US3227556A - Photosensitive elements containing formazans - Google Patents

Photosensitive elements containing formazans Download PDF

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Publication number
US3227556A
US3227556A US243756A US24375662A US3227556A US 3227556 A US3227556 A US 3227556A US 243756 A US243756 A US 243756A US 24375662 A US24375662 A US 24375662A US 3227556 A US3227556 A US 3227556A
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United States
Prior art keywords
formazans
photosensitive
formazan
photosensitive elements
elements containing
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US243756A
Inventor
Gene L Oliver
Jr John W Gates
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US243756A priority Critical patent/US3227556A/en
Priority to GB48460/63A priority patent/GB1074133A/en
Priority to FR956615A priority patent/FR1377715A/en
Application granted granted Critical
Publication of US3227556A publication Critical patent/US3227556A/en
Anticipated expiration legal-status Critical
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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
    • G03C1/34—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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/831—Azo dyes

Definitions

  • Formazans that are useful according to the present invention are a class of compounds having the formulas wherein each of R and R represents a member selected from the group consisting of aryl and substituted aryl.
  • R represents a member selected from the group consisting of aryl, substituted aryl, nitro, alkyl containing 1 to 18 carbon atoms, and H and X represents dialkoxydiphenyl.
  • An object of the present invention is to provide photographic elements for use in photography comprising at least one layer which contains a formazan compound of the class defined above.
  • Spectra of compounds of the class defined above are characterized by rather broad absorption bands in the visible region. Changes of substituent groups R R and R in the class of compounds cause variation of absorption maxima over a considerable range. This is illustrated in Table l which shows absorption maxima of some typical formazans.
  • formazans of the class defined above are incorporated in at least one layer of a photosensitive element for use in photography.
  • a preferred embodiment of the invention is a photographic element comprising a photosensitive silver halide emulsion layer which has incorporated therein an antifoggant consisting of at least one formazan compound of the class defined. Following are examples which describe in more detail this preferred embodiment.
  • EXAMPLE 1 A high-speed, sulfur and gold sensitized bromoiodide emulsion was prepared and coated upon a cellulose acetate film support by conventional procedures. For a control sample, no forrnazan was added to the emulsion. For a test sample, tn'phenylformazan was added to the "ice emulsion prior to coating in a proportion of 30 mg. per mole of silver in the emulsion. Silver coverage was 432 mg. per sq. ft. and gelatin coverage was 978 mg. per square foot. The control and test samples were then exposed on an Eastman 1B sensitometer by conventional procedure and then processed for five minutes in Kodak DK-SO photographic developer. The samples were then fixed, washed and dried. The control sample had relative speed of and fog density of 0.18. The test sample had relative speed of 71 and fog density of 0.17.
  • Control and test samples were prepared as just described but were incubated for one week at F., 50% relative humidity before exposure and development.
  • the control had relative speed, of 59, fog density of 0.42.
  • the test sample had relative density of 65, fog density of 0.27.
  • Example 2 Control and test samples were prepared and tested as in Example 1 but with various formazans added before coating as shown in Table 2. For these samples silver coverage was 460 mg. per sq. ft. and gelatin coverage was 1.04 gm. per sq. ft. The letter reference to the formazan antifoggant corresponds to letter enumeration in Table 1.
  • this invention includes elements having more than one photosensitive emulsion layer, for example color films, in which at least one of such layers contains a formazan of the class defined.
  • formazans have other utility in photographic films and plates in addition to their use as antifoggants in the photosensitive emulsion layer, for example formazans are useful dyes for filter and antihalation layers.
  • a photosensitive element for use in photography comprising a photosensitive silver halide emulsion layer which contains as an antifogging agent at least one formazan compound having the formula selected from the group consisting of wherein each of R and R represent a member selected from the group consisting of aryl and substituted aryl, R3 represents a member selected from the group consisting of aryl, substituted aryl, alkoxy, nitro, alkyl containing 1 to 18 carbon atoms, and H and X represents dialkoxy biphenylene.
  • a photosensitive element as defined in claim 1 wherein said formazan compound is 1,5-diphenyl-3 ethoxycarbonylformazan.
  • a photosensitive element as defined in claim I wherein said formazan compound is 1,5-dipheny1-3-nitro formazan.
  • a photosensitive element as defined in claim 1 wherein said formazan compound is 3,5-diphenyl-1-pphenylazophenylformazan.
  • a photosensitive element as defined in claim 1 wherein said formazan compound is l,1'-(3,3'-dimethoxy- 4,4'-biphenylylene bis 3,5 -diphenylformazan) 7.
  • a photosensitive element as defined in claim 1 wherein said formazan compound is 1,3,5-triphenylformazan.
  • a photosensitive element as defined in claim 1 wherein said formazan compound is l-(4-acetamidophenyl) -3,5-diphenylformazan.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Description

United States Patent PHOTOSENSITIVE ELEMENTS CONTAINING FORMAZANS This invention relates to use of formazans in photosensitive elements for photography.
Formazans that are useful according to the present invention are a class of compounds having the formulas wherein each of R and R represents a member selected from the group consisting of aryl and substituted aryl. R represents a member selected from the group consisting of aryl, substituted aryl, nitro, alkyl containing 1 to 18 carbon atoms, and H and X represents dialkoxydiphenyl.
An object of the present invention is to provide photographic elements for use in photography comprising at least one layer which contains a formazan compound of the class defined above.
Spectra of compounds of the class defined above are characterized by rather broad absorption bands in the visible region. Changes of substituent groups R R and R in the class of compounds cause variation of absorption maxima over a considerable range. This is illustrated in Table l which shows absorption maxima of some typical formazans.
According to the present invention, formazans of the class defined above are incorporated in at least one layer of a photosensitive element for use in photography.
A preferred embodiment of the invention is a photographic element comprising a photosensitive silver halide emulsion layer which has incorporated therein an antifoggant consisting of at least one formazan compound of the class defined. Following are examples which describe in more detail this preferred embodiment.
EXAMPLE 1 A high-speed, sulfur and gold sensitized bromoiodide emulsion was prepared and coated upon a cellulose acetate film support by conventional procedures. For a control sample, no forrnazan was added to the emulsion. For a test sample, tn'phenylformazan was added to the "ice emulsion prior to coating in a proportion of 30 mg. per mole of silver in the emulsion. Silver coverage was 432 mg. per sq. ft. and gelatin coverage was 978 mg. per square foot. The control and test samples were then exposed on an Eastman 1B sensitometer by conventional procedure and then processed for five minutes in Kodak DK-SO photographic developer. The samples were then fixed, washed and dried. The control sample had relative speed of and fog density of 0.18. The test sample had relative speed of 71 and fog density of 0.17.
Control and test samples were prepared as just described but were incubated for one week at F., 50% relative humidity before exposure and development. The control had relative speed, of 59, fog density of 0.42. The test sample had relative density of 65, fog density of 0.27.
EXAMPLE 2 Control and test samples were prepared and tested as in Example 1 but with various formazans added before coating as shown in Table 2. For these samples silver coverage was 460 mg. per sq. ft. and gelatin coverage was 1.04 gm. per sq. ft. The letter reference to the formazan antifoggant corresponds to letter enumeration in Table 1.
Table 2 Exposed Fresh Exposed After Forruazau Formazan Incubation Antifog Conc., Sample No. gant Mg. per
(Table l) Mole Ag Rela- Fog Rela- Fog tive Density tive Density Speed Speed Control (l-(i) 0 100 49 1 A 30 52 .36 30 42 38 3 43 39 9 43 35 3 67 36 30 43 37 0 100 65 3 71 45 30 71 42 3, 000 50 39 F-ormazans of the class defined are effective antifoggants when incorporated at concentrations from about 3 to about 3000 milligrams per mole of silver in silver halide layers.
Although the examples show photographic elements having only one photosensitive silver halide emulsion layer, this invention includes elements having more than one photosensitive emulsion layer, for example color films, in which at least one of such layers contains a formazan of the class defined. In some embodiments of the invention it may be desirable to employ a mixture of the formazans defined above as an antifogging agent for silver halide films.
These formazans have other utility in photographic films and plates in addition to their use as antifoggants in the photosensitive emulsion layer, for example formazans are useful dyes for filter and antihalation layers.
The invention has been described with reference to certain preferred embodiments, but it will be understood that variations and modifications can be made within the scope of the invention defined in the following claims.
We claim:
1. A photosensitive element for use in photography comprising a photosensitive silver halide emulsion layer which contains as an antifogging agent at least one formazan compound having the formula selected from the group consisting of wherein each of R and R represent a member selected from the group consisting of aryl and substituted aryl, R3 represents a member selected from the group consisting of aryl, substituted aryl, alkoxy, nitro, alkyl containing 1 to 18 carbon atoms, and H and X represents dialkoxy biphenylene. i
2. A photosensitive element as defined in claim 1 wherein the concentration of formazan compound in said emulsion layer is in the range from 3 to 3000 milligrams per mole of silver in the layer.
3. A photosensitive element as defined in claim 1 wherein said formazan compound is 1,5-diphenyl-3 ethoxycarbonylformazan.
4. A photosensitive element as defined in claim I wherein said formazan compound is 1,5-dipheny1-3-nitro formazan.
5. A photosensitive element as defined in claim 1 wherein said formazan compound is 3,5-diphenyl-1-pphenylazophenylformazan.
6. A photosensitive element as defined in claim 1 wherein said formazan compound is l,1'-(3,3'-dimethoxy- 4,4'-biphenylylene bis 3,5 -diphenylformazan) 7. A photosensitive element as defined in claim 1 wherein said formazan compound is 1,3,5-triphenylformazan.
8. A photosensitive element as defined in claim 1 wherein said formazan compound is l-(4-acetamidophenyl) -3,5-diphenylformazan.
References Cited by the Examiner UNITED STATES PATENTS 2,160,907 6/1939 Richardson 9684 3,050,393 8/1962 MacDonald 9684 3,071,465 1/1963 Dersch et al. 96109 NORMAN G. TORCHIN, Primary Examiner.

Claims (1)

1. A PHOTOSENSITIVE ELEMENT FOR USE IN PHOTOGRAPHY COMPRISING A PHOTOSENSITIVE SILVER HALIDE EMULSION LAYER WHICH CONTAINS AS AN ANTIFOGGING AGENT AT LEAST ONE FORMAZAN COMPOUND HAVING THE FORMULA SELECTED FROM THE GROUP CONSISITNG OF
US243756A 1962-12-11 1962-12-11 Photosensitive elements containing formazans Expired - Lifetime US3227556A (en)

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US243756A US3227556A (en) 1962-12-11 1962-12-11 Photosensitive elements containing formazans
GB48460/63A GB1074133A (en) 1962-12-11 1963-12-09 Photographic materials
FR956615A FR1377715A (en) 1962-12-11 1963-12-10 New stabilized photosensitive product

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US243756A US3227556A (en) 1962-12-11 1962-12-11 Photosensitive elements containing formazans

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4196002A (en) * 1977-09-19 1980-04-01 Eastman Kodak Company Photothermographic element containing heat sensitive dye materials
US4201590A (en) * 1977-09-19 1980-05-06 Eastman Kodak Company Heat sensitive reactive products of hexaarylbiimidazole and antihalation dyes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2160907A (en) * 1936-03-31 1939-06-06 Eastman Kodak Co Filter for ultra-violet light
US3050393A (en) * 1959-06-26 1962-08-21 Ilford Ltd Filter layer for photographic elements
US3071465A (en) * 1961-03-14 1963-01-01 Gen Aniline & Film Corp Fog reduction in silver halide emulsions by 2h-tetrazolium halides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2160907A (en) * 1936-03-31 1939-06-06 Eastman Kodak Co Filter for ultra-violet light
US3050393A (en) * 1959-06-26 1962-08-21 Ilford Ltd Filter layer for photographic elements
US3071465A (en) * 1961-03-14 1963-01-01 Gen Aniline & Film Corp Fog reduction in silver halide emulsions by 2h-tetrazolium halides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4196002A (en) * 1977-09-19 1980-04-01 Eastman Kodak Company Photothermographic element containing heat sensitive dye materials
US4201590A (en) * 1977-09-19 1980-05-06 Eastman Kodak Company Heat sensitive reactive products of hexaarylbiimidazole and antihalation dyes

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GB1074133A (en) 1967-06-28

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