US3615528A - Photographic silver halide emulsion having an increased sensitivity and reduced fogging - Google Patents

Photographic silver halide emulsion having an increased sensitivity and reduced fogging Download PDF

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Publication number
US3615528A
US3615528A US883606A US3615528DA US3615528A US 3615528 A US3615528 A US 3615528A US 883606 A US883606 A US 883606A US 3615528D A US3615528D A US 3615528DA US 3615528 A US3615528 A US 3615528A
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United States
Prior art keywords
following formula
photographic material
light
compound
silver halide
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Expired - Lifetime
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US883606A
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English (en)
Inventor
Harald Huckstadt
Wilhelm Saleck
August Randolph
Franz Moll
Anita Von Koenig
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/06—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
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • the sensitivity of light-sensitive photographic silver halide emulsions can be increased and the fogging can be decreased if the chemical ripening of that emulsions is performed in the presence of mercapto alkyl quaternary salts or acetothioalkyl quaternary salts of the following formula PI-IOTOGRAPIIIC SILVER IIALIDE EMULSION HAVING AN INCREASED SENSITIVITY AND REDUCED FOGGING
  • the present invention relates to a process for increasing the sensitivity of photographic silver halide emulsions together with reduced fogging by the addition of mercaptoalkyl quaternary salts or acetothioalkyl quaternary salts.
  • the sensitivity of a photographic emulsion can be effected in two ways. First the sensitivity can be increased during the preparation of the emulsion at the stage of so-called chemical ripening, by increasing the ripening time or by the addition of suitable compounds such as thiosulfate or other additives which usually contain sulfur.
  • the other method of increasing the sensitivity of photographic emulsion consists of adding socalled development accelerators or chemical sensitizers. These are usually added to the finished ripened emulsion.
  • Development accelerators which have been described for this purpose include, e.g., compounds which have an onium structure (such as quaternary ammonium and phosphonium and ternary sulfonium salts), and also polyalkylene oxides and polyalkylene oxide derivatives are very frequently employed.
  • R an alkyl group having up to six carbon atoms; two R radicals attached to the same nitrogen atom may, with this nitrogen atom, form a saturated five-, six-, or sevenmembered heterocyclic ring, which may contain further hereto atoms, e.g. a piperidine, morpholine, thiomorpholine, pyrrolidine, or hexamethyleneimine ring or an unsaturated heterocyclic ring such as pyridine, in the latter case R is not present;
  • R an alkyl group having up to six carbon atoms which may be substituted, for example haloalkyl, hydroxyalkyl, cyanoalkyl, carboxyalkyl or an aralkyl group such as benzyl or phenylethyl, the aryl radical of which may be substituted in turn, e.g. with alkyl, alkoxy, halogen, and amino groups;
  • n an integer of from 1 to 6;
  • X any anion such as chloride or bromide, tosylate, perchlorate or sulfate, when R contains a carboxylate group. X is absent.
  • the compounds according to the invention show their advantageous effect particularly clearly when they are used in place of thiosulfate or other conventional sulfur ripening agents for chemical ripening. Apart from the increase in sensitivity described in the example, the considerable reduced fogging in the samples is very noticeable. This reduction in fogging can be seen not only in fresh samples but also after storage in a heating cupboard.
  • the advantage of using the compounds according to the invention lies not so much in the increase in sensitivity, which is to be regarded as only average, but in the combination of increase in sensitivity with reduction in fogging which enables other ingredients, which may possibly increase the fogging to be added to the emulsion without the total fogging then being too great.
  • Emulsion prepared with the substances according to the invention will, therefore, be particularly suitable for use in combination with other development accelerators.
  • the reduced fogging will also be very important in the preparation of color emulsions, since these are normally particularly susceptible to fogging.
  • the compounds do not have any advantageous effect when used in the developer.
  • a quantity of 0.001 to 0.3g. per mol of silver halide will generally be sufficient.
  • the substances according to the invention can be used in any silver halide emulsions.
  • Suitable silver halides are silver chloride, silver bromide or mixtures thereof, optionally with a small silver iodide content of up to 10 mols percent.
  • Silver halides may be dispersed in the usual hydropholic compounds, for example carboxymethylcellulose, polyvinyl alcohol, polyvinyl pyrrolidone, alginic acid and its salts, esters or amides or preferable gelatin.
  • the emulsions may also contain other chemical sensitizers, e.g. quaternary ammonium and phosphonium salts and ternary sulfonium salts, reducing agents as stannous salts, polyamines such as diethylene triamine or sulfur compounds as described in U.S. Pat. No. 1,574,844.
  • the above-mentioned emulsions may also contain salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum or gold for chemical sensitization, as described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 65-72 (1951).
  • the emulsions may be optically sensitized, e.g. with the usual polymethine dyes such as neutrocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes, and oxonols. Sensitizers of this type have been described in the book by F. M. Hamer The Cyanine Dyes and Related Compounds" 1964). i
  • the emulsion may contain the usual stabilizers, e.g. homopolar or salt-type compounds of mercury containing aromatic or heterocyclic rings (for example of mercaptotrazoles), simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • stabilizers e.g. homopolar or salt-type compounds of mercury containing aromatic or heterocyclic rings (for example of mercaptotrazoles), simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • Azaindenes especially tetraor pentaazaindenes, and in particular those which are substituted with hydroxyl or amino groups, are also suitable for use as stabilizers. Compounds of this type are described in the article by Birr, Z. Wiss. Phot. 47, 2-58 (1952).
  • Other suitable stabilizers include heterocyclic mercapto compounds, e.g. phenylmercapto tetrazole. quaternary benzothiazole derivative
  • the emulsions may be hardened in the usual manner, for example with formaldehyde or halogenated aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters, and dialdehydes.
  • formaldehyde or halogenated aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters, and dialdehydes.
  • the emulsions treated with the mercaptoalkyl and S-acetylthio-alkyl quaternarysalts according to the invention may also contain color couplers for the production of color photographic images.
  • EXAMPLE 1 A silver iodobromide emulsion containing 5 mols percent of silver iodide is prepared in the usual manner. For after-ripening, the pAg is adjusted to 8.9. the pH to 6.8. and the viscosity to 8 cp. Gold thiocyanate is then added and the emulsion is divided into 7 equal parts. The following additives are then added to the individual samples (the amounts given are based on 1 kg. of emulsion containing l30 g. of silver halide:
  • Sample A Comparison sample without additive
  • Sample B 3.3 mg. ofCompound V
  • Sample C 3.3 mg. ofCompound Xlll
  • Sample D 7.0 mg. ofCompound lV
  • Sample G 3.3 mg. of a compound of the following formula (for comparison)
  • the after-ripening is carried out to maximum sensitivity and the samples are made ready for casting by the addition of 600 mg. of saponin as wetting agent, 200 mg. of 4-hydroxy-6- methyl-l ,3,3a,7-tetraazaindene as stabilizer and 10 ml. ofa l0 percent aqueous solution of formaldehyde as hardener, per kg. ofemulsion.
  • a difference of 3 represents a difference of one shutter stop.
  • Example 2 An emulsion as in example 1 is divided into 8 equal parts.
  • Sample A Comparison sample-without additive
  • Sample B 3.3 mg. ofCompound 1X
  • Sample C 3.3 mg. ofCompound Vlll
  • Sample D 3.3 mg. ofCompoundl
  • Sample E 3.3 mg. ofCompound 11
  • Sample F 3.3 mg. ofCompound XVI
  • Sample G 3.3 mg. ofCompound XVll
  • Sample 1-1 3.3 mg. ofCompound XIV
  • the samples are cast, exposed and developed as in example 1.
  • a difference of 3 represents a difference of one shutter stop.
  • a light-sensitive photographic material having at least one silver halide emulsion layer which contains a compound ofthe following formula as ripening agent:
  • R represents an alkyl group having up to six carbon atoms; two R radicals attached to the same nitrogen atom may with the said nitrogen atom form a saturated five-, sixor seven-membered heterocyclic ring containing at least one hetero atom or an unsaturated heterocyclic ring, in the latter case R is not present;
  • R represents an alkyl group having up to six carbon atoms, which may be substituted or an aralkyl group, the aryl radicals of which may be substituted;
  • R" represents H or COCH n is an integer offrom l to 6;
  • X 9 is any anion; when R contains a carboxylate group, X e
  • a light-sensitive photographic material according to claim 1 which contains a compound of the following formula:
  • a light-sensitive photographic material according to claim 1 which contains a compound of the following formula:
  • a light-sensitive photographic material according to 6 A light-sensitive photographic material according to claim 1, which contains a compound of the following formula:
  • a light-sensitive photographic material according to claim 1 which contains a compound ofthe following formula:
  • a light-sensitive photographic material which contains a compound of the following formula:
  • R represents an alkyl group having up to six carbon atoms
  • two R radicals attached to the same nitrogen atom may with the said nitrogen atom form a saturated five-, sixor R represents an alkyl group having up to six carbon atoms; two R radicals attached to the same nitrogen atom may seven-membered heterocyclic ring containing at least one with the Said t g atom form a 531i ated -i hetero atom or an unsaturated heterocyclic ring, in the seven-membered heterocyclic ring containing at least one latter case R is notpresent; hetero atom or an unsaturated heterocyclic ring, in the R represents an alkyl group having up to six carbon atoms, ialtef Case is not P which y Substituted alkyl group, the y R represents an alkyl group having up to six carbon atoms, :adlcais Ofwhlch y be substituted; which may be substituted or an aralkyl group, the aryl rePfesems H :1 radicals of

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US883606A 1968-12-23 1969-12-09 Photographic silver halide emulsion having an increased sensitivity and reduced fogging Expired - Lifetime US3615528A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19681816570 DE1816570A1 (de) 1968-12-23 1968-12-23 Photographische Halogensilberemulsion mit erhoehter Empfindlichkeit und vermindertem Schleier

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US3615528A true US3615528A (en) 1971-10-26

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US (1) US3615528A (enrdf_load_stackoverflow)
JP (1) JPS4926135B1 (enrdf_load_stackoverflow)
BE (1) BE746769A (enrdf_load_stackoverflow)
CA (1) CA936037A (enrdf_load_stackoverflow)
CH (1) CH544323A (enrdf_load_stackoverflow)
DE (1) DE1816570A1 (enrdf_load_stackoverflow)
FR (1) FR2026968A1 (enrdf_load_stackoverflow)
GB (1) GB1264562A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3915713A (en) * 1972-11-02 1975-10-28 Fuji Photo Film Co Ltd Silver halide photographic emulsion
US4145218A (en) * 1976-09-02 1979-03-20 Konishiroku Photo Industry Co., Ltd. Process for developing light-sensitive silver halide photographic materials
US4230796A (en) * 1978-01-18 1980-10-28 E. I. Du Pont De Nemours And Company High speed lithographic film element
US5474879A (en) * 1995-01-30 1995-12-12 Eastman Kodak Company Radiographic film developers containing ascorbic acid and thioether development accelerators

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3915713A (en) * 1972-11-02 1975-10-28 Fuji Photo Film Co Ltd Silver halide photographic emulsion
US4145218A (en) * 1976-09-02 1979-03-20 Konishiroku Photo Industry Co., Ltd. Process for developing light-sensitive silver halide photographic materials
US4230796A (en) * 1978-01-18 1980-10-28 E. I. Du Pont De Nemours And Company High speed lithographic film element
US5474879A (en) * 1995-01-30 1995-12-12 Eastman Kodak Company Radiographic film developers containing ascorbic acid and thioether development accelerators

Also Published As

Publication number Publication date
FR2026968A1 (enrdf_load_stackoverflow) 1970-09-25
CA936037A (en) 1973-10-30
DE1816570A1 (de) 1970-07-02
BE746769A (nl) 1970-09-03
GB1264562A (enrdf_load_stackoverflow) 1972-02-23
JPS4926135B1 (enrdf_load_stackoverflow) 1974-07-06
CH544323A (de) 1973-11-15

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