Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
  • B41N1/00—Printing plates or foils; Materials therefor
  • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
  • B41N1/14—Lithographic printing foils
• • 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
  • G03C1/705—Compositions containing chalcogenides, metals or alloys thereof, as photosensitive substances, e.g. photodope systems
• • 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
  • G03C1/76—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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/42—Structural details
  • G03C8/52—Bases or auxiliary layers; Substances therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/10—Bases for charge-receiving or other layers

Definitions

• a hydrophilic external layer such as a silver halide emulsion or a photoconductive layer
• a hydrophobic film support is improved by first applying to the hydrophobic film support a layer of a copolymer formed of from 45-99.5% by weight of at least one chlorine-containing monomer of vinylidene chloride and vinyl chloride, from 05-10% by weight of an ethylenically unsaturated hydrophilic monomer, and from 0-54.5% by weight of at least one other copolymerizable ethylenically unsaturated monomer and then exposing the surface of the copolymer layer to a high voltage electric corona discharge.
• a preferred hydrophobic film support is a film of a highly polymeric linear polyester such as polyethylene terephthalate.
• This invention relates to improved subbing layers in film recording materials and to film recording materials so obtained.
• film recording materials comprising a hydrophobic film support carrying a layer (A), which is directly adherent to the hydrophobic film support and comprises a copolymer formed from 45 to 99.5% by weight of at least one of the chlorine-containing monomers viuylidene chloride and vinyl chloride, from 0.5 to 10% by weight of an ethylenically unsaturated hydrophilic monomer, and from 0 to 54.5% by weight of at least one other copolymerisable ethylenically unsaturated monomer, and a layer (B) comprising in a ratio of 1:3 to 1:0.5 by weight a mixture of gelatin and a copolymer of 30 to 70% by weight of butadiene with at least one copolymerisable ethylenically unsaturated monomer.
• A which is directly adherent to the hydrophobic film support and comprises a copolymer formed from 45 to 99.5% by weight of at least one of the chlorine-containing monomers viuylidene chloride
• film recording materials includes elements and materials for use in a variety of photo-reproduction systems.
• examples of such systems include the well-known use of light-sensitive silver halide emulsions, electrographic and electrophotographic systems, and a recently developed photosensitive system wherein the recording is effected by means of photosensitive semi-conductive substances.
• a process for improving in a recording material the adhesion of a hy- 3,712,812 Patented Jan. 23, 1973 drophilic layer to a layer of a copolymer comprising at least one of the chlorine-containing monomers vinylidene chloride and vinyl chloride, which copolymer layer has been applied to a biaxially oriented polyester film support, the process comprising exposing to a high voltage electric corona discharge the surface of said copolymer layer before the application thereto of said hydrophilic layer.
• the subbed film support is passed between an earthed roller and a corona electrode, the copolymer layer facing the corona electrode.
• An A.C. high voltage is applied to the corona electrode to produce a high frequency corona discharge.
• the corona discharge treatment can occur at any time before the application of further layers to the subbed biaxially oriented polyester film. Very advantageously the treatment occurs immediately before the application of a further layer or layers.
• a frequency range of from 10 to kc. has proved very suitable for performing the process according to the invention.
• Suitable current intensities were between 0.5 x10 and 1.5 10- a./cm., i.e. the current per length unit of the corona electrode.
• the distance between the corona electrode and the layer to be treated depends to a large extent on the corona discharge apparatus used.
• I. C. von der Heide and H. L. Wilson have described in Modern Plastics, May 1961, pages 199-206 and 344 different methods for improving the printability of polyethylene film surfaces by a corona discharge treatment.
• the vinylcovered electrodes were actually in contact with the treated film surface.
• a bar knife-edge electrode was used, the latter was spaced from 0.03 to 0.09 in. (0.76 to 2.28 mm.) from the treater roll, whereas for a shoe-type electrode, the gap between electrodes and treated roll was from 0.06 to 0.12 in. (1.5 to 3 mm.).
• the optimal gap between electrodes and treated layer depends on the form of the electrodes, their number, and the generator used, since there is a relationship between the peak corona discharge voltage and current for various gap sizes. In our case we found that the best results with the above indicated frequency range and current intensities were obtained with distances between the electrodes and the layer to be treated comprised between about 1 and 3 mm.
• polyester films used as supports in the present invention are always films that have been biaxially stretched to improve their strength and dimensional stability. They include films of highly polymeric linear polyesters such as e.g. polyethylene terephthalate. Such film supports are coated with the vinylidene chloride and/or vinyl chloride copolymer layer. The application of the vinylidene chloride and/or vinyl chloride copolymer layer to the polyester film support, may take place after biaxial stretching of the polyester film, or after the longitudinal stretching but before the transverse stretching.
• the surface thereof is exposed to a corona discharge treatment to provide a layer system, which may be used for a variety of purposes.
• a hydrophilic layer may be applied to the electrically treated subbing layer of the sheet material according to the invention, which hydrophilic layer may be either transferred from another material or produced thereon from a liquid system.
• the hydrophilic layer may contain one or more of the following substances:
• light-sensitive substance(s) including light-sensitive silver halide, photoconductive substances, and other light-sensitive compounds, e.g. diazonium salts and diazo-sulphonates;
• dissolved dye(s) e.g. a dye that is bleachable
• colour coupler(s) e.g. a colour coupler that is used in silver halide colour photography
• a hydrophilic layer can be transferred by stripping oif from a temporary support to a permanent support, which has been subbed according to the present invention.
• the hydrophilic layer contains photosensitive semi-conductor compounds, compositions or materials, which are reversibly activated by patterns of radiations to create a latent image, which is developed by an aqueous developing solution (see Unconventional Photographic Systems, Second Symposium, Oct. 26-28, 1967, Washington, D.C., pages 116-117).
• the sheet material according to the invention may be used as a wrapping material, particularly when it carries layers specially adapted to accept printing thereon.
• the sheet material may be used as drafting film.
• Particularly useful recording materials are provided by sheet materials according to the invention, which carry hydrophilic pigment coatings, e.g. pigmented gelatin coatings suited for production of relief images that are produced by means of a photo-hardening or photo-solubilizing reaction.
• pigment coatings are of practical interest in the graphic art more particularly in the field known as colour proofing.
• Colour proofing materials serve to form a showing proof for submission for approval, by which an example is given of the multicolour halftone reproduction, that will be produced eventually by the successive printing in register with separate standard inks yellow, magenta, cyan and black, as described in the US. patent specification 3,642,474 and in Example 16 of the Canadian patent specification 893,631.
• the layer composed of the copolymer of vinylidene chloride and/or vinyl chloride is hereinafter referred to as the vinylidene chloride copolymer layer.
• the vinylidene chloride copolymer comprises from 0.5 to by weight of ethylenically unsaturated hydrophilic monomeric units. These units may be derived from ethylenically unsaturated monoor dicarboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid. Other hydrophilic units, e.g. those derived from N-vinylpyrrolidone, may be present.
• the vinylidene chloride copolymer may be formed from vinylidene chloride and/ or vinyl chloride and hydrophilic monomeric units alone in the ratio indicated above. Preferably up to 54.5% by weight of other recurring units, e.g. acrylamides, methacrylamides, acrylic acid esters, methacrylic acid esters, maleic esters, N-alkyl-maleimides and/or butadiene may also be present.
• acrylamides, methacrylamides, acrylic acid esters, methacrylic acid esters, maleic esters, N-alkyl-maleimides and/or butadiene may also be present.
• Suitable vinylidene chloride copolymers are e.g.:
• copolymers are only examples of the combinations that can be made with the different monomers, and the invention is not limited at all to the copolymers enumerated.
• the different monomers indicated above may be copolymerized according to various methods.
• the copolymerization can be conducted in an aqueous dispersion containing a catalyst and an activator.
• polymerization of the monomeric components may occur in bulk without added diluent or the monomers are allowed to react in appropriate organic solvent reaction media.
• the vinylidene chloride copolymers may be coated on the polyester film base according to any suitable technique, e.g., by immersion of the surfaces of the film into a solution of the coating material. They may also be applied by spray, brush, roller, doctor blade, air brush, or wiping techniques.
• the thickness of the dried layer preferably varies between 0.3 and 3;.
• aqueous dispersions of vinylidene chloride copolymer may be applied to at least one side of the non-stretched film, but may also be applied to polyethylene terephthalate film, which has been oriented biaxially.
• the vinylidene chloride copolymer layer may also be coated on at least one side of a polyester film, which has been stretched in only one direction, e.g. longitudinally, whereafter the subbed polyester film is stretched in a direction perpendicular thereto, in this case transversally.
• the recording material can be subjected to some tests.
• an adhesive tape can be applied, which after some pressure can be torn off at once. If by the corona treatment a good adhesion is accomplished between the hydrophilic layer and the adhesive layer, and consequently also with the hydrophobic support, no substance at all may be torn away from the hydrophilic layer by the adhesive tape and stick to the latter. This method was described in Example 1 of the US. patent specification 3,271,345.
• the adhesive power can be tested. Indeed, the sample that has been soaked with photographic baths is scratched by means of a pin. These scratches in the hydrophilic layer even have to reach the polyester support. In case of a favourable adhesion no pieces of the hydrophilic layer from the edges of these scratches may come loose when these scratches are rubbed over with the finger. This method was described in Example 4 of the above mentioned U.S. patent specification.
• the vinylidene chloride copolymer layer was coated in a ratio of approximatively 2 g. of zinc oxide per sq. m. with a composition prepared as follows.
• the dried light-sensitive material was exposed imagewise through a transparent original and dipped in the following baths:
• the adhesion of the photosensitive layer to the subbed support was very good in dry as well as in wet state.When omitting the corona discharge treatment, the adhesion of the photosensitive layer was rather inferior.
• EXAMPLE 2 To one side of a non-stretched polyethylene terephthalate film a subbing layer was applied from an aqueous suspension of a copolymer of vinyl chloride, vinylidene chloride, n-butyl acrylate and itaconic acid (63:30z5 :2) whereafter the polyethylene terephthalate film was oriented.
• the layer of vinylidene chloride copolymer was exposed to 4 successive electric corona discharges as in Example 1, the electrodes being placed at the same distance and the film moving with the same speed. The current intensity, however, has been reduced to 06x10 a./cm.
• the vinylidene chloride copolymer layer was coated with a pigment dispersion prepared as follows.
• 35 g. of titanium dioxide having a particle size of 15 to 35 nm. and a specific surface of approximately 50 sq. m./g. was stirred for 2 minutes with 150 ml. of demineralized water and 0.75 g. of sodium hexametaphosphate by means of an Ultra-Turrax stirrer, so that a homogeneous dispersion was produced.
• a solution at 35 C. of 35 g. of gelatin in 500 ml. of demineralized water and 100 ml. of ethylenechlorhydrin in 250 ml. of water at 35 C. were added successively with stirring. Finally, 5 ml. of a 4% solution of formaldehyde in demineralized water were added.
• This pigment dispersion was applied to the vinylidene chloride copolymer layer in such a proportion that 2 g. of titanium dioxide was presest per sq. m. of the layer.
• a sharp black negative silver image of the exposed original was obtained upon rinsing and drying.
• the titanium dioxide layer adhered very well to thevinylidene chloride copolymer layer. Without corona discharge the titanium dioxide layer is easily separated from the subbed polyester film.
• EXAMPLE v3 The procedure of Example 2 was repeated, but the composition of the vinylidene chloride copolymer layer used therein was replaced by a mixture of 3 parts by weight of a copolymer of vinylidene chloride, Ntert.- butylacrylamide, n-butyl acrylate and methacrylic acid (-65:15:3:17), and 2.5 parts by weight of a copolymer of vinylidene chloride, N-tert.-butylacrylamide, n-butyl acrylate and N-vinylpyrrolidone (70:23:3z4) dissolved in parts by weight of methylene chloride and 20 parts by weight of methyl glycol.
• Example 4 The procedure of Example 1 was repeated, but the composition of the vinylidene chloride copolymer layer was replaced by a by weight solution of a copolymer of vinylidene chloride, N-tert.-butylacrylamide, butadiene, and itaconic acid (70:18:1022) in 60 parts by volume of methylene chloride, 35 parts by volume of 1,2-dichloroethane and 5 parts by volume of methanol.
• EXAMPLE 5 A non-stretched polyethylene terephthalate film was subbed with an aqueous suspension of a copolymer of vinylidene chloride, methyl acrylate and itaconic acid (88: :2), whereafter the polyethylene terephthalate film was oriented.
• Example 2 The layer of vinylidene chloride copolymer was exposed to 4 successive electric corona discharges as in Example 1, the current intensity, however, being reduced to 1.0)(10 a./cm. A pigment layer as described in Example 1 was then applied thereto.
• EXAMPLE 6 To one side of a non-stretched polyethylene terephthalate film a subbing layer was applied from a 20% by weight latex of a copolymer of vinyl chloride, vinylidene chloride, n-butyl acrylate and itaconic acid (63:30:5:2), containing 3 by weight of formamide.
• the subbed film was biaxially oriented, whereafter the vinylidene chloride copolymer layer was exposed to 4 corona discharges according to the method described in Example 1.
• the material was then coated with a gelatine silver halide emulsion layer as commonly used in X-ray materials.
• the adherence of the emulsion layer to the subbed support was excellent.
• the fog values and the sensitivity of the photographic emulsion were hardly influenced by the corona discharge.
• EXAMPLE 7 A non-stretched polyethylene terephthalate film was subbed with an aqueous suspension of a copolymer of vinyl chloride, vinylidene chloride, n-butyl acrylate, fl-chloroethyl acrylate and itaconic acid (43:3015 :20z2). After the subbed film was biaxially stretched one part of the film was exposed to a corona discharge according to the method described in Example 1, whereas another part of the film remained untreated.
• Both film bases were then coated with a gelatin silver halide emulsion layer for lithographic purposes.
• the adherence of the emulsion layer to the surface of the film treated with the corona discharge was good in dry and wet state, whereas no adherence could be remarked on the non-treated film.
• a pulsating AC. voltage having a frequency of 10-100 kc. being imposed on said corona electrode at a current intensity of O.5-1.5 l0 a./cm. of electrode length.
• ethylenically unsaturated hydrophilic monomer is of the group consisting of acrylic acid, methacrylic acid, itaconic acid and N-vinyl-pyrrolidone.
• copolymer layer has been formed from a latex of a copolymer of vinylidene chloride, vinyl chloride, n-butyl acrylate, and itaconic acid.
• copolymer layer has been formed from a solution of a copolymer of vinylidene chloride, N-tert.-butylacrylamide, n-butyl acrylate, and N-vinylpyrrolidone.
• photosensitive semiconductive material is finely divided titanium dioxide or zinc oxide.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Metallurgy (AREA)
• Architecture (AREA)
• Structural Engineering (AREA)
• Laminated Bodies (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Photoreceptors In Electrophotography (AREA)

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Country Status (10)

Cited By (9)

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• 1968
  • 1968-12-09 GB GB58350/68A patent/GB1286457A/en not_active Expired
• 1969
  • 1969-10-22 SU SU1370156A patent/SU398059A3/ru active
  • 1969-10-24 CA CA065783A patent/CA935019A/en not_active Expired
  • 1969-11-25 JP JP9461269A patent/JPS542090B1/ja active Pending
  • 1969-11-27 ES ES373975A patent/ES373975A1/es not_active Expired
  • 1969-11-28 FR FR6941319A patent/FR2025649A1/fr not_active Withdrawn
  • 1969-12-06 DE DE19691961374 patent/DE1961374A1/de active Pending
  • 1969-12-08 BE BE742769D patent/BE742769A/xx unknown
  • 1969-12-08 SE SE16892/69A patent/SE354528B/xx unknown
• 1972
  • 1972-04-19 US US00245619A patent/US3712812A/en not_active Expired - Lifetime

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