d'un traitement ultrarapide - Google Patents

Matériau photographique à l'halogénure d'argent sensible à la lumière capable d'un traitement ultrarapide Download PDF

Info

Publication number
EP0267019A2
EP0267019A2 EP87309756A EP87309756A EP0267019A2 EP 0267019 A2 EP0267019 A2 EP 0267019A2 EP 87309756 A EP87309756 A EP 87309756A EP 87309756 A EP87309756 A EP 87309756A EP 0267019 A2 EP0267019 A2 EP 0267019A2
Authority
EP
European Patent Office
Prior art keywords
layer
photographic
silver halide
group
structual
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87309756A
Other languages
German (de)
English (en)
Other versions
EP0267019B1 (fr
EP0267019A3 (en
Inventor
Satoru Nagasak
Eiji Yoshida
Akio Suzuki
Masumi Arai
Nobuaki Tsuji
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP61298499A external-priority patent/JP2613378B2/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0267019A2 publication Critical patent/EP0267019A2/fr
Publication of EP0267019A3 publication Critical patent/EP0267019A3/en
Application granted granted Critical
Publication of EP0267019B1 publication Critical patent/EP0267019B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/007—Slide-hopper coaters, i.e. apparatus in which the liquid or other fluent material flows freely on an inclined surface before contacting the work
    • 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
    • G03C1/38—Dispersants; Agents facilitating spreading
    • 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
    • G03C1/46—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer
    • 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
    • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
    • B05C9/04—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material to opposite sides of the work
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
    • 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
    • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
    • G03C2001/7425—Coating on both sides
    • 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
    • G03C2200/00—Details
    • G03C2200/52—Rapid processing

Definitions

  • the present invention relates to a silver halide photo­graphic light-sensitive material, in particular, a silver halide photographic light-sensitive material which does not incur disadvantages in the coating process, and allows super-­rapid photographic processing.
  • the diagnostic result should be noti­fied to a case as soon as possible.
  • the term "super-rapid processing” means the photographic processing whose total duration is within a range of 20 to 60 seconds; within this duration, the leading edge of film is introduced into an automatic developing unit, and transferred via a developing bath, interface portion, fixing bath, interface portion, water-rinsing bath, interface portion, then a drying portion, and the same edge is eventual­ly ejected from the drying portion, wherein the duration equals a quotient in sec. obtained by dividing a line trans­portation rate in m/sec. by a total length of processing line in m.
  • the reason for why the periods associated with the interface portions should be included is well known in the photographic art; even in the interface portions, a gelatin layer in the photographic material contains a processing solution employed in a preceeding process and, accordingly, the photographic treatment substantially proceeds.
  • the current X-ray photography requires a high-precision photographic technique involving smaller exposure dose. This need in turn necessitates the development of a photographic material being capable of providing a high-precision image with a smaller X-ray dosage, in other words, a more sensitive photographic material.
  • the first object of the invention is to solve the above mentioned problems prior art incurs when the super-­rapid processing with the total processing duration of 20 to 60 seconds is performed, in order to provide a silver halide photographic light-sensitive material which excels in the sensitivity, contrast, maximum density, fixing properties, drying properties and other properties.
  • the second object of the invention is to provide a silver halide photographic light-sensitive material having a limited amount of gelatin and seldom incurring failures even in apply­ing a coating solution which has a smaller surface tension.
  • the third object of the invention is to provide a silver halide photographic light-sensitive material less possibly incurring scratch-induced blackening even if a smaller amount of gelatin is used.
  • a silver halide photographic light-sensitive material comprising a support having the first photographic structual layer comprising one or more layers on a side of the support and the second photographic structual layer comprising one or more layers on the other side of the support, wherein at least one of the photographic structual layers comprises a silver halide light-sensitive emulsion layer, the total amount of gelatin contained in the photographic structual layer comprising the silver halide emulsion layer is within the range of from 2.00 g/m2 to 3.50 g/m2, the uppermost layer of the photographic structual layer comprising the silver halide emulsion layer is formed by coating of a solution having a surface tention of from 15 to 26 dyn/cm, and the second photographic stuructual layer is coated and gelled between coating and drying of the first photographic structual layer.
  • the silver halide photographic light-sensitive material of the invention contains a matting agent of which mattnesss is preferably 40 to 150 mmHg.
  • the silver halide photographic light-­sensitive material should be preferably processed with an auto­matic developing unit whose total processing time is 20 to 60 seconds.
  • the term "outermost layer” literally means the upper outermost layer.
  • such an outermost layer may be further coated with coating such as super cost which is applied, for example, by means of spray.
  • the "outermost layer” of the invention may be either a light-sensitive layer or a non-­light-sensitive layer.
  • a support there is disposed, on at least one surface of a support, at least one silver halide emulsion layer.
  • the support may have, on the other surface, either a light-sensitive silver halide layer or non-light-sensitive layer. If more than two silver halide emulsion layers on one surface of the support are formed, a non-light-sensitive layer may be provided between any of these emulsion layers. However, at least, the support should have no its both surfaces a light-­sensitive silver halide emulsion layer and on the other sur­face a non-light-sensitive layer.
  • the term “amount of gelatin” means the total amount of gelatin present in the light-­ sensitive and non-light-sensitive layers both on the light-­sensitive layer surface of a support. If the support have a light-sensitive layer on both surfaces, the term “amount of gelatin” means the total amount of gelatin present on one specific surface.
  • the term "light-sensitive layer” means a layer sensitive to light, for example, a light-­sensitive silver halide emulsion layer.
  • non-light-sensi­tive layer means a layer not sensitive to light, for example, a subbing layer, intermediate layer, protective layer, anti­halation layer, filter layer or the like.
  • a preferred silver halide photographic light-sensitive material has in the silver halide emulsion layer the silver halide particles whose average particle diameter is 0.30 to 1.50 ⁇ m, more specifically, 0.40 to 1.30 ⁇ m, and most specifically, 0.40 to 1.10 ⁇ m.
  • a preferred silver halide photographic light-sensitive material has multi-layered silver halide particles which are substan­tially made of silver iodo-bromide, wherein the difference in average iodine contents between two arbitrary, independently uniform, adjacent layers, between two coating layers, or between the internal core and a coating layer, is more than 10 mol%, and the average iodine content in the outermost layer is less than 10 mol%, and the material has been chemical­ly sensitized.
  • Such multi-layered silver halide particles individually comprise an internal core coated with a layer of an arbitrary halide composition.
  • the layer may comprise one layer, or more than two layers, for example, the lamination of three or four layers. However, the preferred number of layers is less than five.
  • Silver halides useful as internal core and coating layers are silver bromide, silver iodo-bromide and silver iodide. However, any of such silver halides may involve a limited amount of silver chloride. To be more concrete, the silver halide may contain less than 10 mol%, more favorably, less than 5 mol% of silver chloride.
  • each silver halide particle should be substantially made of silver bromide, or silver iodo-bromide containing less than 10% of iodide, and may contain less than several % of chlorine atoms.
  • the preferred average iodide content in whole silver halide particles of the invention is less than 10 mol%, or, more specifically, less than 6 mol%.
  • the iodide content in an X-ray photographic light-sensitive material, the iodide content sometimes worsens the problems such as development inhibition, infectious development and the like. Accordingly, in practice, the iodide content should be preferably limited below a specific level. In any cases, the method according to the invention decreases the stress fogging. However, because of the above reason, the preferred total iodide content in whole silver halide parti­cles is less than 10 mol%, or, more specifically, less than 7 mol%, or, most specifically, less than 5 mol%.
  • the core should preferably be made of a uniform solid solution.
  • the condition of using a diffractometer is ⁇ r/r ⁇ 10, where the scanning rate of goniometer is ⁇ (deg/min), time constant is r(sec), and receiv­ing slit width if r(mm).
  • the preferred average iodine content is less than 40 mol%, in particular, 0 to 20 mol%.
  • the preferred difference in average iodide contents bet­ween two adjacent layers is more than 10 mol%, and more specifically, more than 20 mol%, and most specifically, more than 25 mol%.
  • the preferred silver iodide content in the coating layers other than the outermost coating layer is 10 to 100 mol%.
  • an individual silver halide particle comprises more than three layers, and at the same time, if the coating layers are made of silver iodo-bromide, all the layers are preferably made of uniform silver iodo-bromide, though it is compulsory that these layers are made of uniform silver iodo-bromide.
  • Such a coating layer or an internal core having high iodide content should be preferably present below the outer­most layer, in the case of negative-type silver halide emul­sion.
  • the similar coating layer may be present either on or within the surface of individual silver halide particle.
  • the preferred silver iodide content in the outermost coating layer of the silver halide particle is less than 10 mol%, in particular, 0 to 5 mol%.
  • the iodide contents in the internal core and coating layers of individual silver halide particles which are used in embodying the invention may be determined by a method, for example, disclosed in "X-ray analysis with TEM/ATEM” Scanning Electron Microscopy (1977), by J.I. Goldstein and D.B. Williams, vol. I. IIT Research Institute, p. 651 (May, 1977).
  • the silver halide particles used in embodying the invention are, for example, two-layered, it is advantageous that the internal core has the higher iodide content than the outer layer.
  • a coating layer other than the outermost layer, or the inter­nal core should preferably have the higher iodide content than the outermost layer.
  • the present invention is advantageously applied to the chemically sensitized silver halide particles. This is because non-sensitized particles have extremely low sensitivi­ty, and, naturally, seldom incurs scratch-induced fogging and pressure desensitization.
  • the silver halide particles used in embodying the inven­tion are whichever positive-type or negative-type.
  • the preferred criterion of chemical sensitization is as follows; sensitivity corresponding to a point "fogging + 0.1" in the optical density curve is more than 60% of optimum sensitization degree.
  • the preferred criterion of chemical sensitization for the interior of indi­vidual particles is as follows; sensitivity corresponding to a point "fogging - 0.1" in the optical density curve is more than 60% of optimum sensitization degree.
  • the average particle size of silver halide particles used in the invention is expressed as the average length of edges on imaginary cubes whose volumes are equal to corresponding particles.
  • the outermost layer of light-­sensitive material is formed with a coating solution having a surface tension of less than 26 dyn/cm.
  • a coating solution having a surface tension of less than 26 dyn/cm.
  • an arrangement to incorporate at least one surfactant into the uppermost layer is available.
  • a layer immediately below the uppermost layer may or may not contain a surfactant.
  • Surfactants used respectively in the uppermost layer and the layer immediately below are either identical or different.
  • nonionic surfactants such as saponin, alkylene oxide derivative, aliphatic esters of multivalent alcohols, alkyl esters of sugars, and others
  • anionic surfactants having an acid group such as carboxy group, sulfo group, phospho group, sulfuric ester group, phosphoric ester group, or the like
  • ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric esters, aminoalkyl phosphoric esters, alkylbetaines, amine oxides and the like.
  • cationic surfactants including alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammo­nium salts of pyridinium or the like, and aliphatic or heterocyclic phosphonium salts, and aliphatic or heterocyclic sulfonium salts; fluorine-containing surfactants such as those containing polyoxyethylene group.
  • alkylene oxide surfactant examples are disclosed, for example, in Japanese Patent Publication No. 9610/1976, DT-2648746, Japanese Patent Open to Public Inspection (here­inafter referred to as Japanese Patent O.P.I. Publications) No. 129623/1978, No. 89624/1979, No. 98235/1979, No. 208743/­1983, No. 80848/1985 and No. 94126/1985.
  • fluorine-containing surfactant examples include compounds disclosed in Japanese Patent Publications No. 9303/1972, No. 43130/1973, No. 25087/1977 and No. 1230/1982, Japanese Patent O.P.I Publications No. 46733/1974, No. 16525/1975, No. 34233/1975, No. 32322/1976, No. 14224/1979, No. 111330/1979, nO. 557762/1980, No. 19042/1981, No. 41093/­1981, No. 34856/1981, No. 11341/1982, No. 29691/1982, No. 64228/1982, No. 146248/1982, No. 14944/1981, No. 11945/1981, No.
  • the preferred anionic surfactants not having a poly­alkylene oxide are typified by the following 1 - 1 through 1 - 10.
  • the preferred fluorine containing surfactants are typi­fied by the following 2 - 1 through 2 - 82.
  • the examples of commercial fluorine containing surfac­tants include Unidyne manufactured by Daikin Kogyo Co., Ltd. and Florado manufactured by Sumitomo 3M.
  • the particles employed in embodying the invention are hereinunder described.
  • the size distribution of particles employed may be either small or large.
  • the size distribution of silver halide particles within a photographic emulsion is arbitrarily selected, and the emul­sion may be a monodisperse type.
  • the term-monodisperse means a dispersion system where sizes of 95% of total particles correspond a range of less than ⁇ 60%, or, more favorably, less than ⁇ 40% of number average particle size.
  • number average particle size is the number average diameter of the projected areas of silver halide particles.
  • the silver halide particles in a photographic emulsion may have a regular crystal configuration such as cube, octa­hedron, tetradecahedron or dodecahedron, or an irregular configuration such as spheric and tabular ones, or a combina­tion or any of these crystal configurations. Also, silver halide particles may simultaneously involve various crystal configurations.
  • the silver halide particles may be any of the following crystals: combined silver halide crystals formed by bonding oxide crystals such as of PbO with silver halide crystals such as of silver chloride; epitaxially grown silver halide crys­tals (for example, on individual silver bromide crystals, silver chloride, silver iodo-bromide, silver iodide or the like is epitaxially grown); crystals comprising hexagonal or regular octagonal silver iodide particles overlapped with regular octagonal silver chloride crystals.
  • the above regular silver halide particles may be incorporated into the emulsion.
  • the latter type of particles should not preferably exceed 50% in terms of weight or number of particles.
  • the total amount of silver halide particles involve at least 60 to 70 weight% of regular silver halide particles.
  • the silver halide particles used in the silver halide emulsion are prepared in compliance with any of the neutral method, acid method, ammonium method, normal precipitation method, reverse precipitation method, double jet precipitation method, controlled double jet pre­cipitation method, conversion method, core/shell method and the like discloed in the literatures such as The Theory of the Photographic Process, 4th edition, by T.H. James, published from MacMillan (1977); Chimie et Physique Photographique, by P. Glfkides, published from Paul Montel (1967); Photographic Emulsion Chemistry, by G.F. Duffin, published from The Focal Press (1966); Making and Coating Photographic Emulsion, by V. L. Zelikman et al, published from The Focal Press (1964); and others.
  • a triple jet precipitation method where soluble halides of different compositions, for example, solube silver salt, soluble bromide and soluble iodide, are independently added, is also useful.
  • a method to form particles in the presence of excess silver ions may be used.
  • the controlled double jet method which keeps pAg level con­stant in the liquid phase where silver halide is formed, is also useful.
  • silver halide solvents are useful: ammonium, potassium rhodate, ammonium rhodate and thioether compounds, disclosed for example in U.S. Patents No. 3,271,157, No. 3,574,628, No. 3,704,130, No. 4,297,439 and No. 4,276,374; thionic compounds, disclosed for example in Japanese Patent O.P.I. Publications No. 144,319/1978, No. 82,408/1978 and No. 77,737/1980; amine compounds disclosed for example in Japanese Patent O.P.I. Publication No. 100,717/1979; and others.
  • ammonium is advantageous for this purpose.
  • More than two independently prepared silver halide emul­sions may be mixed together to prepare one emulsion.
  • These silver halide particles or silver halide emulsions should preferably contain at least one salt (soluble salt) of iridium, thallium, palladium, rhodium, zinc, nickel, cobalt, uranium, thorium, strontium, tungsten or platinum.
  • the preferred amount of such a salt is 10 ⁇ 6 to 10 ⁇ 1 mol per mol Ag.
  • the particles or emulsions contain at least one salt selected from those of thallium, palladium and iridium. These salts may be either independently or combined­ ly used. The timing of adding such a salt is arbitrarily selected. By incorporating such a salt, various effects may be resulted; for example, improvement of flash exposure charac­teristics, prevention of pressure desensitization, prevention of fading of the latent image, and sensitization.
  • the preferred example is such that the pAg level of parent solution containing protective colloid, while particles are allowed to grow, as mentioned above, prior to the chemical sensitization, is at least 10.5.
  • the parent solution is subjected at least once to an atmosphere of pAg level more than 11.5 with excess bromine ions.
  • This arrangement increas­es the (111) faces and makes individual particles more spheric, thus further enhancing the effects of the present invention.
  • the (111) faces of particles should preferably account for more than 5% of the total surface area of parti­cles.
  • the increase in (111) faces should be preferably more than 10%, in particular, 10 to 20%.
  • the above-mentioned pAg level should be preferably reached after approximately two thirds of the total amount of silver have been added and before the desalination process which is usually performed prior to the chemical sen­sitization. This is because this arrangement is useful in providing a monodisperse emulsion having a smaller particle size distribution.
  • the ripening in an atmosphere having the pAg level of more than 10.5 is preferably performed for more than two minutes.
  • Controlling the pAg in this manner increases the (111) face more than 5%, and individual particles becomes more spheric, thus providing advantageous particles whose (111) faces account for more than 5% of total surface areas of particles.
  • noodle water-rinsing method where the removal is effected by promoting the gelation of gelatin
  • flocculation method which uses an inorganic salt, anionic sur­factant, anionic polymer such as polystyrene sulfonate or gelatin derivative such as acyl gelatin, carbamoyl gelatin.
  • anionic polymer such as polystyrene sulfonate or gelatin derivative such as acyl gelatin, carbamoyl gelatin.
  • the process to remve soluble salts may be omitted.
  • the silver halide emulsion is preferably chemic­ally sensitized, but it may not be sensitized.
  • chemical sensitizing the emulsion for instance, the methods described in Die Unen der Photographischen Saw mit Silber­halogenieden, Akademishe Verlagegeselshaft, 1968, p.67 - 734 can be used.
  • the silver halide emulsion useful in the invention may be optically sensitized with a dye known in the photographic art as a sensitizing dye so that it may be particularly sensi­tive in a required wavelength range.
  • Sensitizing dyes may be independently used, or otherwise, more than two of them may be combinedly used.
  • the emulsion may contain a supersensitizer which is a dye not pro­viding spectral sensitizing function or a compound not absorb­ing visible light but enhances the sensitizing action of sensitizing dye.
  • sensitizing dye used in the blue-sensitive silver halide emulsion layer or as a sensitizing dye used in the green-sensitive silver halide emulsion layer, or as a red-­ sensitive silver halide emulsion layer, various dyes are available. These dyes may be independently used, or otherwise, various combinations of dyes may be used. The combination of sensitizing dyes is often used especially for the supersensi­tizing purpose.
  • the aromatic organic acid-­formardehyde condensation products for example, those dis­closed in U.S. Patent No. 3,437,510
  • cadmium salts azaindene compound, and aminostylbene compounds having a nitrogen-containing heterocyclic substituent.
  • One preferred embodiment of the invention is provided by incorporating, into a light-sensitive silver halide emulsion layer, at least one sensitizing dye selected from a group of compounds which are expressed by the following formula [I], [II] or [III].
  • R1, R2 and R3 independently represent an alkyl group, alkenyl group or aryl group each of which is allowed to have a substituent, and at least one of R1 and R2 is a sulfo­alkyl group or carboxyalkyl group.
  • X represents an anion
  • Z1 and Z2 independently represent a group of non-metal atoms necessary to complete a substituted or unsubstituted carbon ring
  • n represents 1 or 2 (if form­ing an intramolecular salt, n represents 1)].
  • R4 and R5 independently represent an alkyl group, alkenyl group or aryl group each of which is allowed to have a substituent, and at least one of R4 and R5 is a sulfo­alkyl group or carboxyalkyl group.
  • R6 represents a hydrogen atom, lower alkyl group or aryl group.
  • X represents an anion
  • Z1 and Z2 independently represent a group of non-metal atoms necessary to complete a substituted or unsubstituted carbon ring, and n represents 1 or 2, if forming an intra­molecular salt, n represents 1].
  • R7 and R9 independently represent a lower alkyl group, hydroxyalkyl group, sulfoalkyl group or aryl group each of which is allowed to have a substituent
  • X represents an anion
  • Z1 and Z2 independently represent a group of non-metal atoms necessary to complete a substituted or unsubstituted carbon ring, and n represents 1 or 2 if forming an inter­ molecular salt, n represents 1].
  • the carbon ring Z1 or Z2 forms should be preferably an aromatic ring such as a substituted or unsubsti­tuted benzene or haphthalene ring.
  • the total amount of adding compounds expressed by any of the above formulas [I] through [III] is within a range of 50mg to 1200mg per mol silver halide. However, the amount of 100mg to 100mg is particularly advantageous.
  • the timing for adding the compound expressed by any of the above formulas [I], [II] and [III] is arbitrarily selected from any time points within the preparation of light-sensitive material.
  • the compound is incorporated into the material prior to the chemical ripening, during the chemical ripening, after the chemical ripening or before the coating process.
  • Into the photographic emulsion used in the invention may be incorporated various compounds in order to prevent the fogging during the preparation, storage and photographic processing of the light-sensitive material, or to ensure stable photographic performance.
  • a plasticizer may be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material according to the invention.
  • trimethylolpropane is advantageous.
  • the preferred amount of addition per amount of gelatin is 0.01 to 100 weight%, in particular, 0.1 to 100 weight%, or more specific­ally, 0.1 to 10 weight%.
  • various compounds may be incorporated into the photographic emulsion used in embodying the invention.
  • a water-soluble dye may be added for various purposes; for example, as a filter dye to a hydrophilic colloid layer, or for the prevention of irradiation and halation.
  • the light-sensitive material of the invention contains in a hydrophilic colloid layer a dye, ultraviolet absorbent and the like, these compounds may be mordanted with a cationic polymer or the like.
  • the dyes useful for this purpose are those disclosed in "Absorbing and Filterdyes” in Research Disclosure, vol. 176, pp. 23-26.
  • the photographic emulsion layer in the photo­graphic light-sensitive material of the invention may contain, for example, any of the following compounds: polyalkylene oxide or ether derivative, ester derivative or amine deriva­tive thereof; thioether compound, thiomorpholine, quaternary ammonium chloride, urethane derivative, urea derivative, imidazole derivative, 3-pyrazolidone and the like.
  • Gelatin is advantageous as a binder or protective colloid which may be used in the emulsion layer and intermediate layer of the light-sensitive material of the invention.
  • another hydrophilic colloid may be independently, or together with gelatin, used.
  • the photographic light-sensitive material of the inven­tion may, in the photographic emulsion layer and other hydro­philic colloid layers, contain an inorganic or organic hard­ener.
  • the photographic light-sensitive material of the inven­ tion may, in the photographic emulsion layer and other hydro­philic colloid layers, contain a water-soluble or slightly-­soluble synthetic polymer dispersion.
  • the protective layer is made of a hydrophilic colloid, thereby the useful hydrophilic colloid is selected from the previously mentioned examples.
  • the protective layer may comprise either a single layer or a plurality of layers.
  • a matting agent and/or lubricant may be added to the emulsion layer or protective layer of the silver halide photographic light-sensitive material of the invention.
  • One example of silver halide photographic light-sensitive material embodying the invention contains a matting agent, and the mattness is 40 to 150 mmHg.
  • the term "mattness” means a value expressed in mmHg which is determined under a specific condition by measuring a suction force on an unprocessed light-­sensitive material (the so-called raw film) which has been treated to provide a constant humidity for three hours under 23°C and 48%Rh. The larger the value is, the greater the degree of mattness.
  • the Smoostar manufactured by Toei Denshi Kogyo Co., Ltd. was used.
  • a matting agent should be contained preferably in the outermost layer of light-sensitive material or a layer functioning as the outermost layer, or a layer in the vicinity of outermost layer, and in a layer func­tioning as a protective layer.
  • the preferred amount of added matting agent is 10 to 500 mg/m2, in particular, 20 to 300 mg/m2, or more specifically, 20 to 200 mg/m2 per one side of the light-sensitive material.
  • an identical type of, or different types of matting agent may be added to more than two layers.
  • a layer to contain the matting agent may be arbitrarily selected from the emulsion layer and protective layer, as well as the subbing layer and intermediate layer which are provided according to a specific requirement.
  • the size distribution of particles of matting agent used in the invention may be either small or large, however, the use of monodisperse matting agent is advantageous.
  • the "mono­disperse matting agent” means a matting agent in which the quantity of particles whose diameters being within a range of ⁇ 20% of average particle size accounts for 90% of the whole particles.
  • the type of matting agent is arbitrarily selected, for example, from the known agents.
  • the useful matting agent comprises water-insoluble organic or inorganic fine particles with an arbitrarily particle size.
  • the agent with a particle size of 1 ⁇ m to 10 ⁇ m is used.
  • organic compound examples include as follows: water-dispersion vinyl polymers such as polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylo­nitrile- ⁇ -methylstyrene copolymer, polyvinyl acetate, poly­ethylene carbonate and polytetrafluoroethylene; cellulose derivatives such as methyl cellulose, ethyl cellulose, cellulose acetate and cellulose acetate propionate; starch derivatives such as carboxy starch, carboxy nitrophenyl starch and urea-formadehyde-starch reaction product; gelatin hardened with a known hardener; hardened gelatin which are formed into hollow micro-capsules by hardening with coacervation; and others.
  • water-dispersion vinyl polymers such as polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylo­nitrile- ⁇ -methylstyrene copolymer, polyvinyl acetate, poly­ethylene carbon
  • organic compound examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate and calcium carbonate; silver chloride and silver bromide both being desensitized with a known method; glass, diatomaceous earth and others. Any of the above matting agents may be used as mixed with a different type of material according to a specific requirement.
  • the photographic light-sensitive material of the inven­tion may contain various additives in compliance with a requirement.
  • a dye, development accelerator, fluorescent whitening agent, color-fog restrainer, ultraviolet absorbent and the like More specifically, those useful for this purpose are disclosed in Research Disclosure, vol. 176, pp. 22-31 (RD-17643, 1978).
  • the silver halide photographic light-sensitive material of the invention may; be provided with an anti-halation layer, intermediate layer, filter layer and others.
  • the layers including the photographic emulsion layer are formed by coating on a single side or both sides of a flexible support which is usually employed in a photographic light-sensitive material.
  • the support may be colored with a dye or pigment. To shield light, the support may be provided with dark shade.
  • the surface of a support is usually subbed to ensure better adherence to a photographic emulsion layer and the like.
  • the surface of a support may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like before or after the subbing treatment. More specific­ally, the treatments to be used are disclosed in "Supports" in Research Disclosure, vol. 176, p. 25.
  • the hydrophilic colloid layers including the photo­graphic emulsion layer are formed by coating methods on the support or another layer.
  • the useful coating methods include the dip coating method, roller coating method, curtain coating method, extrusion coating method and others. More specific strictlyally, the applicable methods are disclosed in "Coating Procedures" in Research Disclosure, vol. 176, pp. 27-28.
  • Fig. 1 illustrates one example of coating apparatus suitable for coating process for the silver halide light-­sensitive material of the invention, wherein a coater and an air blower substantially opposing to each other are disposed across a continuously fed support, thereby the position of support is maintained by means of air blowing from the air blower onto the support while the coater is applying a coating solution.
  • Fig. 1 is a longitudinal cross section of a coating apparatus, wherein a two-layer coating method by a slide hop­per is exercised to continuously apply coating solutions for photographic structural layers onto both sides of a support.
  • Fig. 2 is a longitudinal cross section illustrating one ex­ample of air blower associated with the coating apparatus.
  • the support 2 is passed through a cool air zone 8.
  • the cool air is blown onto the coated surface 4 via a slit plate or a group of small holes 7.
  • the other surface of support 2 not coated should be contacted with an array of rollers 6 which are disposed within a central box 5 and in which the rollers are arranged at 2 to 3 mm intervals, and that the suction force is exerted from behind the array of rollers 6 so as to enlarge the contact area between the array of rollers 6 and the support 2.
  • an air blower 3 ⁇ one side the support 2 already provided with a gel layer on the other side is form­ed a layer 11 by means of a coater 1 ⁇ which is disposed as opposed to the air blower 3 ⁇ across the support 2.
  • the air blower 3 ⁇ may be variously configured. However, a roller-­configured blower, which appears to be used most widely be­cause it will allow easy manufacturing procedure, is described below.
  • the air blower 3 ⁇ having a hollow roller constitution has, in its outer shell serving as the non-contact supporting portion, a plurality of through holes 10 to eject air.
  • the air supplied into the interior of the roller is blown from the external circumferential surface of the roller 9 onto the gel layer 4 via the through holes 10, in order to exert lifting force onto the support 2 on the non-contact basis.
  • the fluctuation in thickness of formed emulsion layer whether it is wet or dry should be less than ⁇ 1%. Accordingly, it is necessary that the gap or distance of between the tip of coater 1 ⁇ and the surface on the support 2 to be coated with an emulsion should be maintained as constant as possible.
  • the allowable fluctuation in the gap is preferably within several, or, 10 ⁇ at the maximum.
  • an air blower 3 ⁇ comprises a hollow roller having through holes 10
  • the means to control the fluctuation in distance of floatation it is possible to set not only a speci­fic value for the ratio between the supporting static pressure (back pressure) and source pressure at a specific value bet­ween 1/10 and 1/1000 but the distance of floatation at the area in contact with a coating solution at a specific value between 20 ⁇ m and 500 ⁇ m, by deliberately designating the dia­meter d (Fig. 2) and length l (Fig.
  • the correlation between the support and the amount of blown air should be preferably regulated to satisfy W2 ⁇ Q ⁇ 5 ⁇ 105, where W is the width of support (cm), Q is the amount of blown air per unit area (Nml/min ⁇ cm2)
  • the silver halide photographic light-sensitive material of the invention is typically used as an X-ray light-sensitive material, lith light-sensitive material, monochromatic film, color negative light-sensitive material color reversal light-­sensitive material or color printing paper, or for the colloid transfer process, silver salt diffusion transfer process, dye transfer process, silver dye bleaching process, or as a print-­out sensitive material, light-sensitive material for thermal developing, or the like.
  • An ordinary exposure method may be used to obtain a photographic image with the light-sensitive material of the invention.
  • the light-sensitive material of the invention may be photographically processed with any of the methods and various processing solutions disclosed, for example, in Research Disclosure, Vol. 176, pp. 25-30, (RD-17,643).
  • the photo­graphic process may be a photographic process to form either a silver image (monochromatic photographic process) or a dye image (color photographic process), in accordance with a specific requirement.
  • the processing temperature is usually selected from a range of 18°C to 50°C. However, the tempera­ture may be lower than 18°C or higher than 50°C.
  • the photographic emulsion layer of the photographic light-­sensitive material of the invention may contain a dye forming coupler which is a compound being capable of forming a dye, in the course of color developing, by oxidization-coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative, aminophenol derivative and the like).
  • a dye forming coupler which is a compound being capable of forming a dye, in the course of color developing, by oxidization-coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative, aminophenol derivative and the like).
  • the similar emulsion layer may contain a non-color DIR coupling compound, which releases development restrainer, whose coupling-reaction product has no color.
  • the silver halide photographic light-sensitive material of the invention may contain, as an anti-fogging agent, a hydroquinone derivative, aminophenol derivative, gallic acid derivative, ascorbic acid derivative or the like.
  • the silver halide photographic light-sensitive material of the invention may contain in the hydrophilic colloid layer an ultraviolet absorbent.
  • an anti-fading agent may be also used.
  • silver iodo-bromide emulsion E - 1 containing 2.0 mol% silver iodide was prepared by the full-ammonia normal precipitation method.
  • the average particle size of the silver iodide in the emulsion was 1.10 ⁇ m.
  • Chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added to the silver iodo-bromide emulsion E - 1 in order to perform the optimized gold/sulfur sensitization, then the emulsion was stabilized with 4-hydroxy-6-methyl-1,3,3a-7-tetrazaindene.
  • the two layers were simultaneously formed on one face (front side) of a support made of polyester film having a subbing layer; one layer is a protective layer which containing a hardener, and the other is the silver halide emulsion layer disposed between the protective layer on the support. Then, the layers were allowed to set the gel, and dried, then wound up with a tension of 10.5 kg/36 cm.
  • the other face of support (rear face) was coated in compliance with the conditions identical to those of the front face, then the two-layer coat was allowed to gelate and dried. Thus, samples No. 1 through No. 30 were prepared.
  • melting time means the duration where a sample of silver halide photographic light-­sensitive material cut into 1 cm by 2 cm chip is immersed into 1.5 aqueous sodium hydroxide solution having a constant tempe­rature of 50°C and the emulsion layer eventually starts to melt.
  • the number of coating defects for example, coating streak, coating mottle and the like
  • evaluation was made using five grades, that is, 1 (poor) through 5 (excellent).
  • the grades 3 through 5 satisfy the criteria for practical use, while the grades 1 and 2 fail to satisfy the similar criteria.
  • the sensitivity was measured in the follow­ing manner; a sample was sandwiched between two optical wedges which are aligned with each other so that the density gradi­ents constitute the symmetry relative to plane, thereby both faces were simultaneously exposed for 1/12.5 seconds with a light source having a color temperature of 5400° K.
  • the photographic process comprised the following steps and employed a roller transporting type, automatic developing machine.
  • the total processing time was 45 seconds.
  • the developer used was XD-90, and the fixer used was XF, both manufactured by Konishiroku Photo Industry Co., Ltd.
  • Tables 1-1, 1-2 and 2 demonstrate that one preferred example embodying the invention excels in coating properties (especially, the similar properties with the rear face), sensitivity and dying properties, and, therefore, that the super-rapid processing is feasible.
  • the invention provides the processing capacity twice that of a conventional system, with the processing time reduced to the half, while maintaining the sensitivity of the convention­al system.
  • the emulsion containing the crystals serving as seeds was added to a solution having a temperature constantly kept at 40°C and comprising protective gelatin, as well as ammonia which was added according to a requirement, thereby homogeniz­ed, then the pH was adjusted with glacial acetic acid.
  • aqueous ammoniac silver ion solution as well as aqueous halide solution were added, with the controlled flow rate, by means of the double jet precipitation method, in order to sequentially form a plurality of layers, each having a speci­fic silver iodide content, onto individual core particles.
  • the pAg was adjusted to 7.3, and the pH to 9.7.
  • a layer having 0 mol% of silver iodide was formed by controll­ingly keeping the level of pAg at 9.0 or more than 9.0, as shown in Fig. 3. More specifically, as Fig.
  • the emulsion prepared was monodisperse silver iodo-bromide emulsion in which the average size of silver halide particles was 0.85 ⁇ m, and the ratio of silver iodide to the total amount of silver halide was 2 mol%.
  • the obtained emulsion E - 2 was subjected to the optimum sensitization with gold and sulfur in a manner identical to that of Example - 1, then stabilized with 4-hydroxy-6-methyl-1, 3,3a-7-tetrazaindene.
  • the following sensitizing dye (I) was added to the emulsion at a ratio of 200 mg per mol silver halide.
  • a protective layer containing a hardner and the emulsion layer were formed by coating in a manner identical to that of Example - 1, to prepared the samples No. 61 through 120.
  • the front and rear faces were unsuccessively coated and dried; while both faces of the samples No. 91 through No. 120 were successively coated and simultaneously dried.
  • emulsions E - 3 through E - 7 respectively having multi-layered silver halide particles is hereinunder described.
  • the rate of addition was increased.
  • the emulsion obtained was a monodisperse emulsion contain­ing octahedral particles with an average size of 1.05 ⁇ m.
  • the emulsion obtained was a monodisperse emulsion containing octahedral particles with an average size of 1.10 ⁇ m.
  • the emulsion was designated E - 3.
  • octa­hedral silver iodo-bromide emulsions containing silver iodide respectively at the rate of 5 mol%, 10 mol%, 20 mol% and 30 mol% were prepared by varying the ratio between potassium iodide and potassium bromide, by varying the core diameters in order to make constant the average content of silver iodide after the shell was formed onto individual cores, and by con­trolling the addition rate in the early phase of mixing in order to make identical the sizes of resultant particles.
  • Example - 1 These samples were subjected to the 45 seconds process identical to that of Example - 1, to determine sensitivities. Additionally, the scratch-induced fogging was evaluated in the following manner. More specifically, each sample was subject­ed to moisture control with a temperature of 23°C and humidity of 55% RH for four hours, then scratched using a 0.3 mm radius sapphire stylus with a continuously varied load, and developed, thereby a minimum load (in gram) being capable of inducing the fogging was determined. The smaller the value of load is, the more the sample is prone to the scratch-induced fogging.
  • Table 4 lists the results. As can be understood from Table 4, when compared to particles in which the difference in iodide contents between the core and shell is less than 10 mol%, the particles in which the similar difference is more than 10 mol% are more resistant to the scratch-induced fogging with a smaller amount of gelatin, and provide excellent sensitivity.
  • the second coating layer was formed onto individual particles, in a manner identical to that of E - 3, except that the pAg was 9.0.
  • the monodisperse core/shell emulsions containing cubic silver iodo-bromide particles with an average size of 0.80 ⁇ m were prepared. These emulsions were designated E - 8, E - 9, E - ­10 and E - 11. The average silver iodide content of each emulsion was 3 mol%.
  • Example 2 These emulsion were chemically sensitized in a manner identical to that of Example 1, then to the emulsions was added the sensitizing dye (I) which was used in Example 2, or the following sensitizing dye (II), or the following sensitiz­ing dye (III) serving as a comparison dye, thereby each emul­sion was simultaneously applied to both faces of a support in a manner identical to that of Example 1.
  • the samples No. 131 through No. 146 were prepared.
  • a sample using the particles in which layers the difference in iodide contents between the core and shell is more than 10 mol% is more resistant, espe­cially when the amount of gelatin is smaller, to the scratch­induced fogging and provides excellent sensitivity, even if the sample is a system having a sensitizing dye.
  • the monodisperse emulsion of cubic particles of silver iodo-bromide containing particles of 2.0 mol% of silver iodo-­bromide with an average size of 0.20 ⁇ m was prepared by the double jet precipitation method.
  • core particles were grown up in the following manner.
  • the first coating layer was formed onto individual particles; this layer contain­ed 30 mol% of silver iodide.
  • the second coating layer of pure silver bromide was form­ed onto individual particles in the emulsion, by adding ammoniac silver nitrate solution and potassium bromide solu­ tion with the double jet precipitation method.
  • the mono­disperse emulsion containing cubic silver iodo-bromide parti­cles with an average size of 0.57 ⁇ m was prepared, and design­ated E - 12.
  • the average silver iodide content was 2.5 mol%.
  • the sensitizing dye (I) whose structure is described later was added to the emulsion E - 12 at a rate of 520 mg/­molAg.
  • To the emulsion was further added gold thiocyanate and sodium thiosulfate for the optimum gold/sulfur sensitization, then 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added for stabilization, thereby the gelatin content was adjusted as listed in Table 6.
  • the coating solutions for emulsion layer were prepared.
  • a monodisperse matting agent with an average particle size of 4 ⁇ m was used to attain mattness specified in Table 6 (for this purpose, polymethyl methacry­late PMMA was used), thereby the gelatin content was adjusted as specified in Table 6, then a compound described later and serving as a hardener was added.
  • the coating solution for a protective layer was prepared.
  • the developer used was XD-90, and the fixer used was XF, both manufactured by Konishiroku Photo. Industry Co. LTD.
  • the drying properties were evaluated in the following manner. After being subjected to the above 45 seconds automatic developing, and drying a sample was examined for handling touch, degree of sticking with another sample, and other items, thereby the performance was expressed using five grades, that is, 1 (poor) through 5 (excellent). The grades 3 through 5 satisfy the criteria for practical use, while the grades 1 and 2 fail to satisfy the similar criteria. Additionally, to determine the sensitivity with the conventional 90 seconds treatment, some of the samples were subjected to the process with the above-mentioned 45 seconds automatic developing machine whose line speed being reduced to 1/2 of the original.
  • each sample was evaluated in the following manner. Three sheets of a specific sample, respec­tively cut into 15 cm by 15 cm size, were first controllingly moistened under the conditions of 23°C and 55% RH for siz hours. After being sandwiched with sheets of paper or card­board and vacuum-sealed under specified conditions, each set of sample sheets was allowed to stand for three days at a temperature of 55°C. Then, with each sample sheet, the degree of sticking was evaluated using the intensity, area and the like of sticking as criteria, and the performance was repre­sented by the five grades, that is, 1 (poor) through 5 (excellent). The grades 3 through 5 satisfy the criteria for practical use, while the grades 1 and 2 fail to satisfy the similar criteria.
  • the matt pressure fogging was evaluated in the following manner.
  • the sample developed without being subjected to exposure was evaluated with human vision, thereby the degree, intensity and number of fogs occurring around matting particles were represented by five grades, that is, 1 (poor) through 5 (excellent).
  • the grades 3 through 5 satisfy the criteria for practical use, while the grades 1 and 2 fail to satisfy the similar criteria.
  • a sample of the invention is highly sensitive (100 to 160), and excels in terms of the drying property, scratch-induced fogging, sticking, matt-­pressure fogging and the like (grades range from 3 to 5), and, apparently, suitable for the super-rapid processing. Further additionally, it is apparent that, when compared to the samples treat­ed with the conventional 90 seconds process, a sample accord­ing to the invention permits a processing time, which is the half of the conventional processing time, and enables the processing capacity twice as large, though having sensitivity comparable to or better than a conventional system or sample.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP87309756A 1986-11-04 1987-11-04 Matériau photographique à l'halogénure d'argent sensible à la lumière capable d'un traitement ultrarapide Expired - Lifetime EP0267019B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP262295/86 1986-11-04
JP26229586 1986-11-04
JP298499/86 1986-12-15
JP61298499A JP2613378B2 (ja) 1986-12-15 1986-12-15 超迅速処理可能なハロゲン化銀写真感光材料

Publications (3)

Publication Number Publication Date
EP0267019A2 true EP0267019A2 (fr) 1988-05-11
EP0267019A3 EP0267019A3 (en) 1989-07-19
EP0267019B1 EP0267019B1 (fr) 1995-04-19

Family

ID=26545489

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87309756A Expired - Lifetime EP0267019B1 (fr) 1986-11-04 1987-11-04 Matériau photographique à l'halogénure d'argent sensible à la lumière capable d'un traitement ultrarapide

Country Status (3)

Country Link
US (1) USH674H (fr)
EP (1) EP0267019B1 (fr)
DE (1) DE3751257T2 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0366418A2 (fr) * 1988-10-25 1990-05-02 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière pour traitement ultra-rapide
US4946769A (en) * 1987-11-16 1990-08-07 Konica Corporation Silver halide photographic light-sensitive material and the method of preparing the same
EP0450977A2 (fr) * 1990-04-05 1991-10-09 Konica Corporation Procédé de production de matériaux photographiques à l'halogénure d'argent
US5230994A (en) * 1990-09-20 1993-07-27 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0566374A2 (fr) * 1992-04-15 1993-10-20 Konica Corporation Matériau photographique sensible à la lumière à base d'halogénure d'argent et procédé pour l'obtention d'une image
EP0620484A1 (fr) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Films radiographiques industriels à l'halogénure d'argent
EP0620483A1 (fr) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Traitement de films radiographiques industriels à l'halogénure d'argent
EP0620482A1 (fr) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Méthode de traitements de films radiographiques à l'halogénure d'argent pré-durcis
EP0670517A2 (fr) * 1994-02-28 1995-09-06 Konica Corporation Méthode de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière
EP0706081A1 (fr) * 1994-10-05 1996-04-10 Kodak-Pathe Procédé de revêtement photographique
EP0747760A1 (fr) * 1995-05-22 1996-12-11 Eastman Kodak Company Eléments radiographiques peu sensibles aux expositions parasites à travers le support et capables d'être traité rapidement

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5153112A (en) * 1988-09-05 1992-10-06 Konica Corporation Method of processing silver halide photographic materials
USH1263H (en) 1989-02-07 1993-12-07 Konica Corporation Image forming method and apparatus
DE4435876A1 (de) * 1994-10-07 1996-04-11 Du Pont Deutschland Schnellverarbeitbares photographisches Aufzeichnungsmaterial für die medizinische Radiographie

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2114309A (en) * 1982-01-12 1983-08-17 Konishiroku Photo Ind Silver halide photographic material for radiography
EP0093177A1 (fr) * 1981-11-04 1983-11-09 Konica Corporation Procede et dispositif de revetement des deux cotes d'un substrat
EP0111338A2 (fr) * 1982-12-14 1984-06-20 E.I. Du Pont De Nemours And Company Procédé pour l'étendage avec emploi d'agents tensio-actifs
EP0118793A2 (fr) * 1983-02-15 1984-09-19 Konica Corporation Matériel photographique aux halogénures d'argent
JPS61116349A (ja) * 1984-11-11 1986-06-03 Konishiroku Photo Ind Co Ltd Ｘ線用写真感光材料

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3545971A (en) 1966-06-28 1970-12-08 Eastman Kodak Co Rapid processing of photographic x-ray film
US4030924A (en) 1967-10-11 1977-06-21 Agfa-Gevaert N.V. Method of producing photographic images
GB1293189A (en) 1970-06-04 1972-10-18 Agfa Gevaert Photographic silver halide element
JPS505048B2 (fr) 1971-10-08 1975-02-27
JPS5836893B2 (ja) 1978-06-07 1983-08-12 富士写真フイルム株式会社 写真感光材料
CA1132397A (fr) 1979-02-28 1982-09-28 Hendrik E. Kokelenberg Nouveaux surfactifs contenant du fluor; leur emploi dans des compositions de revetement colloidal hydrophile, et dans des produits a base d'halogenure d'argent sensibles a la lumiere
JPS6047576B2 (ja) 1980-05-07 1985-10-22 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPS5834822B2 (ja) 1980-12-19 1983-07-29 コニカ株式会社 ハロゲン化銀写真感光材料
JPS6142653A (ja) 1984-08-07 1986-03-01 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPS6180237A (ja) 1984-09-28 1986-04-23 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光乳剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0093177A1 (fr) * 1981-11-04 1983-11-09 Konica Corporation Procede et dispositif de revetement des deux cotes d'un substrat
GB2114309A (en) * 1982-01-12 1983-08-17 Konishiroku Photo Ind Silver halide photographic material for radiography
EP0111338A2 (fr) * 1982-12-14 1984-06-20 E.I. Du Pont De Nemours And Company Procédé pour l'étendage avec emploi d'agents tensio-actifs
EP0118793A2 (fr) * 1983-02-15 1984-09-19 Konica Corporation Matériel photographique aux halogénures d'argent
JPS61116349A (ja) * 1984-11-11 1986-06-03 Konishiroku Photo Ind Co Ltd Ｘ線用写真感光材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 10, no. 300 (P-506)[2356], 14th october 1986; & JP-A-61 116 349 (KONISHIROKU PHOTO IND. CO. LTD) 03-06-1986 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4946769A (en) * 1987-11-16 1990-08-07 Konica Corporation Silver halide photographic light-sensitive material and the method of preparing the same
EP0366418A2 (fr) * 1988-10-25 1990-05-02 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière pour traitement ultra-rapide
EP0366418A3 (fr) * 1988-10-25 1992-05-13 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière pour traitement ultra-rapide
EP0450977A2 (fr) * 1990-04-05 1991-10-09 Konica Corporation Procédé de production de matériaux photographiques à l'halogénure d'argent
EP0450977A3 (en) * 1990-04-05 1992-02-26 Konica Corporation Process for producing silver halide photographic materials
US5230994A (en) * 1990-09-20 1993-07-27 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0566374A2 (fr) * 1992-04-15 1993-10-20 Konica Corporation Matériau photographique sensible à la lumière à base d'halogénure d'argent et procédé pour l'obtention d'une image
EP0566374A3 (fr) * 1992-04-15 1994-10-26 Konishiroku Photo Ind Matériau photographique sensible à la lumière à base d'halogénure d'argent et procédé pour l'obtention d'une image.
EP0620483A1 (fr) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Traitement de films radiographiques industriels à l'halogénure d'argent
EP0620482A1 (fr) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Méthode de traitements de films radiographiques à l'halogénure d'argent pré-durcis
EP0620484A1 (fr) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Films radiographiques industriels à l'halogénure d'argent
EP0670517A2 (fr) * 1994-02-28 1995-09-06 Konica Corporation Méthode de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière
EP0670517A3 (fr) * 1994-02-28 1995-11-02 Konishiroku Photo Ind Méthode de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière.
US5516627A (en) * 1994-02-28 1996-05-14 Konica Corporation Method of processing silver halide light-sensitive photographic material
EP0706081A1 (fr) * 1994-10-05 1996-04-10 Kodak-Pathe Procédé de revêtement photographique
FR2725536A1 (fr) * 1994-10-05 1996-04-12 Kodak Pathe Procede d'enduction photographique
US5773204A (en) * 1994-10-05 1998-06-30 Eastman Kodak Company Photographic coating process
EP0747760A1 (fr) * 1995-05-22 1996-12-11 Eastman Kodak Company Eléments radiographiques peu sensibles aux expositions parasites à travers le support et capables d'être traité rapidement

Also Published As

Publication number Publication date
EP0267019B1 (fr) 1995-04-19
USH674H (en) 1989-09-05
DE3751257T2 (de) 1995-11-16
EP0267019A3 (en) 1989-07-19
DE3751257D1 (de) 1995-05-24

Similar Documents

Publication Publication Date Title
EP0178097B1 (fr) Emulsion photographique à l'halogénure d'argent sensible à la lumière
EP0267019A2 (fr) Matériau photographique à l'halogénure d'argent sensible à la lumière capable d'un traitement ultrarapide
JP2004309806A (ja) ハロゲン化銀写真感光材料
JPS60147727A (ja) ハロゲン化銀写真乳剤
EP0430186B1 (fr) Matériaux photographiques à l'halogénure d'argent sensibles à la lumière
EP0317247B1 (fr) Matériau photographique à l'halogénure d'argent sensible à la lumière et procédé pour sa préparation
EP0577138B1 (fr) Matériau photographique à l'halogénure d'argent
JP2613378B2 (ja) 超迅速処理可能なハロゲン化銀写真感光材料
US4912029A (en) Silver halide photographic materials
JPH0433019B2 (fr)
EP0239363B1 (fr) Matériau photographique à l'halogénure d'argent sensible à la lumière utilisable pour un traitement rapide
EP0307867A2 (fr) Matériau photographique à l'halogénure d'argent sensible à la lumière ayant une finesse supérieure et utilisable pour un traitement ultra-rapide
EP0534209B1 (fr) Matériau photographique à l'halogénure d'argent sensible à la lumière
JPH01166031A (ja) ハロゲン化銀写真材料
EP0547912A1 (fr) Emulsion photographique à l'halogénure d'argent et matériau photographique couleur à l'halogénure d'argent sensible à la lumière
JPH03210553A (ja) ハロゲン化銀写真感光材料
EP0589458B1 (fr) Matériau photographique à l'halogénure d'argent
JPS62286033A (ja) 保存安定性のよいハロゲン化銀写真感光材料
EP0670517B1 (fr) Méthode de traitement d'un matériau photographique à l'halogénure d'argent sensible à la lumière
USH874H (en) Process for manufacturing a silver halide photographic material having a support and at least one hydrophilic colloid layer
JPS62286037A (ja) 超迅速処理性に優れたハロゲン化銀写真感光材料
JPS62131247A (ja) ハロゲン化銀写真感光材料
JPS63173040A (ja) 超迅速処理可能なハロゲン化銀写真感光材料
DE69127138T2 (de) Photographisches Silberhalogenidmaterial
JPS63239443A (ja) 超迅速処理可能なハロゲン化銀写真感光材料

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19891215

17Q First examination report despatched

Effective date: 19910903

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19950419

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19950419

Ref country code: FR

Effective date: 19950419

REF Corresponds to:

Ref document number: 3751257

Country of ref document: DE

Date of ref document: 19950524

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20001101

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011104

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20011104

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20061102

Year of fee payment: 20