US3865596A - Direct-positive reduction and gold fogged ammoniac silver halide emulsion - Google Patents

Direct-positive reduction and gold fogged ammoniac silver halide emulsion Download PDF

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US3865596A
US3865596A US368868A US36886873A US3865596A US 3865596 A US3865596 A US 3865596A US 368868 A US368868 A US 368868A US 36886873 A US36886873 A US 36886873A US 3865596 A US3865596 A US 3865596A
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silver halide
emulsion
photosensitive material
direct positive
amount
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Tetsuo Furuya
Yoshio Ibe
Hideo Kanisawa
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485—Direct positive emulsions
    • G03C1/48515—Direct positive emulsions prefogged
    • G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/141—Direct positive material

Definitions

  • a solarization type photosensitive material is known to have a relatively high sensitivity.
  • a silver halide photosensitive material to which a suitable fog has been imparted in advance is employed and a direct positive image is obtained by utilizing the phenomenon of solarization.
  • an ammoniac silver bromoiodide emulsion is suitable as the silver halide emulsion of such direct positive photosensitive material of the solarization type.
  • the fatal defect of this ammoniac silver bromoiodide emulsion is that only a low maximum concentration and only a high minimum concentration are obtained.
  • Various investigations have heretofore been made with a view to improving this defect.
  • a soluble salt of a group VIII metal such as a soluble rhodium salt or a soluble iridium salt.
  • the direct positive photosensitive amterial according to this proposal is defective in that the contrast is low and a sufficient brightness is not obtained in the high-light portion.
  • This invention relates to a direct positive silver halide photosensitive material comprising an ammoniac silver halide emulsion and incorporated therein, (a) at least one compound selected from soluble rhodium salts and soluble iridium salts, (b) a reducing agent, a gold compound, (d) at least 105 mole percent, based on the gold compound, of at least one compound selected from thiosulfates, thiocyanates and prussic acid salts, and (e) and optically sensitizing agent.
  • silver halide emulsions are prepared by the neutral method, the acid method and the ammonia method.
  • the neutral method of acid method has inevitably some defects. For instance, a spectral sensitization by an optically sensitizing dye is insufficient, or a sufficient sensitivity or high brightness in the low concentration portion is not obtained.
  • an ammoniac silver halide emulsion to be used in this invention is one prepared by a customary ammonia method.
  • an ammoniac silver halide emulsion is generally prepared by mixing an aqueous solution of a water-soluble silver salt such as silver nitrate with an aqueous solution of a watersoluble halogen salt such as ammonium bromide and potassium iodide in gelatin or a hydrophilic organic colloid, or with a halogen-saltcontaining, hydrophilic organic colloidal solution. The preparation is conducted in the presence of ammonia, and this ammonia may be in the state incorporated in the silver salt solution or the halogen salt solution.
  • Ammonia may also be in the state incorporated in the hydrophilic colloidal solution, or it may be added separately in the form of an independent solution.
  • the silver salt solution and the halogen salt solution they may beadded simultaneously or separately. Alternately, these solutions are divided into portions, and these divided portions are added in succession. It is also possible to adopt a method in which silver chloride or silver chloride or silver bromide is formed in advance and it is then converted to silver bromide or silver iodide.
  • the foregoing mixing and physical ripening operation is generally carried out at a temperature ranging form 20 to C., preferably from 30 to 50C.
  • the p of the reaction mixture is adjusted above 9, preferably above 11.
  • Ammonia is used in an amount to re-dissolve silver oxide formed when ammonia is added to a water-soluble silver salt solution. This amount is within a range of from 50 to 200 percent, preferably from to percent, based on the silver oxide.
  • a preferable silver halide is silver bromoiodide containing 0.5 to 5 mole percent of silver iodide. It is desired that the average particle diameter of the silver halide is less than 2a, and especially good results are obtained when the average particle diameter of the silver halide is less than 0.6a.
  • the ripening is generally conducted in the presence of excessive silver nitrate or at such a high temperature as ranging from 60 to 80C., or a method of conducting the physical ripening while making present silver chloride having a high solublility is usually adopted.
  • the soluble rhodium salt or iridium salt to be used in this invention exhibits effects of preventing desensitization owing to kinking and giving a good direct positive image even by high-illuminance, short-time exposure.
  • Preferred examples of the soluble rhodium salt include rhodium halides and hexahalogenorhodates.
  • Preferred examples of the iridium salt include iridium trihalides, iridium tetrahalides, hexahalogenoiridic (III) acids, their sa1ts,'and hexahalogenoiridic (IV) acids and their salts.
  • these soluble salts are added to an emulsion at the step of mixing a silver halide (forming an emulsion) or at the step of the physical ripening, and they are added in amounts of 0.001 to 10.0 millimoles per mole of the silver halide.
  • a suitable fog is imparted to the silver halide emulsion to be used in this invention.
  • the fogging is accomplished by incorporating in the silver halide emulsion a reducing agent and a gold compound and making copresent at least one compound selected from thiocyanates, thiosulfates and prussic acid salts. It is also possible to obtain a good fog when the fogging is effected 3 by a reducing agent and a gold compound in advance and then at least one compound selected from thiosulfates, thiocyanates and prussic acid salts is incorporated in the fogged emulsion.
  • Reaction conditions for fogging the silver halide may be varied within'a broad range.
  • the P is generally adjusted within a range of 5.5 to 9, preferably 6 to 7.
  • the PAg is generally within a range of 6.5 to 8.5
  • the temperature is generally adjusted to 40 to 100C., preferably 50 to 75C.
  • the hydrophilic protective colloid for suspending the silver halide particles during the fogging treatment such as gelatin, is used preferably in an amount of 30 to 200g per mole of the silver halide.
  • the reducing agent there are conventiently used aldehyde compounds such as formalin, organic amines such as hydrazine, triethylene tetramine, thiourea dioxide and imino-amino-methane-sulfonic acid,and other organic reducing agents.
  • organic amines such as hydrazine, triethylene tetramine, thiourea dioxide and imino-amino-methane-sulfonic acid,and other organic reducing agents.
  • inorganic reducing agents such as stannous chloride and such reducing agents as amine borane are also conveniently used.
  • concentration of the reducing agent used is changed depending on the silverhalide particle size, the kind of the silver halide, the intended use and other factors, and it differs also depending on eht kind of the reducing per se. In general, however, the reducing agent is used in an amount of 0.001 to l millimoles per mole of the silver halide.
  • gold compound to be used in this invention there maybe mentioned soluble salts of monovalent or trivalent gold, such as chloroauric acd, gold thiocyanate, sodium chloroaurate, potassium aurate, potassium chloroaurate, potassium gold cyanide, potassium bromaurate, potassium iodoaurate, potassium gold thiocyanide, sodium gold thiomaleate, gold thioglucose and the like.
  • soluble salts of monovalent or trivalent gold such as chloroauric acd, gold thiocyanate, sodium chloroaurate, potassium aurate, potassium chloroaurate, potassium gold cyanide, potassium bromaurate, potassium iodoaurate, potassium gold thiocyanide, sodium gold thiomaleate, gold thioglucose and the like.
  • the amount used of the gold compound is changed depending on the size of the silver halide particles, the composition of the silver hlide and the intended use, but it is generally used in an amount of 0.0001 to 0.1 millimoles, preferably 0.005 to 0.5 milliomoes, per mole of the silver halide. Good results are obtained when the gold compound is used at such a low concentration.
  • thiosulfate, thiosulfate, thiocyanate and prussic acid salt there are preferably used sodium thiosulfate, potassium thiocyanate, ammonium thiocyanate, potassium cyanide, sodium cyanide, and complex salts thereof.
  • Such compound is generally used in an amount of 0.0003 to 100.0 millimoles, pref erably 0.01 tolO millimoles per mole of the sliver halide.
  • the ratio of the gold compound and reducing agent used for imparting fog to the silver halide emulsion varies depending on various factors, but optimum results are generally obtained when said ratio is within a range of l 3 to l 200 (on the weight basis).
  • the optically sensitizing dye to be used in this invention is selected from optically sensitizing dyes customarily used for ordinary negative type silver halide emulsions. For instance, cyanines, merocyanines, pseudocyanines, hemicyanines and the like are generally used. Although it has been known in the art to employ these optically sensitizing dyes for direct positive photographic emulsions, they are generally defective in that they cause excessive softening. Accordingly, the specification of British Pat. No. 970,601 proposes indocyanines as optically sensitizing dyes free of-softening, and Japanese Patent Publication No. 1 1623/7] teaches that sufficient results cannot be obtained by use of such indocyanine alone, and it proposes a method using, in combination with such indocyanine, a bis-thiazolyl or selenazolyl compound.
  • Dyes to be used especially preferably in this invention are cyanine dyes expressed by the following general formula (I) wherein Z and Z stand for an atomic group necessary for formation of a heterocyclic ring, m is l or 2 with the proviso that when m is 1, Z, is a 2-quinoline ring, R and R stand for an alkyl group, R designates a hydrogen atom or an alkyl group, X is an anionic group, and n is l or 2, and merocyanine dyes expressed by the following general formula (ll) Wherein Z stands for a non-metallic atomic group necessary for formation of a heterocyclic ring, R R and R stands for an alkyl, alkenyl or aryl group, R designates a hydrogen atom or an alkyl or aryl group, I and dare I or2,andpis 1,2or3.
  • Z stands for a non-metallic atomic group necessary for formation of a heterocyclic ring
  • R R and R stands for an alkyl
  • the heterocyclic ring is preferably a 85- or 6 -membered ring.
  • thiazole type nuclei such as thiazole, 4- methylthiazole, 4-phenylthiazole and 4,5- diphenylthiazole
  • benzothiazole type nuclei such as benzothiazole, S-chlorobenzothiazole, 5- methylbenzothiazole, 6-methylbenzothiazole, 5- V phenylbenzothiazole, 5-methoxybenzothiazole, 6-
  • ethoxybenzothiazole S-hydroxybenzothiazole, tetrahy droxybenzothiazole, 5,6-dimethoxybenzothiazole and 5,6-dioxymethylene benzothiazole
  • naphthothiazole type nuclei such as L -naphthothiazole, -napnthothiazole and, naphthothiazole
  • oxazole type nuclei such as 4-methyloxazole, 4-phenyloxazole and 4,5- diphenyloxazole
  • benzoxazole type nuclei such as benzoxazole, S-chlorobenzoxazole, 5- methylbenzoxazole, S-phenylbenzoxazole, 6- methylbenzoxazole, 5,6-dimethyl benzoxazole and 5- methoxybenzoxazole
  • naphtoxazole type nuclei such as a-naphthoxazole, B-n
  • thiazole, benzothiazole and benzoselenazole nuclei are especially preferred, and as the alkyl group, methyl, ethyl, sulfopropyl, sulfobutyl, sulfate-propyl, carboxymethyl, carboxyethyl and hydroxyethyl groups are preferred. Further, phenyl, sulfophenyl, carboxyphenyl. tolyl and chlorophenyl groups are preferred as the aryl group, and an allyl group is preferred as the alkenyl group.
  • dyes exhibiting a drastic desensitizing effect in ordinary negative type silver halide emulsions such as cyanines and merocyanines having such a desensitizing effect in ordinary negative type silver halide emulsions, such as cyanines and merocyanines having such a desensitizing nucleus as imidazoquinoxaline,
  • pyrazole, indole and pyrrolopyrido nuclei or having such a desensitizing substituent as a No. 2 group stituent may be used in combination with the foregoing optically sensitizing dyes in this invention.
  • the optically sensitizing dye may be incorporated in the photosensitive material according to customray procedures.
  • the optically sensitizing dye is dissolved into a suitable solvent such as water, methanol and ethanol, and the solution is added, preferably, to the emulsion.
  • the dye is used in an amount of about 1 mg to about 300 mg per liter of the emulsion.
  • optically sensitizing dye there may be mentioned the following compounds:
  • cycnine dyes exhibit especially excellent photographic characteris- N tics when they are used in combination with the aboveo l mentioned fluorescent whitening agents.
  • the fluorescent whitening agent is used l preferably in an amount of about 1() mg to about l() g CH GI-F per liter of the emulsion.
  • the direct positive silver halide emul- C sion of this invention may comprise as a stabilizer a CH I polymer compound having in the molecule a group ex- GHZCHZSOSH pressed by the following formula (IV) s 1) CH R r 10 N l c-- s l l g 30 A coo-r'q-n Wherein A designates a hydrogen atom or a group -CooM (in which M, is
  • N C -I lH-R O: 11 2 5 GH SO H-N(G H 5 or other cation)
  • R is a hydrogen atom or a methyl j j N w A group, or a group-CH COOM (only when A is hydrogen atom)
  • R is an lakyl group or a hydroxyl-or phenylsubstituted alk l grou and R and R stand for a h 4s y P y ig g r drogen atom, an alkyl group or a hydroxyl-substituted 0' alkyl group, or they may form a ring.
  • V formula
  • Y is O or an integer of from I to 8
  • R is a m 2 2 hydrogen atom, an alkyl or arylgrouphaving up to l7 o I carbon atoms
  • M is a cation, a trlazole, an azalndene, a quarternary benzothiazolium compound, or a water-soluble inorganic salt of cadmium, cobalt, man- 7 ganese or zinc.
  • the so obtained direct reversal silver halide emulsion is coated and dried on a suitable support according to a customary method, if necessary, after a suitable hydrophilic treatment such as an undercoating treatment, has been conducted.
  • the support there may be exemplified a paper, an olefin resincoated paper, glass, cellulose acetate, cellulose nitrate and a film of a synthetic resin such as polyester, polyamide, polystyrene and the like.
  • the so obtained direct positive silver halide photosensitive material of this invention is used in various fields of the photographic art. For instance, in the field of printing, it is used for duplicating films, reproduction films, offset masters and the like. Furhter, in the general field, it is used as a direct positive photosensitive material for reproduction, microfilm, direct color positive, quick stabilization, diffuse transfer, color diffuse transfer and mono-bath development. Kinds of the photographic additive and silver halide and the preparation conditions are appropriately chosen depending on such uses.
  • the direct positive silver halide photosensitive material of this invention having the above-mentioned structure has excellent photographic characteristics such as a high contrast, a low minimum concentration, a high maximum concentration, a high maximum concentration, a high sensitivity and other improved properties, and the defects of the conventional direct positive photosensitive materials can be overcome by the photosensitive material of this invention.
  • Example 1 An ammoniac silver bromoiodide emulsion containing a rhodium salt and comprising a silver bromoiodide having an average particle diameter of about 0.3 p. and containing about 1.4 mole percent of silver iodide was prepared in the following manner [emulsion (1)].
  • the liquor b) was added to the liquor a) at 40c. and the liquor c) was further added under ripened. Then, the ripening was conducted at 40C. for 5 minutes and the liquor d) was added to neutralize the emulsion to a P value of 5.0. The emulsion was desalted, and there was obtained 1200 cc of a final emulsion.
  • emulsion (ll) was prepared in the same manner as described above except that rhodium chloride was not added, and emulsion (III) comprising a silver bromoiodide having the same average particle size and the same silver halide composition and containing the same amount of rhodium chloride as described above was prepared by the neutral method.
  • Each emulsion was adjusted to P of 6.8 and PAg of 7.5, and 3.5 milligrams of tetraethylene pentamine was added to effect the ripen at 60C. for 30 minutes.
  • the resulting emulsion was divided into 2 portions, and 0.5 milligram (a) of chloroauric acid was added to one portion and 2.5 milligrams (b) of chloroauric acid was aged at 60c. until appropriate fog was obtained.
  • a spreader and a filmhardening agent were further incorporated into the emulsion, and it was coated and dried on a film base in an amount of 4 g, calculated as silver, per square meter of the film.
  • D-72 type developer (recipe by Eastman Kodak Co.) was used for the development.
  • the emulsion was then incorporated with a spreader and a film-hardening agent and coated on a film base in an amount of 4g, calculated as silver, per square meter of the film.
  • the so obtained samples were treated in the same manner as described in Example 1, to obtain results shown in Table 2.
  • an ammoniac silver bromoiodide emulsion was prepared. After completion of the physical ripening, the desalting was carried out, and P and PAg were adjusted to 6.8 and 7.5, respectively. Then, triethylene tetramine was added in an amount of 4.0 mg to the emulsion, and the ripening was effected at 65C. for 30 minutes. The emulsion was divided into several portions, and ammonium thiosulfate was added into the divided portions in amounts indicated in Table 2, and the ripening was conducted at 65C. for 5 minutes Then, chloroauric acid was added and the ripening was carried out until a suitable fog was obtained. 0
  • Example 3 Table 4 Emulsion (B) Amount Added Relative Speed Relative Speed Minimum amma Illustrative of dye under white under yellow value concendye (mg/mol Ag) light exposure light exposure tration not added I I00 2.4 0.l2 (33) I20 I10 580 2.0 0.14 (38) 120 I00 500 L9 014 (I4) I00 I80 2,790 1.8 0.l5 (20) I00 200 2,950 1.6 0.16 (23) I00 ll0 I,I50 1.6 0.15 (39) I00 75 650 1.3 0.21 (40) I00 I05 1.040 l.7 0.18 (25) 50 40 260 l.l 0.23 (2) I00 200 L830 1.9 0.14 (I0) I00 I00 900 2.1 0.l5 (I2) I00 160 1,550 2.0 015 (I3) I00 I20 700 L) 0.17
  • the liquor b) was added to the liquor a) at 38C. and the liquor c) was further added under ripening. The, the ripening was carried out at 38C. for 10 minutes, and the liquor d) was added to neutralize the emulsion to a P value of 5.5.
  • the emulsion was desalted, and 50 g of preparation acid and was further ripened at 60C. for 40 minutes to' impart a fog to the emulsion.
  • the portion (B) was incorporated with I mg of formalin and ripened at 60C. for 60 minutes.
  • 1.5 mg of chloroauric acid was added to the emulsion and ripening was carried out at 60C. for 40 minutes to impart a fog to the emulsion.
  • the so obtained emulsions were divided into portions and these portions were incorporated with optically sensitizing dyes indicated in Tables 3 and 4.
  • a spreader and a film-hardener were added to each emulsion and the emulsion was coated on a film base in an amount of 3.5 g, calculated as silver, per square meter of the film.
  • a direct positive silver halide photosensitive material comprising an ammoniac silver halide photosensitive emulsion and(a) at least one compound selected from soluble rhodium salts and soluble iridium salts, said compound having been incorporated into said emulsion in an amount of 0.001 to 10 millimoles per mole of the silver halide before or at physical ripening, (b) a reducing agent in an amount of 0.001 to 100 millimoles per mole of the silver halide, (c) a gold compound in an amount of 0.0001 to 0.1 millimoles per mole of the silver halide, (d) at least I05 mol percent, based on said gold compound, of at least one compound selected from thiosulfates, thiocyanates, prussic acid salts, and (e) an optical sensitizing dye, said reducing agent and said gold compound being present in sufficient amounts to
  • a direct positive silver halide photosensitive mate- Tab1e 3 and 4 na] according to claim 1, whereln said sensitizing dye Table 3 Emulsion (A) Amount Added Relative speed Relative speed Gamma Minimum Illustrative of dye under white under yellow Value concendye (mg/mole Ag) light exposure light exposure trationnot added I00 I00 4.3 0.04 (33) I20 300 4.000 4.5 0.04 (38) I20 I 2,700 4.3 0.04 I4) I00 520 20,000 4.8 0.03 (20) I00 570 27.600 5.l 0.03 (2 3) I00 495 I0.0ll0 4.4 0.04 (39) I00 260 8,400 3.8 0.05 (40) I00 200 (1,230 4.
  • sensitizing dyes represented by the following general formula (I) or (ll):
  • Z and Z stand for an atomic group necessary for formation of a heterocyclic ring
  • m is l or 2 with the proviso that when m is 1, Z, is a 2-quinoline ring
  • R and R stand for an alkyl group
  • R designates a hydrogen atom or an alkyl group
  • X is an anionic group
  • n is l or 2
  • I and d are individually l or 2
  • p is l, 2 or 3.
  • said reducing agent is selected from formalin, hydrazine, triethylene tetramine, thiourea dioxide, imino-amino-methane-sulfonic acid, stannous chloride and amine borane.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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US368868A 1972-06-17 1973-06-11 Direct-positive reduction and gold fogged ammoniac silver halide emulsion Expired - Lifetime US3865596A (en)

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JP (1) JPS5548292B2 (enrdf_load_stackoverflow)
DE (1) DE2330602A1 (enrdf_load_stackoverflow)
GB (1) GB1419147A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4008089A (en) * 1974-04-03 1977-02-15 Agfa-Gevaert N.V. Direct-positive silver halide emulsion reduction and gold fogged in contact with a palladium compound
US4097285A (en) * 1977-02-17 1978-06-27 Mitsubishi Paper Mills, Ltd. Direct-positive photographic silver halide emulsion containing novel dye
US4495274A (en) * 1982-04-26 1985-01-22 Konishiroku Photo Industry Co., Ltd. Direct-positive silver halide photographic material
US4582779A (en) * 1983-06-29 1986-04-15 Fuji Photo Film Co., Ltd. Internal latent image-type direct positive silver halide emulsions and photographic materials

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58176635A (ja) * 1982-04-09 1983-10-17 Konishiroku Photo Ind Co Ltd 直接ポジ用ハロゲン化銀写真感光材料
JPH0642416B2 (ja) * 1989-07-28 1994-06-01 東光株式会社 積層ｌｃ複合部品用磁性材料の製造方法
US5294532A (en) * 1991-09-19 1994-03-15 Fuji Photo Film Co., Ltd. Silver halide photographic material and method of processing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2717833A (en) * 1952-05-12 1955-09-13 Sperry Rand Corp Direct positive emulsions
US2743182A (en) * 1952-11-08 1956-04-24 Eastman Kodak Co Chemical sensitization of photographic emulsions
US3445235A (en) * 1965-07-15 1969-05-20 Du Pont Rhodium and iridium salts as anti-kinking agent in direct positive silver halide emulsions
US3501307A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Photographic reversal materials containing organic desensitizing compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2717833A (en) * 1952-05-12 1955-09-13 Sperry Rand Corp Direct positive emulsions
US2743182A (en) * 1952-11-08 1956-04-24 Eastman Kodak Co Chemical sensitization of photographic emulsions
US3445235A (en) * 1965-07-15 1969-05-20 Du Pont Rhodium and iridium salts as anti-kinking agent in direct positive silver halide emulsions
US3501307A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Photographic reversal materials containing organic desensitizing compounds

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4008089A (en) * 1974-04-03 1977-02-15 Agfa-Gevaert N.V. Direct-positive silver halide emulsion reduction and gold fogged in contact with a palladium compound
US4097285A (en) * 1977-02-17 1978-06-27 Mitsubishi Paper Mills, Ltd. Direct-positive photographic silver halide emulsion containing novel dye
US4495274A (en) * 1982-04-26 1985-01-22 Konishiroku Photo Industry Co., Ltd. Direct-positive silver halide photographic material
US4582779A (en) * 1983-06-29 1986-04-15 Fuji Photo Film Co., Ltd. Internal latent image-type direct positive silver halide emulsions and photographic materials

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JPS5548292B2 (enrdf_load_stackoverflow) 1980-12-05
JPS4922118A (enrdf_load_stackoverflow) 1974-02-27
DE2330602A1 (de) 1974-01-03
GB1419147A (en) 1975-12-24

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