US3333981A - Photographic material - Google Patents

Photographic material Download PDF

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Publication number
US3333981A
US3333981A US252098A US25209863A US3333981A US 3333981 A US3333981 A US 3333981A US 252098 A US252098 A US 252098A US 25209863 A US25209863 A US 25209863A US 3333981 A US3333981 A US 3333981A
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US
United States
Prior art keywords
silver halide
web
temperature
crucible
photographic
Prior art date
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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US252098A
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English (en)
Inventor
John J Kinsella
Robert A Wilferth
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Technical Operations Inc
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Technical Operations Inc
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Filing date
Publication date
Application filed by Technical Operations Inc filed Critical Technical Operations Inc
Priority to US252098A priority Critical patent/US3333981A/en
Priority to GB1961/64A priority patent/GB1001910A/en
Priority to BE642558A priority patent/BE642558A/xx
Priority to FR960386A priority patent/FR1386598A/fr
Priority to NL6400323A priority patent/NL6400323A/xx
Priority to DE19641447801 priority patent/DE1447801A1/de
Application granted granted Critical
Publication of US3333981A publication Critical patent/US3333981A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0694—Halides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/496—Binder-free compositions, e.g. evaporated
    • G03C1/4965—Binder-free compositions, e.g. evaporated evaporated
    • 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
    • Y10S430/133—Binder-free emulsion
    • 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
    • Y10S430/136—Coating process making radiation sensitive element

Definitions

  • the present invention relates to silver halide photographic materials, and more particularly to such materials fabricated by means of evaporation of the silver halide under reduced pressure and elevated temperature conditions, and the condensation of the silver halide vapors upon a suitable substrate material.
  • the silver halide vapor condenses as a stratum of silver halide microcrystals supported on the substrate by adherence of the microcrystals directly to the substrate and directly to each other.
  • This material is to be distinguished from emulsion or gelatin silver halide photographic materials, in that in the latter the silver halide grains are supported in a binder matrix which isolates the grains from each other and from the substrate, and functions as the means for supporting the grains on the substrate. Accordingly, the evaporated silver halide stratum may be looked upon as binder free, and by this term it is meant to distinguish the present materials from the emulsion or gelatin type of silver halide photographic materials.
  • Silver halide photographic materials include silver bromide, chloride, and iodide, and mixtures thereof.
  • silver bromide is used as the dominant silver halide ingredient, with smaller amounts of the iodide and/or chloride included for particular effects or properties. Accordingly, although the specific examples employed for purposes of illustrating the present invention relate to silver bromide because it is the most important photographic silver halide, the invention is not to be construed as limited thereto.
  • the silver bromide is applied to an open filament and is flash evaporated over a period of some seconds as the filament is heated to about 700 to 800 C. Since silver bromide melts at 434 C., it is apparent that during the few seconds of the evaporation operation, substantial evaporation begins at the melting point and continues in the ensuing seconds as the temperature of the silver bromide rises to some unknown value. Since the character and properties of the deposited silver bromide is dependent upon the temperature of evaporation, the resultant stratum will be nonuniform in its photographic properties. Furthermore, since the flash evaporation is basically an uncontrolled and indefinite procedure, it is apparent that successive coatings of successive photographic plates will vary in properties, and no uniformity of product would be obtained.
  • the principal advantage of evaporating at higher temperatures is the ability to coat the substrate at a much faster rate.
  • evaporating silver bromide from a molten pool with a pool temperature of about 620 C. as compared with a' silver bromide pool temperature of about 765 C., for the same thickness of coating the latter temperature affords a rate of deposition about ten times faster than the former temperature. This unusual increase in deposition rate exists despite the defeating function of decomposition of the silver bromide at this elevated temperature.
  • the web could be moved over the crucible at a rate of only about 44.0 ft./min. to produce a silver bromide stratum on the web of about 0.4 micron 'in thickness.
  • the web could be moved over the crucible at a rate of about 440 ft./min. to produce a silver bromide stratum on the web of about 0.4 micron in thickness.
  • Another object of the present invention is to provide for a photographic stratum of evaporated silver halide, wherein the evaporation of the halide is effected from a pool of molten silver halide under conditions of reduced pressure, and wherein the temperature of the entire molten pool is in excess of the decomposition temperature of the halide.
  • Still another object of the present invention is to provide for such a photographic stratum wherein the principal silver halide constituent is silver bromide.
  • FIG. 1 is a schematic elevation view of a vacuum coating apparatus utilized in practicing the present invention
  • FIG. 2 is a cross-sectional view of the apparatus of FIG. 1 taken along line 22 of FIG. 1;
  • FIG. 3 is a cross-sectional view of the apparatus of FIG. 1 taken along line 3-3 of FIG. 1, but with the parts in a different operational condition than in FIG. 1 for illustration purposes.
  • the apparatus comprises a base 10, having a plate 11 mounted on its top surface
  • a bell jar 12 is removably mounted on the plate 11, the surface of plate 11 and contacting surface of bell jar 12 being appropriately ground and machined to afford a high vacuum seal therebetween.
  • Evacuation of the volume under the bell jar is effected by a pump 41 through line 40.
  • a suitable pumping system is employed to afford a high vacuum with a minimum of contamination in the atmosphere under the bell jar 12.
  • a platform 13 is mounted centrally on plate 11 by means of brackets 14, for supporting the evaporation crucible 32.
  • the crucible 32 from which the silver halide is evaporated, can function as its own electrical heating element, as is afforded by forming the crucible of tungsten, for example.
  • the ends of the crucible are shaped for the attachment of leads 34, one to each end, by means of clips 33 and 39, or the like. With the leads 34 connected to a suitable electrical power source 35, the tungsten crucible 32 functions as its own resistance heater for melting and evaporating the silver halide placed therein.
  • Stand 16 is formed with a central aperture 18, which is the present instance is conveniently rectangular in shape. This aperture is covered on its upper side by a stationary backing plate 19, and on its lower side by a removable shutter 20. Shutter 20 may be pivoted by rotation of shaft 30 through handle 31, from a position underlying and covering the aperture 18 to a position completely exposing said aperture, as illustrated in FIG. 3.
  • Stand 16 further supports a web feed apparatus comprising a take-up roll 23 and a feed roll 24.
  • Roll 23 is rotationally supported by a pair of brackets 21 mounted on stand 16, while roll 24 is similarly supported by a corresponding pair of brackets 22.
  • These rolls are positioned on stand 16 so as to enable the feed of a web 29 from feed roll 24 under the lip 19a of backing plate 19, thence across the aperture 18, out of the aperture past lip 19b, and to take-up roll 23.
  • a web 29 of desired material may be fed from roll 24 to roll 23 across the aperture 18.
  • shutter 20 is removed from the aperture, the web 29 is exposed to vapors issuing from crucible 32 during its traverse across the aperture. The web is otherwise essentially shielded from such vapors by stand 16.
  • a drive for web 29 is effected by a motor 36 acting on shaft 25 through bevel gears 37, 38.
  • a motor 36 acting on shaft 25 through bevel gears 37, 38.
  • another pair of bevel gears 27, 28 connect drive shaft 25 to stub shaft 26, in turn coupled or connected to take-up roll 23.
  • the crucible 32 is charged with a desired quantity of silver halide, as for example silver bromide, iodide or chloride, or mixtures thereof. Or if desired, a plurality of crucibles 32 may be placed on platform 13 and independently electrically heated, one containing one halide and the other containing another halide, or both containing the same halide. For most photographic purposes, the ultimate deposited vapor should be predominantly silver bromide.
  • a web of conventional photographic base material, such as photobase paper, or an acetate or Mylar film, is wound on roll 24, fed across the aperture 18, and connected to roll 23. Shutter 20 is positioned to close aperture 18.
  • the operating pressure within the bell jar or vacuum chamber may be pumped down to between about 10- and 10- mm. Hg.
  • a pressure between the orders of about 10* and 1O mm. Hg is found best suited to our purposes, with about 5 10 mm. Hg being the most convenient value.
  • current is applied to crucible 32 to melt the silver halide therein, and bring it up to the desired evaporation temperature.
  • this evaporation temperature is chosen to be above the decomposition temperature of the halide, and preferably substantially in excess thereof.
  • the temperature of the molten pool of silver halide in the crucible 32 should be in excess of 700 C., the decomposition temperature of silver bromide as reported in the literature.
  • the range of about 725 to 765 C. or higher is preferred, with the higher end of this range being the more efficient.
  • the rate of decomposition of the silver halide becomes so great that the efficiency of the process will be reduced.
  • the shutter 20 is opened to permit the vapors of the silver halide issuing from crucible 32 to impinge upon the web 29 in aperture 18 and to condense and crystallize there in microcrystalline form.
  • motor 36 is energized to drive roll 23, and there-.
  • the rate of feed of the web can be used to control the thickness of the silver halide deposit thereon for a given set of other operating parameters.
  • the silver halide deposit on web 29 should be very thin, in the range of a fraction of a micron, and preferably between about 0.1 and about 0.5 micron depending upon the specific substrate used, and the particular photographic properties desired.
  • the crucible 32 In order to obtain a substantially uniform deposit of silver halide over the area of the web 29 as it advances across the aperture 18, it is preferred that the crucible 32 have a length at least approximating the width of web 29 or the corresponding width dimension of aperture 18. Also, it is apparent that web 29 must be located a sufiicient distance from the crucible 32 so as not to heat up'to a temperature that would inhibit the deposition of the evaporated silver halide thereon. For the silver bromide evaporating temperatures hereinabove suggested, it has been found that a distance from crucible 32 to the web in aperture 18 of about 3 inches is suitable. Under these conditions it was found that the web reaches a temperature of about 50 C. It is apparent that these physical parameters can be varied, and the web can be temperature controlled substantially independent of the spacing from crucible 32 by artificial or controlled cooling of the aperture-backing plate 19.
  • the prior art .admonishes against the preparation of evaporation silver halide layers for photographic purposes with evaporation temperatures in excess of the silver halide decomposition temperature.
  • the findings of the present invention indicate that comparable photographic properties can be obtained with silver halide strata formed by evaporation at temperatures substantially in excess of the decomposition temperature of the silver halide, as compared with strata formed by evaporation at temperatures below the decomposition temperature; and indeed, higher photographic speeds have been obtained with the higher temperatures.
  • the rate of coating or deposition of the silver halide layer can be increased many fold above that obtainable under prior teachings.
  • the samples of photographic material utilized in the examples tabulated hereinbelow are all prepared in the following manner.
  • a Web of photographic quality baryta paper is inserted in the apparatus of the drawings in the manner above-described, the crucible is charged with pure silver bromide, for example silver bromide synthesized according to the procedures of Malinowski, described in The Journal of Photographic Science, vol. 8, 1960, pages 69-71, and the bell jar is sealed to the vacuum plate 11.
  • the vacuum chamber is evacuated to a stabilized pressure of about 5 'l0 mm. Hg, and then the silver bromide charge is heated to a stable temperature of a value for each sample as indicated in the tabulation of examples.
  • the shutter 20 is then opened and the paper web is advanced across the aperture 18 at a rate which effects a uniform deposit of silver bromide on the paper substrate of about 0.4 micron thick (which was found photographically optimum for this substrate material). Because of the residual gas load in the paper web, when coating is startedand the web advances, the pressure of the system rises to about 3X10 mm. Hg during the coating operation.
  • the resultant photographic products where similarly exposed to an optical image and developed, and the average relative photographic properties of these samples are set forth in the following table:
  • Solution B Sodium carbonate: 78 g. anhydrous (or 91.26 g. of monohydrate) Potassium bromide: 2.0 g.
  • a method of vacuum coating silver halide composed at least predominantly of silver bromide onto a substrate comprising evacuating a housing having therein a crucible containing a supply of said silver halide and a web of substrate material spaced from said crucible to a pressure of between about 10 and about 10- mm. Hg, heating said silver halide and maintaining it at a substantially stable temperature between a temperature in excess of its decomposition temperature and about 765 C.
  • a method of vacuum coating silver halide composed at least predominantly of silver bromide onto a substrate comprising evacuating a housing having therein a crucible containing a supply of said silver halide and a supply of substrate material spaced from said crucible to a pressure of less than about 10- mm. Hg, heating said silver halide and maintaining it at a substantially stable temperature between a temperature in excess of its decomposition temperature and about 765 C.
  • a method of vacuum coating silver halide composed at least predominantly of silver bromide onto a substrate comprising evacuating a housing having therein a container holding a supply of said silver halide and a supply of substrate material spaced from said container, heating said silver halide and maintaining it at a temperature between a temperature in excess of its decomposition temperature and about 765 C., and exposing said substrate material to the evaporated silver halide to collect a microcrystalline photographically sensitive layer of evaporated silver halide thereon while said silver halide is maintained at said temperature.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Physical Vapour Deposition (AREA)
US252098A 1963-01-17 1963-01-17 Photographic material Expired - Lifetime US3333981A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US252098A US3333981A (en) 1963-01-17 1963-01-17 Photographic material
GB1961/64A GB1001910A (en) 1963-01-17 1964-01-14 Improvements in or relating to the manufacture of photographic materials
BE642558A BE642558A (en, 2012) 1963-01-17 1964-01-15
FR960386A FR1386598A (fr) 1963-01-17 1964-01-15 Procédé de fabrication d'un matériau photographique à l'halogénure d'argent
NL6400323A NL6400323A (en, 2012) 1963-01-17 1964-01-17
DE19641447801 DE1447801A1 (de) 1963-01-17 1964-01-17 Fotografisches Material und Verfahren zu seiner Herstellung

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US252098A US3333981A (en) 1963-01-17 1963-01-17 Photographic material

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US3333981A true US3333981A (en) 1967-08-01

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US (1) US3333981A (en, 2012)
BE (1) BE642558A (en, 2012)
DE (1) DE1447801A1 (en, 2012)
GB (1) GB1001910A (en, 2012)
NL (1) NL6400323A (en, 2012)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3999506A (en) * 1975-07-15 1976-12-28 Jones & Laughlin Steel Corporation Vapor deposition apparatus
US6461667B1 (en) * 2000-04-04 2002-10-08 Eastman Kodak Company Apparatus and method for vapor depositing lubricant coating on a web

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1970496A (en) * 1931-10-05 1934-08-14 Philips Nv Carrier provided with a light sensitive substance and process of manufacturing the same
US2945771A (en) * 1953-07-03 1960-07-19 Mansfeld Hubert Formation of light-sensitive layers on photographic films
FR1267623A (fr) * 1959-09-18 1961-07-21 Technical Operations Inc Matériau sensible pour photographie et son procédé de fabrication
US3219488A (en) * 1961-12-15 1965-11-23 Union Carbide Corp Reinforced combination safety blow-out and gas permeable membrane for alkaline galvanic cells

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1970496A (en) * 1931-10-05 1934-08-14 Philips Nv Carrier provided with a light sensitive substance and process of manufacturing the same
US2945771A (en) * 1953-07-03 1960-07-19 Mansfeld Hubert Formation of light-sensitive layers on photographic films
FR1267623A (fr) * 1959-09-18 1961-07-21 Technical Operations Inc Matériau sensible pour photographie et son procédé de fabrication
US3219488A (en) * 1961-12-15 1965-11-23 Union Carbide Corp Reinforced combination safety blow-out and gas permeable membrane for alkaline galvanic cells

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3999506A (en) * 1975-07-15 1976-12-28 Jones & Laughlin Steel Corporation Vapor deposition apparatus
US6461667B1 (en) * 2000-04-04 2002-10-08 Eastman Kodak Company Apparatus and method for vapor depositing lubricant coating on a web

Also Published As

Publication number Publication date
DE1447801A1 (de) 1969-02-20
GB1001910A (en) 1965-08-18
BE642558A (en, 2012) 1964-05-04
NL6400323A (en, 2012) 1964-07-20

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