US3091535A - Photographic - Google Patents

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Publication number
US3091535A
US3091535A US86308559A US3091535A US 3091535 A US3091535 A US 3091535A US 86308559 A US86308559 A US 86308559A US 3091535 A US3091535 A US 3091535A
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United States
Prior art keywords
layer
colloid
film
antihalation
weight
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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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English (en)
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Priority to US86308559 priority Critical patent/US3091535A/en
Priority to GB41830/60A priority patent/GB906330A/en
Priority to BE598155D priority patent/BE598155A/fr
Priority to DEP26231A priority patent/DE1210320B/de
Priority to FR847976A priority patent/FR1279623A/fr
Application granted granted Critical
Publication of US3091535A publication Critical patent/US3091535A/en
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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
    • 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
    • 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
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
    • 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
    • Y10S430/151—Matting or other surface reflectivity altering material
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Definitions

  • the present invention relates to photographic elements and more particularly it relates to photographic films. Still more particularly it relates to photographic translucent print films having improved antihalation and resolution characteristics.
  • Photographic emulsions on translucent to opaque film supports have a wide variety of applications in the fields of cartography, transilluminated display and mural Work, drafting and chart work, and technical and sales manuals.
  • An object of this invention is to provide improved translucent photographic print films. Another object is to provide such films which have improved antihalation and resolution characteristics. Yet another object is to provide such films which are relatively simple in construction and embody commercially available and economical antihalation materials and pigments. A further object is to provide such films which do not produce objectionable stain when the exposed films are developed and fixed. A still further object is to provide such films which can be made by the use of conventional mixing and coating apparatus. Still further objects will be apparent from the following description of the invention.
  • the photographic elements of the present invention have (1) a transparent hydrophobic copolymer film base, (2) a translucent layer on one side of the base comprising dispersed finely divided particles of an inert inorganic white pigment having an average particle size in the range 0.1 to 2.0 microns in a water-permeable macromolecular atent ice organic colloid of high molecular weight as a binding agent, (3) a photographic silver halide emulsion layer on the translucent layer and on the other surface of the base (4) an antihalation layer comprising a binding agent, colloidal antihalation material, e.g., a dye or pigment, and finely divided particles of a white pigment is described for the translucent layer.
  • a transparent hydrophobic copolymer film base comprising dispersed finely divided particles of an inert inorganic white pigment having an average particle size in the range 0.1 to 2.0 microns in a water-permeable macromolecular atent ice organic colloid of high molecular weight as a binding agent
  • the white pigment is present in an amount from 1.5 to 3.0 parts by weight per part of binding agent.
  • the antihalation dye or pigment in general will be colloidal (in the range of 1 to 100 millimicrons) in their largest diameter.
  • the amount of antihalation material present is that used in conventional antihalation layers and in general comprises 0.05 to 0.10 part per part of binding agent.
  • the support may be any conventional transparent hydrophobic film such as cellulose esters, e.g., cellulose acetate, cellulose nitrate, cellulose butyrate, cellulose mixed esters; vinyl polymers, e.g., polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrenes and copolymers thereof; polyamides, e.g., polypentamethylene sebacamide, polyhexamethylene sebacamide, polypentamethylene suberamide, polydecamethylene adipamide and superpolyesters, e.g., a highly polymeric linear polyester of a dicarboxylic acid with a dihydric alcohol.
  • cellulose esters e.g., cellulose acetate, cellulose nitrate, cellulose butyrate, cellulose mixed esters
  • vinyl polymers e.g., polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrenes
  • a prefered type of support comprises a polyester film as disclosed in Whinfield et al. US. 2,465,319 bearing a thin layer of an adherent film-forming essentially hydrophobic copolymer made and coated in the manner taught by Alles et al., U.S. Patent 2,627,088, and Alles, US. Patent 2,779,684, and patents referred to in the specifications of these patents.
  • Patent 2,779,684 which may or may not be coated with a thin gelatin substratum is coated on one surface with an aqueous gelatin dispersion comprising from about 30 to 50% of gelatin and from about 50 to of titanium dioxide based on total dry weight to give a layer having a dry coating weight of about 10mg./dm. of gelatin. Over this layer, any suitable light-sensitive layer may be coated.
  • Gelatino-silver halide emulsions are preferred, however.
  • the variable gamma gelatino-silver halide emulsions dislcosed in Potter et al. US. Patent 2,280,300 have been found to be particularly useful.
  • the type of light-sensitive layer will, however, depend on the manner in which the novel film elements are to be used.
  • an aqueous gelatin dispersion containing from about 50 to 70% of titanium dioxide and from about .25 to 10% of colloidal manganese dioxide.
  • the layer is coated and dried in a conventional manner to give a dry weight about 70 mg./dm. of gelatin.
  • delustering or matting agents i.e., silica, starch, etc.
  • the highly porous siliceous compounds disclosed in Webster US. Patent 2,626,867 are suitable for this purpose.
  • Titanium dioxides of various crystalline forms may be used as the white pigment, however, the rutile crystalline form is preferred because of its greater hiding power (greater opacity for a given weight).
  • Other white pigments such as barium sulfate can also be used.
  • colloidal manganese dioxide is preferred as the bleachable non-halation coloring component, other bleachable non-halation dyes or pigments, i.e., Aur-amine (C. 1.655), Acid Blue Black (C. 1.246) and Nigrosine (C. 1.864) may be used.
  • Other ingredients for various purposes may be added to any one or all of the layers.
  • so-called optical brightener i.e., compounds which fluoresce under the influence of visible radiation to increase the brightness of the layers
  • optical brightener i.e., compounds which fluoresce under the influence of visible radiation to increase the brightness of the layers
  • Example I A dimensionally stable vinylidine chloride/methyl acrylate/itaconic acid copolymer-coated polyethylene terephthalate film made as described in Example IV of -Alles US. Patent 2,779,684 was coated on one surface with an aqueous dispersion containing 3.5% gelatin and 7.0% of rutile'crystalline titanium dioxide (Du Pont Ti- Pure R-1-00) based on the total weight and to which had been added a small amount of an alkyl naphthalene sulfonate Wetting agent and a small amount of a bis-triazinostilbene compound as an optical brightening agent. The dispersion was coated at 56 feet per minute to give a dry gelatin coating weight of -mg./dm.
  • rutile'crystalline titanium dioxide Du Pont Ti- Pure R-1-00
  • the dry coating weight was 33 mg./dm. of silver halide expressed as AgNO
  • an aqueous dispersion containing 6% gelatin, 12% rutile crystalline titanium dioxide, and 0.4% colloidal manganese dioxide was coated on the opposite side of the film. This aqueous dispersion was coated to give a dry gelatin coating weight of 70 mg./dm.
  • the resulting photographic film element was exposed by conventional projection enlarging equipment.
  • exposed film was developed for 1 /2 minutes at 20 C.
  • the film elements for halation they were exposed behind a neutral wedge with a density range of 0 to 7 over a length of 12 cm. and a mask with a 1 mm. slit with clean cut-edges parallel to theslope of the wedge. Sufficient exposure was given to cause inversion of the image by solaiization under the lightest part of the wedge. At this level of exposure the image of the slit is bordered on either side, at a distance which depends on the thickness of the film support, by two bands due to halation.
  • the efiiciency of antihalation protection can be measured as the ratio of the exposures corresponding respectively to the threshold of halation and the threshold of blackening of the bands.
  • the resolution was determined by the method outlined in National Bureau of Standards Circular C248, A Test of Lens Resolution for the Photographer.
  • Opacity was determined as the transmission density to blue light. The measurements below show the comparison of the novel films of the inventions with known structures.
  • Example I Example I was repeated except that in place of the variable contrast silver iodo-bromide emulsion of that examplethere was coated a gelatino-silver chlorobromide emulsion.
  • the emulsion contained about 34% silver chloride and the rest silver bromide.
  • the dry coating had a weightof 22 mg./dm. of silver-halide expressed as AgNO
  • the backing was coated to a dry weight of v mg./dm. of gelatin (instead of 70 mg./dm;
  • the resulting film had similar characteristics to the film of Example 1. Because of the warm image color and response to direct toning, the product was particularly suited to portrait and photomini-ature application requiring special effects.
  • Example III Example I was repeated except that in place of the emulsion of that example, there was coated a high contrast contact speed bromochloride emulsion containing 30% silver bromide and 70% silver chloride.
  • the dry coating weight was 22 mg./dm. of silver halide expressed as AgNO
  • the backing was coated to a weight of 40 mg/drn. of gelatin.
  • a planar, non-curling film was obtained whichwas exposed in a conventionalcontact printer for 20 seconds at 15 feet using a single 50 ampere arc lamp. The film was developed for 2 /2 minutes at.20 C. in a developer having the following composition Grams .p-Methylaminophenol sulfate 1.5 Hydroquinone 6.0 Sodium sulfite, anhydrous 19.5 Sodium carbonate, monohydrated 28.0 Potassium bromide 0.8
  • the film was then fixed for ten minutes in the fixing composition set forth in Example I.
  • the film showed excellent sensitometric resolution and non-halation characteristics.
  • Example IV Example I was repeated except that-in place of the silver halide emulsion of that example, there was coated a high contrast direct positive silver chloride emulsion to a dry weight of 35 rng./dm. of silver halide expressed as AgNO The film was exposed through an amber filter to a high intensity mercury vapor lamp. The exposed film was developed for one minute in the developer described in Example '1 but diluted 1:1 with water. The film was fixed for 10 minutes in the fixing composition described in Example I. The resulting direct positive image showed good resolution and non-halation characteristics.
  • emulsions such as cold tone projection and contact speed emulsions may also be coated on the novel film structures to advantage.
  • gelatin for the various layers may be replaced by other water-permeable colloids.
  • natural or synthetic, essentially hydirophilic polymers may be used to form the aqueous dispersions.
  • Casein, albumin, interpolyamides, agar-agar, polyvinyl alcohol, polyacrylamides and polyvinylacetals may be used.
  • certain other polymers or polymer mixtures such as polyvinyl-N-vinyllactams, butadiene-acrylonitrile copolymers, vinyl acetate-vinyl stearate copolymers, styrene-butadiene copolymers, alkyd and acrylic resins may be used in combination with gelatin.
  • bleachable coloring materials may be used in place of colloidal manganese dioxide although it is preferred because of its greater stability under adverse storage conditionings.
  • coloring materials disclosed in Baldsiefen, US. Patent 2,203,7 67 may be used.
  • white pigments may be used in place of the rutile crystalline titanium dioxide mentioned above, e.g., barium sulfate, calcium sulfate and zinc oxide.
  • planar, non-curling characteristics offer superior advantages over paper based products.
  • the durability of the films of the instant invention they are especially applicable to making sales manuals and instruction charts, etc.
  • a striking effect can be achieved by coloring only the side opposite the silver halide emulsion layer with appropriate colors. With reflection lighting only, the print appears black and white, but with transmission lighting the image appears in color. In this application, non-penetrating coloring matters are most suitable.
  • a translucent photographic print film comprising (1) transparent hydrophobic copolymer film base,
  • a translucent layer on one surface of the base comprising dispersed finely divided particles of an inert inorganic white pigment having an average particle size in the range 0.1 to 2.0 microns in a waterpermeable macromolecular organic colloid of high molecular weight as a binding agent, there being 30 to 50%, by weight, of colloid and 50 to by weight, of said pigment,
  • an antihalation layer comprising a water-permeable colloid binding agent, bleachable colloidal antihalation material and finely divided particles of the white pigment and having the particle size defiined in layer (2), said antihalation layer having a coating weight of 40 to mg. per sq. dm. of colloid, there being present about 50 to 70% of the white pigment and about 0.25 to 10% of the antihalation material, based on the colloid.
  • a photographic print film as set forth in claim 1 wherein said antihalation material is manganese dioxide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Laminated Bodies (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Paper (AREA)
US86308559 1959-12-31 1959-12-31 Photographic Expired - Lifetime US3091535A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US86308559 US3091535A (en) 1959-12-31 1959-12-31 Photographic
GB41830/60A GB906330A (en) 1959-12-31 1960-12-05 Improvements in or relating to photographic materials
BE598155D BE598155A (en)) 1959-12-31 1960-12-14
DEP26231A DE1210320B (de) 1959-12-31 1960-12-16 Photographischer Opalfilm
FR847976A FR1279623A (fr) 1959-12-31 1960-12-26 Nouvelles pellicules d'impression photographique contenant des matières colorantes blanchissables

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US86308559 US3091535A (en) 1959-12-31 1959-12-31 Photographic

Publications (1)

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US3091535A true US3091535A (en) 1963-05-28

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US86308559 Expired - Lifetime US3091535A (en) 1959-12-31 1959-12-31 Photographic

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US (1) US3091535A (en))
BE (1) BE598155A (en))
DE (1) DE1210320B (en))
FR (1) FR1279623A (en))
GB (1) GB906330A (en))

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415644A (en) * 1967-03-10 1968-12-10 Polaroid Corp Novel photographic products and processes
US4144064A (en) * 1977-09-26 1979-03-13 Agfa-Gevaert N.V. Photographic material for use in the silver complex diffusion transfer process
US4224402A (en) * 1978-10-03 1980-09-23 Agfa-Gevaert N.V. Photographic material for use in the silver complex diffusion transfer process
US5252424A (en) * 1992-09-04 1993-10-12 Eastman Kodak Company Photographic paper
US5288570A (en) * 1990-09-05 1994-02-22 Hoechst Celanese Corporation Composite black and white substrate for color proofing films
US5360688A (en) * 1990-09-05 1994-11-01 Hoechst Celanese Corporation Composite black and white substrate for color proofing films

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1597727A (en) * 1922-10-20 1926-08-31 Ig Farbenindustrie Ag Film
US1631421A (en) * 1923-03-09 1927-06-07 Ig Farbenindustrie Ag Photographic film
US2095018A (en) * 1933-10-04 1937-10-05 Agfa Ansco Corp Manufacture of antihalation layers
US2313570A (en) * 1940-09-25 1943-03-09 Eastman Kodak Co Photographic layer capable of receiving writing
US2698235A (en) * 1950-03-16 1954-12-28 Du Pont Photographic elements
US2773769A (en) * 1953-01-29 1956-12-11 Max H Goldschein Instant drying photostat

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1597727A (en) * 1922-10-20 1926-08-31 Ig Farbenindustrie Ag Film
US1631421A (en) * 1923-03-09 1927-06-07 Ig Farbenindustrie Ag Photographic film
US2095018A (en) * 1933-10-04 1937-10-05 Agfa Ansco Corp Manufacture of antihalation layers
US2313570A (en) * 1940-09-25 1943-03-09 Eastman Kodak Co Photographic layer capable of receiving writing
US2698235A (en) * 1950-03-16 1954-12-28 Du Pont Photographic elements
US2773769A (en) * 1953-01-29 1956-12-11 Max H Goldschein Instant drying photostat

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415644A (en) * 1967-03-10 1968-12-10 Polaroid Corp Novel photographic products and processes
US4144064A (en) * 1977-09-26 1979-03-13 Agfa-Gevaert N.V. Photographic material for use in the silver complex diffusion transfer process
US4224402A (en) * 1978-10-03 1980-09-23 Agfa-Gevaert N.V. Photographic material for use in the silver complex diffusion transfer process
US5288570A (en) * 1990-09-05 1994-02-22 Hoechst Celanese Corporation Composite black and white substrate for color proofing films
US5360688A (en) * 1990-09-05 1994-11-01 Hoechst Celanese Corporation Composite black and white substrate for color proofing films
US5252424A (en) * 1992-09-04 1993-10-12 Eastman Kodak Company Photographic paper
US5300415A (en) * 1992-09-04 1994-04-05 Eastman Kodak Company Photographic paper

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Publication number Publication date
DE1210320B (de) 1966-02-03
BE598155A (en)) 1961-03-31
GB906330A (en) 1962-09-19
FR1279623A (fr) 1961-12-22

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