US3525622A - Light-sensitive silver halide emulsions - Google Patents

Light-sensitive silver halide emulsions Download PDF

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Publication number
US3525622A
US3525622A US623207A US3525622DA US3525622A US 3525622 A US3525622 A US 3525622A US 623207 A US623207 A US 623207A US 3525622D A US3525622D A US 3525622DA US 3525622 A US3525622 A US 3525622A
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United States
Prior art keywords
silver halide
emulsion
series
ethyl
silver
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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.)
Expired - Lifetime
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US623207A
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English (en)
Inventor
Jozef Frans Willems
Albert Lucien Poot
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B26/00Hydrazone dyes; Triazene dyes
    • C09B26/02Hydrazone dyes
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • This invention relates to light-sensitive silver halide emulsions.
  • Light-sensitive silver halide emulsions are in general characterized by their sensitivity, gradation and fog.
  • sensitivity, gradation and fog can be regulated by the way of preparing the silver halide and the use of special chemical ingredients effecting a desired improvement or result.
  • Addenda to the emulsion which are of particular importance for the stability of the lightsensitive characteristics of a silver halide emulsion are the so-called stabilizers.
  • Stabilizers or antifoggants protect the light-sensitive silver halide emulsions against spontaneous growth of fog during prolonged storage or storage at high temperatures and humidities or during development to maximum contrast and speed.
  • photographic silver halide emulsions can be stabilized against the formation of spontaneous fog by incorporating in the emulsions certain silver complexing agents, more particularly heterocyclic hydrazone compounds which can be represented by the following general formula (I):
  • benzoxazole S-chlorobenzoxazole, S-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6- dimethylbenzoxazole, S-methoxybenzoxazole, 6-methoxybenzoxazole, S-hydroxybenzoxazole, 6-hydroxybenzoxazole), those of the naphthoxazole series (e.g. naphtho [2, l-d] oxazole, naphtho 1,2-d] oxazole) those of the selenazole series (e.g.
  • 4-methylselenazo1e, 4-phenylsele'nazole those of the benzoselenazole series (e.g. benzoselenazole, S-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 4,5,6,7-tetrahydrobenzoselenazole), those of the naphthoselenazole series (e.g. naphtho [2,1-d] selenazole, naphtho[1,2-d]selenazole), those of the Z-quinoline series (e.g.
  • benzimidazole series e.gL l-ethylbenzimidazole, l-phenylbenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-hydroxy-ethyl-5,6-dichlorobenzimidazo1e, 1-ethyl-S-chlorobenzimidazole, l-ethyl-5,6-dibromobenzimidazole, 1-ethyl-5-chloro-6-amino-benzirnidazole, 1-ethy1-5-chloro-6-bromobenzimidazole, 1-ethyl-S-phenylbenzimidazole, l-ethyl-S-fluorobenzimidazole, 1-ethyl-5,6-difiuorobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-
  • Z' represents the necessary atoms to close a heterocyclic ring containing as heteroatoms one or more nitrogen atoms e.g. a 2H-pyrrole, imidazole, benzimidazole, l-H-indazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, s-triazine, isoquinoline, quinoline, phthalazine, quinoxaline, quinazoline, cinnoline, phenanthridine or condensed ring systems containing said nuclei e.g. B-purine, pteridine, fi-carboline and phenanthroline.
  • nitrogen atoms e.g. a 2H-pyrrole, imidazole, benzimidazole, l-H-indazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, s-triazine, isoquinoline
  • HaC N 02 mCUChMHj CH NNH-W [000mm OJhN-NH-).
  • Z represents the necessary atoms to close a heterocyclic nucleus of the thiazole series (e.g. thiazole, 4- (p-t01yl)- thiazole, 4,5-diphenylthiazole, 4-m-nitrophenylthiazole, 4-p-bromophenylthiazole, 4 methyl-S-ethoxycarbonylthiazole, benzthiazole, carboxylic acid substituted benzthiazole and sulphonic acid substituted benzthiazole) and those of the thiadiazole series (e.g. 4-phenylthiadiazole, 4-ethylthiothiadiazole, 4 -benzylthiothiadiazole and 4-benzylsulphonylthiadiazole), and
  • the addenda of the present invention can be added to photographic emulsions using any of the well-known techniques in emulsion preparation. For example, they can be added in dissolved state to the silver halide emulsion, or they can be added to the emulsion in the form of a dispersion similar to techniques used to incorporate colour couplers in the emulsion.
  • the stabilizing agents are preferably added to the photographic emulsion after the final digestion or after-ripening, although they can advantageously be added prior to digestion.
  • hydrazone compounds described above can 'be used in combination with other stabilizing agents e.g. of the hydroxy-triazolopyrimidine series (azaindolizines), cadmium salts, mercury compounds and with chemically sensitizing compounds, for instance sulphur compounds and noble metal salts e.g. gold salts.
  • other stabilizing agents e.g. of the hydroxy-triazolopyrimidine series (azaindolizines), cadmium salts, mercury compounds and with chemically sensitizing compounds, for instance sulphur compounds and noble metal salts e.g. gold salts.
  • addenda such as hardening agents, wetting agents, plasticizers, developing agents, and optical sensitizing agents can be incorporated into the emulsion in the usual way.
  • the amount of hydrazone compounds employed in the silver halide emulsion depends on the particular type of the emulsion and the desired effect, usually said compounds are employed in a ratio of 0.05 millimole to 50 millimole per mole of silver halide.
  • silver chlorlide and silver chloride-bromide emulsions wherein they show useful spectral sensitizing effects (a sensitizing maximum in the range of 420 nm to 520 nm) they are preferably used in an amount of 0.05 millimole to 10 millimole per mole silver halide.
  • the stabilizing addenda of the invention can be used in various kinds of photographic emulsion, e.g. spectrally nonsensitized emulsions, spectrally sensitized emulsions, X-ray emulsions, and emulsions sensitive to infrared radiation.
  • Various silver salts may be used as lightsensitive salt, e.g., silver bromide, silver iodide, silver chloride, or mixed silver halides, e.g., silver chlorobromide or silver bromo-iodide.
  • They may be used in silver halide emulsions for application in the silver halide complex diffusion transfer process or other transfer processes based on silver halide photography, in which, e.g., tlie diifusion of a developer, a coupler, or a dye is appied.
  • the stabilizing and anti-fogging action is determined by an incubation test of the emulsions as indicated in the following Table 2.
  • the fog, gradation and sensitivity values are expressed as a relative increase or decrease in respect of a control emulsion (blank).
  • the tested emulsion is a silver bromide-iodide (4.5 mole percent iodide) emulsion.
  • the incubated emulsions are for 5 min. at 20 C. developed in a developing bath of the following composition:
  • a photographic material comprising a silver halide emulsion layer containing a compound according to the following general formula:
  • R is hydrogen or an alkyl radical
  • Z represents the atoms necessary for completing a heterocyclic ring
  • Z represents the atoms necessary for completing a heterocyclic ring, containing as hetero atoms only one or more nitrogen atoms.
  • a photographic material according to claim 1 comprising a silver halide emulsion layer containing silver chloride or silver chloride-bromide, the speed of which has been increased by a compound according to the following general formula:
  • a photographic material according to claim 1 comprising a silver halide emulsion layer containing a compound according to the following general formula:
  • R is hydrogen or a methyl group
  • Z represents the atoms necessary for completing a pyridine nucleus, a quinoline nucleus, a pyrimidine nucleus, a quinazoline nucleus, a phthalazine nucleus, a quinoxaline nucleus, a benzimidazole nucleus, a thiazole nucleus or a benzithiazole nucleus, and
  • Z represents the atoms necessary to complete a pyridine nucleus or a quinoline nucleus.
  • a photographic silver chloride or silver chloridebromide material according to claim 2 containing said compound in a ratio of 0.05 millimole to 10 millimole per mole silver halide.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
US623207A 1966-03-15 1967-03-15 Light-sensitive silver halide emulsions Expired - Lifetime US3525622A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB11345/66A GB1118654A (en) 1966-03-15 1966-03-15 Improved light-sensitive silver halide emulsions

Publications (1)

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US3525622A true US3525622A (en) 1970-08-25

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US (1) US3525622A (en:Method)
BE (1) BE695443A (en:Method)
DE (1) DE1522429A1 (en:Method)
FR (1) FR1515642A (en:Method)
GB (1) GB1118654A (en:Method)
NL (1) NL6702919A (en:Method)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4075019A (en) * 1974-04-15 1978-02-21 Eastman Kodak Company High gain cobalt(III)complex composition and element
US4094683A (en) * 1975-06-27 1978-06-13 Fuji Photo Film Co., Ltd. Direct positive silver halide photographic materials
US4243737A (en) * 1977-11-25 1981-01-06 Eastman Kodak Company Image forming composition and elements with Co(III) complex, conjugated π bonding compounds and photoreductant
EP0147105A3 (en) * 1983-12-20 1985-08-28 Eastman Kodak Company Photographic products employing novel nondiffusible hydrazone dye-releasing compounds
US20030166658A1 (en) * 2000-06-05 2003-09-04 Johann Hofmann Heterocyclic hydrazones for use as anti-cancer agents
US20040056378A1 (en) * 2002-09-25 2004-03-25 Bredt James F. Three dimensional printing material system and method
CZ303748B6 (cs) * 2011-10-11 2013-04-17 Vysoká skola chemicko - technologická v Praze Ftalazin-1-ylhydrazony a jejich pouzití k lécbe nádorových onemocnení
US20170290830A1 (en) * 2016-04-08 2017-10-12 Baylor College Of Medicine Small molecule regulators of steroid receptor coactivators and methods of use thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB447109A (en) * 1934-08-03 1936-05-04 John David Kendall Improvements in or relating to the sensitisation of photographic emulsions
US2295008A (en) * 1940-03-12 1942-09-08 Eastman Kodak Co Photographic color forming compound
GB636403A (en) * 1946-07-16 1950-04-26 Gen Aniline & Film Corp Azamerocyanine dyes and a process for the preparation thereof
US2588538A (en) * 1948-08-06 1952-03-11 Ilford Ltd Stabilizers in photographic emulsions and developers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB447109A (en) * 1934-08-03 1936-05-04 John David Kendall Improvements in or relating to the sensitisation of photographic emulsions
US2295008A (en) * 1940-03-12 1942-09-08 Eastman Kodak Co Photographic color forming compound
GB636403A (en) * 1946-07-16 1950-04-26 Gen Aniline & Film Corp Azamerocyanine dyes and a process for the preparation thereof
US2588538A (en) * 1948-08-06 1952-03-11 Ilford Ltd Stabilizers in photographic emulsions and developers

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4075019A (en) * 1974-04-15 1978-02-21 Eastman Kodak Company High gain cobalt(III)complex composition and element
US4094683A (en) * 1975-06-27 1978-06-13 Fuji Photo Film Co., Ltd. Direct positive silver halide photographic materials
US4243737A (en) * 1977-11-25 1981-01-06 Eastman Kodak Company Image forming composition and elements with Co(III) complex, conjugated π bonding compounds and photoreductant
EP0147105A3 (en) * 1983-12-20 1985-08-28 Eastman Kodak Company Photographic products employing novel nondiffusible hydrazone dye-releasing compounds
US20030166658A1 (en) * 2000-06-05 2003-09-04 Johann Hofmann Heterocyclic hydrazones for use as anti-cancer agents
US7112680B2 (en) * 2000-06-05 2006-09-26 Austria Wirtschaftsservice Gesellschaft Mit Beschrankter Haftung Heterocyclic hydrazones for use as anti-cancer agents
US20040056378A1 (en) * 2002-09-25 2004-03-25 Bredt James F. Three dimensional printing material system and method
CZ303748B6 (cs) * 2011-10-11 2013-04-17 Vysoká skola chemicko - technologická v Praze Ftalazin-1-ylhydrazony a jejich pouzití k lécbe nádorových onemocnení
US20170290830A1 (en) * 2016-04-08 2017-10-12 Baylor College Of Medicine Small molecule regulators of steroid receptor coactivators and methods of use thereof
US10265315B2 (en) * 2016-04-08 2019-04-23 Baylor College Of Medicine Small molecule regulators of steroid receptor coactivators and methods of use thereof
US10512647B2 (en) 2016-04-08 2019-12-24 Baylor College Of Medicine Small molecule regulators of steroid receptor coactivators and methods of use thereof
US11253517B2 (en) 2016-04-08 2022-02-22 Baylor College Of Medicine Small molecule regulators of steroid receptor coactivators and methods of use thereof

Also Published As

Publication number Publication date
NL6702919A (en:Method) 1967-08-25
FR1515642A (fr) 1968-03-01
DE1522429A1 (de) 1969-09-11
BE695443A (en:Method) 1967-09-14
GB1118654A (en) 1968-07-03

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