US3326690A - Silver halide emulsions with increased sensitivity - Google Patents

Silver halide emulsions with increased sensitivity Download PDF

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Publication number
US3326690A
US3326690A US359415A US35941564A US3326690A US 3326690 A US3326690 A US 3326690A US 359415 A US359415 A US 359415A US 35941564 A US35941564 A US 35941564A US 3326690 A US3326690 A US 3326690A
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US
United States
Prior art keywords
gold
silver halide
emulsion
salts
halide emulsions
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.)
Expired - Lifetime
Application number
US359415A
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English (en)
Inventor
Muller-Bardorff Wolfgang
Saleck Wilhelm
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.)
Agfa Gevaert NV
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Agfa AG
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Publication date
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21D—NUCLEAR POWER PLANT
    • G21D5/00—Arrangements of reactor and engine in which reactor-produced heat is converted into mechanical energy
    • G21D5/04—Reactor and engine not structurally combined
    • G21D5/08—Reactor and engine not structurally combined with engine working medium heated in a heat exchanger by the reactor coolant
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin

Definitions

  • Numerous compounds are known which can be used as additives to the emulsion or developer to increase the sensitivity of a photographic layer. Many different terms are used for substances that have this effect, e.g., chemical sensitizers or activators.
  • the best known class of substances in this field are polyalkylene oxides, in particular polyethylene oxides and water-soluble onium compounds such as quaternary ammonium, phosphonium and sulphonium salts or combinations thereof or derivatives of thiourea, for example, thiouraniurn salts.
  • the most commonly used combination for gold sensitization consists of gold-(III)-sa1ts and thiocyanate or thiosulphate, although the solutions of thiocyanate are not very stable and those of thiosulphate are difiicult to prepare.
  • Reaction kinetic investigations e.g., by Protass, Bjirrum and Kirschner (Z. Wiss. Angew. Phot. Kine 1 455 (1956)
  • on gold complexes with thiocyanate ions admit of the assumption that sensitization is caused by a controlled, slow decomposition of the Au-(I)-complexes in which the thiocyanate ions participate.
  • X represents hydrogen, metal ions preferably alkali metal cations or ammonium ions in which the hydrogen may be substituted and n in an integer between 0 and 8, preferably 0 and 5.
  • Suitable cations are, for example, those of sodium, potassium, ammonium and the like.
  • the invention can be used for all photographic silver halide emulsions.
  • the silver halide may be silver chloride, bromide or iodide or mixtures thereof, but iodosilver bromide emulsions are preferred.
  • These emulsions may be further chemically sensitized, for example, with sulfur compounds, polyalkylene oxides, water-soluble onium compounds or combinations of polyethylene oxides and onium compounds.
  • they may be optically sensitized, e.g., by methine cyanine, merocyanine, rhodacyanine dyes or the like.
  • Organic mercapto compounds may be added as stabilizers.
  • a further advantage of the process according to the invention is that the sensitized emulsions can be used for the production of black-and-white photographic material or color photographic material; in the latter case, hydrophobic or hydrophilic color couplers can be incoprorated.
  • the noble metal salts and the aliphatic hydroxycarboxylic acids of the present invention can be added to the emulsion at any stage of the preparation of the emulsion either before or during the after-ripening.
  • Aliphatic hydrocarboxylic acids or their salts may be added in solution or in solid form before, during or after the addition of the noble metal salt.
  • a mixture of a solution of .the noble metal salt, for example, gold-(III)chloride and a solution of an aliphatic hydroxy carboxylic acid or their salts can be added to the emulsions.
  • the compounds are used in concentrations of 0.1 g. to .5 g. per 1 kg. emulsion, preferably about 0.1 to 0.5 g./kg.
  • the optimum quantity to be added depends on the reduction capacity of the aliphatic hydroxy carboxylic acid or their salts and on the type of emulsion. It can easily be determined by a few tests.
  • Example 1 To a highly sensitive iodobromide gelatin emulsion with 4 mol percent of silver iodide containing silver halide equivalent to 50 g. silver per liter are added an aqueous solution of 35 to 40 mg. KBr per liter and sulfur compounds in order to effect chemical ripening. Thereafter the emulsion is divided into three samples A, B and C before after-ripening.
  • Sample A is a standard sample. Before after-ripening, the following mixture is added per liter of emulsion to sample B:
  • Example 2 A highly sensitive iodo silver bromide emulsion as described in Example 1 is divided into three samples A, B, C.
  • Sample A is a standard sample.
  • sample B is added per liter of emulsion a mixture of 3 mol. of a aqueous solution of compound I and 1 ml. of a 0.08% gold-III-chloride solution.
  • sample C is added per liter of emulsion a mixture of 3 ml. of a 10% aqueous solution of compound I and 2 ml. of a 0.08% gold-III-chloride solution.
  • Example 2 The three samples are after-ripened as described in Example 1 and applied to a sheet-like support of polyethyleneterephthalate. The resulting light sensitive photographic material is developed in the same way.
  • the noble metal salts are not limited to the previously mentioned, because it is possible to use any suitable salt which is soluble in water or lower alcohols.
  • suitable salt which is soluble in water or lower alcohols.
  • Such compounds are: gold halides, such as auric chloride,
  • gold halides such as potassium chloroaurate (KAuCl and sodium chloroaurate (NaAuCl
  • gold compounds such as auric sulfate
  • Aurous as well as auric compounds
  • Complex gold salts such as alkali metal aurous thiosulfates, alkali metal aurous sulfites (e.g., sodium or potassium aurous thiosulfate and sodium or potassium aurous thiosulfate and sodium or potassium aurous sulfite).
  • Potassium chloroaurite, potassium bromoaurite, potassium iodoaurite, or the corresponding sodium, calcium, strontium, cadmium or gallium salts can also be used.
  • Pyridinotrichloro-gold, ethylenediamine bis trichloro gold, diethyl monobromogold and diethyl gold acetone and gold complexes with sulfur compounds such as are commonly present in gelatin, e.g., the gold thiosinamine complexes, can also be used.
  • Suitable salts of noble metals of the VIII group are ammonium or potassium, chloropalladate, ammonium, sodium and potassium chloroplatinate, ammonium potassium and sodium bromoplatinate, ammonium chlororhodate, ammonium chlororuthenate, ammonium chloroiridate, ammonium, potassium and sodium chloroplatinite, ammonium, potassium and sodium chloropalladite, etc.
  • the after-ripening of the emulsion with the noble metal salt and the o-hydroxybenzylamine compounds is performed at an appropriate temperature particularly between 30 and 60 C.
  • the pH of the emulsion is advantageously adjusted to the acid side of neutrality preferably between 5 and 7. Maintenance of the emulsion on the acid side of neutrality during coating of the emulsion is also preferred.
  • the noble metal salts are employed in an amount below that which produces a substantial fog.
  • a quantity of the noble metal salt is employed, equivalent to between 0.1 and 50 mg. of the noble metal per mol of silver halide in the emulsion.
  • the noble metal compounds are preferably incorporated in the emulsions in the form of their solutions in a suitable solvent such as water, methyl alcohol, ethyl alcohol or the like.
  • emulsion additionally contains as chemical sensitizers sulphur compounds, onium compounds and polyalkylene oxides.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US359415A 1963-04-13 1964-04-13 Silver halide emulsions with increased sensitivity Expired - Lifetime US3326690A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA42878A DE1185481B (de) 1963-04-13 1963-04-13 Verfahren zur Steigerung der Empfindlichkeit von Halogensilberemulsionen

Publications (1)

Publication Number Publication Date
US3326690A true US3326690A (en) 1967-06-20

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US359415A Expired - Lifetime US3326690A (en) 1963-04-13 1964-04-13 Silver halide emulsions with increased sensitivity

Country Status (6)

Country Link
US (1) US3326690A (de)
BE (1) BE646466A (de)
CH (1) CH449416A (de)
DE (1) DE1185481B (de)
FR (1) FR1389299A (de)
GB (1) GB1057938A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862843A (en) * 1972-06-01 1975-01-28 Itek Corp Photographic element containing a layer of physical development nuclei less than two microns in thickness and a development activator
DE2508137A1 (de) * 1974-02-25 1975-09-04 Fuji Photo Film Co Ltd Verfahren zur herstellung von lithographischem lichtempfindlichem material
US3973967A (en) * 1972-06-01 1976-08-10 Itek Corporation Processes utilizing photographic element containing a physical development activator

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8624704D0 (en) * 1986-10-15 1986-11-19 Minnesota Mining & Mfg High contrast scanner photographic elements

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862843A (en) * 1972-06-01 1975-01-28 Itek Corp Photographic element containing a layer of physical development nuclei less than two microns in thickness and a development activator
US3973967A (en) * 1972-06-01 1976-08-10 Itek Corporation Processes utilizing photographic element containing a physical development activator
DE2508137A1 (de) * 1974-02-25 1975-09-04 Fuji Photo Film Co Ltd Verfahren zur herstellung von lithographischem lichtempfindlichem material

Also Published As

Publication number Publication date
FR1389299A (fr) 1965-02-12
DE1185481B (de) 1965-01-14
CH449416A (de) 1967-12-31
GB1057938A (en) 1967-02-08
BE646466A (de) 1964-10-13

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