US3551158A - Photographic silver halide emulsions with increased sensitivity - Google Patents

Photographic silver halide emulsions with increased sensitivity Download PDF

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Publication number
US3551158A
US3551158A US603168A US3551158DA US3551158A US 3551158 A US3551158 A US 3551158A US 603168 A US603168 A US 603168A US 3551158D A US3551158D A US 3551158DA US 3551158 A US3551158 A US 3551158A
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United States
Prior art keywords
silver halide
sample
per mol
emulsion
compounds
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US603168A
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English (en)
Inventor
Harald Huckstadt
August Randolph
Wilhelm Saleck
Erwin Ranz
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides

Definitions

  • Z an alkylen radical having up to 18 carbon atoms that can be substituted with at least one hydroxyl, carboxyl or epoxy group, and can be interrupted by a hetero atom such as at least one oxygen atom, or aralkylen;
  • the present invention relates to photographic silver halide emulsions chemically sensitized by the addition of heterocyclic sulfur compounds.
  • the sensitivity of silver halide emulsions can be increased by chemical ripening or after-ripening during the preparation of the emulsion, by either prolonging the ripening time or by the addition of suitable substances such as compounds of noble metals or thiosulfate or other sulfur compounds.
  • the sensitivity of a photographic emulsion can be increased by the addition of development accelerators or chemical sensitizers to the emulsion, usually when it is completely ripened.
  • Suitable development accelerators are, for example, compounds containing onium groups (for example, quaternary ammonium or phosphonium and ternary sulfonium salts) and polyalkylene oxides and derivatives of polyalkylene oxides.
  • the object of the present invention is to provide new chemical sensitizers which do not suffer the above disadvantages. Another object is to provide photographic silver halide emulsions having increased sensitivity and satisfactory keeping qualities.
  • the sulfonium salts correspond to the following formulae:
  • R a branched or unbranched alkyl or alkenyl radical containing up to 6 C-atoms, which may be interrupted by hetero atoms, in particular oxygen and which is substituted by at least one hydroxyl, carboxyl or epoxy p;
  • Z (1) an alkylene radical having up to 18 C-atoms, preferably up to 6 C-atoms, which alkylene radical may be substituted by at least one hydroxyl, carboxyl or epoxy group or which may be interrupted by hetero atoms, in particular at least one ether oxygen atom to give, for instance, ethylene ether or polyethylene ether groupings, or (2) aralkylene such as xylylene, and
  • X any anion, for example, halide ions, such as chloride or bromide, perchlorate, paratoluenesulfonate or methane sulfonate ions.
  • halide ions such as chloride or bromide, perchlorate, paratoluenesulfonate or methane sulfonate ions.
  • the sulfonium salts used according to the invention can be prepared in known manner. They may usually be obtained by reacting suitable sulfides, such as thiodiglycol, with monoor dihalides. The preparation of two compounds is given in detail below. The other compounds can be prepared in a similar manner.
  • COMPOUND II 12.2 g. (0.1 mol) of thiodiglycol and 25.5 g. (0.3 rnol) of ethylene chlorohydrin are heated with 60 ml. of Water for 13 hours on a water bath. The water is then boiled off and the solid residue is recrystallized from alcohol. Yield g., M.P. 126127 C.
  • COMPOUND V 12.2 g. (0.1 mol) thiodiglycol and 8.7 g. (0.05 mol) 1,4-di-(chloromethyl)-benzene are boiled under reflux for 6 hours in 250 ml. of methanol. The solvent is then distilled oil and the solid residue is recrystallized from methanol/water. Yield: 5.5 g., M.P. 133-135 C.
  • any polyalkylene oxides or derivatives thereof can be used in combination with the above sulfonium compounds.
  • the molecular weight of these polyalkylene oxides should be above 300, and preferably from 1500 to 10,000.
  • Compounds of this type have, for example, the following formula R stands for hydrogen or alkyl having preferably up to 18 carbon atoms such as ethyl or dodecyl, or an acyl group which is preferably derived from an aliphatic carboxylic acid having up to 18 carbon atoms such as lauric acid or oleic acid, or a radical of the phenyl group such as phenyl or alkyl substituted phenyl, for instance, p-dodecylphenyl; and
  • n is an integer from 8 to 200.
  • This latter class of compounds include condensation products of spirocyclic pentaerythritol-di-phosphoric acid monohalides and polyethylene glycols containing about 3 4 to ethylene oxide units. They correspond to the following general formula wherein:
  • R represents a hydrogen atom or an alkylene oxide chain containing 3 to 100 alkylene oxide units
  • y is an integer from 1 to 100 and m an integer from 3 to 100*.
  • This group of chemical sensitizers also includes condensation products of amidophosphoric acid derivatives with polyethylene glycols of the type described above. Such compounds are represented by the following formula:
  • the sulfonium salts according to the invention may be advantageously used in combination with the cross-linked or non-cross-linked water-soluble quaternation products of tertiary polyamines with bifunctional polyalkylene oxide derivatives, which quaternation products have been described in German patent application No. A 50,595 corresponding to U.S. application Ser. No. 591,974, filed Nov. 4, 1966.
  • the compounds according to the invention can be used in any silver halide emulsions.
  • Silver halides which may be used are silver chloride, silver bromide or mixtures thereof, if desired with a small amount of silver iodide of up to 10 mols percent.
  • the silver halides can be dispersed in the usual hydrophilic compounds, for example, in carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, alginic acid and its salts, esters or amides, and preferably in gelatin.
  • the preparation of photographic silver halide emulsions include 3 separate steps: (1) emulsification and physical ripening which is also called Ostwald ripening, (2) the freeing of the emulsion of excess water soluble salts, usually by washing with water and drying; and (3) the after ripening which is also called chemical ripening to obtain increased emulsion speed or general sensitivity.
  • the sensitizer of the present invention can be added to the emulsion before, during or after the chemical ripening or they can be added immediately prior to the casting.
  • the compounds can be added to the developer solution with similar efiect.
  • the compounds according to the invention are added to the emulsion in quantities of 0.3 to 30 g. per mol of silver halide, preferably 0.3 to 3 g. per mol of silver halide.
  • the above quantities correspond to a concentration of 0.1 to g. per liter of emulsion, preferably 0.1 to 1 g. per liter of emulsion.
  • the polyalkylene oxides or polyalkylene oxide derivatives are used in the usual quantity.
  • concentration of the polyalkylene oxides can vary within wide limits depending upon the effect desired, and the nature of the emulsion used. In general, the addition of preferably 0.3 to 3 g. of polyalkylene oxide or derivatives thereof per mol of silver halide is suflicient.
  • the sensitizers can be dissolved in water or a solvent miscible with water or a mixture of water and water miscible solvents and added in this form to the emulsion.
  • the solvent is not critical and should be selected so that it should have no harmful eifect to the photographic properties of the silver halide emulsion.
  • any sensitizer of the present invention can be determined for any particular emulsion by running a series of comparison tests in which the quantity of the sensitizer is varied over a given range. Exposure of the emulsion containing the sensitizer'in a manner well known and measuring of the sensitivity in conventional apparatuses will reveal most advantageous concentrations. Such technic is well understood by those skilled in the art.
  • the emulsions may also contain other chemical sensitizers, e.g., quaternary ammonium or phosphonium salts as well as ternary sulfonium salts, reducing agents such as stannous salts, polyamines such as diethylene triamine or sulfur compounds as described in US. Patent 1574,- 944.
  • the given emulsions may contain, for the purpose of chemical sensitization, salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum or gold, as described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 6572 (1951).
  • the emulsions may contain stabilizers such as homopolar or salt-type compounds of mercury which contain aromatic or heterocyclic rings (e.g., mercaptotriazoles), simple mercury salts, sulfonium-mercury double salts and other mercury compounds.
  • stabilizers are azaindenes, preferably tetra or pentaaza- 'indenes, especially those substituted with hydroxy or amino groups. Such compounds have been described by Birr, Z. Wiss. Phot. 47. 2-58 (1952).
  • Other suitable stabilizers include heterocyclic mercapto compounds such as phenylmercapto-tetrazole, quaternary benzthiazole derivatives and benztriazoles.
  • the emulsions may also contain optical sensitizers such as the usual polymethine dyes such as neutrocyanines, basic or acid carbocyan'ines, rhodacyanines, her'nicyanines, styryl dyes and oxonoles. Examples of these sensitizers have been described in the work by F. M. Hamer The Cyanine Dyes and Related Compounds (1964).
  • the emulsions may be hardened in the usual manner, for example, using formaldehyde or halogen-substituted aldehyde which contain a carboxyl group, e.g., mucobromic acid diketones, methane sulfonic acid ester and dialdehydes.
  • formaldehyde or halogen-substituted aldehyde which contain a carboxyl group, e.g., mucobromic acid diketones, methane sulfonic acid ester and dialdehydes.
  • Sample 4--1 g. per mol of silver halide of compound I Sample 51 g. per mol of silver halide of compound IV
  • Sample 6-1 g. per mol of silver halide of compound V Sample 7.1 g. per mol of silver halide of compound IX
  • Sample 8-1 g. per mol of silver halide of compound X Sample 91 g. per mol of silver halide of ethylene-bisdi-n-butylsulfonium-dibromide and 750 mg. per mol of silver halide of a polyethylene oxide derivative of the type added to Sample 2.
  • Sample 13-1 g. per mol of silver halide of compound IX and 750 mg. per mol of silver halide of a polyethylene oxide derivative of the type added to Sample 2.
  • EXAMPLE 2 TABLE 1 Developed for 6 minutes EXAMPLE 2 The procedure employed was the same as that described in Example 1. The emulsion was divided into 7 parts and the following substances were then added to the different parts of the emulsion:
  • Sample 6-1 g. per mol of silver halide of Compound IX and 750 mg. per mol of silver halide of a polyethylene oxide derivative of the type added to Sample 2.
  • EXAMPLE 3 The procedure employed was the same as that described in Example 1. The emulsion was then divided into 4 parts and the following substances were then added to the different parts of the emulsion:
  • Sample 8-1 g. per mol of silver halide of compound No. VII and 750 mg. per mol of silver halide of a polyethylene oxide derivatitive of the type added to Sample 2.
  • Example 1 The samples were applied onto a cellulose acetate support and developed as in Example 1.
  • R hydrogen, alkyl having up to 18 carbon atoms, aeyl derived from an aliphatic carboxylic acid having up to 18 carbon atoms, a phenyl ring;
  • R a branched or unbranched alkyl or alkenyl radical containing up to 6 carbon atoms and substituted by at least one hydroxyl, carboxyl or epoxy group;
  • Z an alkylene radical having up to 18 carbon atoms that can be substituted with at least one hydroxyl, carboxyl or epoxy group, and can be interrupted by at least one oxygen atom, or aralkylene;

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US603168A 1965-12-28 1966-12-20 Photographic silver halide emulsions with increased sensitivity Expired - Lifetime US3551158A (en)

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DEA0051190 1965-12-28

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US (1) US3551158A (enEXAMPLES)
BE (1) BE691854A (enEXAMPLES)
CH (1) CH472049A (enEXAMPLES)
DE (1) DE1472791A1 (enEXAMPLES)
FR (1) FR1506229A (enEXAMPLES)
GB (1) GB1174058A (enEXAMPLES)
NL (1) NL6617873A (enEXAMPLES)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901709A (en) * 1972-05-25 1975-08-26 Mitsubishi Paper Mills Ltd Lith-type silver halide photographic material containing a polyalkylene oxide and a heterocyclic mercaptan
DE2508280A1 (de) * 1974-02-28 1975-09-04 Agfa Gevaert Ag Entwicklung belichteter silberhalogenidemulsionen vom lith-typ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901709A (en) * 1972-05-25 1975-08-26 Mitsubishi Paper Mills Ltd Lith-type silver halide photographic material containing a polyalkylene oxide and a heterocyclic mercaptan
DE2508280A1 (de) * 1974-02-28 1975-09-04 Agfa Gevaert Ag Entwicklung belichteter silberhalogenidemulsionen vom lith-typ

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BE691854A (enEXAMPLES) 1967-06-28
GB1174058A (en) 1969-12-10
CH472049A (de) 1969-04-30
FR1506229A (fr) 1967-12-15
DE1472791A1 (de) 1969-03-13
NL6617873A (enEXAMPLES) 1967-05-25

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