US3910795A - Fogged, direct positive silver halide emulsion sensitized with a nitrophenyl mercapto heterocyclic compound - Google Patents

Fogged, direct positive silver halide emulsion sensitized with a nitrophenyl mercapto heterocyclic compound Download PDF

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Publication number
US3910795A
US3910795A US426146A US42614673A US3910795A US 3910795 A US3910795 A US 3910795A US 426146 A US426146 A US 426146A US 42614673 A US42614673 A US 42614673A US 3910795 A US3910795 A US 3910795A
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United States
Prior art keywords
silver halide
emulsion
halide photographic
ring
compound
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Expired - Lifetime
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US426146A
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English (en)
Inventor
Keisuke Shiba
Masanao Hinata
Reiichi Ohi
Tadao Shishido
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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

Definitions

  • ABSTRACT A silver halide photographic emulsion for direct positives containing at least one compound represented by the general formula (I).
  • n represents an integer of from 1 to 3.
  • the instant invention relates to a direct positive emulsion sensitive to the blue color region by the incorporation of an organic densensitizer.
  • an organic densensitizer such as pinakryptol yellow or 5-m-nitrobenzilidene rhodanine. It is known that an emulsion fogged using a relatively small amount of a gold compound or salt and a reducing agent and containing at least 50 mol of silver bromide can be advantageously used to obtain a particularly high reversal sensitivity and that an organic densensitizer is effective for the sensitization of such an emulsion.
  • known organic densensitizers which have hitherto been used for the sensitization in the blue color region have various disadvantages.
  • an organic densensitizer having a relatively high reversal sensitivity reduces the maximum density of an original emulsion, while, on the other hand, a sensitizer which does not reduce the maximum density gives only a low reversal sensitivity.
  • an organic densitizer-free emulsion will hereinafter be referred to as an original emulsion.
  • pinakryptol yellow reduces the maximum density of an original emulsion and colors a photographic material used yellow.
  • 3-Ethyl-5-m-nitrobenzilidene rhodanine does not reduce the maximum density as much, but the clarity is bad, that is, the value of minimum density is large.
  • S-m-Nitrobenzilidene rhodanine Compound 1 does not reduce the maximum density as much and the value of minimum density is small, that is, the clarity is good, but a lower reversal sensitivity is obtained. Therefore, it is very important to find an organic densitizer for sensitizing in the blue color region, which is capable of giving a high reversal sensitivity without reducing the maximum desnity and with a high clarity.
  • heterocyclic rings in the above described general formula are 1,2,4-triazole ring. a 1,3,4-thiadiazole ring, a l,3,3a,7-tetrazaindene ring, a benzothiazole ring, a benzoimidazole ring and a pyrimidine ring.
  • the heterocyclic ring formed by Z can be either a substituted ring or an unsubstituted ring.
  • the particular substituent(s) on the ring is not important so long as the substituent(s) used does not deteriorate substantially the photographic properties in terms of sensitivity, residual coloring and maximum density.
  • substituents include an alkyl group preferably having up to 20 carbon atoms (e.g., CH n-C H n-C H n-C I-I etc.), an aryl group ⁇ e.g., an unsubstituted aryl and a substituted aryl substituted with a substituent such as a halogen atom (e.g., a chlorine atom), an alkyl group (e.g., a methyl group) and an alkoxy group (e.g., a methoxy group) ⁇ , a nitro group, a hydroxy group, a halogen atom (e.g., a chlorine, bromine, or iodine atom), an alkoxy group (e.g., a methoxy or ethoxy group), and an amide group ⁇ i.e., an NI-ICORo group (R0 is an alkyl group having up to 8 carbon atoms) ⁇ .
  • Compound 22 A general method of synthesis of the compound repwere added to a 10% aqueous solution of sodium hyresented by the general formula is as follows: droxide followed by heating for 4 hours on a warm water bath. After the heating, the reaction solution was cooled and the solution made acidic with hydrochloric acid. The so obtained crystals were recrystallized from 20.2 g of 4-phenylthiosemicarbazide was dissolved in methanol to obtain 21.2 g of needle-like crystals meltml of pyridine and stirred with along with cooling ing at 103C.
  • a previously fogged silver halide emulsion is favorably used which does not have free electron trapping nuclei in the interior of silver halide.
  • An emulsion of this type is a silver halide emulsion consisting of normal crystals, preferably pure silver bromide, which has no twin surface and hardly has any crystal defects.
  • This emulsion can further be improved with respect to the maximum density (Drnax), sensitization and clearness by the addition of bromide ions or iodide ions in an amount of from 1 to 20 mol preferably 3 to 10 mol of bromide or from 0.2 to 3 mol preferably from 0.5 to 2 mol of iodide per mole of silver.
  • This emulsion does not provide directly a positive image by itself but a high reversal sensitization is provided by the incorporation of the nitrophenylmercapto group-containing heterocyclic compound of this invention. Examples of using an original emulsion having no electron trapping nuclei are described in British Pat. Nos.
  • nitrophenylmercapto group-containing heterocyclic compound used in this invention can also be used for the sensitization of a previously fogged silver halide photographic emulsion having free electron trapping nuclei in the interior of silver halide.
  • the silver halide photographic emulsion used in the invention is previously fogged optically or chemically as disclosed in U.S. Pat. Nos. 2,497,875 and 3,537,858.
  • the chemical fogging nuclei can be provided by the addition of organic reducing compounds, for example, hydrazine derivatives, formaldehyde, thiourea dioxide, a polyamine compound, an aminoborane and methyldichlorosilane.
  • gelatin is mainly used as a protective colloid and, in particular, an inert gelatin is preferably used.
  • an inert gelatin is preferably used.
  • photographically inert acylated gelatin derivatives such as phthalated gelatin, and water-soluble synthetic polymers such as polyvinyl acrylate, polyvinyl alcohol, polyvinylpyrrolidone and polyvinyl aginate can be used.
  • the silver halide emulsion according to the invention can also contain mercapto compounds, thione compounds and tetrazaindene compounds as a stabilizer for the fog nuclei as disclosed in US. Pat. Nos. 2,444,605; 2,444,606; 2,444,607 and 2,444,608; stilbene compounds and triazine compounds as a modifier of the clarity; chrome alum, 2,4-dichloro-s-triazine compounds, aziridine compounds, epoxy compounds and mucohalogenic acid compounds, halogenoformyl and maleic acid compounds as a brightening agent as disclosed in US. Pat. Nos. 3,406,070 and German Pat. Nos.
  • a spectrally sensitizing dye is used jointly with the nitrophenylmercapto group-containing heterocyclic compound.
  • Suitable spectral sensitizers are dyes such as cyanines, merocyanines, composite trinuclear cyanines, composite trinuclear merocyanines, styryl dyes and hernicyanines.
  • a high sensitivity emulsion is obtained by the joint use of a dimethine dye such as is described in US. Pat. Applications Ser. Nos. 318,047, filed on Dec. 26, 1972; 351,386, filed Apr. 16, 1973; and 379,887, filed on July 16, 1973.
  • emulsions can contain color couplers or can be developed with solutions containing couplers.
  • color couplers can be incorporated in silver halide photographic emulsions for direct positives using suitable techniques as disclosed in US. Pat. Nos. 2,322,027, 2,801,171, 1,055,155, 1,102,028 and 2,186,849.
  • the grain size of silver halide in the photographic emulsion used in the invention is not limited, but the average grain size is preferably 0.05 to 1.0 microns.
  • the form of the silver halide used can be either regular or irregular, but, in particular, the regular form is preferable.
  • the effect of the invention is favourably provided by a monodispersed emulsion, although other emulsions than the monodispersed emulsion can, of course, be used.
  • the quantity of the nitrophenylmercapto group-containing heterocyclic compound used in the invention will vary depending upon the quantity of silver halide in the emulsion, the surface area and the end-use desired, and, preferably, 1 X 10 to 5 X mol per 1 mol of the silver salt is generally employed.
  • the nitrophenylmercapto group-containing heterocyclic compound is ordinarily added in the form of a solution in a suitable solvent such as water and organic solvents miscible with water, e.g., alcohols such as methanol and ethanol, ethers such as ethylene glycol monomethyl ether, ketones such as methyl ethyl ketone and acetone, N-con' taining compounds such as pyridine or mixtures of these solvents.
  • a suitable solvent such as water and organic solvents miscible with water, e.g., alcohols such as methanol and ethanol, ethers such as ethylene glycol monomethyl ether, ketones such as methyl ethyl ketone and acetone, N-con' taining compounds such as pyridine or mixtures of these solvents.
  • the addition of the nitrophenylmercapto group-containing heterocyclic compound to an emulsion is preferably carried out immediately before coating, but can be carried out during the chemical ageing or during the precipitating of the silver halide.
  • the silver halide photographic emulsion for direct positives according to the instant invention is suitable for not only high contrast light-sensitive materials for direct positives, such as light-sensitive materials for lith-film copying originals, but also relatively low contrast light-sensitive materials for direct positives, such as light-sensitive materials for microphotographs or X-ray photographs. Moreover, it can be adapted to color light-sensitive materials, in particular, blue-sensitive layers, and, in addition to the use of light radiation, irradiation with electron rays, X'-rays and 'y-rays can also be used.
  • a first feature of the invention is to obtain a high reversal sensitivity within the blue range (e.g., about 400 to 500 nm) where a nitrophenylmercapto group-containing compounds used for sensitization.
  • a phenylmercapto group-containing compound substituted with two nitro groups such as Compound 2 and Compound 6 described previously gives a high sensitiv ity.
  • the heterocyclic ring of the general formula (1) is a 1,2,4-triazole ring, l,3,3a,7-tetrazaindene or 7- tetrazaindene ring, in particular, a high sensitivity can be attained.
  • a second feature of the invention is that the nitrophenylmercapto group-containing heterocyclic compound used in the invention does not reduce the maximum density (Dmax) of an original emulsion.
  • a third feature of the invention is that a direct positive emulsion sensitized with the nitrophenylmercapto group-containing compound of the invention retains a predetermined maximum density and, simultaneously, retains a good clearness.
  • a fourth feature of the invention is that the nitrophenylmercapto group-containing heterocyclic compound used in the invention leaves substantially no residual color on a light-sensitive material after processing.
  • the nitrophenylmercapto group-containing heterocyclic compound of the invention can be used not only for the sensitization of previously fogged emulsions for direct positives, but also for various photographic objects in which a known desensitizer for silver halide photography is used.
  • a known desensitizer for silver halide photography For example, (1) using an aqueous solution of the desensitizer as a pretreatment bath, a high sensitivity photographic material photographed is treated in this bath and developed while observing the progress of the development under a relatively bright illumination; (2) development is carried out in a mixed solution of the desensitizer and a developer used, whereby the sensitivity of a photographic lightsensitive material is reduced and the development can be accomplished under a relatively bright illumination; and (3) as described in Japanese Pat. Disclosure No.
  • the desensitizer can be used for an emulsion consisting of an internally latent image type silver halide doped with a multi-valent metal ion.
  • suitable metal ions include Pb, Sb, As, Au, Bi, Rh, Pt, Os, 1r and lr as disclosed in Japanese Patent Application Laid Open to Inspection No. 32813/72.
  • EXAMPLE 1 The method of preparing the emulsion used in this example was follows.
  • a first solution prepared by adding 8 g of an inert gelatin to 5 ml of a l N solution of potassium bromide and 500 ml of water and warming to dissolve at 60C were added a second solution prepared by adding l g of silver nitrate to 500 ml of water and warming to dissolve at 60C and a third solution prepared by add ing 70 g of potassium bromide to l50 m] of water and warming to dissolve at 60C with stirring for a period of 50 minutes. and then the mixture was subjected to physical ageing for minutes. Then ml ofa 0.2 N solution of potassium iodide was added and the pAg was adjusted to 6.0 using a solution of silver nitrate.
  • the compound of the invention was added to the above described original emulsion with 2.0 ml of an aqueous solution containing 1% by weight of saponin per kg of emulsion, and coated onto a film of cellulose triacetate to provide a thickness of 5 microns on dry basis.
  • the coated specimen was exposed to a tungsten light at a color temperature of 2,854K through an optical wedge, developed at C for 2 minutes with the following developer, fixed to give a strip and the strip was then subjected to a measurement of the density using a P-type Densitometer manufactured by the Fuji Photo Film Co, Ltd. thus obtaining a characteristic curve.
  • the dyes represented by the general formula of the invention provide a direct positive silver halide emulsion having excellent photographic properties.
  • EXAMPLE 2 The method of preparing the emulsion used in this example was as follows.
  • a first solution prepared by adding 10 g of an inert gelatin to 5 ml of a l N solution of sodium chloride and 500 ml of water and warming to dissolve at 60C were added with agitation for a period of 20 minutes a second solution prepared by adding 100 g of silver nitrate to 500 ml of water and warming to dissolve at 60C and a third solution prepared by adding 35 g of sodium chloride to 300 ml of water and warming to dissolve at 60C.
  • the mixture was aged for 5 minutes, mixed with agitation with a fourth solution prepared by adding M g of potassium bromide to 200 ml of water and warming to dissolve at 60C, for a period of 20 minutes, then aged for l0 minutes, cooled and washed with water. After melting, the pH was adjusted to l0. Hydrazine and a chloroaurate, both in the proportion used in Example 1, were then added followed by ageing for 10 minutes and the pH was adjusted to 6.5 using citric acid.
  • a fifth solution was prepared by dissolving g of an inert gelatin in 300 ml of water and added to obtain a silver halide emulsion.
  • the thus resulting silver halide emulsion original emulsion
  • the coated specimen was exposed to a tungsten light at a color temperature of 2,854K through an optical wedge, developed at 20C for 3 minutes with a developer consisting mainly of a polyhydroxybenzene as described in Example 1, fixed to give a strip and the strip was then subjected to a measurement of the density using a P-type Densitometer manufactured by the Fuji Photo Film Co., Ltd. thus obtaining a characteristic curve.
  • the results of the sensitometrv are shown in Table 2.
  • the silver halide photographic emulsion of claim I wherein said compound is n 5 N E 02H r m2 c n n 02H N s-Z no x l 2 n-C H N 2 W N A 11 n-C ll 0 R Q Y- 11 23 N T N 2 kn) 13 2? Z B' T 5 N02 f wug n Continued 11- N02 s H OH l0 O N s -C-(CH co 13.
  • a silver halide photographic material for direct Q N positives, comprising a support having coated thereon a the silver halide photographic emulsion of claim 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
US426146A 1972-12-19 1973-12-19 Fogged, direct positive silver halide emulsion sensitized with a nitrophenyl mercapto heterocyclic compound Expired - Lifetime US3910795A (en)

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DE (1) DE2363308A1 (enrdf_load_stackoverflow)
GB (1) GB1424850A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4820625A (en) * 1986-09-19 1989-04-11 Fuji Photo Film Co., Ltd. Direct positive silver halide photographic material
US4851321A (en) * 1986-11-14 1989-07-25 Fuji Photo Film Co., Ltd. Superhigh contrast negative-type silver halide photographic material
US4908293A (en) * 1986-09-05 1990-03-13 Fuji Photo Film Co., Ltd. Superhigh contrast negative type silver halide photographic material
US5100761A (en) * 1987-03-20 1992-03-31 Fuji Photo Film Co., Ltd. Silver halide photographic materials
US5858913A (en) * 1994-10-14 1999-01-12 Agfa-Gevaert Receiving element for use in thermal transfer printing
WO2007011759A3 (en) * 2005-07-15 2007-04-12 Kalypsys Inc Inhibitors of mitotic kinesin

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6375738A (ja) * 1986-09-19 1988-04-06 Fuji Photo Film Co Ltd 直接ポジ型ハロゲン化銀写真感光材料
JP2604157B2 (ja) * 1987-05-28 1997-04-30 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
EP0713133B1 (en) * 1994-10-14 2001-05-16 Agfa-Gevaert N.V. Receiving element for use in thermal transfer printing
US6319660B1 (en) 1998-12-28 2001-11-20 Eastman Kodak Company Color photographic element containing speed improving compound

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2901351A (en) * 1954-12-10 1959-08-25 Gavaert Photo Producten N V Direct positive photographic material
US2947629A (en) * 1958-09-17 1960-08-02 Eastman Kodak Co Nitrosopyrimidine desensitizing compounds and photographic emulsions containing them
US3615607A (en) * 1967-03-13 1971-10-26 Takako Watatani Method of desensitizing light-sensitive silver halide photographic materials with cycloheptimidazole derivatives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2901351A (en) * 1954-12-10 1959-08-25 Gavaert Photo Producten N V Direct positive photographic material
US2947629A (en) * 1958-09-17 1960-08-02 Eastman Kodak Co Nitrosopyrimidine desensitizing compounds and photographic emulsions containing them
US3615607A (en) * 1967-03-13 1971-10-26 Takako Watatani Method of desensitizing light-sensitive silver halide photographic materials with cycloheptimidazole derivatives

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4908293A (en) * 1986-09-05 1990-03-13 Fuji Photo Film Co., Ltd. Superhigh contrast negative type silver halide photographic material
US4820625A (en) * 1986-09-19 1989-04-11 Fuji Photo Film Co., Ltd. Direct positive silver halide photographic material
US4851321A (en) * 1986-11-14 1989-07-25 Fuji Photo Film Co., Ltd. Superhigh contrast negative-type silver halide photographic material
US5100761A (en) * 1987-03-20 1992-03-31 Fuji Photo Film Co., Ltd. Silver halide photographic materials
US5858913A (en) * 1994-10-14 1999-01-12 Agfa-Gevaert Receiving element for use in thermal transfer printing
WO2007011759A3 (en) * 2005-07-15 2007-04-12 Kalypsys Inc Inhibitors of mitotic kinesin

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DE2363308A1 (de) 1974-06-27
GB1424850A (en) 1976-02-11
JPS4984639A (enrdf_load_stackoverflow) 1974-08-14

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