US3619157A - Thermo recording - Google Patents

Thermo recording Download PDF

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US3619157A
US3619157A US677759A US3619157DA US3619157A US 3619157 A US3619157 A US 3619157A US 677759 A US677759 A US 677759A US 3619157D A US3619157D A US 3619157DA US 3619157 A US3619157 A US 3619157A
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recording
heat
layer
recording layer
exposure
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Eric Maria Brinckman
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • 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 present invention relates to a method for recording or reproducing information by means of electromagnetic radiation and to a heat-sensitive element containing substances wherein heat is produced by exposure to electromagnetic radiation.
  • a preferred method of recording information according to the present invention essentially comprises he following features:
  • a recording material is information-wise exposed to electromagnetic radiation preferably containing visible light;
  • the said recording material comprising at least one recording layer containing a binder and a liquid material and/or solid material dispersed in said binder, the liquid and/or solid material being more hydrophobic than the binder and at leats partly forming a compatible mixture with the binder upon heating i.e. an an increase in homogeneity in the mixture consisting of the binder and the liquid and/or solid material is obtained upon heating, the light-transparency of said compatible mixture being higher than that of the dispersion before heat- 8;
  • the said recording material also comprising a substance or substances, which is or are in heat-conductive relationship with said dispersion and absorb(s) at least part of the radiation that strikes said recording material, thereby causing heating of said recording material;
  • the recording material may be composed of one single layer i.e. the recording material may be a self-sustaining layer or sheet. However, the recording material may also be composed of several layers including a support.
  • the dispersed liquid material and/or solid material which is more hydrophobic than the binder, may be composed of one single substance or a mixture of substances. For convenience sake reference is made hereinafter to the hydrophobic material.” A dispersed material solid at room temperature C.) is preferred.
  • the binder may consist of one single binding agent or of a mixture of different binding agents, examples of which are given further on. For convenience sake reference is made hereinafter to "the hydrophilic binder".
  • a dispersion of said hydrophobic material in said binder is applied to a transparent support, e.g. a glass plate. At least part of the coated support is then heated to a temperature ranging between 20 to 250 C. beyond room temperature and finally is cooled back to room temperature. If the heat-sensitive layer after having been heated and cooled back transmits at least 10 percent more light than the nonheated material, the dispersion is suited for recording purposes. Preferably a heat-sensitive layer is used, transmitting at least 20 percent more light after heating in the temperature range between 50 and C.
  • wetting agents which are solid at room temperature eg, polyoxyalkylene waxes.
  • an amount of dispersing agent varying between 5 and 30 percent by weight based on the total weight of the recording layer may be present therein.
  • the required ratio of hydrophobic material to hydrophilic binder in the recording layer depends on the degree of dissolution of the particular hydrophilic and hydrophobic ingredients into each other on heating as well as on the desired degree of differentiation.
  • the ratio by weight of dispersed hydrophobic material to hydrophilic binder is at least 1:4 and at most 25:1.
  • hydrophobic material use is preferably made of a substance or substances that soften(s) or melt(s) between 20 and 250 C. beyond room temperature. In dispersed form the particles preferably size between 0.01 p. and 50 u.
  • the substance or mixture of substances for yielding heat energy under the action of radiation is or are preferably provided in the recording layer in particle form. Finely divided blackor dark-colored pigments or dyes are very suitable.
  • the said substance or mixture of substances is or are preferably provided in the recording layer, e.g. in the hydrophobic thermoplastic material itself, it may as an alternative be added to another composite layer of the recording material, e.g. to an interlayer between the recording layer and the support or to a surface layer covering the recording layer.
  • the light-absorbing substance or substances may be used in an amount up to 30-50 percent by weight of the total weight of the recording layer, in such an amount that the optical density varies between 0.2 and 5.0, and preferably between 0.2 and 1.0 in the case of a reflectographic exposure. Recording may occur by direct exposure or, provided that the recording material is sufficiently transparent, by reflectographic exposure.
  • the intensity of the exposure must be such in relation to the heat-sensitivity of the recording layer that the light-rays initially incident upon the recording layer, undifierentially over its whole area, do not in themselves suffice to cause heating sufficient to result in a significant reduction of the opacity of any part of the recording layer.
  • the additional heating required for achieving a significant differentiation in transparency is due to the additional heating resulting from reflected radiation.
  • the record in terms of a difference in transparency of different areas of the recording layer may constitute a laterally reversed or a legible record of the graphic original, depending on the orientation of the recording material relative to the original and the radiation source during the exposure.
  • the intensity and duration of the radiation affecting the recording layer are also important factors influencing image quality.
  • the exposure should be as short as possible.
  • the exposure is not more than 10 second in duration and the best results are obtained with exposures of less than 10 second, e.g. between 10 and 10 second.
  • the intensity of the radiation incident upon the recording material is at least 0.1 Watt. see/cm. 2.
  • the radiation incident upon the recording material includes radiation first incident upon such material from the radiation source andradiation reflected onto such material from the original.
  • Suitable radiation sources e.g. gas discharge lamps emitting radiation substantially in the wavelength range of 0.3 ,u. to 1.2 p..
  • the radiation employed contains at least 30 percent of the energy in the wavelength range below 700 mp"
  • the performance of the recording method according to the present invention gives in all cases a visible image or record in the form of an image-wise difference in transparency of the recording element, which becomes more transparent in the heated areas.
  • the recording material can be applied in a considerable variety of reproduction techniques including e.g. chemical, physical and photomechanical reproduction techniques.
  • the invention can be employed in the production of printing masters, such as a planographic printing master, a screen printing master, a hectographic printing master and a hydrotype master.
  • the top layer must not prevent the subsequent development step.
  • the top layer may be composed so, that it can easily be removed, e.g. with a solvent for its binder followin g the exposure step, leaving the recording layer in place.
  • the incorporation of the pigment into a top layer, which is removed after the exposure step has definite advantages since the final image quality is improved by the absence of any overall grey tones due to the presence of dispersed pigment.
  • top layer is itself permeable for the developer liquid, it can remain in place provided the development step does not result in overall coloration of this top layer.
  • coloration can be avoided by using, e.g. a colorless developer liquid containing a color coupler for a component in the recording layer and/or subjacent layer, or a developer liquid containing an ingredient for initiating a color reaction between compounds present in the recording layer and/or subjacent layer.
  • a third possibility consists in the incorporation of light-sensitive silver halide into a sublayer beneath the recording layer so that after exposure, liquid silver halide developer can reach this sublayer to bring about image-wise development via the permeable top layer and the still permeable areas of the recording layer.
  • hydrophilic binding agent for the heat-sensitive layer hydrophilic natural colloids
  • modified hydrophilic natural colloids and synthetic hydrophilic polymers can be used.
  • the hydrophilic binding agent should not necessarily be watersoluble, so that use can be made of colloids or hydrophilic polymers such as, e.g., ethylcellulose and methylcellulose of low methoxy substitution degree.
  • Suitable water-soluble binding agents are e.g. casein, zein, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, carboxymethylhydroxyethyl-cellulose, starch derivatives such as hydroxyethylstarch, and hydroxypropylstarch, sucrose octaacetate, ammonium alginate and hydrophilic derivatives of such colloids, synthetic water-soluble hydrophilic polymers e.g., poly(N-vinyl pyrrolidone), polyvinylamine, polyethylene oxide, polyacrylic acid and hydrophilic copolymers and derivative of such polymers.
  • synthetic water-soluble hydrophilic polymers e.g., poly(N-vinyl pyrrolidone), polyvinylamine, polyethylene oxide, polyacrylic acid and hydrophilic copolymers and derivative of such polymers.
  • partly water-soluble or water-insoluble polymers are particularly mentioned the cellulose derivatives that contain an insufficient amount of water-solubilizing substituents, such as partly etherified or esterified cellulose e.g. belonging to the group of ethylcellulose, benzylcellulose, hydroxyethylcellulose acetate, cellulose acetate sorbate, cellulose acetate butyrate, and further vinyl polymers containing hydrophobic and hydrophilic recurring units (e.g., containing a carboxy, hydroxy or sulpho group), e.g.
  • water-solubilizing substituents such as partly etherified or esterified cellulose e.g. belonging to the group of ethylcellulose, benzylcellulose, hydroxyethylcellulose acetate, cellulose acetate sorbate, cellulose acetate butyrate, and further vinyl polymers containing hydrophobic and hydrophilic recurring units (e.g., containing a carboxy, hydroxy or s
  • copolymers of vinyl acetate and crotonic acid copolymers of ethylene and vinyl acetate, prepolymers of diallyl phthalate, poly(diallyl o-phthalate), copolymers of cumarone and indene, copolymers of styrene and allyl alcohol, polyvinylbutyral containing unacetalized hydroxyl groups, copolymers of vinyl chloride, vinyl acetate and maleic anhydride, copolymers of vinylidene chloride, acrylonitrile, copolymers of vinyl stearate and vinyl acetate, and copolymers of hydrophilic vinyl compounds, styrene and/or a-methylstyrene e.g. copolymers of methyl acrylate and styrene, and copolymers of styrene and acrylic acid.
  • binding agents are e.g. sandarac, colophony, pyrogenated copal resin and shellac resin.
  • the binding agent has to be more hydrophilic or more wettable with water than the said dispersed material.
  • hydrophobic liquid or solid substances solid at room temperature
  • hydrophobic dispersed phase use can be made of e.g. paraffins e.g. petrolatum, liquid or solid fatty acids e.g. oleic acid, stearic acid and adipic acid, alcohols e.g. lauryl alcohol and n-hexadecyl alcohol and waxlike substances, so waxes in the broadest sense of the word.
  • waxes of the known six classes i.e. vegetable, mineral, insect, petroleum, animal and synthetic waxes can be used.
  • Carnauba wax, ouricury wax, candellila wax, japan wax, and sugar cane wax which belong to the vegetable wax class
  • beeswax and Chinese insect wax, which belong to the insect class
  • paraffin wax which is a member of the petroleum class
  • spermacetic wax from the sperm whale which wax is of the animal class, may be used.
  • These waxes, e.g. ceresin can be mixed with oil.
  • Vegetable, insect, and animal waxes are usually composed of a mixture of various high-melting fatty acids, alcohols, and esters.
  • Chemically modified natural waxes such as the IG waxes made from the natural montan wax can also be used.
  • Another modified natural wax is a partly oxidized paraffin that can be a substitute for camauba wax.
  • Castor wax and Opalwax are waxes obtained from hydrogenated castor oil.
  • Acrawax is a registered trade name of Glyco Chemicals, New York, NY. U.S.A.) for complex nitrogen derivatives of the higher fatty acids.
  • ARMID is a registered trademark of Armor Industrial Chemical Company, Chicago, Ill, U.S.A. for a waxlike material containing fatty acid amides.
  • Voltalef is a registered trade mark of PechineySt. GobainParis-France for chlorineand fluorine-substituted hydrocarbons.
  • Carlisle is a registered trade mark of Carlisle Chemical Works, U.S.A. for synthetic waxes, the physical constants of which are mentioned in Bennett I-I., Industrial waxes, Vol. I Natural & Synthetic waxes (1963) Chemical Publishing Corp., New York, U.S.A.
  • Use can also be made of monomeric organic hydrophobic substances, e.g. aromatic compounds which are sparingly or not soluble in water eg biphenyl, o-terphenyl, naphthalene, anthracene, terpene compounds and derivatives thereof, e.g., camphene, camphane, and camphor.
  • aromatic compounds which are sparingly or not soluble in water eg biphenyl, o-terphenyl, naphthalene, anthracene, terpene compounds and derivatives thereof, e.g., camphene, camphane, and camphor.
  • Higher aliphatic aldehydes, ketones, ethers, esters e.g., sucrose distearate, sorbitol tristearate; ehtylene glycol monohydroxystearate, glycerol monostearate and diethylene glycol stearate, nitrogen containing hydrophobic organic compounds of the class of the amides, anilides, and thio compounds, e.g., biphenylsulphone and thionaphthenequinone.
  • Halogenated organic compounds such as a-bromocamphor, carbon tetrabromide, trichlorobenzene, hexachloroethane, and iodoform.
  • the hydrophobic material which has proved to form a useful combination with a selected more hydrophilic binder, is dispersed in a solvent for said binder preferably together with the radiation-absorbing substances converting radiation into heat.
  • the binder may be dissolved in the dispersing liquid after or before the hydrophobic material is dispersed therein.
  • solvents can be mentioned, e.g., water, methanol, ethanol, acetone, methylene chloride, diethyl ether, cyclohexane, cyclohexanone, dioxane, toluene, and mixtures of these solvents.
  • the hydrophobic particles in dispersion may size from 0.0lp. to 5011., However, the larger the particles, the less the resolving power on recording. Very good results are obtained with dispersions, the dispersed hydrophobic particles of which size form 0.05 p, to 2,1,. Dispersions wherein the dispersed particles size from 1/1. to Imp. are considered as colloidal systems, which can be obtained in a colloid mill or by means of an ultrasonic wave generator.
  • Particularly suitable substances for use according to the present invention and which convert radiation, e.g., visible light into heat are, e.g., carbon black, graphite, oxides or sulfides of heavy metals, particularly of those heavy metals having an atomic weight between 45 and 210, such as iron oxides, manganese or lead sulfide, or these heavy metals themselves in finely divided state e.g., silver, bismuth, lead, iron, cobalt, or nickel.
  • Carbon black is preferred because of its high radiationabsorptive character, heating power, and low cost.
  • the substances converting absorbed radiation into heat may be present in the hydrophilic binder and/or in the hydrophobic material.
  • the coating composition for forming the recording layer may also contain other ingredients, e.g., dyes, reaction components for the formation of dyes, catalysts for color reactions, metal particles that can be dissolved or etched away, development nuclei, light-sensitive substances, e.g., light-sensitive silver halide, developing agents for exposed silver halide, hardening agents, softening agents, fluorescent compounds, and fillers, e.g., hydrophilic fillers such as silica, zinc oxide barium sulfate and other substances suited for filling purposes.
  • other ingredients e.g., dyes, reaction components for the formation of dyes, catalysts for color reactions, metal particles that can be dissolved or etched away, development nuclei, light-sensitive substances, e.g., light-sensitive silver halide, developing agents for exposed silver halide, hardening agents, softening agents, fluorescent compounds, and fillers, e.g., hydrophilic fillers such as silica, zinc oxide barium sulfate and
  • ingredients may also be incorporated into a waterpermeable top-coating on the recording layer or into a subjacent layer.
  • Dyes may be present in dissolved or dispersed form. They can advantageously be applied in dispersed form and selected in such a way that they dissolve in the melted hydrophobic material.
  • the thickness of the recording layer preferably varies between 0.2 1. and p.
  • the support may be hydrophobic or hydrophilic and may be porous or nonporous.
  • use can be made of e.g., supports of paper, natural, modified natural or synthetic resins, metal, glass and the like.
  • the support is contrasting in color in respect of the recording layer so that the image-wise change in transparency of the latter is detected as a difference in color between the image and nonimage areas.
  • the image-wise irradiated and consequently heated recording material which then contains a reproduction of the original in terms of a different transparency of different portions of the recording layer, can be used as a legible document or can be applied as a transparency in diazo-type printing with ultraviolet radiation.
  • the image-wise differentiation in water-permeability can be utilized for moving by diffusion image-forming substance or substances into the recording element in correspondence with the nonheated areas, the water-permeability of which is not decreased.
  • the image-wise exposed recording material is dipped into an aqueous dye solution, so that the dye can diffuse into the recording element (layer or sheet) only at the areas that remained water-permeable.
  • a solution of a catalyst that initiates a color reaction between components in the recording material or a solution of a colorless reaction component capable of entering into a color reaction with a colorless or slightly colored reaction component in the recording material can be used instead of a dye solution.
  • the recording element it is also possible to incorporate into the recording element colored substances that can be bleached out and are bleached by a bleaching agent diffusing into the areas of the recording layer that remained permeable.
  • metal particles e.g., colloidal silver can be dispersed homogeneously in the recording element and image-wise etched away or dissolved by a suitable liquid penetrating into the water-permeable areas.
  • an image-forming substance incorporated into the recording material is transferred by diffusion from the areas that remained permeable to an image-receiving material.
  • silver salts that can be complexed, and in their complexed form can diffuse to a receiving material containing reduction nuclei or development nuclei, on which in accordance with the areas of the recording layer that remained permeable, silver is deposited image-wise.
  • the recording material and/or the receiving material may contain (a) developing substance(s) to reduce silver salts.
  • a dye which on moistening of the recording material can be leached out gradually through the permeable areas and transferred to a receiving sheet.
  • the second application substances of the image portions of the recording layer that remained hydrophilic can be transferred to an imagereceiving material by bringing the latter in contact with the exposed recording layer either or not in the presence of this processing liquid an afterwards separating the materials from each other.
  • moderate heating may be applied to the recording and or the receiving material.
  • an exposed recording layer containing, e.g., a water-soluble binder is treated with water or an aqueous liquid in order to wash away nonheated portions, thus leaving a relief image.
  • the recording layer contains a pigment or a dye, the relief image forms a colored pattern of the original.
  • the heat-sensitive recording layer composition is applied to a screening material, e.g., a Japan paper, a nylon fabric, or a support of woven bronze wire, a screen-printing master (stencil) can be produced after washing away the water-soluble portions.
  • a screen-printing master stencil
  • the exposed recording layer possessing such differentiation in a sufficiently strong degree is used as planographic printing master.
  • a common offset-ink or a hydrotype ink e.g., an ink as described in the Belgian Pat. Specification 676,898 filed Feb. 23, 1966 by Gevaert-Agfa N.V. may be used.
  • the exposure is carried out with a xenon gas discharge lamp, which can supply an energy of ZOO-2,000 Watt.sec. in a period of 10" to 10 seconds, the energy that impinges on the recording layer preferably varying between 0.5 to 1.5 Watt.sec. per sq.cm.
  • the discharge lamp is in the form of a thin tube fitted in a hollow glass cylinder in order to make possible a uniform exposure of the recording material applied according to the periphery of the cylinder. More details about such a gas discharge lamp can be found in the Belgian Pat. Specifications 664,868 filed June 3, 1965 by Agfa-Gevaert AG and 681,138 filed May 17, 1966 by Gevaert-Agfa N.V.
  • the intensity of the light emitted by such a gas discharge lamp is particularly high in the region of the visible spectrum.
  • Radiation sources with a much lower energy output than the aforementioned may be used if the light energy is focused onto a relatively small heat-sensitive area, e.g., by using a laser beam or by carrying out the exposure progressively and/or intermittently.
  • the heat-sensitive material containing the radiation-absorbing substances, which convert the radiation, e.g., light, into heat may be scanning-wise exposed, e.g., light, into heat, may be scanning-wise exposed, e.g., by means of an image-wise modulated high-intensity light spot, and may be progressively exposed e.g., through a slot wherein light, e.g., ofa tubelike radiation sources, is focused.
  • the heat-sensitive material can be integrally heated before or during the image-wise heating, to a certain temperature below the temperature at which a material increase in transmittance is obtained.
  • EXAMPLE 1 A mixture consisting of ethylcellulose 30 5. carbon black 0.5 g. methanol 400 is ground for 6 hours in a ball mill. To this fine suspension a dispersion is added obtained by grinding in a vibrating ball mill for 2 hours a mixture consisting of:
  • the mixture obtained is then coated on a subbed support of polyethylene terephthalate in a proportion of 60 g. per sq.m. After having been dried at room temperature the layer has a grey and opaque appearance. Then the material is laid with its heat-sensitive layer on an original to be reproduced and the whole is reflectographically irradiated with an electronic flash lamp, the energy output of which amounts to 0.75 Watt.sec. per sq.cm. Hereby the heat-sensitive material becomes transparent on the areas corresponding with the white areas of the After drying a heat-sensitive layer is applied thereto in a proportion of 50 g./sq.m. from a composition, which is obtained by grinding for 6 hours in a ball mill the following substances:
  • EXAMPLE 3 A subbed cellulose triacetate support is coated in a proportion of g./sq.m. with the barium sulfate dispersion of example 2. After drying at heat-sensitive layer is applied thereto in a copoly(vinylidene chloride/acrylonitrile/ n-butyl acrylatelethyl acrylate) (86/3/7/4! by weight) 60 g. carbon black having a particle size of 0.01 p 0.5 g. oleic acid 20 g. methanol 800 cc.
  • This material is reflectographically irradiated with flashlight as described in example 1. A positive transparency is obtained.
  • EXAMPLE 4 A transparent paper support of 40 g./sq.m. is coated in a proportion of 50 g./sq.m. with a dispersion consisting of:
  • cthylcellulose (degree of substitution of ethoxy groups 2.45) 20 g. carbon black 0.5 g. glycerol monostearate 80 g. methanol 800 cc.
  • Example 4 Example 4 is repeated but the heat-sensitive material is reflectographically exposed with its backside facing the original. The material is then inked with an ink composition consisting of 20 percent aqueous methylene blue. inking is carried out by means of an offset-roller. Since the ink is only accepted at those areas corresponding with the text parts of the original, a direct-reading positive print is obtained.
  • EXAMPLE 6 A subbed support of polyethylene terephthalate is coated with a baryta suspension as described in example 2. Then a coating is applied thereto in a proportion of 50 g./sq.m. from the following suspension, which has been ground for 6 hours in a ball-mill:
  • the nonheated areas i.e., the parts corresponding with the image markings of the original, can easily be rubbed away with water. In this way a grey negative image is obtained from the original.
  • EXAMPLE 7 A transparent paper support of 40 g./sq.m. is coated in a proportion of 50 g./sq.m. with a dispersion, which has been ground for 6 hours in a ball-mill and which consists of:
  • the material After having been exposed reflectographically by a flash lamp as described in example 2, the material is heated at 60 C. for 10 sec. while being held in contact with a sheet of common writing paper. On the latter a grey positive print is obtained from the original.
  • EXAMPLE 8 A subbed support of cellulose triacetate is coated with a solution of the following composition in a proportion of 85 g./sq.m.:
  • ethylcellulose (degree of substitution of ethoxy groups 2.45) 35 g. carbon black 0.5 g. stearic acid 65 g. methanol 800 cc.
  • the material After reflectographic flash exposure as described in example 2, the material is wetted for a short while with water and then for 15 sec. brought in contact with a receiving paper prepared by dipping common writing paper in a 5 percent solution of 2,4-dinitrophenylpyridinium chloride in ethanol and drying. A brown positive image is obtained on this receiving paper. By wetting the master again and pressing it repeatedly to fresh sheets of receiving paper, some four prints can be obtained from the original.
  • EXAMPLE 9 A transparent paper support weighting 40 g./sq.m. is coated with the following suspension in a proportion of 60 g./sq.m.:
  • this material After having been dried, this material is reflectographically exposed by means of an electronic flash lamp as described in example 2, then wetted with water and pressed against a sheet of common writing paper. After having separated the material therefrom, a black positive reproduction of the original is obtained on the receiving material.
  • EXAMPLE i0 japan paper support weighing l6 g.lsq.m. is coated with a dispersion obtained by grinding for 8 hours in a ball-mill the following substances:
  • copoly (styrene ally) carbon black 05 g.
  • polyethylene glycol having an average molecular weight of l0,000 20 g.
  • a transparent negative to be copied is then laid with its backside onto the heat-sensitive plate and the whole is irradiated by means of an electronic flash lamp having an energy output of 0.75 Watt.sec./sq.cm.
  • the plate is then rubbed by means of a plug of wadding soaked with a 1 percent aqueous solution of sodium hydroxide. In this way the nonheated parts of the composition are eliminated from the plate and the subjacent metal parts are rendered strongly hydrophilic.
  • the treated plate can now he used as an offset printing plate. by means of which positive prints can be obtained.
  • EXAMPLE 12 Common paper of 60 g./sq.m. is coated in a proportion of 50 g./sq.m. with the following dispersion, which has been ground for 6 hours in a ball-mill:
  • ethylcellulose (degree of substitution of ethoxy groups: 2.45) 4 g, stearic acid 70 carbon black 0.5 g. ethanol 800 cc.
  • EXAMPLE 13 A subbed cellulose triacetate film is coated in a proportion of 80 g./sq.m. with the barium sulfate dispersion described in example 2. After drying, a heat-sensitive layer is applied thereto in a proportion of 50 g./sq.m. from the following suspension, which has been ground for 7 hours in a ball-mill:
  • the material obtained is irradiated with flash light in the way described in example 10 and can then be used as a master hydrotype printing.
  • an ink paste is used, which is prepared as follows:
  • 75 g. of a carbon black dispersion containing per 100 g. 53 g. of carbon black, 23 g. of water, 18 g. of glycol, and 6 g. of nonylphenyl polyethylene oxide (containing 15 ethylene oxide units) are mixed with 225 g. of a 20 percent aqueous solution of cellulose acetophthaiate (degree of substitution of acetyl groups 1.3 to 1.5, degree of substitution of phthalyl groups 0.9 to 1.2; viscosity 12 cps., measured at 20 C. as a 3 percent solution in a mixture of 35 cc. of methyiglycol, 60 cc. of ethanol and cc. of acetone), g.
  • EXAMPLE 14 A subbed cellulose triacetate support is coated with a heatsensitive layer pro rate of 50 g./sq.m. from a coating compost tion prepared by grinding the following substances for 6 hours in a ball-mill: I
  • the heat-sensitive material After having been dried, the heat-sensitive material is reflectographically exposed as described in example 1, but with an energy intensity of 0.98 Watt.sec. per sq.cm. Subsequently a paper wetted with methanol is pressed against the exposed heat-sensitive layer and then immediately separated therefrom. A dark grey positive image is obtained from the original on the paper. By repeating the latter steps some 5 copies having the same quality can be produced.
  • EXAMPLE 16 A subbed polyethylene terephthalate support is coated pro rata of g./sq.m. with a composition prepared as follows:
  • a graphic paper original in contact with the heat-sensitive layer is reflectographically exposed with a flash lamp irradiating the heat-sensitive layer with an energy of 0.53 Watt.sec. per sq.cm. in 8.10" seconds.
  • the exposed material is suited for use as hydrotype master.
  • As printing ink the following composition is used:
  • a carbon layer with which useful results are obtained is prepared as follows:
  • ethylcellulose degree of substitution of ethoxy groups: 2.45) 35 g. bleached montan wax 55 g. poly(isobutylene) (average molecular weight: 150,000) 10 g. methanol 800 cc.
  • a method for reproducing an original having image markings of radiation-absorbing material comprises the step of uniformly exposing to electromagnetic radiation, a recording material comprising at least one recording layer formed by a substantially opaque dispersion of a hydrophilic binder of finely divided particles of a hydrophobic nonpolymeric fatty or waxy material which is solid at room temperature, said finely divide material forming with the binder upon heating a substantially compatible mixture of significantly increased light-transparency, said recording layer also having uniformly distributed therethrough at least one finely divided pigment adapted to absorb at least part of electromagnetic radiation impinged thereon and convert such absorbed radiation into heat internally within said layer, said exposure being carried out while said recording layer is in direct heat conductive relation with the image markings of said original with a radiation source of sufficient intensity and for a time of such duration up to seconds that as a consequence of the generation of heat by said pigment a pattern corresponding to the nonimage areas of said is produced in said layer having increased transparency and decreased hydrophlity, the area of said layer corresponding to the image
  • said recording layer is prepared from a dispersion of said relatively hydrophobic material in a hydrophilic binder, the ratio by weight of dispersed hydrophobic material to hydrophilic binder being at least 1:4 and at most 25: l.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Printing Plates And Materials Therefor (AREA)
US677759A 1966-10-24 1967-10-24 Thermo recording Expired - Lifetime US3619157A (en)

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US3945318A (en) * 1974-04-08 1976-03-23 Logetronics, Inc. Printing plate blank and image sheet by laser transfer
US3962526A (en) * 1974-07-23 1976-06-08 The Mazer Corporation Tissueless pre-printed spirit duplicating masters
US3964389A (en) * 1974-01-17 1976-06-22 Scott Paper Company Printing plate by laser transfer
US3967034A (en) * 1971-12-22 1976-06-29 Canadian Patents And Development Limited Pressure sensitive coatings
US4005237A (en) * 1974-07-23 1977-01-25 The Mazer Corporation Non-bleed pre-printed spirit duplicating masters
US4020762A (en) * 1974-01-17 1977-05-03 Scott Paper Company Laser imaging a lanographic printing plate
US4088073A (en) * 1973-12-27 1978-05-09 Xerox Corporation Process for preparing ink releasing stencil
US4091727A (en) * 1973-08-03 1978-05-30 Asahi Dow Limited Heat-sensitive copying method for preparation of printing stencils
US4132168A (en) * 1974-01-17 1979-01-02 Scott Paper Company Presensitized printing plate with in-situ, laser imageable mask
US4158648A (en) * 1971-12-12 1979-06-19 Canadian Patents And Development Limited Pressure- and heat-sensitive coatings
US4199359A (en) * 1968-05-16 1980-04-22 Xerox Corporation Photographic screen stencil printing process
US4252890A (en) * 1968-08-26 1981-02-24 Xerox Corporation Imaging system which agglomerates particulate material
US4272569A (en) * 1977-08-24 1981-06-09 Allied Paper Incorporated Water and solvent resistant coated paper and method for making the same
US4304626A (en) * 1977-08-24 1981-12-08 Allied Paper Incorporated Method for making water and solvent resistant paper
US4731317A (en) * 1984-06-08 1988-03-15 Howard A. Fromson Laser imagable lithographic printing plate with diazo resin
US5234797A (en) * 1989-02-20 1993-08-10 Jujo Paper Co., Ltd. Optical recording medium
US6001536A (en) * 1995-10-24 1999-12-14 Agfa-Gevaert, N.V. Method for making a lithographic printing plate involving development by plain water
US6040113A (en) * 1997-03-11 2000-03-21 Agfa-Gevaert, N.V. Heat-sensitive imaging element for making positive working printing plates
US6153353A (en) * 1998-03-14 2000-11-28 Agfa-Gevaert, N.V. Method for making positive working printing plates from a heat mode sensitive imaging element
US6244181B1 (en) * 1998-07-16 2001-06-12 Agfa-Gevaert Dry method for preparing a thermal lithographic printing plate precursor
US6248503B1 (en) 1997-11-07 2001-06-19 Agfa-Gevaert Method for making positive working printing plates from a heat mode sensitive imaging element
US6250225B1 (en) * 1998-07-16 2001-06-26 Agfa-Gevaert Thermal lithographic printing plate precursor with excellent shelf life
US6267055B1 (en) * 2000-07-18 2001-07-31 Howard A. Fromson Dual laser thermal imaging
US6340815B1 (en) 1998-04-15 2002-01-22 Agfa-Gevaert Heat mode sensitive imaging element for making positive working printing plates
US6342336B2 (en) 1998-03-06 2002-01-29 Agfa-Gevaert Heat mode sensitive imaging element for making positive working printing plates
US6391517B1 (en) 1998-04-15 2002-05-21 Agfa-Gevaert Heat mode sensitive imaging element for making positive working printing plates
US6815139B2 (en) 2000-12-07 2004-11-09 Agfa-Gevaert Method of processing a printing plate material with a single-fluid ink
EP2993054A1 (de) * 2014-09-06 2016-03-09 Mitsubishi HiTec Paper Europe GmbH Bahnförmiges wärmeempfindliches Aufzeichnungsmaterial mit mindestens zwei Lagen

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US4251564A (en) * 1979-02-12 1981-02-17 Cannella Vincent D Heat-sink imaging method and apparatus for live skin tissue using pulsed energy source
EP0770497B1 (en) * 1995-10-24 2002-04-03 Agfa-Gevaert A method for making a lithographic printing plate involving development by plain water
US6110644A (en) * 1995-10-24 2000-08-29 Agfa-Gevaert, N.V. Method for making a lithographic printing plate involving on press development
EP0770494B1 (en) * 1995-10-24 2000-05-24 Agfa-Gevaert N.V. A method for making a lithographic printing plate involving on press development
EP0770495B1 (en) * 1995-10-24 2002-06-19 Agfa-Gevaert A method for making a lithographic printing plate involving on press development
EP0770496B1 (en) * 1995-10-24 2002-03-13 Agfa-Gevaert Printing apparatus for making a lithographic printing plate involving on press development
EP0773113B1 (en) * 1995-11-09 2000-05-24 Agfa-Gevaert N.V. Heat sensitive imaging element and method for making a printing plate therewith
EP0773112B1 (en) 1995-11-09 2001-05-30 Agfa-Gevaert N.V. Heat sensitive imaging element and method for making a printing plate therewith
EP0774364B1 (en) * 1995-11-16 2000-10-11 Agfa-Gevaert N.V. Method for making a lithographic printing plate by image-wise heating an imaging element using a thermal head
EP0795998A1 (en) * 1996-03-14 1997-09-17 Agfa-Gevaert N.V. Producing a lithographic printing plate by sequentially exposing a thermo-sensitive imaging element by a set of radiation beams
EP0800928B1 (en) 1996-04-09 1999-07-28 Agfa-Gevaert N.V. A heat sensitive imaging element and a method for producing lithographic plates therewith
EP0816070B1 (en) * 1996-06-24 2000-10-18 Agfa-Gevaert N.V. A heat sensitive imaging element and a method for producing lithographic plates therewith
EP0839648A1 (en) * 1996-10-29 1998-05-06 Agfa-Gevaert N.V. Method for making lithographic printing plates allowing for the use of lower laser writing power
EP0839647B2 (en) * 1996-10-29 2014-01-22 Agfa Graphics N.V. Method for making a lithographic printing plate with improved ink-uptake
EP0846571B1 (en) 1996-12-04 2001-04-11 Agfa-Gevaert N.V. Method for the formation of an improved heat mode image
EP0849090A3 (en) * 1996-12-19 1998-07-01 Agfa-Gevaert N.V. Thermosensitive imaging element for the preparation of lithographic printing plates with improved transporting properties
GB9709404D0 (en) * 1997-05-10 1997-07-02 Du Pont Uk Improvements in or relating to the formation of images
EP0914941B1 (en) * 1997-11-07 2001-12-12 Agfa-Gevaert N.V. A method for making positive working printing plates from heat mode sensitive imaging element
EP0940266B1 (en) * 1998-03-06 2002-06-26 Agfa-Gevaert A heat mode sensitive imaging element for making positive working printing plates.
EP0943451B3 (en) * 1998-03-14 2018-12-12 Agfa Graphics NV A heat mode imaging element and a method for making positive working printing plates from said heat mode imaging element
DE69901642T3 (de) 1998-03-14 2019-03-21 Agfa Nv Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus einem wärmeempfindlichem Bildaufzeichnungsmaterial
EP0950516B1 (en) * 1998-04-15 2004-05-06 Agfa-Gevaert A heat mode sensitive imaging element for making positive working printing plates
EP0950514B1 (en) * 1998-04-15 2001-11-07 Agfa-Gevaert N.V. A heat mode sensitive imaging element for making positive working printing plates
EP1232858B1 (en) * 2001-02-16 2003-10-15 Agfa-Gevaert On-press coating and on-press processing of a lithographic material
US6789480B2 (en) 2001-02-16 2004-09-14 Agfa-Gevaert On-press exposure and on-press processing of a lithographic material
EP1232859B1 (en) * 2001-02-16 2003-11-26 Agfa-Gevaert On-press exposure and on-press processing of a lithographic material
US6789481B2 (en) 2001-02-16 2004-09-14 Agfa-Gevaert On-press coating and on-press processing of a lithographic material

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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4199359A (en) * 1968-05-16 1980-04-22 Xerox Corporation Photographic screen stencil printing process
US4252890A (en) * 1968-08-26 1981-02-24 Xerox Corporation Imaging system which agglomerates particulate material
US4158648A (en) * 1971-12-12 1979-06-19 Canadian Patents And Development Limited Pressure- and heat-sensitive coatings
US3967034A (en) * 1971-12-22 1976-06-29 Canadian Patents And Development Limited Pressure sensitive coatings
US4091727A (en) * 1973-08-03 1978-05-30 Asahi Dow Limited Heat-sensitive copying method for preparation of printing stencils
US4088073A (en) * 1973-12-27 1978-05-09 Xerox Corporation Process for preparing ink releasing stencil
US4020762A (en) * 1974-01-17 1977-05-03 Scott Paper Company Laser imaging a lanographic printing plate
US4132168A (en) * 1974-01-17 1979-01-02 Scott Paper Company Presensitized printing plate with in-situ, laser imageable mask
US3964389A (en) * 1974-01-17 1976-06-22 Scott Paper Company Printing plate by laser transfer
US3945318A (en) * 1974-04-08 1976-03-23 Logetronics, Inc. Printing plate blank and image sheet by laser transfer
US4005237A (en) * 1974-07-23 1977-01-25 The Mazer Corporation Non-bleed pre-printed spirit duplicating masters
US3962526A (en) * 1974-07-23 1976-06-08 The Mazer Corporation Tissueless pre-printed spirit duplicating masters
US4272569A (en) * 1977-08-24 1981-06-09 Allied Paper Incorporated Water and solvent resistant coated paper and method for making the same
US4304626A (en) * 1977-08-24 1981-12-08 Allied Paper Incorporated Method for making water and solvent resistant paper
US4731317A (en) * 1984-06-08 1988-03-15 Howard A. Fromson Laser imagable lithographic printing plate with diazo resin
US5234797A (en) * 1989-02-20 1993-08-10 Jujo Paper Co., Ltd. Optical recording medium
US6001536A (en) * 1995-10-24 1999-12-14 Agfa-Gevaert, N.V. Method for making a lithographic printing plate involving development by plain water
US6040113A (en) * 1997-03-11 2000-03-21 Agfa-Gevaert, N.V. Heat-sensitive imaging element for making positive working printing plates
US6248503B1 (en) 1997-11-07 2001-06-19 Agfa-Gevaert Method for making positive working printing plates from a heat mode sensitive imaging element
US6342336B2 (en) 1998-03-06 2002-01-29 Agfa-Gevaert Heat mode sensitive imaging element for making positive working printing plates
US6153353A (en) * 1998-03-14 2000-11-28 Agfa-Gevaert, N.V. Method for making positive working printing plates from a heat mode sensitive imaging element
US6340815B1 (en) 1998-04-15 2002-01-22 Agfa-Gevaert Heat mode sensitive imaging element for making positive working printing plates
US6391517B1 (en) 1998-04-15 2002-05-21 Agfa-Gevaert Heat mode sensitive imaging element for making positive working printing plates
US6250225B1 (en) * 1998-07-16 2001-06-26 Agfa-Gevaert Thermal lithographic printing plate precursor with excellent shelf life
US6244181B1 (en) * 1998-07-16 2001-06-12 Agfa-Gevaert Dry method for preparing a thermal lithographic printing plate precursor
WO2002006050A1 (en) * 2000-07-18 2002-01-24 Fromson H A Dual laser thermal imaging
US6267055B1 (en) * 2000-07-18 2001-07-31 Howard A. Fromson Dual laser thermal imaging
US6815139B2 (en) 2000-12-07 2004-11-09 Agfa-Gevaert Method of processing a printing plate material with a single-fluid ink
EP2993054A1 (de) * 2014-09-06 2016-03-09 Mitsubishi HiTec Paper Europe GmbH Bahnförmiges wärmeempfindliches Aufzeichnungsmaterial mit mindestens zwei Lagen

Also Published As

Publication number Publication date
BE705529A (enrdf_load_stackoverflow) 1968-04-24
DE1671519A1 (de) 1971-09-30
FR1561957A (enrdf_load_stackoverflow) 1969-04-04
GB1208414A (en) 1970-10-14
NL6714061A (enrdf_load_stackoverflow) 1967-12-27

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