US3674483A - Reproduction method - Google Patents

Reproduction method Download PDF

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US3674483A
US3674483A US819100A US3674483DA US3674483A US 3674483 A US3674483 A US 3674483A US 819100 A US819100 A US 819100A US 3674483D A US3674483D A US 3674483DA US 3674483 A US3674483 A US 3674483A
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Prior art keywords
hydrophilic
recording
photoconductive
layer
recording layer
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Marcel Nicolas Vrancken
Eric Maria Brinckman
Frans Clement Heugebaert
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Agfa Gevaert NV
Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/12—Production of screen printing forms or similar printing forms, e.g. stencils
    • 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
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/366—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles

Definitions

  • the ratio by weight of hydrophilic particles to hydrophilic colloid is about 1:1 to :1 and the proportion of the organic photoconductive dye is at least about 0.05% by weight of the hydrophilic non-photoconductive particles.
  • the present invention relates to photographic recording and reproduction of information and to recording and reproduction materials suited therefor.
  • this invention relates to a process for producing an irreversible change in physical behaviour in the areas where a photosensitive material is subjected to a sufiicient degree of electromagnetic radiation.
  • the photosensitive element which will be described more in detail hereinafter undergoes by the action of active electromagnetic radiation a decrease of permeability and removability by water. This means that in said element an image or signal in the form of electromagnetic radiation is recorded as a pattern of differences in permeability for and removability by water.
  • a printing master e.g. a planographic or screen printing master.
  • the present invention resides in a method for recording respectively reproducing information, which method comproses (1) information-wise exposing to active electromagnetic radiation a recording material comprising at least one waterpermeable recording layer essentially consisting of dispersed finely divided hydrophilic particles and one or more photoconductive compounds and (a) hydrophilic colloid(s), said photoconductive compounds and hydrophilic dispersed material and hydrophilic colloid(s) being present in the recording layer in such an amount and the exposure being of such an intensity that the irradiated portions of the recording layer undergo a reduction in waterpermeability and removability with water in the irradiated portions, and (2) developing the so formed image by allowing to penetrate a liquid into the non-irradiated or in sufliciently irradiated portions of the recording layer bringing about a visible change in these portions or by removal of the non-irradiated or insufiiciently irradiated portions of the recording layer.
  • the finely divided hydrophilic particles are itself photoconductive and consequently need not to be surrounded by other photoconductive substances.
  • the dispersed hydrophilic particles should be for the most part in very near proximity with each other (only separate from each other over a very small distance) in order that neighbouring particles in any given area of the recording layer can coagulate when the layer in that area, which is sensitive to electromagnetic radiation, is sufliciently irradiated.
  • a preferred recording material for use according to the present invention consists of or incorporates a waterpermeable recording layer or sheet containing a finely divided hydrophilic photoconductive substance and/or non-photoconductive substance surrounded with a photoconductive substance in a hydrophilic proteinaceous binder, preferably in a ratio by weight of at least 1:1 in respect of said binder.
  • the finely divided hydrophilic substance is preferably composed wholly or mainly of (a) hydrophilic photoconductive inorganic substances( s), which is (are) preferably applied from an aqueous dispersion.
  • the photoconductive substances which can be applied in the present invention may be n-type as Well as p-type semiconductors or combination of both types.
  • a change of the conductivity, possibly also charging capacity, electron-accepting or electron-emission power in other words a change of the potential level of the photoconductive particles in respect of the dispersed material in the surrounding medium is assumed as being the cause that a coagulation of the said dispersed hydrophilic particles and probably also a reduction in watersolubility (flocculation) of the surrounding hydrophilic colloid takes place.
  • This assumption is based on the knowledge that theoretically flocculation and coagulation are the same phenomena. Indeed, in a suspended solid system both phenomena are characterized by interparticular surface reactions annihilating or decreasing the repelling forces between separate dispersed particles (ref. Ind. Eng. Chem., C. P. Priesing, vol. 54, No. 8, 1962, p. 38-45 A Theory of Coagulation Useful for Design).
  • Stability of colloidal particles in aqueous dispersions is attributed to hydration and electrostatic charge.
  • the dispersed particles present to the dispersing medium an electronic or electrostatic capacity, which means that they can lose, gain or share electrons by forming bonds such as ionic, covalent, hydrogen, dipolar, or induced dipolar bonds. These bonds can be classified in terms of bond energies (given as kilocalories per mole). Ionic crystal bonds are the strongest, viz more than to 200, covalent bonds about 50 to 100, hydrogen bonds 1 to 10, and dipolar bonds less than 5. Similar to dipolar bonds are bonds being the result of induced polarization (London-van der Waals forces) in molecules and atoms,
  • the electrical capacity formed around a dispersed particle is built up by the electrical double layer surrounding the particle.
  • Collodial stability depends on several parameters, the most important being the water-adsorbing character of substances, valence and concentration of ions surrounding the dispersed particle having an electrical double layer. -It is assumed that at least one of said parameters is changed by the exposure of the photoconductive compounds surrounding the hydrophilic dispersed material and/or being itself the hydrophilic dispersed material. Probably a discharge or reduction of charge present in the electrical double layer of the dispersed particles results in the coagulation of said particles.
  • hydrophilic colloid binder molecules which are preferably of the proteinaceous type and are strongly solvated (with water) undergo a dehydration by building up an irreversible hydration layer around the irradiated hydrophilic dispersed photoconductive substances.
  • the photoconductor increases the electrolyte concentration above a critical value so that the conditions of coagulation for the hydrophilic binder are attained.
  • the water-permeable recording layer used in the present invention preferably contains a water-soluble binding agent.
  • a water-soluble binding agent preferably benzophenone and benzyl alcohol.
  • caseine and gelatin are preferred hydrophilic colloids.
  • Proteinaceous binding agents of the same origin as gelatin and which replace gelatin for lowering the cost of the recording material can be used too.
  • animal glue is to be mentioned particularly.
  • Useful but not especially interesting are further hydratable polymeric polyhydroxy compounds e.g. cellulose derivatives such as hydroxyethylcellulose.
  • gelatins with a high gel strength preferably having a Bloom number greater than 180 are used.
  • the photoconductive substances may be sensitive to any type of electromagnetic radiation e.g. X-rays, ultraviolet light, visible light and/or infra-red light. If they are not sensitive for visible light they can be spectrally sensitized for that part of the spectrum by means of properly selected spectrally sensitizing agents.
  • electromagnetic radiation e.g. X-rays, ultraviolet light, visible light and/or infra-red light. If they are not sensitive for visible light they can be spectrally sensitized for that part of the spectrum by means of properly selected spectrally sensitizing agents.
  • Suitable hydrophilic photo-sensitive semiconductive compounds have been found in the group of heavy metal compounds of an element of the group 6B of the periodic table of elements.
  • photoconductive heavy metal oxides and sulphides of the following list: ZnO, ZnS, PbO, TiO Cr O MnO Pb 'O and CdS.
  • the particle size of the dispersed hydrophilic material is preferably as fine as possible.
  • the specific surface ex pressed in sq.m. per g. of the photoconductive powders is as high as possible, preferably at least 0.3 sq.m. per g.
  • the average particle diameter is preferably below 0.1; 110 50 11..
  • photoconductive Zinc oxide is used, that is applied in electrophotographic recording materials, more preferably white photoconductive zinc oxide prepared by the oxidation of zinc vapour (according to the French process).
  • the zinc oxide particles have e.g. an average grain size of 0.1 to 50
  • photoconductive lead- (I I) oxide yields excellent results.
  • lead(II) oxide There are two types of lead(II) oxide viz red lead (II) oxide having a tetragonal crystal structure and yellow lead(II) oxide having an orthorhombic crystal structure.
  • Leadfll) oxide powders consisting mainly of orthohombic lead (II) oxide are preferred for the purpose of the present invention.
  • This specification relates to a method of producing a visible image in a copy medium comprising a radiation-sensitive metal-containing semiconductor compound, which becomes conductive on the impingement of radiation thereon, which method comprises exposing said medium to an image pattern of activating radiation, thereby reversibly activating said semiconductor compound to render it capable of causing chemical reaction at portions of said medium corresponding to said image pattern of radiation, and then developing reversibly activated portions of said medium by contacting at least said portions with a liquid redox system reacting on contact at said reversibly activated portions to form reaction products defining a visible image corresponding to said image pattern.
  • Titanium(IV) oxide particles having particularly good properties for use according to the present invention have an average particle size not greater than 250 millimicrons.
  • Such finely divided titanium(IV) oxide is preferably produced by processes involving the pyrolysis of titanium (IV) chloride (see United Kingdom patent specification 1,101,516).
  • Titanium(IV) oxides having an average particle size between 25 and millimicrons are preferably used.
  • average particle size we mean the particle size at the peak of the frequency distribution graph of a mixture of particles having decreasingly numbers of larger particles and of smaller particles.
  • the inorganic photoconductive compound(s) is or (are) preferably used in a ratio by weight varying between 1:1 and 5:1 in respect of the hydrophilic binder.
  • the inorganic photoconductive semiconductor materials can be sensitized by a number of techniques known in the art such as doping with foreign ions, dye sensitization and heating.
  • the recording layer contains as photoconductive substances photoreducible dyes.
  • the photoreducible dyes intended here are incapable of being reduced in the absence of light by a thiol polymer such as gelatin to which sulfhydryl groups were added, (so-called thiolated gelatins), but capable of being reduced by the sulfhydryl groups of the polymer when photo-excited with visible light.
  • photo-reducible dyes include members of the fiuorescein class, the thiazine class, the acridine class and the porphyrin class. Suitable photoreducible dyes are e.g. rose bengal, phloxine, erythrosine, cosine, fiuorescein, acriflavine, thionine, riboflavine, and methylene blue. The dyes soluble in an aqueous medium are preferred.
  • Photoconductive substances that are compatible (form a solid state solution) with the hydrophilic binder can be used advantageously in combination with dispersed nonphotoconductive hydrophilic substances such as hydrophilic non-photoconductive pigments e.g. waterinsoluble hydrophilic salts e.g. barium sulphate, hydrophilic carbon black, and hydrophilic metal or non-photoconductive metal oxide particles.
  • hydrophilic non-photoconductive pigments e.g. waterinsoluble hydrophilic salts e.g. barium sulphate, hydrophilic carbon black, and hydrophilic metal or non-photoconductive metal oxide particles.
  • the non-photoconductive hydrophilic pigments are preferably surrounded with organic photoconductive dyes that are spectrally sensitizing agents for photoconductive zinc oxide.
  • Such dyes are found in the class of: xanthene dyes preferably fluorescein dyes, thiazine dyes, and acridine dyes. A large number of these dyes are characterized by their fluorescein and are described e.g. in the U.S. patent specification 2,875,047.
  • fiuorescein dyes such as cosine reference is made e.g. to Semiconductive properties of organic dyes by A. T. Vartanyan, Izvest. Akad. Nauk, U.S.S.R., Ser. Fiz. 16 (1952), pp. 169485, cf. CA. 45, 3709 i).
  • the dyes are preferably applied in dissolved form. Preferably they are dissolved in water and added in that state to the dispersion of the hydrophilic particles in the hydrophilic binder.
  • fluorescein dyes such as eosine, erythrosine and rose bengal.
  • the photoreducible photoconductive dyes can be used in an amount as low as 0.05% by weight in respect of the hydrophilic dispersed particles, which are preferably dispersed photoconductive pigments.
  • spectral sensitizing dyes for the dispersed hydrophilic photoconductive substances or the use of coloured photoconductive substances for obtaining spectral sensitivity in the visible light range it is possible to increase the total sensitivity of recording layers suited for use according to the present invention by means of waterattracting substances, e.g. waterattracting polyols more preferably glycerol.
  • waterattracting substances e.g. waterattracting polyols more preferably glycerol.
  • Other useful polyol compounds are e.g. sorbitol and ethylene glycol.
  • Ionic hygroscopic or slightly hyroscopic compounds or compounds crystallizing with a fairly large number of crystal water (hydratable ionic compounds) e.g. lithium chloride, potassium bromide, sodium chloride, sodium sulphate and lead acetate give also rise to an increase in photosensitivity.
  • Preferred recording layers contain glycerol and gelatin in a ratio of by weight from to 80%. Optimal results are obtained by using 40% by Weight of glycerol in respect of a proteinaceous colloid such as gelatin and casein.
  • hydrophilic visible light absorbing inorganic pigments such as hydrophilic carbon black, prussion blue, coloured hydrophilic oxides and sulphide of carbonates of heavy metals, particularly of those heavy metals having an atomic weight between 45 and 210, such as iron(IIl) oxide, cadmium sulphide, manganese oxides, or these heavy metals themselves in finely divided state such as silver, bismuth, lead, iron, cobalt, and nickel.
  • organic dyestuffs in pigments form preferably organic dyes, which are dispersable in a hydrophilic colloid medium, are used, e.g. water-insoluble azo dyes, anthaquinone dyes and phthalocyanine dyes.
  • the recording element used according to the present invention may further contain dyes that can be bleached, plasticizers, fillers, e.g. silica, coating aids, e.g. wetting or spreading agents, substances influencing the gloss or ageing, metal particles, e.g. metal particles that can be etched, reaction components or dyes that can be distilled preferably below 80 C., developing nuclei for e.g. complexed silver halide, photo-sensitive substances that directly on exposure or by a development can form a visible image e.g. photosensitive silver halide, diazonium compounds etc., possibly in the presence of developing agents or colour coupling agents. Further this layer may comprise latent hardening agents for the binder, which harden the binder at elevated temperatures.
  • the amount by weight of dispersed hydrophilic substance (which can be a photoconductive substance itself) in respect of the hydrophilic binder is one of the main features determining the photo-sensitivity.
  • the recording layers contained 40% by weight of glycerol in respect of the hydrophilic binder.
  • the recording layers were exposed through a grey step wedge (constant 0.1) with a 1500 w. quartz-iodine lamp held at a distance of 65 cm. of the recording layers.
  • the exposure light is poor in ultra-violet rays and the photoconductive zinc oxide is mainly UV. light sensitive.
  • the materials comprising a photosensitive element according to this invention may be composed dilferently.
  • the photosensitive layer containing the photocoagulable composition may be applied to a hydrophilic layer, which occasionally serves as a support.
  • hydrophilic layer is understood a layer that is wettable by water or by aqueous solutions. Such a layer may be porous or water-permeable.
  • this hydrophilic layer may be composed mainly of natural or synthetic colloids that are soluble or dispersible in water.
  • Such layers are a gelatin layer, a light-sensitive silver halide emulsion layer, a Water-permeable nuclei-containing colloid layer for application of the silver complex diffusion transfer process, a baryta-coating comprising gelatin and barium sulphate, a gelatin layer containing pigments or dissolved dyes, or containing reaction components capable to produce a colour reaction, a gelatin layer containing developing substances for silver halide or complexed silver halide, or a gelatin layer containing finely divided metal that can be etched away, e.g. silver.
  • the recording layer according to the present invention can be applied between two hydrophilic layers, a hydrophilic and a hydrophobic layer, between two permeable layers, or between a permeable and in impermeable layer.
  • a layer or sheet being in contact or water-permeable relationship with the photosensitive layer may contain all kinds of ingredients, e.g. ingredients that can be of practical interest to provide adherence to the recording layer. In other words such a layer may act as a subbing layer.
  • ingredients may be of interest to develop the recorded image, e.g. pigments, dyes, reaction components for the formation of dyes, developing substances, reaction components or dyes, which can be distilled preferably below 80 C., light-sensitive substances, e.g. silver halide or diazonium salts, developing nuclei suited for use in the silver halide diffusion transfer process, catalysts for colour reactions, and/or conductive particles, e.g.. metal particles.
  • light-sensitive substances e.g. silver halide or diazonium salts
  • developing nuclei suited for use in the silver halide diffusion transfer process
  • catalysts for colour reactions e.g.. metal particles.
  • the support of the recording layer may be rigid or flexible.
  • a sheet element such as e.g. a paper sheet, a plastic film, a metal foil or the like is used.
  • a metal foil or the like When flexibility is unimportant, plates of metal, glass, plastics, fiber board, cardboard or the like may be used.
  • the support may be permeable as well as impermeable e.g. it may be water-permeable such as a wire screen or a web of textile.
  • Suitable water-impermeable supports are made of hydrophobic resins, e.g. of cellulose ester derivatives, polyesters, polystyrene, hydrophobic metal, hydrophilic metal coated with a hydrophobic layer e.g. an oxide layer, glass and the like.
  • hydrophobic resins e.g. of cellulose ester derivatives, polyesters, polystyrene, hydrophobic metal, hydrophilic metal coated with a hydrophobic layer e.g. an oxide layer, glass and the like.
  • subbing layers may be applied.
  • Recording according to the present invention can proceed in different ways according to the method in which radiation is supplied to the recording element.
  • the exposure can be of any type known in the art, although a direct exposure (non-reflectographic exposure) is preferred.
  • the recording material may be heated to speed up or improve the information-wise impermeabilization of the recording layer.
  • a transparent original bearing light-absorbing indicia is recorded by bringing the photosensitive element of a recording material according to the present invention into contact with said original, and exposing said photosensitive element with electromagnetic radiation modulated by the contacting original.
  • the irradiation is of such spectral composition, intensity and duration that the information contained in the original is recorded in terms of water-permeability diiferences and removability differences (e.g. by wash-off) of the recording layer.
  • the present invention offers the possibility of making enlarged photographs by projection-exposure.
  • the image-wise differentiation in permeability is utilised for applying by image-wise diffusion image-forming substance or substances in the recording element by a liquid treatment or from the recording element to a receiving material respectively, said image-wise diffusion being possible as a consequence of the permeability differentiation.
  • said imaged recording material is dipped into an aqueous dye solution, whereby the dye diffuses in the recording element (layer or sheet) only on the areas that remained permeable and sufficiently hydrophilic.
  • a dye solution instead of a dye solution, a solution of a catalyst for initiating a colour reaction between components in the recording material or a solution of a colourless reaction component capable of giving a colour reaction with a colourless or slightly coloured reaction component in the recording material can be used.
  • the first system it is possible to incorporate into the recording element coloured substances which can be bleached out by a bleaching agent diffusing in the areas of the recording material that remained permeable.
  • a conductive substance e.g. a metal that can be etched away such as colloidal silver, and that is homogeneously dispersed in the recording element, is imagewise etched away by an etching liquid diffusing into the permeable areas.
  • the photosensitive layer can be applied to an etchable base material, e.g. a resin sheet coated with aluminium. When using this material it is possible by image-wise etching to produce a planographic, lettertype or intaglio printing master.
  • the image-forming substance incorporated into the recording material is transferred by diffusion from the areas that remained permeable to an image-receiving material.
  • a colourless reaction component or catalyst for the formation of a colour reaction with a reaction component in the receiving material can be incorporated into the recording element.
  • silver salts that can be complexed and that in their dissolved form can diffuse to a receiving material containing reduction nuclei or development nuclei, whereupon according to the areas of the recording material that remained permeable, silver is deposited imagewise.
  • the image-forming substances such as a dye, a metal that can be etched away, or reaction components need not be present in the recording element itself; they can also be incorporated into a layer or support being in a water-permeable relationship therewith.
  • the portions of the information-wise electromagnetically irradiated recording material that remained sufficiently Water-permeable and water-soluble are eliminated e.g. by washing out or degrading of the hydrophilic binder.
  • a direct visbile copy of the information is obtained when the recording element comprises already before its exposure a dye, e.g. a (coloured) pigment and/or a dissolved dyestuif.
  • a gravure master can be produced by starting from the imaged recording layer, which is applied to a metal support that can be etched. After elimination of the portions of the recording layer that remained permeable and hydrophilic, e.g. by washing out and after making the portions of the recording layer left sufliciently resistant to the etching solution, the uncovered metal can be etched away image-wise. In this way eg' printed circuits can be produced. After the elimination, e.g. by intensively rubbing the portions of the recording layer left after the Wash-oi? development, the etched metal plate according to the depth and measure of etching can be used as a planographic printing master, a gravure master, or a letter press master.
  • a stencil or screenprinting master can be manufactured by starting from an information-wise electromagnetically irradiated recording material according to the invention.
  • an information-wise electromagnetically irradiated recording material for this technique either one or both sides of a screen material are coated with a recording layer, or the screening material makes part of a self-supporting sheet as described hereinbefore.
  • screen material Japan paper (Yoshino paper), nylon fabrics with a size of mesh of 0.2 to 0.08 mm. and woven bronze wire are especially suited.
  • the screen-printing technique it is known that only on the open (permeable) areas of the fabric (screen material) ink can pass and deposit on the material to be printed corresponding to these areas.
  • the image-wise open areas are obtained according to the present invention by washing out or degrading the recording layer composition in the areas where this layer or sheet remained permeable and hydrophilic.
  • the image portions that remained permeable and hydrophilic are transferred onto a receiving material by sqneegeeing and tearing out.
  • This transfer successfully occurs when separating after pressing together a wetted information-wise electromagnetically irradiated recording element according to the present invention from a receiving material preferably having a hydrophilic and/or porous surface, e.g. a paper sheet.
  • a dye layer of a carbon paper being little hydrophobic on its surface, such as is used in the process according to the French patent specification 1,466,223, after being pressed onto the moistened heator pressure-imaged material, can be transferred image-wise to the permeable and hydrophilic areas of the recording material on separating it therefrom.
  • the hydrophilic binder of the recording layer can be swollen so that a relief image is formed that makes possible a closer contact with the dye layer.
  • the pulled out material can contain a hectographic dye that is soluble in the transfer liquid of can contain a reaction component forming a dye with a reaction component present, e.g., in the transfer liquid or transfer material.
  • a fourth system it is possible by using a low melting dye in the recording element, to transfer this dye by heating the recording element after wash-E development in contact with a receiving material.
  • the present ratios are by weight if not otherwise indicated.
  • EXAMPLE 1 24 g. of a commercial massicot (yellow lead(II) oxide containing 30 p.p.m. of bismuth and having an average particle size of 5a) were ball-milled for 1 h. in the presence of 32 ccs. of demineralized water.
  • the composition was coated onto a subbed cellulose triacetate support at such a rate that after drying, a recording layer of 40, thick was obtained.
  • the light-sensiti've material was contact-exposed for 5 min. through a screened halftone transparency by means of a Philips HPR 125 lamp placed at a distance of 30 cm.
  • the exposed light-sensitive layer was treated with water of 40 C. resulting in the removal of the non-exposed portions of the recording layer.
  • the residual portions of the recording layer were treated with a 5% aqueous solution of sodium sulphide in order to increase the optical density of the portions containing non-exposed yellow lead(II) oxide.
  • the thus treated material was rinsed and a stable, black, very dense negative print of the original was obtained.
  • EXAMPLE 2 24 g. of lead(II) oxide as described in Example 1 were ball-milled for 1 h. in the presence of 60 ccs. of demineralized water and 4 g. of sodium hexametaphosphate as dispersing agent.
  • the composition was coated onto a subbed cellulosetriacetate support at such a rate that after drying a recording layer of 18 thickness was obtained.
  • the recording material was placed with its support into contact with a negative halftone transparency of an original and through the transparency exposed for 20 min. with a Philips HPR 125 lamp placed at a distance of 30 cm. Next, the exposed material was treated as described in Example 1. A black positive halftone print of the original was obtained.
  • EXAMPLE 4 24 g. of lead (II) oxide as described in Example 1 were ball milled for 1 h. in the presence of 32 ccs. of demineralized water.
  • the exposed recording layer was treated with water of 35 C. till all the non-exposed portions were washed off. A treatment of the exposed remaining portions with a 5% aqueous solution of sodium sulphide resulted in a black negative copy of the original.
  • EXAMPLE 6 24 g. of lead(II) oxide as described in Example 1, 2 g. of sodium hexametaphosphate and 60 ccs. of demineralized water were ball-milled for 1 h.
  • the recording material was image-wise exposed through a transparent line original in a diazotype copying apparatus as in Example 5 at a copying speed of 8 cm. per min.
  • the exposed recording layer was moistened with water of 15 C. and after 2 min. the recording layer was pressed against a sheet of porous paper (filter paper).
  • the filter paper was peeled olf from the recording layer and for a while dipped into a 5% aqueous solution of sodium sulphide. A good black copy of the original was obtained on the filter paper.
  • EXAMPLE 7 24 g. of zinc sulphide having an average particle size of 5a and 2 g. of sodium hexametaphosphate were ballmilled for 1 h. in the presence of 60 ccs. of demineralized water.
  • the whole composition was coated onto a subbed cellulose triacetate support at such a rate that after drying a recording layer of 68 1. thickness was obtained.
  • the recording material was laid with its support onto a transparent line original and exposed through the latter for 30 min. by means of a 500 watt tungsten filament lamp placed at a distance of 25 cm. Thereupon the nonexposed portions were washed-0E with Water of 35 C. A negative copy of the original was obtained. In said copy the image parts have a white opaque aspect due to the zinc sulphide of the recording layer.
  • EXAMPLE 8 15% solution of gelatin in demineralized water g 12.5 solution of saponine in demineralized water ml 1 The whole composition was coated onto a subbed cellulose triacetate support at such a rate that a recording layer with 15.5 g. of titaniun1(lV) oxide per sq. m. was obtained.
  • the recording material was image-wise exposed through a transparent line original in a diazotype copying apparatus as in Example 5. Copying was eifected by conveying the whole sandwich twice through the apparatus at a speed of 8 cm. per min.
  • EXAMPLE 9 15% solution of animal glue in demineralized water g 100 Glycerol Q 6 12.5 solution of saponine in demineralized water ml 1 The whole composition was coated onto a subbed cellulose triacetate support at such a rate that after drying a recording layer of 2514 thickness was obtained.
  • the recording material was image-wise exposed through a transparency of a line image in a diazotype copying apparatus as in Example 5, at a copying speed of 30 cm. per min.
  • the non-exposed portions of the recording layer were washed out with water of 35 C.
  • An opaque yellow-grey negative copy of the original was obtained.
  • the greyish tone of the copy was the result of a print-out elfect whereby some lead metal is formed on exposure.
  • EXAMPLE 10 A poly(ethylene terephthalate) support of 0.1 mm. thickness was coated with the following subbing layer This subbing layer was dried at 30 C. On this layer a light-sensitive layer from the following composition was coated in a proportion of 30 g./sq.m.:
  • EXAMPLE 11 24 g. of zinc sulphide having an average particle size of 5a and 1 g. of sodium hexametaphosphate were ballmilled for 1 h. in the presence of 60 ccs. of demineralized water.
  • the recording material was laid with its support onto a transparent line original and exposed through the latter for 3 h. by normal daylight. Thereupon the non-exposed portions were washed away with water of 35 C. A negative copy of the original was obtained. In said copy the image parts had a white opaque aspect owing to the zinc sulphide in the recording layer.
  • a poly(ethylene terephthalate) base of 0.1 mm. thick ness provided with a subbing layer for gelatin coatings was coated with the following composition in a proportion of 60 g./sq.rn.
  • EXAMPLE 13 A poly(ethylene terephthalate) base of 0.1 min. thickness provided with a subbing layer was coated with the following composition in a proportion of 60 g./sq.m.:
  • EXAMPLE 14 A poly(ethylene terephthalate) base provided with a subbing layer as described in Example 12 was coated with the following composition in a proportion of 50 g./sq.m.:
  • This layer was dried at 25 C. and exposed for 3 min. through a negative line original with a quartz iodine lamp of 1500 w. at a distance of 60 cm. After exposure the material was kept in the dark for 30 min. and then treated with water of 30 C. The non-exposed parts were washed-off and a positive image was obtained.
  • lithium chloride was replaced by a same amount of 15 sodium chloride or sodium sulphate the same results and when replaced by a same amount of lead acetate still better results were obtained.
  • EXAMPLE 15 40 g. of barium sulphate as used in baryta-coatings of photographic silver halide materials were ball-milled for 1 h. in the presence of 160 ml. of demineralized water and 5 ml. of sodium hexametaphosphate.
  • the recording material was vacuum-contact exposed for 10 min. through a transparent line original using a 1500 watt quartzdodine lamp mounted in a reflector and placed at a distance of 65 cm. above the vacuum-frame.
  • a method for recording information comprises (1) image-wise exposing to substantially visible or ultra-violet light a recording material comprising at least one water-permeable recording layer essentially consisting of finely divided particles of a hydrophilic inorganic photoconductive compound of the group consisting of the oxides and the sulfides of zinc, lead, titanium, chromium, manganese and cadmium dispersed in at least one proteinaceous hydrophilic colloid binder, said photoconductive compound undergoing a change in conductivity upon exposure to said substantially visible or ultra-violet light, said photoconductive particles and hydrophilic colloid binder being present in the recording layer in a ratio by weight of about 1:1 to 5:1, the exposure being of such an intensity and duration that the hydrophilic colloid in the exposed regions of said recording layer becomes substantially impermeable to water as a consequence of the response of said photoconductive particles to said exposing light, and (2) forming said impermeabilized regions into a visible relief image by removing the unexposed layer regions of unchanged permeability by washing
  • hydrophilic particles are applied from an aqueous dispersion.
  • the photoconductive compound is selected from the group consisting of photoconductive zinc oxide, zinc sulphide, titanium(IV) oxide, lead(II) oxide, red lead oxide (Pb chromium(1II) oxide, and cadmium sulphide.
  • a method of recording information which comprises (l) image-wise exposing to active electromagnetic radiation a recording material consisting essentially of a continuous phase of a proteinaceous hydrophilic colloid binder having uniformly distributed therethrough finely divided particles of a non-photoconductive hydrophilic pigment and a photoconductive fluorescein, thiazine, acridine or porphyrin dye compatible with said bydrophilic binder, said particles and said binder being present in a ratio by weight of about 1:1 to 5:1 and said dye in the amount of at least about 0.05% by weight of said particles, said exposure being of such an intensity and duration that the irradiated portions of the layer become substantially impermeable to water, and (2) developing the resultant image by contacting the recording layer with an aqueous liquid permeating the unexposed regions of the layer and removing the thus-permeated regions while the exposed regions of the layer remain intact.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Metallurgy (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Printing Plates And Materials Therefor (AREA)
US819100A 1968-06-17 1969-04-24 Reproduction method Expired - Lifetime US3674483A (en)

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JP (1) JPS5028021B1 (enrdf_load_stackoverflow)
BE (1) BE734659A (enrdf_load_stackoverflow)
DE (1) DE1930684A1 (enrdf_load_stackoverflow)
FR (1) FR2011046A1 (enrdf_load_stackoverflow)
GB (1) GB1264308A (enrdf_load_stackoverflow)
NL (1) NL6909129A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865587A (en) * 1971-07-20 1975-02-11 Agfa Gevaert Nv Electrophographic bichargeable materials and process
US4123271A (en) * 1974-01-22 1978-10-31 Mita Industrial Company, Limited Alkali metal dichromate as memory resistance improver for zinc oxide photoconductors in electrostatic photography
US9566569B2 (en) * 2015-05-11 2017-02-14 Eastman Kodak Company Metal catalytic compositions and articles therefrom

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2393345A1 (fr) * 1977-06-01 1978-12-29 Agfa Gevaert Nv Fabrication d'elements modifies sous forme d'images

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865587A (en) * 1971-07-20 1975-02-11 Agfa Gevaert Nv Electrophographic bichargeable materials and process
US4123271A (en) * 1974-01-22 1978-10-31 Mita Industrial Company, Limited Alkali metal dichromate as memory resistance improver for zinc oxide photoconductors in electrostatic photography
US9566569B2 (en) * 2015-05-11 2017-02-14 Eastman Kodak Company Metal catalytic compositions and articles therefrom

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BE734659A (enrdf_load_stackoverflow) 1969-12-17
JPS5028021B1 (enrdf_load_stackoverflow) 1975-09-11
DE1930684A1 (de) 1969-12-18
FR2011046A1 (enrdf_load_stackoverflow) 1970-02-27
GB1264308A (enrdf_load_stackoverflow) 1972-02-23
NL6909129A (enrdf_load_stackoverflow) 1969-11-25

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