US3105762A - Photographic overcoating - Google Patents

Photographic overcoating Download PDF

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Publication number
US3105762A
US3105762A US31555A US3155560A US3105762A US 3105762 A US3105762 A US 3105762A US 31555 A US31555 A US 31555A US 3155560 A US3155560 A US 3155560A US 3105762 A US3105762 A US 3105762A
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US
United States
Prior art keywords
solution
overcoating
cupric
water
vinyl acetate
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
Application number
US31555A
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English (en)
Inventor
John F Byrne
Philip F Kurz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell Inc
Original Assignee
Honeywell Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE604191D priority Critical patent/BE604191A/xx
Application filed by Honeywell Inc filed Critical Honeywell Inc
Priority to US31555A priority patent/US3105762A/en
Priority to GB18604/61A priority patent/GB991893A/en
Priority to DEM49133A priority patent/DE1147844B/de
Application granted granted Critical
Publication of US3105762A publication Critical patent/US3105762A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D131/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04Homopolymers or copolymers of vinyl acetate
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/49Print-out and photodevelopable emulsions
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/162Protective or antiabrasion layer

Definitions

  • the invention relates specifically to an overcoating composition to be applied to such photosensitive base compositions which will improve the print-out characteristics of the photosensitive
  • print-on refers to that type of photosensitive substance upon which a visible image is obtained after an exposure to light or other electromagnetic radiation has been initially utilized to form a latent image, the visible image being obtained simply by an additional exposure to such radiation, normally at a somewhat ilower intensity.
  • This additional exposure is known as latensification and is general in its application, including exposing the area upon which the initial image was formed as Well as the surrounding background area to an added amount of radiation.
  • the further discussion of the latensification type photographic compositions can be found in the application of Troy A. Scott, No. 737,758, filed May 26, 1958, and assigned to the same assignee as the present invention. 3
  • Photographic compositions of the print-out type showing the latensification have found use in oscillographic recording and the like.
  • the invention as disclosed in the Scott application noted above, is particularly adaptable to this type of recording in that it shows a sensitivity equivalent to 200,000 lineal inches per second capability. Utilizing the overcoating of the present invention, the over-all properties of the photosensitive material are enhanced and a decidedly superior product results.
  • the overcoating of the present invention provides a water proofing that is desirable to reduce the need for special storage and handling conditions prior to use.
  • the overcoating is a necessary adjunct to the base of photosensitive material for two reasons. First, a water proofing coating is highly desirable to reduce the need forspecial storage and handling conditions, and second, the trace definition of exposed paper is improved considerably by the use of the overcoating. The exact mechanism by which the improved definition is obtained is not known.
  • the polymer utilized to act as a water proofing agent and a carrier for the other constituents of the overcoating, a' cupric halide and aformate can be any of a number of commercially available polymers. be an effective water barrier and not affect the sensitivity of the photographic compositions. While other materials prove usable, the most desirable all-around properties have been found with vinyl acetate polymer emulsions.
  • the silver nitrate was weighed and dissolved in the prescribed amount of distilled water. Then the ammonia solution was added with stirring until the solution cleared as the precipitate of silver oxide formed by the first added portions of the ammonia was redissolved.
  • Potassium Halide Solution Compound Amount KI 1.66 gr. (0.010 mol). KBr 143 gr. (1.20 mol). H O (distilled) 300 cc.
  • the potassium iodide was weighted carefully in order to insure precise control over the iodide content of the resultant silver halide mixture.
  • the potassium halides were dissolved in the prescribed amount of water contained in a two-liter beaker which was set in a water-ethylene glycol bath. The bath was heated on a hot plate to about 80 C. The solution of potassium halide was stirred mechanically with a stainless steel stirrer.
  • Ammonia and potassium bromide act as solvents for' the silver halides formed and promote crystal growth.
  • the smaller silver halide crystals may dissolve and be red-eposited on the surfaces of larger crystals by a process known as Ostwald ripening. This process can occur during the slow precipitation step.
  • the mixture was stirred vigorously with a mechanical stirrer during the precipitation periodf
  • the silver halide mixture was filtered by suction on a. Biichner funnel'and was washed five times with distilled water. It is not normally necessary to dry the silver halides after filteringfand washing.
  • cadmium iodide was employed to' increase the print-out elfeot and to assist in suppressing background dur'ingla'tensificationf
  • Compound Amount Silver halide (as prepared hereinabove) ..gr Cadmium iodide ..gr 5' Water (distilled) cc 50 Hydroxyethyl starch (30% hydroxyethyl starch in water solution) gr 67
  • the ingredients listed above withfthe exception of the hydroxyethyl starch solution were placed in a pint porcelain jar of a ball mill containing 200 grams of one-half inch porcelain pebbles. The bottle was rotated at about 60 rpm. for a period of one hour. The hydroxyethyl starch was then added and the mixture ball-milled for i water.
  • the thickness of the coatings to be applied to paper or other supports is dependent on the characteristics desired in the end product, it has been found that if the composition disclosed above is applied in layers calculated to be in the range of about 0.5 mil in thickness a useful product results. As the thickness of the wet film is difficult to measure, it is somewhat easier to use the weight per unit area of solids deposited as a reference. About 1 gram of solids per square foot of the dried film ap pears to be satisfactory. The critical features are that the coating be uniform, flexible, and adherent to the base material. After application to the base plate, the coating was permitted to dry.
  • the above components are prepared as follows: Vinyl acetate polymer emulsion of approximately 50% solid is used as received. We have found that vinyl acetate polymer emulsion supplied by B. F. Goodrich Chemical Company under their designation Geon Latex (970Xl1) is especially well suited for this purpose.
  • cupric chloride solution is prepared by dissolving 25 grams of cupric chloride dihydrate (CuCl .2H O) in 500 ml. of water. Use 60 ml. of this solution for each gallon of overcoating mixture compounded.
  • the sodium formate solution is prepared by dissolving 40 grams of sodium formate (HCOONa) in 1,600 ml. of Use 1,200 ml. of this solution for each gallon of overcoatin-g mixture to be compounded.
  • the cupric chloride solution and the formate solution are then combined into one solution in the proportion tabulated above, 180 ml. cupric chloride to 3,600 ml. of formate solution.
  • a blending of the above materials into a common solution must be made in the order in which they are designated above. That is, the vinyl acetate polymer emulsion is first diluted by addition of the distilled water and 'then the cupric chloride solution is added to the mixture of the vinyl acetate polymer emulsion and the dis-tilled water. Unless these steps are followed in the order indi cated there is a possibility of breaking the dispersion oi the vinyl acetate polymer emulsion and water. Blending should be accomplished with sufiicien-t stirring to insure a homogeneous end product- This mixture is applied over the main coating to increase image density and stability. An extremely thin coating suflices. Measurements of coating weight indicate that about 0.3 gram of solid per square foot should be present in the overcoat. This overcoating may be applied in the same manner as noted above. That is,
  • transfer roller coating dipcoating using an air-knife to wipe off the excess upon emergence from the bath, or by conventional spreading using a doctor knife to control the thickness of the film.
  • Example 11 over,-. coating for Example 11 was prepared as follows:
  • the potassium formate solution is prepared by dissolving 494 grams of potassium formate into 1,600 ml. of H 0.
  • cupric bromide solution is prepared by dissolving 33 grams of cupric bromide into 500 ml. of Water. Use 60 ml. of this solution for each gallon of ovcrcoating mixture. The blend-.
  • Example 1 ing of the materials of the overcoating mixture is the same as in Example I. That is, the vinyl acetate polymer emulsion is first diluted by addition of the distilled water and then the mixture of cupric bromide solution and Y potassium formate solution, blended together, are added to the mixture of the vinyl acetate polymer emulsion and distilled water. Th overcoating is applied by any methods of Example 1.
  • Example III including the photosensii tive coating initially applied to the paper are prepared in. the same manner as in Example I.
  • the overcoating mix ture is as follows:
  • the above components were prepared in the same manner as indicated in Example I with the exception of theformic acid solution.
  • the ammonium formate solution was prepared by dissolving 350 grams of ammonium formate into 1,600 ml. of water- 'Use of 1,200 ml. of this solution for each gallon of overcoating mixture to be compounded.
  • the cupric chloride solu- H tion is added to the formate solution to compriseone gallon of the over-all mixture.
  • the blending of the vinyl acetate emulsion, the distilled Water, and the cupric chloride-formate solution follows the same. procedures out lined above.
  • the mixture is applied in the same manners as'in Examples I and II with a coating thickness equivalent to that previously noted, 0.3 gram of solid per square foot.
  • the sensitive material and overcoating prepared in ac? cordance with the examples hereinabove was yellow in color, and upon the desired exposure to light, a uniform medium dark brown image or trace having extremely uniform and fine edge definition was'formed.
  • Sensitive. papers, prepared according to this process were capable of writing speeds equivalent to more than 200,000 inches et al.
  • the Osram lamp is manufactured by Osram, Kunststoff, West Germany and identified as their model of .the 1 composition of the invention produced traces that were much more dense than those traces on identically coated paper Without the 'overcoating.
  • the traces produced on paper having the overcoating of the invention were more stable than those traces on non-overcoated paper on prolonged exposure to fluorescent light of desk level intensity (50-400 fc.).
  • a photosensitive silver halide print-out emulsion having thereon an overcoating consisting essentially of a Water insoluble vinyl acetate polymer emulsion carrier and including as a constituent thereof, cupric halide selected from a class consisting of cupric bromide and cupric chloride, and a compatible Water soluble formate.
  • a photosensitive silver halide print-out emulsion having thereon an overcoating consisting essentially of a Water insoluble vinyl acetate polymer emulsion carrier and including as a constituent thereof cupric chloride and a formate selected from the class consisting of sodium formate, potassium formate, and ammonium form-ate.
  • a photosensitive silver halide print-out emulsion having thereon an overcoating consisting essentially of a Water insoluble vinyl acetate polymeric emulsion carrier and including as a constituent thereof, a cupric halide selected from the class of cupric bromide and cupric chloride, and an alkali metal formate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Catalysts (AREA)
  • Chemically Coating (AREA)
US31555A 1960-05-25 1960-05-25 Photographic overcoating Expired - Lifetime US3105762A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE604191D BE604191A (en(2012)) 1960-05-25
US31555A US3105762A (en) 1960-05-25 1960-05-25 Photographic overcoating
GB18604/61A GB991893A (en) 1960-05-25 1961-05-23 Improvements in or relating to photographic materials
DEM49133A DE1147844B (de) 1960-05-25 1961-05-24 UEberzugsschicht fuer fotografische Auskopier-Halogensilberemulsionen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US31555A US3105762A (en) 1960-05-25 1960-05-25 Photographic overcoating

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US3105762A true US3105762A (en) 1963-10-01

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BE (1) BE604191A (en(2012))
DE (1) DE1147844B (en(2012))
GB (1) GB991893A (en(2012))

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3416920A (en) * 1963-03-14 1968-12-17 Zindler Lumoprint Kg Photographic method of producing a copy from an endless silver surface
US3425857A (en) * 1962-08-20 1969-02-04 Eastman Kodak Co Method of making multilayer coatings containing a water resistant layer
US4746594A (en) * 1983-01-24 1988-05-24 Fuji Photo Film Co., Ltd. Silver halide photographic material for photomechanical process and reductive processing method using the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3178292A (en) * 1962-10-25 1965-04-13 Eastman Kodak Co Direct-print photographic silver halide emulsions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3425857A (en) * 1962-08-20 1969-02-04 Eastman Kodak Co Method of making multilayer coatings containing a water resistant layer
US3416920A (en) * 1963-03-14 1968-12-17 Zindler Lumoprint Kg Photographic method of producing a copy from an endless silver surface
US4746594A (en) * 1983-01-24 1988-05-24 Fuji Photo Film Co., Ltd. Silver halide photographic material for photomechanical process and reductive processing method using the same

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Publication number Publication date
DE1147844B (de) 1963-04-25
BE604191A (en(2012))
GB991893A (en) 1965-05-12

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