US3420670A - Stabilization of synergistically sensitized photographic systems - Google Patents

Stabilization of synergistically sensitized photographic systems Download PDF

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US3420670A
US3420670A US510054A US3420670DA US3420670A US 3420670 A US3420670 A US 3420670A US 510054 A US510054 A US 510054A US 3420670D A US3420670D A US 3420670DA US 3420670 A US3420670 A US 3420670A
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pyrazolidone
silver halide
emulsion
selenium
sensitizer
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US510054A
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Kirby M Milton
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • 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
    • 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
    • G03C2001/091—Gold
    • 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
    • G03C2001/097—Selenium
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C5/3028—Heterocyclic compounds
    • G03C5/3035—Heterocyclic compounds containing a diazole ring

Definitions

  • 3-pyrazolidones can be used in the silver halide emulsions of the invention.
  • Typical suitable 3-pyrazolidones are disclosed in US. Patent 2,289,367; US. Patent 2,685,516; US. Patent 2,751,297; US Patent 2,772,282; British Patents 679,677 and 679,678; and the Journal of Organic Chemistry, 26, 2803 (1961).
  • 3-pyrazolidones can be represented by the following formula wherein: R, R R R and R can be alkyl radicals (preferably having 1 to 4 carbon atoms) and including substituted lower radicals such as chloro-substituted alkyl radicals; hydrogen atoms; aryl radicals and including substituted aryl radicals such as phenyl, chlorophenyl, ptolyl, naphthyl and B-hydroxyethylphenyl, and the like; and heterocyclic radicals such as those having at least one hetero atom like sulfur, nitrogen or oxygen.
  • R, R R R R and R can be alkyl radicals (preferably having 1 to 4 carbon atoms) and including substituted lower radicals such as chloro-substituted alkyl radicals; hydrogen atoms; aryl radicals and including substituted aryl radicals such as phenyl, chlorophenyl, ptolyl, naphthyl and B-hydroxyethylphenyl, and the
  • At least about 1 mg. is useful, and more generally 1 to 1000 mg., and preferably 5 to mg., of 3-pyrazolidone per mole of silver halide in the emulsion.
  • the 3- pyrazolidone stabilizers are added to the present emulsions during the sensitization or finishing of the emulsion.
  • the selenium sensitizers useful in my invention include a wide variety of labile selenium sensitizers, many having been previously suggested for use alone in sensitizing photographic silver halide emulsions. Suitable selenium addenda are disclosed in Sheppard et al. US. Patent 1,623,- 499, issued Apr. 5, 1927, as well as Sheppard US. Patents 1,574,944, issued Mar. 2, 1926, and 1,602,592 issued Oct. 12, 1926.
  • the labile selenium sensitizers of my invention which have been found to be particularly useful are organic selenium compounds wherein the selenium atom is doubly bonded to a carbon atom of the organic compound through a covalent linkage.
  • especially useful compounds include selenoamides, selenoketones (especially ketones having an alkyl radical attached to the moiety), selenocarboxylic acids and esters, etc.
  • Useful groups of selenium sensitizers include aliphatic selenoureas wherein the aliphatic radical is, for example, an alkyl radical such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, etc.
  • Such selenoureas have at least one hydrogen atom attached to the nitrogen atom thereof, thus making possible the formation of an enol tautomer.
  • analogous selenoureas containing one or more aromatic radicals, such as phenyl, tolyl, etc., or heterocyclic radicals, such as benzothiazolyl, pyridyl, etc., and aliphatic isoselenocyanates.
  • aromatic radicals such as phenyl, tolyl, etc.
  • heterocyclic radicals such as benzothiazolyl, pyridyl, etc.
  • aliphatic isoselenocyanates are also useful labile selenium sensitizers.
  • selenophosphates such as tri-alkyl and tri-aryl selenophosphates. It has also been found that colloidal selenium itself is a useful sensitizer.
  • Illustrative addenda suitable for furnishing the labile selenium moiety in the stabilized silver halide emulsions of the invention include:
  • the concentration of selenium sensitizer can be varied considerably depending upon the particular selenium addendum employed (some sensitizers being more efficacious than others), the nature of the silver halide emulsion, the amount and chemical nature of the noble metal sensitizer, etc. I have found that useful results can be obtained using amounts as small as 0.05 mg. of selenium sensitizer per mole of silver halide although considerably larger amounts can also be employed, such as 5.0 mg. or more per mole of silver halide.
  • labile as used herein has the meaning well understood by those skilled in the art of photography, i.e., a material which yields a silver salt that is insoluble in water at room temperature (20 C.) upon addition to an aqueous silver nitrate solution.
  • selenourea is a labile selenium compound, since silver selenide precipitates when selenourea is added to an aqueous silver nitrate solution.
  • colloidal selenium precipitates silver selenide upon addition to aqueous silver nitrate and is, therefore, a labile selenium addendum or sensitizer of invention.
  • the noble metal sensitizers useful in the photographic systems stabilized in accordance with my invention include the well-known gold sensitizers which have been previously recognized as useful in the photographic art and found to be outstanding in their sensitizing action, including water-soluble and water-insoluble organic and inorganic gold compounds and salts, although other noble metal sensitizers can be used, including palladium, platinum, etc., sensitizers such as are disclosed in Smith et al. U.S. Patent 2,448,060 issued Aug. 31, 1948. Typical suitable gold sensitizers are described in Waller et al. U.S. Patent 2,399,083 issued Apr. 23, 1946, and Damschroder et al. U.S. Patent 2,642,361 issued June 16, 1953.
  • Illustrative addenda suitable for furnishing the noble metal moiety in the sensitizer combinations of the invention include:
  • Ammonium chloroplatinite i.e., (NH PtCl Ammonium chloropal-ladate, i.e., (NI-LQ PdCI and Organic gold sensitizers such as Compounds I to X described in columns 2 and 3 of U.S. Patent 2,642,361.
  • the quantity of noble metal sensitizer useful in sensitizing the photographic systems of the invention can likewise be varied as in the case of selenium sensitizers. I have found, for example, that amounts varying from about 0.1 to 25.0 mg. of gold sensitizer per mole of silver halide are quite satisfactory.
  • the noble metal moiety and the labile selenium moiety used in sensitizing the photographic systems stabilized in accordance with the invention are more generally added to the photographic system as separate entities, although such is not necessary.
  • Typical thiocyanates include sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, etc.
  • Other water-soluble thiocyanates can be employed to equal advantage.
  • the amount of thiocyanate compound used can likewise be varied, depending upon the particular system being sensitized, relative amounts of selenium and noble metal sensitizers, etc.
  • the sensitizing addenda used in sensitizing the photographic systems stabilized in accordance with the invention can be added in a variety of ways to photographic systems and at various stages in the preparation of such. In general, such addenda can be added with useful effects at the completion of the Ostwald ripening and prior to one or more of the final digestion operations.
  • the sensitizing addenda of the invention are preferably added to silver halide emulsions after the silver halide grains are substantially in their final size and shape.
  • the addenda can be added in the form of their aqueous solutions, where they are soluble in water, or in an innocuous organic solvent where the sensitizer does not have sufficient solubility in water to be used in the form of an aqueous solution.
  • Particularly useful organic solvents include ethanol, methanol, pyridine, acetone, dioxane, etc. That is, organic solvents which have a rather high degree of polarity are preferred. Where it is desired to add the sensitizing addenda in some other form than a solution, this procedure is also possible, especially where the sensitizer is available in the form of a colloidal suspension. In some cases, it is possible to add the sensitizers suspended in an organic solvent which forms very small suspended particles or globules in the photographic emulsion similar to the type of colloidal particle produced in preparing coupler dispersions. Dispersing media useful for this purpose include tricresyl phosphate, dibutyl phthalate, triphenyl phosphate, etc.
  • gelatin or some other colloidal hydrophilic material, such as colloidal albumin, a cellulose derivative or a synthetic resin, for instance, a polyvinyl compound, an acrylateacrylic acid copolymer, and the like.
  • Patent 2,886,437 issued May 12, 1959; as well as the thio polymers of Graham and Sagal US. Patent 3,046,129 issued July 24, 1962, and the Dann and Chechak US. Patent 3,046,134 issued July 24, 1962.
  • useful effects can be obtained by adding the aforementioned speed-increasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emulsions.
  • Particularly useful silver halide emulsions sensitized with a noble metal and a labile selenium sensitizer as described above are obtained when a thioether silver halide solvent is present during the grain formation of the silver halide.
  • Typical suitable thioethers include the polythiaalkylenediols described in Williams and Cossar US. Patent 3,021,215, issued Feb. 13, 1962, and in Dann and Gates US. Patent 3,062,646, issued Nov. 6, 1962.
  • the feature 3-pyrazolidone stabilizing agents have particular utility for stabilizing noble metal and selenium sensitized silver halide emulsions having at least 50 mole percent chloride as the halide moiety.
  • Suitable silver halide emulsions include silver chloride, silver chlorobromide, silver chloroiodide and silver chlorobromoiodide.
  • the present invention is particularly directed to stabilizing high contrast or graphic arts-type of silver halide emulsions.
  • the present emulsions are also useful in X-ray and other nonspectrally sensitized systems, as well as in orthochromatic, panchromatic and infrared systems
  • the subject emulsions can be utilized in conventional color photographic systems such as in color diffusion transfer system using dye developers or couplers that form diffusible dyes, dye bleach systems, color systems utilizing couplers or color formers in processing compositions or incorporated in the emulsion, and related we'll-known color systems.
  • Example 1 One mole of a high contrast, graphic arts-type gelatino silver chlorobromoiodide emulsion comprising 90 mole percent chloride and 9 mole percent bromide and 1 mole percent iodide was treated with 1.72 mg. of potassium chloroaurate, 1.33 mg. of N,N-dimethylselenourea and 4 methyl-l-phenyl-3-pyrazolidone as an antifoggant at the concentrations set out in Table I below. The emulsions were heated for 60 minutes at 65 C., cooled and coated on a cellulose acetate film support at a coverage of 477 mg. silver and 473 mg. gelatin per square foot.
  • Example 2 An emulsion similar to that described in Example 1 was prepared except that 50 mg. per mole of silver halide of l-phenyl-4,4-dimethyl-3-pyrazolidone was utilized in lieu of the 4-inethyl-l-phenyl-3-pyrazolidone during the sensitization with the gold and selenium salts. The emulsion was coated, exposed and processed as described in Example 1. A fog level substantially below that of a similar emulsion sensitized in the absence of a 3-pyrazolidone was obtained.
  • Example 3 One mole of an emulsion similar to that in Example 1 was sensitized with 9.7 mg. gold sulfide and 0.89 mg. N,N-dimethylselenourea, in lieu of the sensitizing salts and concentrations described in Example 1, in the presence of 15 mg. 4-methyl-1-phenyl-3-pyrazolidone. The emulsion was heated as indicated in Table II below, cooled and the various samples were coated as in Example 1. A second mole of the same emulsion was similarly treated in the absence of 4-methyl-l-phenyl-3-pyrazolidone. The resulting emulsions were coated, exposed and processed as described in Example 1. The results are summarized in Table II below.
  • the speed of the control without heat treatment was set equal to 100 upon development in the D-19.
  • Example 4 The relative ineffectiveness of the subject 3-pyrazolidones to stabilize low chloride-content gold and selenium sensitized silver halide emulsions is illustrated in Example 4 below, and the relative ineffectiveness of several conventional silver halide developing agents to stabilize gold and selenium sensitized silver halide emulsions is illustrated in Example 5 below.
  • Example 4 To one mole of a medium grain gelatino silver bromoiodide mole percent bromide and 5 mole percent chloride) emulsion was added 2.6 mg. of potassium chloroaurate, mg. of sodium thiocyanate and 1.06 mg. of N,N-dimethylselenourea. The emulsion was then split into two portions. One portion was retained as a control. To the remaining portion was added 15 mg. 4- methyl-l-phenyl-3-pyrazolidone per silver mole. Both portions were then digested at 65 C. to obtain optimum speed therein, then coated on a cellulose acetate film support to yield a silver coverage of 540 mg. per square foot and a gelatin coverage of 725 mg. per square foot. Samples of each of these coatings were exposed on an Eastman type IB sensitometer, processed for 5 minutes in Kodak DK-5O developer, fixed in hypo, washed and dried in the usual manner. The results are sumarized in Table III below.
  • Example 5 To one mole of a gelatino silver halide emulsion of the type described in Example 1 was added 0.89 mg. of N,N- dimethylselenourea, and 7.7 mg. gold sulfide. The emulsion was then split into four parts and further treated as follows:
  • a photographic silver halide emulsion wherein said halide comprises at least 50 mole percent chloride sensitized with a noble metal and labile selenium, the improvement wherein a 3-pyrazolidone is used as a stabilizer during the sensitization of said emulsion.
  • a photographic silver halide emulsion as described in claim 1 wherein the 3-pyrazolidone has the formula wherein each R substituent is selected from the group consisting of a hydrogen atom, an alkyl radical, an aryl radical and a heterocyclic radical containing at least one hetero atom selected from the group consisting of sulfur, nitrogen and oxygen.
  • a stabilizer is used during the sensitization of said emulsion, said stabilizer being about 1 to 1000 mg. per mole of said silver halide of a 3-pyrazolidone having the formula References Cited UNITED STATES PATENTS 2/1963 Willems et a1 96-109 X 1/1967 McVeigh 96-109 NORMAN G. TORCHIN, Primary Examiner.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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US510054A 1965-11-26 1965-11-26 Stabilization of synergistically sensitized photographic systems Expired - Lifetime US3420670A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0122125A1 (en) * 1983-04-06 1984-10-17 Konica Corporation Silver halide emulsion
US4734358A (en) * 1984-10-05 1988-03-29 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material
US5112733A (en) * 1989-05-31 1992-05-12 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP0514675A1 (en) 1991-04-22 1992-11-25 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for processing the same
EP0512496A3 (en) * 1991-05-10 1993-03-24 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5310631A (en) * 1992-04-20 1994-05-10 Fuji Photo Film Co., Ltd. Method of processing a silver halide photosensitive material containing a silver halide sensitized with a selenium sensitizer using a black-and-white developer containing a chelate complex salt of a transition metal
EP0693710A1 (en) 1994-07-18 1996-01-24 Konica Corporation Silver halide photographic element and processing method thereof
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
US20060121397A1 (en) * 2003-01-31 2006-06-08 Konica Minolata Photo Imaging Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3078163A (en) * 1959-12-02 1963-02-19 Gevaert Photo Prod Nv Spot prevention in light-sensitive silver halide emulsion layers
US3297447A (en) * 1964-07-22 1967-01-10 Eastman Kodak Co Stabilization of synergistically sensitized photographic systems

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3078163A (en) * 1959-12-02 1963-02-19 Gevaert Photo Prod Nv Spot prevention in light-sensitive silver halide emulsion layers
US3297447A (en) * 1964-07-22 1967-01-10 Eastman Kodak Co Stabilization of synergistically sensitized photographic systems

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0122125A1 (en) * 1983-04-06 1984-10-17 Konica Corporation Silver halide emulsion
US4734358A (en) * 1984-10-05 1988-03-29 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material
EP0177884A3 (en) * 1984-10-05 1989-11-23 Konishiroku Photo Industry Co. Ltd. Silver halide photographic light-sensitive material
US5112733A (en) * 1989-05-31 1992-05-12 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP0514675A1 (en) 1991-04-22 1992-11-25 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for processing the same
US5415991A (en) * 1991-05-10 1995-05-16 Fuji Photo Film Co., Ltd. Stable, rapidly-developable silver halide photographic material
EP0512496A3 (en) * 1991-05-10 1993-03-24 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5310631A (en) * 1992-04-20 1994-05-10 Fuji Photo Film Co., Ltd. Method of processing a silver halide photosensitive material containing a silver halide sensitized with a selenium sensitizer using a black-and-white developer containing a chelate complex salt of a transition metal
EP0693710A1 (en) 1994-07-18 1996-01-24 Konica Corporation Silver halide photographic element and processing method thereof
US5556738A (en) * 1994-07-18 1996-09-17 Konica Corporation Silver halide photographic element and processing method thereof
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
US20060121397A1 (en) * 2003-01-31 2006-06-08 Konica Minolata Photo Imaging Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
US7220537B2 (en) 2003-01-31 2007-05-22 Konica Minolta Photo Imaging, Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation

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FR1501596A (fr) 1967-11-10
GB1160680A (en) 1969-08-06
DE1547753A1 (de) 1970-10-01

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