US3615631A - Photographic silver halide emulsion with increased sensitivity - Google Patents

Photographic silver halide emulsion with increased sensitivity Download PDF

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Publication number
US3615631A
US3615631A US784909A US3615631DA US3615631A US 3615631 A US3615631 A US 3615631A US 784909 A US784909 A US 784909A US 3615631D A US3615631D A US 3615631DA US 3615631 A US3615631 A US 3615631A
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United States
Prior art keywords
emulsion
sensitizer
silver halide
group
compounds
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US784909A
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English (en)
Inventor
Harald Huckstadt
Wolfgang Himmelmann
Wilhelm Saleck
Bergisch-Gladbach
August Randolph
Erwin Ranz
Walter Simmler
Hans-Dietrich Golitz
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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
    • 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
    • G03C1/10—Organic substances

Definitions

  • the invention relates to photographic silver halide emulsions chemically sensitized by the addition of cyclic amine compounds containing at least one dialkylsilyl group.
  • the sensitivity of silver halide emulsions can be increased by chemical ripening or afterripening during the preparation of the emulsion, by either prolonging the ripening time or by the addition of suitable substance such as compounds of noble metals or thiosulfate or other sulfur compounds.
  • suitable substance 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.
  • Suitable compounds include those of the following formula:
  • 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 includes 3 separate steps:
  • 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. In many cases it has proved advantageous to add the chemical sensitizer of the present invention before or during the afterripening.
  • the particular quantity of the sensitizers of the invention used in a given emulsion can vary, depending upon the effects desired, the silver content of the emulsion, the silver halide composition etc.
  • the amount used is also dependent upon the particular state at which the sensitizer was added during the preparation of the emulsion. Generally they are added in amounts of 0.005 to 5 g. preferably 0.05 to 1 g. per liter of emulsion ready for casting.
  • 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 such form to the emulsion.
  • the solvent is not critical and should be selected so that it should have no harmful effect on the photographic properties of the silver halide emulsion.
  • the optimum amount for any sensitizer of the present invention can be determined for any particular emulsion by running a series ofcomparison 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 technique is well understood by those skilled in the art.
  • the photographic emulsion in which the sensitizers according to the invention are used can contain additional chemical sensitizers customarily employed. They can be sensitized, for example, with sulfur compounds as referred to, e.g., in the book The Theory of the photographic Process, by Mees (I954).Pages 149-161.
  • the emulsions can also be chemically sensitized with salts of noble metal such as gold, ruthenium, rhodium, palladium, iridium and platinum, used in amounts below that which produce any substantial fog.
  • noble metal such as gold, ruthenium, rhodium, palladium, iridium and platinum
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate, potassium chloroaurate, auric trichloride and the like.
  • the emulsions can be sensitized with reducing agents, stannous salts or polyamines and the like.
  • the spirocyclic quaternary salts are used in combination with chemical sensitizers of the polyalkylene oxide type.
  • Suitable compounds of this type are, for example, those of the following formula:
  • R denotes a hydrogen atom or an alkyl group with preferably up to 18 carbon atoms such as an ethyl or dodecyl, an acyl group, preferably an acyl radical of an aliphatic carboxylic acid having up to 18 carbon atoms such as lauric acid or oleic acid, or an aryl group such as phenyl or pdodecylphenyl;
  • n an integer between 8 and 200.
  • the ethylene oxide groups CH .CH- ..0 may be substituted for instance wit alkyl having up to 18 carbon atoms. Molecular weights of from 1,500 to 10,000 are preferred for the polyethylene oxides. examples of which are described in U.S. Pats. Nos. 2,240,472 and 2,400,532.
  • Suitable chemical sensitizers are derivatives of phosphoric acid which contain polyalkylene oxide chains. Suitable products have been described in British Pat. Nos. 1,045,183 and 1,045,184 or French Pat. Nos. 1,396,860 and 1,423,680.
  • Such compounds are condensation products of spirocyclic pentaerythritol-di-phosphoric acid monohalides and polyethylene glycols containing about three to 100 ethylene oxide units in the molecule. They correspond to the following formula:
  • R a hydrogen atom or an alkylene oxide chain having 3 to 100 alkylene oxide units
  • n an integer from 3 to 100 and Y an integer from 1 to 10.
  • This group of chemical sensitizers also include the condensation products of amidophosphoric acid derivatives and polyethylene glycols of the above-mentioned type. Such compounds are represented by the following formula:
  • R a hydrogen atom, an alkyl, aryl or aralkyl group and R an alkyl, aryl or aralkyl group;
  • R and R may together represent the ring members required for completing a 5- or 6-membered heterocyclic ring
  • in is an integer between 2 and 100 preferably between 3 and 50;
  • p an integer from 0 to 100 and q an integer from 1 to 5.
  • the spirocyclic quaternary salts according to the invention may also be used advantageously in combination with the cross linked or noncross linked water-soluble quaternated products of tertiary polyamines with bifunctional polyalkylene oxide derivatives. These quaternated products have been described in German Pat. application A 50 5 lXa 57 b.
  • the accelerators according to the invention may also be used in combination with the morpholine or thiomorpholine derivatives described in French Pat. Nos. 1,506,230 and 1,548,191.
  • the accelerators described in the published Dutch applications 6,614,230 and 6,711,152 are also highly effective.
  • the emulsions may contain stabilizers such as homoopalar 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 of pentaazaindenes, especially those substituted with hydroxyl 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 carbocyanines, rhodacyanines, hemicyanines, styryl dyes and oxonoles. Examples of these sensitizers have been described in the work by F. M. Hamer The Cyanine Dyes and related Compounds, Interscience Publishers (1964).
  • optical sensitizers such as the usual polymethine dyes such as neutrocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes and oxonoles. Examples of these sensitizers have been described in the work by F. M. Hamer The Cyanine Dyes and related Compounds, Interscience Publishers (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.
  • the sensitizing compounds the synergistic combinations mentioned are not confined to black-white emulsions but also show similar desirable effects in color photographic emulsions containing color couplers. In this connection it is noteworthy that only negligible fog occurs when used in color-photographic silver halide emulsions which are particularly liable to fogging.
  • the emulsion is divided into 24 equal parts and the substances shown in the following table are added per liter of emulsion to the individual samples.
  • the emulsions are applied on a cellulose triacetate support and the layer is dried.
  • Table 1 The results of the sensitometric measurements are summarized in table 1 below.
  • EXAMPLE 2 sodium sulfite anhydrous 70.0 g. borax 7.0 g. hydroquinone 3.5 g. p-monomethyl-aminophenol 3.5 g. sodium citrate 7.0 g. potassium bromide 0.4 g.
  • sensitizer control 0.67 0.05 sensitizer sensitizer control 1.25 0.10
  • EXAMPLE 3 To a mixed emulsion which is composed of 90 percent of a silver iodobromide gelatin and percent of a silver iodochlorobromide emulsion which has been chemically ripened to a maximum sensitivity in known manner with gold and sulfur compounds are added the following ingredients per liter of emulsion:
  • l-(3'-sulfo-4'-phenoxy)-phenyl-3-heptadecylpyrazolone as magenta coupler 250 mg. of 1,3,3a, 7-(4-hydroxy-6-methyl)-tetraazaindene as stabilizer ml. of an aqueous 5 percent solution of saponin as wetting agent 2.5 ml. of an aqueous 30 percent solution of formaldehyde as hardener and 45 mg. of the green sensitizer of the following formula
  • the above emulsion is divided into 20 equal parts and the sensitizer shown in table 3 are added per liter of emulsion to the individual samples.
  • the samples are on a cellulose acetate support and dried.
  • Color-fonning developer Diethyl-p-phenylenediaminc sulfate 2.75 g. 'hydroxylamine sulfate 1.20 g. sodium sulfite anhydrous 2.00 g. sodium hexametaphosphatc 2.00 g. potassium carbonate anhydrous 75.00 g. potassium bromide 2.00 g. make up to 1 liter Stop bath Sodium acetate 30.00 g. acetic acid 6.00 g. make up with water to 1 liter Bleaching bath Potassium ferricyanidc 100.00 g. potassium bromide 20.00 g. acetic acid 4.00 g. make up with water to 1 liter Fixing bath Sodium thiosult'ate 200.00 g. make up with water to 1 liter The color density of the magenta layers was determined with a Macbeth Quanta Log, Model TD 102" densitometer, interposing the green filter into the path of the beam of measuring light.
  • EXAMPLE 4 The silver iodobromide gelatin emulsion of example 1 is divided into 13 equal parts and the substances specified in the following table, table 4.. are added. The emulsion is applied onto a support and dried as in example 1 and developed for 6 minutes at 20 C. in the developer given in example 2. Sensitizers A and B have the formulae given in example 2.
  • V 0.120 and A 0.480 and H 0.480 +3.1 1.10 0.40
  • a light-sensitive silver halide emulsion which contains a sensitivity increasing amount of a chemical sensitizer of the following formula:
  • Z represents oxygen or the group NR
  • R stands for a saturated or olefinically unsaturated aliphatic group containing up to 18 carbon atoms
  • X is a methylene or a dialkylsilyl group
  • R" represents an alkyl group containing up to six carbon atoms, the sensitizer containing at least one dialkylsilyl group.
  • R represents hydrogen or an alkylene oxide chain with 3 to alkylene oxide units
  • m is an integer of between 3 and 100 andy is an integer of between 1 and 10.

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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)
US784909A 1967-12-22 1968-12-18 Photographic silver halide emulsion with increased sensitivity Expired - Lifetime US3615631A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19671597511 DE1597511A1 (de) 1967-12-22 1967-12-22 Photographische Halogensilberemulsion mit erhoehter Empfindlichkeit
DEA0057779 1967-12-22

Publications (1)

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US3615631A true US3615631A (en) 1971-10-26

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US (1) US3615631A (de)
BE (1) BE725624A (de)
CH (1) CH500508A (de)
DE (1) DE1597511A1 (de)
FR (1) FR1598075A (de)
GB (1) GB1244878A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105454A (en) * 1976-02-05 1978-08-08 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion spectrally sensitized with merocyanine dyes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105454A (en) * 1976-02-05 1978-08-08 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion spectrally sensitized with merocyanine dyes

Also Published As

Publication number Publication date
DE1597511A1 (de) 1970-05-14
BE725624A (de) 1969-06-18
CH500508A (de) 1970-12-15
FR1598075A (de) 1970-06-29
GB1244878A (en) 1971-09-02

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