US3615473A - Diazo process of forming infrared absorbing record - Google Patents

Diazo process of forming infrared absorbing record Download PDF

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Publication number
US3615473A
US3615473A US873886A US3615473DA US3615473A US 3615473 A US3615473 A US 3615473A US 873886 A US873886 A US 873886A US 3615473D A US3615473D A US 3615473DA US 3615473 A US3615473 A US 3615473A
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United States
Prior art keywords
process according
soundtrack
record
zone
emulsion
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Expired - Lifetime
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US873886A
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English (en)
Inventor
John M Andreas
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Vantiva SA
Technicolor Inc
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Technicolor SA
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/002—Recording, reproducing or erasing systems characterised by the shape or form of the carrier
    • G11B7/003—Recording, reproducing or erasing systems characterised by the shape or form of the carrier with webs, filaments or wires, e.g. belts, spooled tapes or films of quasi-infinite extent
    • G11B7/0032—Recording, reproducing or erasing systems characterised by the shape or form of the carrier with webs, filaments or wires, e.g. belts, spooled tapes or films of quasi-infinite extent for moving-picture soundtracks, i.e. cinema
    • 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
    • G03C5/18—Diazo-type processes, e.g. thermal development, or agents therefor
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/22—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
    • G03C7/25—Dye-imbibition processes; Materials therefor; Preparing or processing such materials

Definitions

  • a soundtrack is prepared in the form of a gelatin relief record on an imbibition matrix film strip.
  • the gelatin relief is dyed with a strong reducing action dye and the dye transferred to the soundtrack zone of an imbibition blank.
  • the blank is then treated with ferric ferricyanide to form prussian blue (one of the several names for iron blue).
  • lron blue is a wholly acceptable silver substitute, having high absorption in the 700 to 1,000 nanometer infrared region, the region of maximum response of motion picture projector photocells.
  • the object of the present invention is to produce an iron blue record from a less expensive raw sock and with a simpler, faster and more economical process and apparatus, which nevertheless produces a greater number of prints of higher image quality and finer detail.
  • a process of producing a nonsilver photographic record comprises applying a photosensitive diazocompound to a support, exposing the compound to a light image to form a latent record therein of the image, and toning the latent record with a solution of iron blue former to produce an iron blue, infrared absorbing record.
  • FIGURE shows, schematically, apparatus for printing a soundtrack record on motion picture film.
  • a conventional motion picture imbibition blank film 18 comprising a support stripof cellulose nitrate, cellulose acetate-butyrate, cellulose triacetate, polycarbonate, polystyrene, polyester or similar flexible motion picture base which is coated with a layer of gelatin, polyvinyl alcohol, hydroxyethyl cellulose or like colloid.
  • Eastman Kodak Emulsion 30-93624 is suitable. The colloid is hardened sufficiently to withstand wet processing and contains a mordant not incompatible with the photosensitive salt and iron toner to be described.
  • the mordant may be a hydrous oxide of aluminum, chromium, tin or thorium, but preferably is a relatively nondiffusing cationic, high molecular weight organic material such as a synthetic polymer carrying tertiary or quarternary nitrogen groups, all of which are well known in the art.
  • the imbibition blank 1B comprises an area A reserved for picture records and a longitudinal zone 2 in which the soundtrack is produced.
  • a known applicator 1 stripes the soundtrack zone Z with a weakly acid, aqueous solution of a photosensitive diazosalt such as pdiazodiphenylamine sulfate as will be described more fully.
  • a suitable applicator is shown in British Pat. No. 660,742.
  • the film may run at 150 feet per minute as the solution is allowed to soak into the colloid for approximately 15 seconds. it is then rapidly and briefly rinsed off away from the picture area as by a nozzle device 2 which preferably is directed as shown to wash excess solution away from the picture area A.
  • the rinse should be brief to avoid removing the diazosalt.
  • the rinse is acidified with a volatile acid such as acetic acid.
  • the blank is then immediately dried in a dry box 3. Thereafter it may be used immediately or stored for long periods.
  • a conventional variable area soundtrack negative N is prepared in any suitable way and with standard equipment on a normal soundtrack negative film, e.g., Eastman Kodak Emulsion 5362, black and white silver negative having a maximum density of about 1.00 and a minimum of 0.08 is suitable. To minimize image growth it is desirable to produce a density somewhat lower than the conventional optimum.
  • the sensitized imbibition blank 18 is fed into emulsion-toemulsion contact with the silver soundtrack negative N in a known belt printer 4.
  • a speed of 350 feet per minute may be used with a high-pressure xenon or mercury vapor exposing lamp 6, e.g., Osram HBD-200-W2.
  • Such lamps are preferred for their high blue and near ultraviolet emission in the 330 to 430 nanometer region of diazosalt sensitivity.
  • a latent record of the soundtrack is thus produced in the sensitized zone in the form of a photodecomposition product of the sensitizing salt.
  • the latent dye record is then toned with an iron blue former, e.g., ferric ferricyanide, applied in the soundtrack area only by a device 7 like the previously described applicator l.
  • the latent record is thus developed as a nonsilver, infrared-absorbing iron blue record of the original variable area soundtrack on the silver negative N.
  • the film is then fed for 60 seconds through a cabinet 8 heated to 130 F. dry bulb and wet bulb, and passed through a clean water wash 9 for 30 seconds and dried in a dry box 11 in preparation for imbibition printing of the picture area A.
  • the gelatin reliefs of a series of imbibition matrices M are coated with an appropriate colored dye l2 and their graphic information is transferred by imbibition to the picture area.
  • the final print P thus comprises the printed picture record PR and the iron blue soundtrack record SR.
  • the present process employs a silver soundtrack negative made by a conventional, simple and reliable process rather than by use of a special imbibition matrix raw stock, tanning development and etching.
  • the fine-grain silver negative is appreciably less expensive than matrix stock, has much higher speed, and thus can be used on standard high-speed equipment as compared to the specialized, low-speed imbibition printer.
  • a contact printer is much smaller and less expensive than an imbibition machine, and several times'as many contact prints may be made from a silver negative as from an imbibition matrix.
  • the present process may also be compared favorably with a well-known blueprint soundtrack process which employed a film sensitized with a mixture of ferricyanide and ferric oxalates or citrates. Because the film stock was sensitized prior to exposure, the iron salts might undergo a dark reaction during storage and become fogged within a few weeks, which period was shortened by the addition of mordants. Adding acid to increase sensitivity increased fogging.
  • the sensitized blank of the present process has a shelf life of many months without fogging even with acidified salts, and its mordants are in contact with iron salts only during the seconds of processing through the iron toner 7 and heater 8 prior to the wash 8 Approximately five times greater light intensity or exposure time was required to expose blueprint sensitized film, and yet the resulting soundtrack was barely acceptable as to contrast and density.
  • the present process produces a soundtrack of high contrast and density and substantially greater stability under projection lighting.
  • a preferred sensitizing solution comprises 1 liter of water, 12 grams 4-diazodiphenylamine sulfate, and, to increase viscosity, 5 grams of commercial grade hydroxyethyl cellulose such as that sold by Hercules Powder Company under the trade name Natrosol 250 M.
  • Other thickeners may be used, for example, hydroxypropyl cellulose sold by I. C. I. as Klucel G and Klucel M.
  • the solution has a clear orange-yellow color, and is stored and applied at normal ambient temperature.
  • Other photosensitive acid water soluble diazosalts are suitable which photodecompose to form the strong reducing agents with affinity for gelatin as are listed in British Pat. No. 855,438.
  • the best sensitizers are derivatives of 4-aminodiphenylamine and of 4-amino-N,N-dialkyl-aniline.
  • high-speed diazosalts are available from General Dyestuff as Variamine Blue Salts RT FGN and BD, from Hostachem as Diazo M, from Fairmount as Sensitizer DP and Sensitizer HD-23, and from American Aniline as Fast Blue Salt VB.
  • Fairmount Sensitizers D-l6 and D-l7 preferably developed with iron toner for 60 seconds at 45 and 40 C. respectively.
  • the iron blue toner is made of three stock preparations: the first consisting of 5 grams of Natrosol 250 M in 1 liter of water; the second consisting of 90 milliliters of water, 0.2 grams potassium dichromate to control fogging, 8 milliliters of 85 percent phosphoric acid and 16.3 grams potassium ferrieyanide; and the third consisting of 200 milliliters water, 125 grams ferric nitrate-9H,,0, 40 milliliters 70 percent nitric acid and 3 milliliters of commercial polyoxyethylated fatty alcohol used to insure wetting and spreading, and sold as a nonionic surfactant by Antara Chemicals Division of General Aniline and Film Corporation under the trade name Diazopon AN.
  • Ferric chloride hexahydrate or commercial ferric chloride solution may be substituted for ferric nitrate nonahydrate, although the latter is presently preferred.
  • the iron blue toning solution is prepared by mixing 350, 100 and 85 milliliters of the three stock preparations.
  • iron blue former which comprises a water soluble ferric salt, a water soluble ferricyanide compound and an acid, to produce an iron blue infrared absorbing record in the exposed areas.
  • diazosalt is selected from the group consisting of a 4-diazodiphenylamine salt and a 4-diazo-N,N-dialkyl-aniline salt.
  • diazosalt is selected from the group consisting of the salts of paraphenylenediamine, para-aminodiphenylamine and 4-diazodiphenylamine.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US873886A 1969-11-04 1969-11-04 Diazo process of forming infrared absorbing record Expired - Lifetime US3615473A (en)

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US87388669A 1969-11-04 1969-11-04

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GB (1) GB1297320A (xx)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856528A (en) * 1972-08-10 1974-12-24 Keuffel & Esser Co Color toned photopolymerization imaging process
EP0684506A1 (en) * 1994-05-17 1995-11-29 Eastman Kodak Company Soundtrack interface for motion picture projector

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856528A (en) * 1972-08-10 1974-12-24 Keuffel & Esser Co Color toned photopolymerization imaging process
EP0684506A1 (en) * 1994-05-17 1995-11-29 Eastman Kodak Company Soundtrack interface for motion picture projector

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Publication number Publication date
GB1297320A (xx) 1972-11-22

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