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
  • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
  • G03C1/93—Macromolecular substances 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
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
  • G03C1/915—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means using mechanical or physical means therefor, e.g. corona
• • 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
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
• • 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
  • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
  • G03C1/7954—Polyesters

Definitions

• This invention relates to a method for modifying the surface properties of polymer substrates. More particularly, the present invention relates to modification of the surface of polyester supports to improve adhesion of subsequently applied layers.
• Disadvantages of the above described approaches include the requirement of organic solvents, such as chlorophenol and resorcinol, which pose an environmental problem, and the use of chlorinated materials which degrade at elevated temperature and therefore cannot be recycled in the polyester extrusion process, causing economic and environmental problems.
• organic solvents such as chlorophenol and resorcinol
• GDT is a vacuum technique so is quite expensive, requiring either very large vacuum chambers (for batch treatment) or expensive interlocks for air-to-air in-line treatment.
• UV treatment is preferred because it provides the necessary surface modification and can be conducted at atmospheric conditions so is less expensive than GDT.
• the present invention is a photographic film base comprising a polyester support having a layer thereon.
• the layer thereon is a polymer/hydrophilic binder blend wherein the polymer contains a photoreactive moiety having an abstractable hydrogen, and the polymer and hydrophilic binder are present in a ratio of from 1:20 to 20:1.
• the present invention includes a photographic element wherein a light sensitive silver halide emulsion is superposed on the layer.
• the present invention provides a method of making the film base described above.
• the present invention utilizes radiation treatment to modify the surface of polyester support, followed by coating with a blend of polymer and hydrophilic binder wherein the polymer is photo-reactive, thus providing excellent adhesion of gelatin or emulsion layers to the support. Further, the present invention comtemplates photograpic elements having at least one light-sensitive silver halide emulsion layer on the free surface of the polymer/hydrophilic binder layer. In addition the present invention contemplates a method of making a photographic support and element wherein a polymer/hydrophilic binder layer is applied to the surface of a polyester support.
• any suitable radiation treatment for the polyester support may be employed such as, for example, corona discharge treatment, flame treatment, high energy visible light treatment, ultraviolet light, high frequency wave treatment, glow discharge treatment, active plasma treatment, laser treatment and the like.
• Ultraviolet light is the preferred radiation source. Ultraviolet radiation in the range of 170 nm to 400 nm is most preferred. This can be obtained by utilizing a quartz UV lamp.
• a preferred intensity of UV radiation is from 100 to 5000 mJ/cm 2 per pass under the lamp, and most preferably from 800 to 2400 mJ/cm 2 per pass as measured by a UVICURE high energy UV integrating radiometer produced by Electronic Instrumentation and Technology, Inc., Sterling, VA. Typically 1-10 passes at 30 ft/min are required (preferrably 3-6 passes).
• polymers which are suitable for this photo-reactive layer include, but are not limited to, a terpolymer of vinylidene chloride, acrylonitrile, and acrylic acid (VdCl 2 -AN-AA); a terpolymer of vinylidene chloride, methylacrylate, and itaconic acid (VdCl 2 -MA-IA); a terpolymer of vinylidene chloride, acrylonitrile, and an ethanaminium salt of trimethyl-2-[(2-methyl-1-oxo-2-propenyl)oxy]-methyl sulfate (VdCl 2 -AN-S); a terpolymer of butylmethacrylate, 2-methyl-2-aminoethyl ester of propenoic acid, and 2-methyl-2-hydroxyethyl ester of propenoic acid (BAmH); polyurethanes, polyurethane-ureas, polystyrene, poly(styren
• the polyester support is exposed to radiation, preferable UV radiation in the range of 170 nm to 400 nm.
• radiation preferable UV radiation in the range of 170 nm to 400 nm.
• This is obtained using, for example, a quartz UV lamp.
• a preferred intensity of UV irradiation ranges from 100 to 5000 mJ/cm 2 per pass under the lamp and more preferably from 800 mJ/cm 2 to 2400 mJ/cm 2 per pass under the lamp, as measured by a UVICURE high energy UV integrating radiometer calabrated in the UVA range, from 320 nm to 390 nm, produced by Electronic Instrumentation and Technology, Inc., Sterling, VA.
• One to ten passes under the lamp at 30 ft/min are typically used to obtain the desired adhesion.
• hydrophilic binder in the polymer layer.
• Suitable hydrophillic binders include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, cellulose ester, such as carboxymethyl cellulose and hydroxy ethyl cellulose; latex polymers such as a vinyl chloride-containing copolymer, a vinylidene chloride-containing copolymer, an acrylic acid ester-containing copolymer, a vinyl acetate-containing copolymer, a butadiene-containing copolymer, and the like.
• Gelatin is preferred.
• the polymer typically a latex polymer
• hydrophilic binder preferably gelatin
• Polymer/gelatin ratios of 1/20 to 20/1, preferably 1/10 to 2/1, are coated on the irradiated support. Total solids concentration of 0.1% to 20% are used (preferably 1-5%) and coated to obtain dry coverages of from 0.5 to 10 mg/dm 2 , preferably 1 - 5 mg/dm 2 .
• the polymer/gelatin blend is then coated onto the irradiated support using a suitable surfactant to obtain sufficient wetting of the coating.
• Such surfactants include, but are not limited to, sodium lauryl sulfonate, dioctyl sodium sulfosuccinate, sodium octylphenylpolyether sulfonate, saponin and the like.
• the polymer/hydrophilic binder blend may contain an antistatic agent, a matting agent, a surface active agent, a crosslinking agent, and/or a dye.
• the polymer/gelatin blend is then dried at a temperature ranging from 80°C to 140°C, preferably between 100°C and 140°C for a period of 10 s to 10 min, preferably between 1 min and 5 min.
• the polymer/hydrophilic binder layer can be coated by any suitable coating process well known in the art, for example, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or extrusion, utilizing a hopper as described in U.S. Patent 2,681,294.
• suitable coating process for example, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or extrusion, utilizing a hopper as described in U.S. Patent 2,681,294.
• two or more layers can be applied sequentially or simultaneously according to the processes described in U.S. Patents 2,761,791; 3,508,947; 2,941,898 and 3,526,528.
• the emulsion surface of the green sample (before development) or processed dry sample (after development) was cross-hatched with a razor at 5 mm intervals to make nine squares.
• An adhesive tape (3M 610 tape) was adhered thereto and rapidly stripped off at a peel angle of 180°. The adhesion was evaluated according to the estimated percent removal of the emulsion.
• the sample is run through the standard C41 development process. Dry adhesion is then measured as described above.
• Example 2 The procedure of Invention Example 1 was repeated except that the uncoated PEN sample was passed under the lamp three times at a conveyor speed of 30 fpm and the 0.6 weight percent of BAmH was used for component 2. The coated sample was dried for 3 min at 130°C in a standard convection oven.
• Example 1 The procedure of Invention Example 1 was repeated using 0.6 weight percent of a polymethylmethacrylate latex polymer for component 2. The coated sample was dried for 3 min at 130°C in a standard convection oven.
• Example 1 The procedure of Invention Example 1 was repeated using 0.6 weight percent of a polystyrene-butadiene latex copolymer (GenFlow 8045) for component 2. The coated sample was dried for 3 min at 130°C in a standard convection oven.
• GenFlow 8045 polystyrene-butadiene latex copolymer
• Example 1 The procedure of Invention Example 1 was repeated using 0.6 weight percent gelatin for component 1, 1.2 weight percent of a polystyrene-butadiene latex copolymer (GenFlow 8045) for component 2, and the PEN support was passed under the lamp three times at a conveyor speed of 30 fpm, prior to coating. The coated sample was dried for 3 min at 130°C in a standard convection oven.
• a polystyrene-butadiene latex copolymer GenFlow 8045
• Example 1 The procedure of Invention Example 1 was repeated using 0.6 weight percent gelatin for component 1 and 1.2 weight percent of a polyurethane-urea (Witcobond 236) for component 2.
• the uncoated PEN sample was passed under the lamp three times at a conveyor speed of 30 fpm.
• the coated sample was dried for 3 min at 120°C in a standard convection oven.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

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Citations (7)

• 1997
  • 1997-12-05 EP EP97203832A patent/EP0849629A1/fr not_active Withdrawn
  • 1997-12-16 JP JP34616197A patent/JPH10186580A/ja active Pending

Patent Citations (8)

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