US3506444A - Dry stabilization of photographic images - Google Patents

Dry stabilization of photographic images Download PDF

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Publication number
US3506444A
US3506444A US612080A US61208067A US3506444A US 3506444 A US3506444 A US 3506444A US 612080 A US612080 A US 612080A US 61208067 A US61208067 A US 61208067A US 3506444 A US3506444 A US 3506444A
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United States
Prior art keywords
silver halide
photographic
emulsion
heating
silver
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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
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US612080A
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English (en)
Inventor
Grant M Haist
Donald M Burness
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Eastman Kodak Co
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Eastman Kodak Co
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Filing date
Publication date
Priority claimed from US371124A external-priority patent/US3301678A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US612080A priority Critical patent/US3506444A/en
Priority to DE19681622268 priority patent/DE1622268A1/de
Priority to FR137246A priority patent/FR93748E/fr
Priority to BE709900D priority patent/BE709900A/xx
Priority to GB4270/68A priority patent/GB1218443A/en
Priority to CH122668A priority patent/CH477707A/fr
Application granted granted Critical
Publication of US3506444A publication Critical patent/US3506444A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/262—Processes using silver-salt-containing photosensitive materials or agents therefor using materials covered by groups G03C1/42 and G03C1/43
    • 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
    • G03C1/43—Processing agents or their precursors, not covered by groups G03C1/07 - G03C1/42
    • 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
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G03C5/39—Stabilising, i.e. fixing without washing out
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/156—Precursor compound

Definitions

  • the silver halide in the unexposed areas is commonly removed by treatment with sodium thiosulphate or other fixing solutions to produce a soluble silver compound when a permanent silver image is desired. It is possible to stabilize the unexposed and undeveloped silver halide by reaction with a compound that forms a silver salt or complex that is colorless or relatively light in color and resistant to print-out. It is often convenient toincorporate a fixing or image stabilizing agent as an integral part of the photographic element. However, commonly used fixing agents are often not suitable for use in layers contiguous to photographic silver halide because they react with the silver halide in unexposed form and render the emulsion useless for photographic purposes.
  • an exposed photographic silver halide may be stabilized by a process wherein a sulfur-containing isothiourea derivative is incorporated in a photographic silver halide element.
  • the isothiourea derivative of the invention is a so-called precursor which breaks down at elevated temperatures to form a compound which combines with the silver halide in the unexposed areas of the emulsion to form a mercaptide compound which is more stable to light, atmospheric and ambient conditions than silver halide.
  • the isothiourea derivative of the process of the invention may be represented by the structure:
  • R is an alkylene or alkyl or aryl substituted alkylene radical such as alkyl or phenyl substituted alkylene radical, lower alkyl or phenyl substituted radicals including an ethylene, propylene or butylene radical and methyl or phenyl substituted propylene or butylene radical.
  • Y is an anion, or acid radical, such as -SO H, which form a so-called inner acid salt.
  • Y is preferably a sulfonate radical forming an inner acid salt with the isothiuronium moiety of the above structure.
  • One embodiment of the invention comprises a substantially dry stabilization method which comprises heating at a temperature above about C. to about 260 C., an exposed photographic silver halide element comprising a silver halide emulsion in the presence of an active stabilizing amount of sulfoalkyl thiopseudo urea, also known as thiuroniurn alkane sulfonate, represented by the structure:
  • the above sulfur-containing compounds function as precursors for image stabilizers in the present process and are stable and substantially inert in silver halide emulsions or in layers contiguous to such silver halide emulsions at temperatures which ordinarily prevail during conventional storage and use of photographic products. These compounds do not break down or cause adverse photographic elfects in the absence of elevated temperatures or activating amounts of alkalis. However, at the elevated temperatures set out above, the sulfur-containing compounds of the invention are converted to thiol compounds which form light-stable mercaptides with the silver halide in the unexposed areas of the photographic emulsion.
  • the isothiourea derivatives can be activated at a temperature above about 90 C. and preferably above about QII'he temperature range at which the derivatives are treated Will be determined by the various components of the emulsion, the developing agent and activator employed, the degree of development or stabilization desired and other factors including the type of support and photographic emulsion.
  • Heating in general, can be conveniently carried out by contact of the photographic element containing the ism thiourea compound with heated rollers, plates, or other heated carrier means, with steam, infra-red radiation, or by any other suitable means for effecting the desired temperatures.
  • the time or period of heating in the present process can be varied widely. Factors such as the temperature Patented Apr. 14, 1970 I employed and the ease of heat cleavability of the fixing or stabilization agent employed and other factors will determine the duration of the heating step. Generally, however, the heating period ranges from about 1 to about 5 seconds and is preferably as short as possible to produce the desired stabilization. The optimum heating period considering temperature, development, fixing, stabilizing and other factors can be readily determined by those skilled in the art.
  • the isothiourea derivatives are utilized in the present process typically at concentrations of at least A mole of the isothiourea derivative for each mole of the silver halide present in the emulsion, suitably to about 20 moles of the isothiourea for each mole of silver halide. However, it is preferable to utilize molar excesses of the isothiourea derivatives to assure effective stabilization of the unexposed and undeveloped areas of the silver halide emulsion.
  • the isothiourea derivatives used in the process of the invention can be employed with various kinds of photographic emulsions. Suitable emulsions which are useful include orthochromatic, panchromatic, infra-red emulsions, as well as X-ray films and other non-optically sensitized emulsions. Various silver salts may be employed in such emulsions as the sensitive salts. These include such salts as silver bromide, silver iodide, silver chloroiodide, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
  • the emulsion containing such salts has these salts dispersed or suspended in gelatin or other suitable permeable vehicles such as polyvinyl alcohol, polyacrylates, acrylic acids and other permeable polymers.
  • suitable permeable vehicles such as polyvinyl alcohol, polyacrylates, acrylic acids and other permeable polymers.
  • suitable permeable vehicles such as polyvinyl alcohol, polyacrylates, acrylic acids and other permeable polymers.
  • Other permeable materials which may be used include colloidal albumin and cellulose derivatives.
  • Suitable binding agents may be employed with the photographic elements of the invention such as cellulose acetates and cellulose ethers.
  • the emulsion utilized in preparing the photographic elements can be coated on a wide variety of supports.
  • suitable photographic supports are cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films or resinous materials.
  • Suitable supports such as glass, paper, wood, metals and others employed in the photographic art can be used. It is desirable to employ a support which is resistant to decomposition or other adverse effects on the photographic element at the temperatures employed in the process. It is, accordingly, desirable to employ a support resistant to charring at elevated temperatures.
  • the silver halide elements processed according to the invention may be sensitized using any of the well-known techniques in emulsion making. For example, they may be prepared by digesting with naturally active gelatin or various sulfur, sellenium, tellurium or gold compounds. They may also be sensitized with salts of noble metals and may also contain speed-increasing addenda such as quaternary ammonium salts, polyethylene glycols or other suitable sensitizers.
  • the emulsions treated according to the invention may also contain conventional addenda or have such addenda in layers contiguous to the emulsion layers. These addenda include suitable antifoggants, plasticizers, toners, coating aids, development restrainers, buffers and hardeners. Sensitizing dyes may have also been employed as Well as spectral sensitizers.
  • a matting agent such as silica
  • a matting agent such as silica
  • the isothiourea compounds can be added to or incorporated in photographic emulsions or layers of photographic elements by using any of the photographic techniques used in emulsion making. For example, they may be dissolved in a suitable solvent and added as such, or they can be added in the form of a dispersion similar to the techniques used to incorporate certain types of colorforming compounds, such as couplers, in a photographic emulsion. Techniques of this type are disclosed in, for instance, US. Patent 2,322,027Jelley et a1., and US. Patent 2,801,17l-Fierke et al. Solvents or dilutents which are miscible with water may be utilized to aid in the addition also. Such solvents should be selected in order to avoid adverse effects upon the emulsion or processing steps according to the invention.
  • the photographic elements described can be exposed and developed by dry or solution methods. Thereafter they can be fixed or stabilized in accordance with the invention by heating to an elevated temperature. It is also often suitable to incorporate a developing agent into the emulsion or a layer contiguous thereto whereby development and stabilization may be effected, without separate steps, upon heating to the desired temperature.
  • Development can be effected with conventional developers including phenolic developing agents such as hydroquinone, halogen-substituted hydroquinone developers such as chlorohydroquinone, bromohydroquinone, and dichlorohydroquinone, as Well as other suitable hydroquinone compounds such as alkyl-substituted hydroquinones.
  • phenolic developing agents such as hydroquinone, halogen-substituted hydroquinone developers such as chlorohydroquinone, bromohydroquinone, and dichlorohydroquinone
  • Amino phenol developers such as N-mcthyl-pamino-phenol sulfate can also be employed.
  • 3-pyrazolidone developers as, for example, 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxy-methyl-1-phenyl-3 pyrazolidone, lphenyl-4,4-dimethyl-3-pyrazolidone, 1 phenyl-2-acetyl-4- methyl-3-pyrazolidones such as disclosed in British Patent 930,572 or other related developers are also suitable.
  • Mixtures of developers are especially suitable including, for example, mixtures of hydroquinone developers with 3-pyrazolidone developers.
  • the developer can be applied in a thin layer over the exposed photographic element, for example, and undeveloped and unexposed silver halide thereafter lightstabilized or fixed by bringing the photographic element in contact with a heating means such as a heated roller or plate.
  • an activator such as an organic activator precursor
  • Activator as employed herein is intended to refer to an agent which causes the isothiourea derivatives to form a compound which combines with the unexposed silver halide of a photographic silver halide emulsion.
  • Suitable activators need not be incorporated activators in the silver halide emulsion or silver halide element.
  • Inorganic alkalis which may be employed as activators include potassium and/or sodium carbonates, and potassium and/or sodium hydroxides.
  • the amount of alkali to be used will be influenced by the solubility and activity of the alkali. Ordinarily, however, about A mole of alkali per mole of silver present in the emulsion as silver halide up to about 20 moles of alkali per mole of silver is suitable. Typically about /2 mole of alkali per mole of silver present in the emulsion as silver halide up to about 10 moles of alkali per mole of silver can be employed.
  • the isothiourea compounds can be activated by these inorganic alkalis, it is usually desirable not to contact the isothiourea compounds according to the process of the invention with such inorganic alkalis until stabilization is desired. For example, in most instances, it would not be desirable to contact a silver halide emulsion with an alkaline aqueous solution of a developer since it would be possible that the stabilization effect caused by the precursors of the invention would take place before the desired degree of development.
  • an organic activator precursor incorporated in a silver halide emulsion or in a layer contiguous to the silver halide emulsion according to the present process.
  • Such activator precursors break down or cleave when treated at the elevated temperatures set out above forming compounds which cause the isothiourea derivatives, according to the process, in turn to break down.
  • Organic activator precursor as employed herein, is intended to refer to organic compounds which upon heating form moieties which cause or aid in causing cleavage or break down of the described isothiourea derivatives. Suitable activator precursors are typically those which upon heating form an alkaline component.
  • quaternary ammonium activator precursors such as guanidinium organic acid salts, including guanidinium trichloroacetate; tetraalkyl ammonium trichloroacetates, such as tetraethyl ammonium trichloroacetate; quaternary ammonium malonates, such as piperazinium malonate; amino acids, such as aminobutyric acid and amino caproic acid; hydrazide compounds, such as benzhydrazide and isonicotinic acid hydrazide.
  • Suitable activator precursors are set out, for example, in British Patent 930,572.
  • EXAMPLE 1 3-S-thiuronium propane sulfonate A white paper photographic support having a gelatin layer coating, coated at the rate of 270 mg. per square foot, was coated with a solution, at the rate of grams per square foot, containing the following composition:
  • the element was further coated in the dark with a slow projection speed silver chloride photographic emulsion at a coverage of mg. per square foot of silver and 57 mg. per square foot of gelatin. Strips of the above prepared light-sensitive coatings were exposed to a line image and a photographic step tablet using conventional tungsten light. The exposed element was then brought into contact with a heated metal block at 190 C. After 2 seconds, a visible image having a maximum density of 1.2 was completely developed and stabilized. 'Exposure of the thus processed paper to daylight fluorescent light at 250 foot-candles for 1 hour caused no visible change in the image.
  • Example 2 The process of Example 1 was repeated employing the same compositions as set out in Example 1 with the exception that the coating containing t-butyl hydroquinone and S-S-thiuronium propane sulfonate was applied to the initial gelatin layer after the slow projection speed silver chloride emulsion was applied. Similar results were obtained to those in Example 1.
  • a silver chlorobromide emulsion containing 40 mg. per square foot of silver and 120 mg. per square foot of gelatin was coated over the above layer. After exposure, pieces of the coatings were fully developed and stabilized by heating them at 220 C. for 2 seconds.
  • EXAMPLE 4 Coatings were prepared employing the procedure and compositions of Example 3 with the exception that the diguanidinium oxalate was replaced with one of the alkalline activator precursor compounds set out in Table I. In each case, the amounts by weight used were equal to that set out in Example 3 for diguanidinium oxalate.
  • Oxazolidone p4 220 0. 80 N-methyloxazolidone p4 220 0. 80 Tetramethylammonium fumarate 8 190 0. 90 Sodium trichloroacetate 2 220 1. 00
  • EXAMPLE 5 The procedure set out in Example 4 was repeated with the exception that the light-sensitive silver halide emulsion was applied to the support below the layer containing the processing chemicals. The results achieved with this procedure were substantially the same as those observed in the prior examples.
  • EXAMPLE 7 The procedure set out in Example 6 was repeated with the exception that 3-S-thiuronium propane sulfonate was employed in place of the 2-S-thiuronium ethane sulfonate. Similar results were obtained to those set out in Example 6.
  • Example 8 The procedure set out in Example 6 was repeated with the exception that 4-S-thiuronium butane sulfonate was employed in place of 2-Sthiuronium ethane sulfonate. Similar results were obtained to those in Example 6.
  • EXAMPLE 10 The procedures set out in Examples 6, 7, 8 and 9 were repeated with the exception that in each case 2 grams of guanidinium thichloroacetate was added to the coating solution before application to the paper support. The results obtained in each instance were substantially the same as those obtained in Examples 6-9 with the exception that D in each case was increased to about 1.0
  • EXAMPLE 11 A coating solution was prepared containing the following components:
  • the resulting solution was coated at the thickness of 0.004 inch on a silver chloride emulsion coating on a baryta paper support.
  • the resulting coating was allowed to dry and then a portion thereof was exposed to white light through a step tablet.
  • the exposed coating was then processed by pressing the side of the paper support opposite the emulsion layer against a metal sheet heated to C. for 15 seconds.
  • a strong, pungent mercaptide odor was clearly present. Such odor especially during the heat processing step is particularly undesirable.
  • the processed area of the resulting element was then subjected F0 250 foot-candles of illumination for a period of one hour.
  • the temperature for processing a given coating will effect the time required to produce a stable element.
  • the following example illustrates, however, that a range of temperatures is suitable for the process of the invention.
  • EXAMPLE 12 A silver chloride photographic emulsion coating, containing 30 mg. per square foot of silver in gelatin, was applied to a white baryta paper support. The resulting layer was then coated at the rate of 9.5 grams per square foot with a polyvinyl alcohol layer containing the following components:
  • the coatings were exposed through a photographic step tablet to tungsten light and a series of strips each measuring about 1" by 7" was held in contact with a heated plate at a range of temperatures for periods of 2, 4 and '8 seconds.
  • the surface for each sample contacted with the heated plate was the surface opposite that having the emulsion layer. Temperatures between 190 C. and 220 C. produced stabilization in each instance.
  • EXAMPLE 13 The following procedure demonstrates the various operable concentration ranges which can be employed in the stabilization process of the invention.
  • a white baryta paper support was coated with an emulsion containing 23 ml. per square foot of silver.
  • a processing layer was coated over the resulting emulsion layer at the rate of 9.5 g. per square foot.
  • the processing layer was applied as an aqueous solution containing the following components:
  • a substantially dry stabilization method which comprises heating at a temperature above about 90 C. an exposed photographic element comprising a photographic emulsion containing silver halide and, contiguous to said silver halide, a stabilizer precursor represented by the structure:
  • R is selected from the group consisting of alkylene, alkyl substituted alkylene and aryl substituted alkylene radicals;
  • Y is selected from the group consisting of anions and acid radicals which form an inner acid salt, said compound upon said heating forming an organic thiol which combines with unexposed silver halide to form a silver mercaptide which is more stable to light t a s id s e halide- 2.
  • a process as in claim 1 wherein said stabilizer is an isothiourea derivative represented by the structure 7.
  • a process as in claim 1 wherein said heating is carried out at temperatures of about C. to about 260 C.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US612080A 1964-05-28 1967-01-27 Dry stabilization of photographic images Expired - Lifetime US3506444A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US612080A US3506444A (en) 1964-05-28 1967-01-27 Dry stabilization of photographic images
DE19681622268 DE1622268A1 (de) 1964-05-28 1968-01-24 Verfahren zum Stabilisieren eines photographischen Materials
FR137246A FR93748E (fr) 1964-05-28 1968-01-24 Nouveau procédé pour stabiliser des images photographiques.
BE709900D BE709900A (fr) 1964-05-28 1968-01-25
GB4270/68A GB1218443A (en) 1964-05-28 1968-01-26 Stabilisation of photographic silver halide materials
CH122668A CH477707A (fr) 1964-05-28 1968-01-26 Procédé d'obtention d'une image photographique stabilisée

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US371124A US3301678A (en) 1964-05-28 1964-05-28 Process for stabilizing photographic images with heat
US612080A US3506444A (en) 1964-05-28 1967-01-27 Dry stabilization of photographic images

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US3506444A true US3506444A (en) 1970-04-14

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US612080A Expired - Lifetime US3506444A (en) 1964-05-28 1967-01-27 Dry stabilization of photographic images

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US (1) US3506444A (fr)
BE (1) BE709900A (fr)
CH (1) CH477707A (fr)
DE (1) DE1622268A1 (fr)
FR (1) FR93748E (fr)
GB (1) GB1218443A (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3732103A (en) * 1971-05-03 1973-05-08 Eastman Kodak Co Silver halide emulsions containing alkyl selenols and thiols as antifoggants
US3844788A (en) * 1973-04-02 1974-10-29 Eastman Kodak Co Incorporation of sulfonyl derivatives of isothiourea in light-sensitive elements
USRE28668E (en) * 1971-05-03 1975-12-30 Silver halide emulsions containing alkyl selenols and thiols as antifoggants
US3985564A (en) * 1973-01-30 1976-10-12 Eastman Kodak Company Photographic element and process for developing
US4088496A (en) * 1976-12-22 1978-05-09 Eastman Kodak Company Heat developable photographic materials and process
EP0143424A2 (fr) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Matériel photosensible développable à chaud
JPH01291239A (ja) * 1988-05-18 1989-11-22 Fuji Photo Film Co Ltd 感光材料
US5492805A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Blocked leuco dyes for photothermographic elements
US5492804A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Chromogenic leuco redox-dye-releasing compounds for photothermographic elements
US5492803A (en) * 1995-01-06 1996-02-20 Minnesota Mining And Manufacturing Company Hydrazide redox-dye-releasing compounds for photothermographic elements
US20060141403A1 (en) * 2004-12-29 2006-06-29 Eastman Kodak Company Blocked aliphatic thiol stabilizers for photothermographic materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5196292A (en) * 1991-10-17 1993-03-23 Eastman Kodak Company Nucleated high contrast photographic elements containing ballasted thioether isothioureas to inhibit pepper fog and restrain image spread

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3140178A (en) * 1961-08-25 1964-07-07 Eastman Kodak Co Photographic silver halide emulsions containing thioether derivatives as antifoggants and stabilizers
US3189453A (en) * 1961-08-25 1965-06-15 Eastman Kodak Co Photographic emulsions containing thio derivatives as fixers and method of using same
US3220839A (en) * 1961-08-25 1965-11-30 Eastman Kodak Co Photographic emulsions containing isothiourea derivatives
US3301678A (en) * 1964-05-28 1967-01-31 Eastman Kodak Co Process for stabilizing photographic images with heat
US3306884A (en) * 1965-02-10 1967-02-28 Eastman Kodak Co Isothiuronium salts

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3140178A (en) * 1961-08-25 1964-07-07 Eastman Kodak Co Photographic silver halide emulsions containing thioether derivatives as antifoggants and stabilizers
US3189453A (en) * 1961-08-25 1965-06-15 Eastman Kodak Co Photographic emulsions containing thio derivatives as fixers and method of using same
US3220839A (en) * 1961-08-25 1965-11-30 Eastman Kodak Co Photographic emulsions containing isothiourea derivatives
US3301678A (en) * 1964-05-28 1967-01-31 Eastman Kodak Co Process for stabilizing photographic images with heat
US3306884A (en) * 1965-02-10 1967-02-28 Eastman Kodak Co Isothiuronium salts

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3732103A (en) * 1971-05-03 1973-05-08 Eastman Kodak Co Silver halide emulsions containing alkyl selenols and thiols as antifoggants
USRE28668E (en) * 1971-05-03 1975-12-30 Silver halide emulsions containing alkyl selenols and thiols as antifoggants
US3985564A (en) * 1973-01-30 1976-10-12 Eastman Kodak Company Photographic element and process for developing
US3844788A (en) * 1973-04-02 1974-10-29 Eastman Kodak Co Incorporation of sulfonyl derivatives of isothiourea in light-sensitive elements
US4088496A (en) * 1976-12-22 1978-05-09 Eastman Kodak Company Heat developable photographic materials and process
EP0143424A2 (fr) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Matériel photosensible développable à chaud
JPH01291239A (ja) * 1988-05-18 1989-11-22 Fuji Photo Film Co Ltd 感光材料
US5492805A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Blocked leuco dyes for photothermographic elements
US5492804A (en) * 1994-06-30 1996-02-20 Minnesota Mining And Manufacturing Company Chromogenic leuco redox-dye-releasing compounds for photothermographic elements
US5696289A (en) * 1994-06-30 1997-12-09 Minnesota Mining And Manufacturing Company Blocked leuco dyes for photothermographic elements
US5705676A (en) * 1994-06-30 1998-01-06 Minnesota Mining And Manufacturing Company Chromogenic leuco redox-dye-releasing compounds for photothermographic elements
US5492803A (en) * 1995-01-06 1996-02-20 Minnesota Mining And Manufacturing Company Hydrazide redox-dye-releasing compounds for photothermographic elements
US20060141403A1 (en) * 2004-12-29 2006-06-29 Eastman Kodak Company Blocked aliphatic thiol stabilizers for photothermographic materials
US7169543B2 (en) 2004-12-29 2007-01-30 Eastman Kodak Company Blocked aliphatic thiol stabilizers for photothermographic materials

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BE709900A (fr) 1968-05-30
GB1218443A (en) 1971-01-06
CH477707A (fr) 1969-08-31
DE1622268A1 (de) 1971-12-30
FR93748E (fr) 1969-05-09

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