Classifications

• • 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
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
  • G03G5/0553—Polymers derived from conjugated double bonds containing monomers, e.g. polybutadiene; Rubbers
• • 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
  • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
  • G03C1/89—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
  • G03C1/93—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
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
  • G03G5/0571—Polyamides; Polyimides
• • 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
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
  • G03G5/087—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and being incorporated in an organic bonding material
• • 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
• • 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
  • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
• • 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
  • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
  • G03G5/142—Inert intermediate layers
• • 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
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/913—Material designed to be responsive to temperature, light, moisture
• • 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
  • Y10S430/155—Nonresinous additive to promote interlayer adhesion in element
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/3188—Next to cellulosic
  • Y10T428/31884—Regenerated or modified cellulose
  • Y10T428/31891—Where addition polymer is an ester or halide

Definitions

• ABSTRACT Improved adherence is obtained for sheet material having a hydrophobic film support or base, such as a hydrophobic cellulose ester or polyester, by the combination of a vinyl polymer subbing layer arranged directly on the hydrophobic support, the subbing layer being formed of a copolymer containing at least 45 percent by weight of vinylidene chloride and/or vinyl chloride monomer along with a minor amount of a hydrophilic vinyl monomer with the balance being constituted by any other vinyl monomer, and superimposed upon the vinyl subbing layer a layer containing a mixture of gelatin with a copolymer of butadiene and a vinyl monomer containing 30-70 percent by weight of butadiene, the ratio of the gelatin to the butadiene copolymer being in the range of 1:3 to 2:1 by weight.
• An additional layer can be applied over the gelatin/copolymer layer and constituted by such ingredients as are desirable for the particular utility of the resultant sheet material, such as light-sensitive silver halide emulsion photographic layers, electrophotographic layers containing finely divided photoconductive material such as zinc oxide or some other photosensitive semiconductive material, matte layers containing pigment, diffusion transfer layers containing development nuclei and so on.
• ingredients appropriate to some particular ultimate utility can be incorporated into the gelatin/butadiene copolymer layer directly.
• This invention relates to sheet material which comprises a hydrophobic support film and a layer system which is capable, if so desired, of providing a bond between a hydrophilic layer and the said hydrophobic support film, provide a vehicle for light-sensitive material as hereinafter described, and particularly relates to film recording materials, films and foils consisting of or comprising said sheet material.
• photographic film elements and film recording materials include elements and materials for use in a variety of photoreproduction systems. Examples of such systems include the wellknown 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 semiconductive substances.
• images are produced by the action of electromagnetic radiation on photosensitive semiconductor compounds, compositions or materials, which are reversibly activated by patterns of radiations to create a latent image of corresponding activated patterns.
• the latent image is capable of producing a chemical reaction with a dissolved reactant by an oxidationreduction chemical process to form a visible image (see Unconventional Photographic Systems, Second Symposium, Oct. 26-28, 1967, Washington D.C., pages 116-117).
• electrostatic charges are applied to an insulating surface.
• an electrostatic charge pattern is built up on an insulating layer, e.g., by means of a modulated electron beam, while a conductive element, e.g., a conductive support or layer stands in electrical contact with the backside of said insulating layer, to which a voltage is applied.
• the electrostatic charge pattern is developed, for instance by the application of a powder.
• the conductive backing element may be removed ifdesired.
• An alternative development technique is to bring about an imagewise deformation (ripple image) of the insulating layer as hereinafter described.
• the recording of images is based on a differentiation in electrostatic charge condition, chargeability or electrical conductivity, of a recording layer containing a photoconductive substance, the said layer initially being electrically insulating in the absence of light, but becoming electrically conductive on exposure to light, and being in electrical contact with an electroconductive support or layer.
• imagewise exposing the recording layer to imagewise modulated activating electromagnetic radiation a pattern of the said differential charge condition is obtained.
• the electrostatic charge images may be developed by an electrostatically attractable marking material, or the conductivity images by electrolysis.
• a particular technique of developing the latent image on a recording layer from either an electrographic or an electrophotographic process involves the deformation of the exposed areas to produce a so-called ripple image, by imagewise distortion of the surface under the influence of a differential electrical potential between the recording element and the backing element, and reference may be made to United Kingdom Patent specification No. 964,881; to Photographic Science and Engineering", Vol. 7, No. l (1963) pages 12-13; to RCA Review, Dec. 1964, pages 692-709, and to United Kingdom Patent application No. 5307/66.
• the invention consists of a hydrophobic support film carrying superposed thereon in succession, a layer (A) which is directly adherent to the said hydrophobic support film and comprises a copolymer formed from 45 to 99.5 percent by or which may itself weight of at least one of the chlorine-containing monomers vinylidene chloride and vinyl chloride, from 0.5 to 10 percent by weight of an ethylenically unsaturated hydrophilic monomer, and from 0 to 54.5 percent by weight of at least one other copolymerizable ethylenically unsaturated monomer; and a layer (B) comprising in a ratio of 1:3 to 1:05 by weight of a mixture of gelatin and a copolymer of 30 70 percent by weight of butadiene with at least one copolymerizable ethylenically unsaturated monomer.
• Hydrophobic support films suitable for use in the sheet material according to the invention include, e.g., a hydrophobic cellulose ester, e.g., cellulose acetate, cellulose aceto-butyrate and cellulose nitrate; or a highly polymeric linear polyester such as for example polyethylene terephthalate, polystyrene or polymethacrylic acid esters.
• Such hydrophobic support films are coated with successive layers (A) and (B) according to the invention to provide a layer system which may be used for a variety of purposes.
• the sheet material may be used for the transference thereto of a hydrophilic layer.
• a hydrophilic layer may be a stripped-off hydrophilic layer carrying a relief pattern.
• the sheet material according to the invention may be wetted with a liquid system capable of providing a hydrophilic film thereon.
• the sheet material according to the invention may contain in the said layer (B) photosensitive semiconductor compounds, compositions or materials which are reversibly activated by patterns of radiations to create a latent image, and the said liquid system may then be an aqueous developing solution for the development of such a latent image.
• a hydrophilic layer may be applied to layer (B) of the sheet material according to the invention which hydrophilic layer may be, e.g., either transferred from another material or produced thereon from a liquid system.
• layer (B) and the hydrophilic layer when present may contain one or more other substances, e. g., as follows;
• dissolved dye(s) e.g., a dye that is bleachable g. color coupler(s) e.g., a color coupler that is used in silver halide color photography
• the sheet material according to the invention may be used as a wrapping material, particularly when having layers thereon particularly adapted to accept printing thereon, or the sheet material may be used as tracing film.
• Particularly useful recording materials are provided by sheet material according to the invention, having hydrophilic pigment coatings thereon, e.g., pigmented gelatin coatings suited for the production of relief images, which are produced by means of a photohardening or photo-solubilizing reaction.
• pigment coatings are of practical interest in the graphic art more particularly in the field known as color proofing.
• Color proofing materials serve to form a showing proof for submission for approval, whereby an idea may be obtained of the multicolor halftone reproduction which will finally be produced by the successive printing in register with separate standard inks yellow, magenta, cyan and black.
• the layer formed from the copolymer of vinylidene chloride and/or vinyl chloride is hereinafter referred to as the vinylidene chloride copolymer layer
• the layer formed with the mixture of gelatin and butadiene copolymer is hereinafter referred to as the copolymer layer.
• the vinylidene chloride copolymer comprises from 0.5 to percent 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 vinyl pyrrolidone, 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 percent by weight of other recurring units, for instance acrylamides, methacrylamides, acrylic acid esters, methacrylic acid esters, maleic esters and/or N-alkylmaleimides, may also be present.
• Suitable vinylidene chloride copolymers are, e.g.,:
• copolymers are only examples of the combinations, which 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 may be conducted in 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 hydrophobic 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 may vary between 0.3 and 3 1. preferably.
• aqueous dispersions may be used when the vinylidene chloride copolymer layer is applied from an aqueous dispersion. These dispersions are obtained directly when the copolymer has been made by an emulsion polymerization process.
• aqueous dispersions of vinylidene chloride copolymer on a polyethylene terephthalate film support a very strong adherence to the support is obtained when said dispersions are applied before or during stretching of the polyethylene terephthalate film.
• the aqueous dispersion may be applied to at least one side of the nonstretched 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 biaxially oriented coated polyester film is provided with the second subbing layer of the mixture of gelatin and butadiene copolymer latex.
• the butadiene copolymer comprises 30 to percent by weight of monomeric butadiene units.
• the balance is formed by units deriving from other ethylenically unsaturated hydrophobic monomers, such as acrylonitrile, styrene, acrylic acid esters, methacrylic acid esters, and acrolein.
• the butadiene copolymer is formed by emulsion polymerization and the primary latex obtained is directly mixed with the aqueous gelatin solutions in such a way that the ratio of gelatin to butadiene copolymer in the dried layer varies between 1:3 parts and 1:05, all parts being by weight.
• plasticizers for gelatin such as polyethylene oxides and glycerol may also be added.
• the mixture of aqueous gelatin solution and of butadiene copolymer latex is coated onto the vinylidene chloride copolymer layer by known means.
• the thickness of the dried layer generally varies between 0. l 0 and 20 ,u..
• the subbed film support consists of a hydrophobic film support and the combination of the two anchoring subbing layers used according to the invention.
• the hydrophobic film support may be a film of cellulose triacetate, of polyethylene terephthalate, of polycarbonate, of polystyrene, of polymethacrylic acid ester, etc.
• the subbed hydrophobic film support may be provided on only one side or on both sides with the combination of subbing layers.
• a colloid layer may be deposited on the subbed film support thus obtained.
• This colloid layer may be a simple gelatin layer, a gelatin silver halide emulsion layer, a gelatin filter layer, a gelatin matting layer containing, e.g., finely divided silica, an antistatic layer or an antihalation layer containing a hydrophilic colloid binding agent.
• known antistatic agents e.g., salts
• these salts may be added already to the aqueous gelatin solution, which is to be mixed with the butadiene copolymer for the formation of the second layer of the subbing layer combination.
• an electrically conductive interlayer having a coiiductivity substantially higher than the conductivity in the dark of the photoconductive recording layer.
• Such an interlayer preferably contains a hydrophilic colloid in combination with antistatic or hygroscopic agents, e.g., those described in the U.S. Pat. No.
• conductive pigments e.g., carbon black and/or polyionic polymers, e.g., those containing quaternized nitrogen atoms as described in the United Kingdom Patent specification No. 950,960.
• Good results are obtained with CALGON CONDUCTIVE POLYMER 261 manufactured by Calgon Corporation, Calgon Center Box 1346, Pittsburgh, U.S.A. (Calgon is a registered Trademark).
• Such antistatic or electroconductive hydrophilic colloid layers perfectly adhere to hydrophobic film supports subbed according to the present invention.
• semiconductive light-sensitive pigments are dispersed in a binder containing a hydrophilic colloid.
• n-type photoconductor pigment is dispersed in a binder having a hydrophilic character.
• a hydrophobic film support is firmly bonded to such pigment coatings by means of the composite subbing layer according to the present invention.
• At least one layer is deposited on top of the butadiene copolymer layer.
• the layer deposited thereon may be a simple hydrophilic colloid layer, e.g., a gelatin layer, a hydrophilic colloid layer containing light-sensitive silver halide salts, a hydrophilic polymer or colloid layer containing all kinds of special additives such as antihalation dyestuffs, antistatic agents, electroconductive pigments, photoconductive insulating pigments, photosensitive semiconductive pigments and matting agents. All these additives may also be added already to the coating composition of the butadiene copolymer layer.
• the butadiene copolymer layer can be incorporated into the butadiene copolymer layer finely divided silicium dioxide, photosensitive titanium dioxide, photoconductive zinc oxide and carbon black. According to a preferred embodiment these additives are dissolved when they are soluble in the coating composition or homogeneously dispersed in the mixture of aqueous gelatin solution and butadiene copolymer latex before casting of the second subbing layer on top of the vinylidene chloride copolymer layer.
• the subbed hydrophobic film support is to be used as a tracing film support
• a white pigment e.g., titanium dioxide and/or silicium dioxide
• urea-formaldehyde or melamine-formaldehyde resins to render the surface of the layer more resistant to writing and tracing operations.
• a n-type photoconductive substance e.g., photoconductive zinc oxide is dispersed in the butadiene copolymer layer and no further radiation sensitive layers are deposited on top of the said layer.
• a photographic material is produced, which is suited for use according to the process described in the United Kingdom Patent application No. 16,459/66, now British Pat. No. 1,l56,822.
• a photosensitive semiconductor material is dispersed in the butadiene copolymer layer and no further radiation-sensitive layers are deposited on top of the said layer.
• a photographic recording material is obtained by which visible or latent images can be formed in the absence of an externally applied electric field by means of the imagewise modulated action of electromagnetic radiation reversibly activating the photosensitive semiconductor material in such a way that by means of a dissolved reactant, a portion of which may be present in the recording material before the exposure, images corresponding to the light-activated pattern are produced by an oxidation-reduction reaction, the said photosensitive semiconductor itself being substantially chemically unchanged at the end of the process,
• the recording material according to the present invention is composed of a hydrophobic film support coated with the vinylidene chloride copolymer layer and having thereon the butadiene copolymer layer, in which the photosensitive semiconductor material is dispersed.
• Titanium dioxide is of special interest as semiconductor material, but other known semiconductors, which become conductive on irradiation, can also be used, e.g., zinc oxide, zinc sulphide, lead monoxide, red lead oxide, silicium dioxide, aluminum dioxide, chromium oxide, osmium oxide, and cadmium sulphide.
• the average particle size of the finely divided semiconductors is important. Particle sizes not larger than 250 millimicrons and preferably comprised between 5 and millimicrons are very advantageous.
• the finely divided semiconductor is dispersed in the abovedescribed binder material consisting of gelatin and butadiene copolymer in such a proportion that in the dried layer the ratio of binding agent to semiconductor varies between 3:] and 1:10 by weight.
• the thickness of the radiation-sensitive coating applied on the vinylidene chloride copolymer layer by known means should be generally situated between 0.10 and 20 p. after drying.
• Activation of the semiconductor surfaces is effected by exposure to radiation of sufficient energy.
• Ultraviolet radiation having a wavelength of less than approximately 4,000 A. is very appropriate.
• sensitization of the semiconductors e.g., by doping with foreign ions or dye sensitization techniques can be employed to make the semiconductor sensitive to radiation in the visible spectrum.
• Exposure to a suitable source of radiation modified by an image pattern establishes gradients of differential chemical reactivity between the exposed and nonexposed portions and establishes an image pattern in the exposed portions of the semiconductor material.
• Said image pattern is reversible and can be erased therefrom, e.g., by heating. It can also be made permanent by bringing the activated portions in contact with suitable oxidizing or reducing agents according to known techniques. This reaction forms a visible image pattern.
• the reversible image which was obtained upon exposure to a source of radiation need not be treated with the oxidizing or reducing agents directly after exposure. It can be stored for a certain time and at a later stage it can be erased or developed to produce either positive or negative images corresponding with the image stored in the exposed semiconductor. After development, the semiconductor surface is thoroughly washed to remove any remaining developer, whereupon the semiconductor surface can be reused if new information should be added to the already developed image. For development, numerous developers including silver ions, can be employed.
• the degree of semiconductor activation is high, the quantity of, e.g., metallic silver formed by reduction of silver ions by the light-activated photoconductor will be sufficient to form a visible image directly. If not so, a latent developed image is produced in the semiconductor. Such an image is irreversible and can be stored for long periods.
• It can also be intensified by an image intensification development according to which, e.g., solutions containing substances such as univalent silver ions, mercurous ions, and mercuric ions, which are reducible by the light-activated semiconductor to finely divided black-appearing metallic silver or mercury, are used in combination with chemical redox systems, preferably organic redox systems such as those containing hydroquinone or p-monomethylamino-phenol sulphate.
• chemical redox systems preferably organic redox systems such as those containing hydroquinone or p-monomethylamino-phenol sulphate.
• the semiconductor surfaces are rendered incapable of further development by thoroughly washing, e.g., in water containing a solubilizing or complexing agent to aid removal of residual developer.
• a solubilizing or complexing agent to aid removal of residual developer.
• such solutions solubilize the remaining developer, e.g., silver ion, and they facilitate the removal thereof by washing.
• hydrophobic film e.g., polyester film
• subbing layers were needed hitherto, to obtain a sufficient adhesion between the semiconductor coating and the support.
• EXAMPLE 1 In a reaction flask equipped with a stirrer, a nitrogen inlet, a dropping funnel, and a condenser were placed l liters of water and 2.88 liters of a 10 percent aqueous solution of the sodium salt sulphonated dodecyl benzene. Then the reaction flask was rinsed with nitrogen and the liquid was heated to 60 C. In another flask were placed successively 800 cc. of isopropanol, 144 g. of N-vinyl-pyrrolidone, 108 g. of n-butyl acrylate, 830 g. of N-tert.-butylacrylamide and 2,520 g. of vinylidene chloride. The mixture was stirred and brought to dissolution by gentle heating.
• the latex formed was poured into a mixture of 40 liters of 10 percent aqueous sodium chloride solution and 40 liters of methanol while stirring. The fine grainy precipitate which was obtained was repeatedly washed with water and finally dried.
• the copolymer latex was prepared as follows:
• a second layer was applied to the resulting dried layer in a ratio of 0.4 to 0.6 g./sq.m at 35-50 C. from the following composition:
• a light-sensitive gelatin silver halide emulsion layer was coated thereon.
• the layers of the photographic material thus obtained possessed an excellent adherence in wet as well as in dry state.
• EXAMPLE 3 In an autoclave were placed 1,650 cc. of water and 9.6 g. of itaconic acid. After dissolution a solution of 6 g. of sodium hydrogen carbonate in 120 cc. of water was added. Subsequently 98 cc. of a 10 percent aqueous solution of the disodium salt of disulphonated dodecyl diphenyl ether and 49 cc. of a 10 percent aqueous solution of the sodium salt of sulphonated dodecyl benzene were added as emulsifying agents. Then 96 g. of n butyl acrylate, 144 g. of vinylidene chloride, 9.8 g.
• a subbing layer was applied in a ratio of about 2 g./sq.m from an aqueous suspension containing:
• latex of copolymer of butadiene and methyl methacrylate of example 1 7.5 g. gelatin 1 g.
• This subbed film was provided with a light-sensitive gelatin silver halide emulsion layer as commonly used for graphic purposes.
• the layers of photographic material thus obtained possessed a good adherence before as well as after processing.
• a gelatin silver halide emulsion layer as used in photographic X-ray material was then coated on this antistatic layer.
• the layers of the photographic material thus obtained possessed a good adherence in all circumstances.
• This coating composition was applied in such a way that the dried layer had a thickness of 1.5 to 1.75
• a layer was applied in a proportion of 0.4 to 0.6 g./sq.m from the following composition at 35-50 C.:
• the dried combination of subbing layers was coated successively with an antistatic gelatin layer and a light-sensitive gelatin silver halide emulsion layer as commonly used in X-ray photographic material.
• the layers of the material thus obtained showed an excellent adherence before, during as well as after processing.
• This layer was coated successively with a known antistatic gelatin layer and a light-sensitive gelatin silver halide emulsion layer as commonly used in X-ray material. The adherence of the layers was excellent.
• a layer was applied at 25 C. in a proportion of about 5 g./sq.m from a latex of a copolymer of vinyl chloride, nbutyl acrylate, and itaconic acid (66:30:4).
• This subbed film was simultaneously stretched longitudinally and transversally to about ten times its original size.
• Another layer was applied at 40 C. to the vinylidene chloride layer in a proportion of 0.4 to 0.6 g./sq.m from the following coating composition:
• gelatin 0.80 g. water 60 ccs.
• the dried material was then coated with a gelatin silver halide emulsion layer as commonly used for graphic purposes.
• the graphic material formed possessed an excellent adherence of the layer in dry as well as in wet state.
• EXAMPLE 13 A first subbing layer as described in example 4 and a second subbing layer as described in example 3 were applied successively to a biaxially stretched polyethylene terephthalate support of l00 ,u. thickness. The resulting material was then coated with a light-sensitive layer prepared as follows:
• the dried light-sensitive material was exposed image-wise through a transparent original and dipped in the following baths:
• EXAMPLE 14 A biaxially oriented polyethylene terephthalate support having a thickness of ,u. was coated with a subbing layer consisting of a solution in dichloroethane of a copolymer of vinylidene chloride, N-tert.butylacrylamide, n-butyl acrylate, and vinyl pyrrolidone prepared as described in example I, in such a way that the resulting dried layer had a thickness of l p.
• the resulting pigment dispersion was applied to the polyester film subbed with vinylidene chloride copolymer in such a proportion that 1.59 g. of titanium dioxide were present per sq.m. of the layer.
• a sharp black negative silver image of the exposed original was obtained upon rinsing and drying.
• EXAMPLE 15 One side of a biaxially oriented polyethylene terephthalate film having a thickness of p. was coated with the following composition at 25-30 C. in a ratio of 1.5 to 1.75 g./sq.m:
• the resulting layer was coated with a mixture of 95 parts by weight of water and 5 parts by weight of ethylenechlorhydrin, which mixture comprises 13.5 percent by weight of titanium dioxide, 1.6 percent by weight of gelatin, and 5 percent by weight of a latex of the copolymer of butadiene and methylmethacrylate (50:50 percent by weight) prepared as described in example 1. Upon drying the layer formed had a thickness of 4-5 .4..
• the coating composition was prepared as follows: 2,025 g. of titanium dioxide was dispersed in 7,500 cc. of water with 37 cc. of hexametaphosphate as dispersing agent. The dispersion was stirred fastly for 10 min. at 5l5 C. and then heated to 35 C. A 10 percent by weight aqueous solution of gelatin was added thereto while stirring rapidly. The following composition was then added while stirring slowly to avoid scumming:
• the butadiene copolymer layer was then covered with a gelatin silver halide emulsion layer as known in the graphic art.
• the thus formed photographic material can be used whenever a dimensionally stable support is needed and whenever the favorable light reflection characteristics of the titanium dioxide layer are needed.
• titanium dioxide can be replaced by other pigments, e.g., silicium dioxide.
• EXAMPLE 16 In the same way as in example 15, a biaxially oriented polyester film is coated with a layer of a vinylidene chloride copolymer. The resulting layer was coated with a composition comprising 3 percent by weight of carbon black, 1 percent by weight of gelatin, and 3 percent by weight of the copolymer of butadiene and methyl methacrylate prepared as described in example 1.
• This composition was prepared as follows:
• l87.5 cc. of a 16 percent by weight aqueous dispersion of carbon black comprising 2 percent by weight of poly-N-vinyl pyrrolidone wasdiluted with 300 cc. of water.
• 5 cc. ofa 40 percent by weight latex of the copolymer of ethyl acrylate and N- vinyl pyrrolidone (90:10 percent by weight) and 100 cc. of a percent by weight aqueous solution of gelatin were added thereto at 35 C. The mixture was stirred rapidly for 5 min.
• the vinylidene chloride copolymer layer was coated with this composition so that upon drying a layer having a thickness of 4-5 p. was formed.
• the latter layer was then coated successively with a gelatin subbing layer and a high-sensitive gelatin silver halide emulsion layer having a soft gradation.
• the black-pigmented photographic material could be used for producing images according to a silver complex diffusion transfer process, wherein the sandwich formed by the lightsensitive and the image-receiving layer can be removed from the camera or the cassette during development of the negative image and during the positive image formation by diffusion transfer.
• Sheet material comprising a hydrophobic film support having superposed thereon in succeeding order, a first layer directly adherent to said hydrophobic film support and comprising a copolymer formed from 45 to 99.5 percent by weight of at least one vinylidene chloride or vinyl chloride monomer, from 0.5 to 10 percent by weight of an ethylenically unsaturated hydrophilic monomer, and from O to 54.5 percent by weight of at least one other copolymerizable ethylenically unsaturated monomer; and a second layer comprising in a ratio of 1:3 to 1:05 by weight a mixture ofgelatin and a copolymer of 30 to percent by weight of butadiene with at least one copolymerizable ethylenically unsaturated monomer.
• Sheet material according to claim 1 wherein the copolymer of said first layer contains up to 54.5 percent by weight of at least one acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, maleic acid ester or N-alkylmaleimide monomer.
• Sheet material according to claim 1 wherein the said first layer is formed from a dried solution of a copolymer of vinylidene chloride, N-tert.-butyl acrylamide, n-butyl acrylate and itaconic acid.
• Sheet material according to claim 1 wherein the said first layer is formed from a dried solution of a copolymer of vinylidene chloride, vinyl chloride and methacrylic acid.
• Sheet material according to claim 1 wherein the said first layer is formed from a dried solution of a copolymer of vinyl chloride, n-butyl acrylate and itaconic acid.
• Sheet material according to claim 1 wherein the said first layer is formed from a dried latex of a copolymer of vinylidene chloride, vinyl chloride, n-butyl acrylate and itaconic acid.
• Sheet material according to claim 1 wherein the said second layer is formed from a dried mixture of gelatin and a latex of a copolymer of butadiene and at least one acrylonitrile, styrene, acrylic acid esters, methacrylic acid esters or acrolein monomer.
• Sheet material according to claim 8 wherein a matting agent has been added to the mixture of gelatin and butadiene copolymer latex.
• Sheet material according to claim 11, wherein the matting agent is finely divided silica.
• Sheet material according to claim 8 wherein an antistatic agent has been added to the mixture of gelatin and butadiene copolymer latex.
• Sheet material according to claim 1, wherein the hydrophobic film support is a cellulose triacetate film.
• Sheet material according to claim 1, wherein the hydrophobic film support is a biaxially oriented polyethylene terephthalate film.
• Sheet material according to claim 1 wherein the first layer has been applied to an unstretched polyethylene terephthalate film, which is then oriented biaxially.
• Sheet material according to claim 1 wherein the first layer has been applied to a polyethylene terephthalate film oriented in only one direction, which is then oriented in a direction perpendicular to the first one.
• Sheet material according to claim 1 including a separate hydrophilic colloid layer containing gelatin on the side of said second layer remote from said film support.

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• 1967
  • 1967-09-28 GB GB4411467A patent/GB1234755A/en not_active Expired
• 1968
  • 1968-09-21 JP JP6871468A patent/JPS51446B1/ja active Pending
  • 1968-09-25 FR FR167607A patent/FR1582378A/fr not_active Expired
  • 1968-09-26 DE DE1797425A patent/DE1797425C3/de not_active Expired
  • 1968-09-27 US US3649336D patent/US3649336A/en not_active Expired - Lifetime
  • 1968-09-27 CS CS675968A patent/CS160091B2/cs unknown
  • 1968-09-27 SE SE1304768A patent/SE353611B/xx unknown
  • 1968-09-27 BE BE721469D patent/BE721469A/xx unknown
  • 1968-09-27 SU SU1275369A patent/SU370807A3/ru active
  • 1968-09-30 NL NL6813952A patent/NL156249B/xx not_active IP Right Cessation

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