US3839028A - Imaging process - Google Patents

Imaging process Download PDF

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US3839028A
US3839028A US00214141A US21414171A US3839028A US 3839028 A US3839028 A US 3839028A US 00214141 A US00214141 A US 00214141A US 21414171 A US21414171 A US 21414171A US 3839028 A US3839028 A US 3839028A
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Prior art keywords
compound
image
recording layer
layer
water
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Inventor
E Hasegawa
T Miyazako
N Tsuji
T Shishido
S Honjo
R Ohi
Y Tamai
M Takimoto
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • 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
    • B41M5/20—Duplicating or marking methods; Sheet materials for use therein using electric current
    • 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
    • B41M5/368—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 involving the creation of a soluble/insoluble or hydrophilic/hydrophobic permeability pattern; Peel development
    • 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
    • G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances
    • 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
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/26—Electrographic processes using a charge pattern for the production of printing plates for non-xerographic printing processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G17/00—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process
    • G03G17/02—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process with electrolytic development

Definitions

  • ABSTRACT An imaging process which comprises selectively elimi nating or adding imagewise at least a component of a system consisting of a hydrophilic macromolecular substance, a metal ion, a compound capable of maintaining the pH value of the surrounding medium at not less than 8 when brought into contact with water or a substance which provides such a compound when decomposed and a compound represented by the follow ing general formula:
  • protein is insolubilized against water by means of various organic compounds, for example, aldehydes such as formalin, chlorotriazine, mucoehromic acid, etc. It is known as well that protein is insolubilized by certain metal ion such as chromium ion. These compounds have been important in photographic industry, but the insolubilizing effect thereof is excessively slow or the stability of compounds themselves is not sufficient.
  • the presentare capable of extremely rapidly solidifying hydrophilic macromolecular substances such as gelatin, at a pH value not lower than 8 and in the presence of metal ions.
  • the present inventors have reached a novel and useful imaging process which comprises selectively eliminating or adding imagewise at least a compound of a system consisting of (A) hydrophilic macromolecular substance, (B) a metal ion belonging to groups 6A, 7A, 8, 1B or 2B of the periodic table (periodic table of IUPAC Comptes Rondus XXIII Conference, p.
  • Z and 2' represent a group of non-metallic atoms necessary to complete a heterocyclic structure; X represents an anion; and Y represents an atom belonging to group 68 of the periodic table, from or to said system thereby obtaining an image containing water-insoluble macromolecular substance.
  • the imagewise elimination or addition of component(s) of said system can be realized by various methods such as electrolytic electroconductographic process, electrophotographic processes, electroconductive recording processes, thermal recording processes, etc., or naturally by direct manual addition.
  • all four components must be present to form an image.
  • the image can be formed only at those portions where all components are present.
  • a gelatin layer (A) containing metal ion (B) and compound (D) with alkali solution(C) an image is formed by an addition process.
  • one (or more) component may be eliminated imagewise. The latter is an eliminating process.
  • the present invention may be carried out by eliminating at I least one component from a system containing all of four components, (A), (B), (C), and (D).
  • the alkali (C) may be removed by adding an acid.
  • One preferable embodiment according to this purpose comprises (1) introducing into a system containing all of four components a substance which can release a compound acting as an acid by action of electromagnetic radiation, (2) imagewise exposing the system to an electromagnetic radiation to form an acid which neutralizes an alkali (that is removes alkali (C)) whereby an image is formed.
  • organic halogen compounds may be used such as carbon tetrabromide, iodoform, hexachlorethan, polyvinylchloride and polyvinylidene-chloride. These compounds release a halogen radical upon exposure to electromagnetic radiation. The halogen radical catches a hydrogen atom from the system to form hydrogen halide which is a strong acid.
  • the image obtainable according to this invention is composed of a macromolecular substance and therefor can be utilized not only for ordinary recording and copying but also for preparing printing plate for spirit printing, offset printing, intaglio printing, letterpress printing, and mimeographic printing and preparing gelatin reliefs for dye transfer prints. Also the image obtainable according to this invention can be applied to the preparation of printed circuits, braille printing and transparencies for overhead projection. Also, according to the invention it is possible to produce electron beam recording materials.
  • the main object of this invention is to provide a macromolecular image and processes for forming the image.
  • FIG. 5 shows the method of removing the photoconductive layer from the photosensitive element after said treatment with warm water.
  • FIG. 6 shows the method of removing electroconductive layer.
  • FIG. 7 shows the metallic image obtained according to this invention.
  • FIG. 8 shows the method of thermographic copying according to this invention.
  • FIG. 9 shows the polymer image obtained by thermographic copying according to this invention.
  • FIG. 10 shows the mimeographic plate material according to this invention.
  • FIG. 11 shows the mimeographic plate prepared according to this invention.
  • FIG. 12 shows the method of transferring the polymer image obtained according to this invention onto a metallic plate.
  • FIG. 13 shows the method of etching the surface of metallic plate after said transfer.
  • FIG. 14 shows the printing plate obtained by removing the polymer image after said etching.
  • the hydrophilic macromolecular substance (A) employed in this invention preferably contains a primary amino radical.
  • Such macromolecular substance can be, for example, a natural protein containing lysine or arginine as amino acid units such as gelatin, glue, casein, aloumin, protamin, globrin, etc.
  • various synthetic macromolecular substances containing primary amino radicals can be used for this purpose.
  • Such synthetic macromolecular substances there are polymers obtained from aminecontaining monomers, i.e. aminoethylvinylether (Liebigs Annales der Chemie, 601, 81 (1956)); aminostyrene (Chemical Abstract 34, 389 (1940)); aminophenyvinyI-ether (Chemical Abstract 56, 12,781 (1962 or vinylbenzylamine (Berichte der Deutschen Chemischenmaschine 56, 2,154 (1923)). Copolymers containing the above-mentioned monomers can be utilized for this purpose.
  • aminecontaining monomers i.e. aminoethylvinylether (Liebigs Annales der Chemie, 601, 81 (1956)); aminostyrene (Chemical Abstract 34, 389 (1940)); aminophenyvinyI-ether (Chemical Abstract 56, 12,781 (1962 or vinylbenzylamine (Berichte der Deutschen Chemischenmaschine 56, 2,154 (1923)).
  • polymers obtained from macromolecular reactions such as between polymethyl acrylate and diamines (Die Macromolecular Chemie, 22, 31 (1957)) or the reduction of polyacrylamide by lithium aluminum hydride (The Journal of Organic Chemistry, 26, 1274 (1961)).
  • Polymerized primary amines such as polyvinylamines, polylysine, etc. fall within this category.
  • polymers can be prepared by conventional The metallic ion (B)to be employed in this invention processes, as shown by the following examples. is preferred to-be an ion of an element belonging to Synthesis of polymer 1 groups 6A, 7A, 8 1B or 2B of the periodic table, such 76 g of a copolymer of methyl acrylate (30 mol. peras chromium, manganese, iron, cobalt, nickel, copper,
  • acrylamide 70 mol. percent was dissolved 5 zinc, palladium, silver, cadmium mercury, gold, etc., in 2 l. of water, and 25 g of 1,3-propane diamine added and particularly suitable for this purpose are the ions of under agitation.
  • the system was kept at 40 50C for manganese, cobalt, nickel, copper, zinc, silver and cad- 4 hours.
  • These metal ions can be employed in the imagprimary amine thus obtained was subjected to dialysis ing process as a water-soluble salt, or as a salt sparingly with distilled water for one night and then freeze-dried.
  • the ions are particularly preferred copolymers and the reaction conditions shown in the to be divalent, but ions of other valence states such as following table. Cr or Fe can be employed, depending on the Polymer 2 3 4 5 6 Starting copolymer composition acrylamide 90 80 95 90 80 methylacrylate 10 5 10 20 Reaction time 4 4 3 3 3 (hour) r Reaction temperature (C) 40-50 40-50 -40 30-40 30-40 Synthesis of p lym r 7 conditions for forming the image. Some kinds of the 14.2 g (0.2 mol.) of powdered polyacrylamide (mo- 30 aforementioned metal ions can per se render gelatin inlecular weight about 100,000) was dispersed in 11.
  • Macromolecular substance (A) can be associated with y ating o render the atmosphere alkaline due to other macromolecular substances miscible with subgenerated ammonia.
  • substrates stance (A) for example, polyacrylic acid, polyvinyl alcapable of generating a basic material under electron cohol, polyacrylamide, polyvinylbenzene sulfonic acid, eam radiati n. for e amp p ya y n d po ypolyamide, etc. or copolymers thereof where the ratio methy ol ac y am de, p ly mylpynd e.
  • the macromolecular substance (A) must be to the polyvinylamidazole or copolymers containing said other macromolecular substances is typically greater compounds.
  • a pH value not lower than than 0.1. 8 is required for the formation of the image.
  • the minimum mumber of primary amino groups in Compound represented by the foregoing general the polymer is two (2).
  • the preferable amount may be formula (I) is found to be particularly effective when more than 2 per 1,000 of recurring units of the poly- Y therein stands for sulfur or selenium atom.
  • the terminal groups of the polymer are not necessarily a substantial 0386-508 part of the invention.
  • Reaction between the polymer, the compound and the metal ion is thought to occur as follows: a primary amino group of the polymer reacts with compound (D) and bonds to a carbon atom which is attached to S and Y to form a Schiff base and simultaneously ring Z is opened to form an SH group. (Ring Z is usually remained). Then two SH groups thus formed are bonded through the metal ion by forming a complex.
  • a cross-linking reaction is completed as illustrated l y hei l winamodels--.
  • a- Polymercompound metal polymer As mentioned above, the compound (D) must react with the primary amino group and form an -SH group ion 4565mm which reacts with the metal ion. In this respect the cyclic compound (D) having the linkages represented by the foregoing general formula (I) are suitable. Compound (D) easily reacts with a primary amino group and causes a ring-opening reaction to form an Sl-l group.
  • Z and Z may be non-metallic atoms which form a five or six membered heterocyclic ring which may have further substituen ts including fusing rings.
  • Compound (D) can generally be easily synthesized by heating an azole compound containing a methylmercapto radical and ethylene bromide or 1,3- dibromopropane at ca. C, as shown by the following examples.
  • Compounds 8 and 9 and Compound 10 can be synthesized according to the process described in Chemical Abstracts 72, 31666 (1970), and ibid. 63, 11569 (1965), respectively.
  • compound (D) when added to the hydrophilic macromolecular substance (A), shows an effect of lowering the solubility thereof in warm water (typically above 35C. due to a crosslinking reaction, and that said effect is enhanced in the presence of a metal ion and in alkaline conditions.
  • the metal ion (B) is found to be effective even in trace amounts, and does not show any adverse effect so long as it is totally soluble in the system.
  • the amount of the compound (D) should not be less than 0.2 parts (hereinafter amounts will be represented by parts by weight), preferably not less than 2 parts, per 1,000 parts of the macromolecular substance (A).
  • the amount of metal ion (B) can be very small, and is found to be effective in an amount of 0.002 parts with respect to 1,000 parts of compound (D), but is preferably present in an amount of 0.01 parts or more with respect thereto.
  • component I (A) As well as component (C).
  • component I (A) As well as component (C), certain synthetic polymers containing primary amino radicals as mentioned above show a pH value higher than 8 in aqueous solution, and therefore can be employed as component (A) as well as component (C).
  • APPLICATION I APPLICATION IN ELECTROLYTIC ELECTRO- PI-IOTOGRAPI-IIC PROCESS The process of this invention can be applied to an electrolytic-electrophotographic process to obtain an image by means of the decrease of electrical resistance resulting from light exposure on a photoconductive material.
  • Known electrolytic-electrophotographic process consist of the steps of projecting a light image on a photoconductive layer which is composed of a powdered photoconductive material such as cadmium sulfide, titanium oxide, zinc sulfide, zinc oxide, etc.
  • This invention provides extremely desirable results .when applied to such an electrolytic electrophotographic process.
  • an ordinary photosensitive element for the electrolytic electrophotographic process namely, one composed of a support material provided with suitable mechanical properties and a photosensitive layer provided thereon and consisting of powdered photoconductive material in an electroinsulative binder.
  • the interface between the support material and the photosensitive layer is required to be highly electroconductive. Consequently, if the support material is composed of a plastic material etc., it is necessary to provide the surface thereof with a thin layer of aluminum or other metal though ordinarily vacuum deposited aluminum is used. Examples of other available support materials are electroconductive glass provided with a thin layer of tin oxide, paper containing carbon black, paper containing fine metal fibers, paper laminated with aluminum foil, etc. The use of a metal plate as the support is naturally desirable.
  • the photosensitive layer consists of a thin layer of an intimate mixture of, for example, photoconductive zinc oxide and an electroinsulative binder.
  • the zinc oxide is preferably manufactured by the French method.
  • the binding material has a significant influence on the electr'sphsts' rassre"ptaasaias'and cah b'aesresipnasa s styrene-butadiene copolymers (Pliolite S--5D and S7; Goodyear Tire and Rubber).
  • Fatty acid epoxy esters, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, etc. can also be utilized for this purpose.
  • the binder can have added thereto plasticizers, inactive pigments (for example colloidal silica, talc, titanium dioxide, etc.), lubricants, etc., if desired.
  • plasticizers for example colloidal silica, talc, titanium dioxide, etc.
  • lubricants etc.
  • surface active agents is often desirable in order to regulate the coating properties.
  • sensitizing dyes are often added in order to widen the photosensitive wavelength range of the zinc oxide, which is basically limited to the ultraviolet to blue region. Other sensitizing materials may also be added as minor additives.
  • This invention can be applied to electrolytic electroconductographic process by adding the components (A) hydrophilic macromolecular substance; (B) metal ion; and (D) the aforementioned compound to the surface of the photosensitive layer or to the electrolytic bath.
  • the alkali generating compound (C), water in this case, renders the proximity of the cathode alkaline upon electrolysis.
  • pared photosensitive element 10 which is composed of a transparent or opaque support material 11, an electroconductive layer 12 and an insulative photoconductive layer 13, on which is provided a hydrophilic macromolecular layer 14 consisting, for example, of gelatin and aforementioned compound 1.
  • a macromolecular layer 14 preferably has a thickness of 0.1 500 microns in the dry state.
  • FIG. 2 shows the step of imagewise light projection on the photosensitive element shown in FIG. 1, in which a transparency original 21 consists of opaque areas 22 and translucent area 23 distributed according to the image.
  • the uniform light from above (indicated by the arrows) is transmitted through the transparent area 23 of original plate 21 and the macromolecular layer 14 and reaches the photoconductive layer 13 to thereby form a low resistance area [a] and high resistance area [b].
  • Layer 14 may previously have added thereto a dye or pigment. If such a dye or pigment has an absorption within the sensitive wavelength range of layer 13, it is also possible to form said macromolecular layer 14 after the imagewise exposure of the photoconductive layer 14 to light.
  • FIG. 3 shows the step of effecting electrolysis on the photosensitive element 10 after imagewise exposure, thereon, where 31 is a container for electrolytic solution 32 consisting, for example, of an aqueous solution of metal ions (B). It has been found in this step that a slightly acidic electrolytic bath is capable of providing a sharper image.
  • the photosensitive material 10 after imagewise exposure thereon and a counter electrode 33 are, respectively, connected with the cathode and anode of an electric source 34 which supplies a voltage of 0.3 100 volts DC for the electrolysis.
  • gelatin in area [a] of the macromolecular layer is rendered insoluble in water which is warm by means of a crosslinking reaction with metal ions (B) and compound (D) due to alkalinity generated by the electrolysis of water.
  • a crosslinking reaction with metal ions (B) and compound (D) due to alkalinity generated by the electrolysis of water.
  • Such a reaction does not proceed in unexposed area [b] in macromolecular layer 14 due to the absence of an increase in the pH value.
  • the electrolytic bath can be substituted for by absorbent materials capable of holding electrolytic solution in an amount sufficient to effect the electrolytic treatment, such as brushes, sponges, porous papers, etc.
  • Contact between the electrolytic bath and the photosensitive layer can be made either at one time over the whole surface thereof or progressively in small portions thereof, such as by a roll covered with sponge.
  • FIG. 4 shows the step of treatment with hot water of the photosensitive material after the electrolytic treatment thereon, in which uncrosslinked area is removed 'by the hot water 42 supplied from the nozzle 41,
  • the macromolecular image 43 thus obtained can be utilized in various printing processes.
  • the image can be employed in dye transfer printing by impregnating the image with a water-soluble dye.
  • the sheet holding the macromolecular image 43 thereon can be used as the gelatin relief for dye transfer printing.
  • the photosensitive material is composed of zinc oxide, it has also been found preferable to remove the zinc oxide with acid, etc., in order to obtain a clearer transfer image.
  • the image can also be utilized in spirit printing by impregnating the image with a sufficient amount of a dye soluble in water and alcohol.
  • the macromolecular image can be utilized for offset printing since image 43 is hydrophilic whereas the photoconductive layer 13 is hydrophobic. Furthermore, it is possible to obtain a thick macromolecular image 43 by subjecting macromolecular layer 14 with a dry thickness larger than 10 microns to electrolytic treatment. Such an image constitutes a relief of considerable height in the water-containing state, and therefore can be utilized in braille printing or in letterpress printing with an aqueous printing ink.
  • Such treatment may comprise, as shown in FIG. 5, spraying a solvent 52 for the binder of the photoconductive layer 13 from a nozzle 51 thereby removing the photoconductive layer except for the area 53 protected by the macromolecular image 43, and then spraying an etching solution 62 from a nozzle 61 to thereby remove the thus exposed elcctroconductive layer as shown in FIG. 6.
  • the said electroconductive layer 12 and the etching solution 62 are, respectively, composed of a copper chloride and ferric chloride solution.
  • the pressing can be accomplished by means of a roller 121.
  • the area [f] indicates the nonetched surface of the plate.
  • a photosensitive element for preparing mimeographic printing plate is shown in FIG. as composed of a support material 11, an electroconductive layer 12, a photoconductive layer 13 and a porous sheet 101 composed, for example, of Japanese paper impregnated with hydrophilic macromolecular material 100 and aforementioned compound (D).
  • the Japanese paper layer can be provided on the photosensitive layer 13 prior to or after the imagewise exposure thereof, but it is preferred to provide the layer after imagewise exposure in order to obtain a mimeographic plate of higher quality.
  • the area [d] indicates the unexposed portion of the photosensitive layer.
  • the electrolytic bath employed in this case is preferred to be slightly acidic and to contain metal ions (B).
  • the mimeographic printing plate as shown in FIG. 11 can be obtained by washing the element with hot water after electrolytic treatment to thereby remove unexposed areas, and peeling off the Japanese paper layer from the element in a solvent for the binder of the photosensitive layer 13.
  • the plate is composed of uncrosslinked area 111 permeable to printing ink and crosslinked area 112 constituting a barrier to ink.
  • the temperature of the electrolytic bath is preferred not to exceed 45C, since a temperature exceeding this limit will accelerate the decay of retentive photoconduction resulting from light irradiation and makes complete crosslinking reaction impossible.
  • a layer of hydrophilic macromolecular substance (A) provided on a water-resistant support material is moistened with an alkaline aqueous solution and pressed against a xerographic plate holding developed toner image thereon. After pressing, the sheet provided with the macromolecular layer is peeled from the xerographic plate and treated with hot water.
  • the macromolecular layer after treatment is found to be insolubilized exclusively in the area which has been in contact with the toner image.
  • the hydrophilic macromolecular image is obtained exclusively in the area where the four components are all present.
  • the hydrophilic macromolecular substance (A) is preferred not to be used in the toner but to be applied in a layer on the support material in order to facilitate handling.
  • the electrophotographic process used in conjunction with the present invention can employ any conventional developing processes, such as cascade developing, magnetic brush developing powder cloud developing, liquid developing, toner sheet developing, etc.
  • cascade developing magnetic brush developing powder cloud developing
  • liquid developing toner sheet developing
  • a macromolecular image by bringing an aqueous alkali solution impreg: nated in a porous material, such as sponge, into contact for a short period with the surface holding the electrostatic latent image to thereby form the distribution pattern of alkaline material on the xerographic plate, and then press a sheet provided with a wet layer containing components (A), (B) and (D) against the surface of the xerographic plate.
  • This invention can easily be applied to an electroconductive recording process to obtain a macromolecular image by means of a crosslinking reaction initiated by the alkalinity generated at the proximity of a cathode by an electric current.
  • a recording layer of hydrophilic macromolecular substance (A) containing compound (D) and metal ion (B) provided on an electroconductive support material is moistened with water or water vapor prior to recording thereon and a metal needle is displaced while keeping contact therewith.
  • An electric voltage modulated by means of an electric signal is applied to the metal needle in order to generate alkalinity on the layer in correspondence with the electric signal.
  • the alkalinity causes the crosslinking reaction in the macromolecular layer according to the amount of electric current passed therethrough.
  • a water-insoluble macromolecular image can thus be obtained by treating the recording layer with hot water.
  • the image thus obtained can be utilized for multiple copying by means of dye transfer process.
  • Metal ion (B) can be supplied from the metal needle instead of being incorporated as a water-soluble salt in said recording layer.
  • the metal needle can be composed, for example, of silver, nickel, cobalt, zinc, etc.
  • Metal ions are generated from the metal needle connected with the anode of the electric source and supplied into the recording layer. Excessive metal ion is again reduced to the metallic state and deposited on the surface of the recording layer, giving a colored macromolecular image in this case.
  • the metal needle can be used singly or in the form of pin matrix.
  • thermosensitive recording layer 82 is composed of hydrophilic macromolecular substance (A), metal ion (B), a compound capable of generating alkali when decomposed (C) and compound (D).
  • Alkaline source (C) can be, for example, urea, thiourea, ammonium carbonate, etc., which liberates alkali on decomposition by heatmg.
  • recording layer 82 contacted tightly against an original 83, is exposed to uniform irradiation of infrared light for a short period.
  • the image area 84 in the original which absorbs infrared light shows a local temperature increase, resulting in a local temperature increase by thermal conduction in the corresponding area [0] in the recording layer.
  • compound (C) is thermally decomposed to render the area alkaline, thereby causing a reaction between the hydrophilic macromolecular substance (A), metal ion- (B) and compound (D) to insolubilize the macromolecular substance (A) against water.
  • a macromolecular image 91 is obtained on the support material 81 by treating the recording layer with hot water after the exposure to infrared light.
  • the sheet holding the thus prepared image thereon can be utilized as a gelatin relief for dye transfer printing, as an offset printing plate, as a spirit printing plate, etc.
  • a recording layer containing the macromolecular substance (A), metal ion (B), alkali source (C), compound (D) and a colored powder such as a pigment or dye is suitable for direct recording with laser light.
  • the colored powdered material absorbs the light to elevate the temperature thereof, resulting in the decomposition of alkali source (C) and initiating the crosslinking reaction.
  • a recording layer containing hydrophilic macromolecular substance (A), metal ion (B) and compound (D) is provided .on a transparent support material, and the recording is directly inscribed on the layer with a pen, painting brush, felt pen, etc., containing an aqueous solution of alkali (C).
  • This aqueous solution may be colored, if desired.
  • the recording layer is treated with hot water to remove unrecorded areas, thereby leaving a macromolecular image on the transparent support.
  • the sheet thus prepared can be utilized as a transparency for overhead projection as an original plate for making multiple transparencies by the dye transfer process.
  • this invention can be applied to electron beam recording.
  • a recording element consisting of a recording layer containing the hydrophilic macromolecular substnace (A), metal ion (B), compound (D) and a compound capable of generating alkali when decomposed under electron beam irradiation and a support material is subjected to electron beam irradiation
  • compound (C) is decomposed in the irradiated area to cause a hardening reaction.
  • hydrophilic macromolecular image by providing pressure-rupturable microcapsules containing alkaline material (C) on the bottom surface of a paper sheet, placing thereunder another paper sheet provided with a layer containing components (A), (B) and (D) and rupturing the microcapsules by means of scribing pressure, etc.
  • the process of this invention is thus characterized by the co-existcnce at imaging of the aforementioned four components (A), (B), (C), and (D),
  • Example 1 The following composition was kneaded for 20 hours in a porcelain ball mill:
  • Photoconductive zinc oxide (Sakai Chemical, Sazex) I00 parts Pliolites S-SD (Goodyear Tire and Rubber) (styrene butadiene copolymer, the molar ratio of styrene and butadiene being 851l5) 25 parts Toluene parts Methylethylketone 25 parts
  • the white paste thus prepared was diluted with tolu- (Photographic grade) gelatin 6 parts Compound-l 0.4 parts Nickel chloride hexahydrate 9 parts Distilled water parts
  • the periphery of the sheet was covered with insulative adhesive tape prior to dipping into the electrolytic bath in order to prevent direct contact between the bath and the aluminum layer.
  • the electrolysis was carried out by placing a nickel plate as an anode at a distance of 1.5 cm from the sheet of which the aluminum layer acted as cathode. A DC. potential of 4 volts was applied therebetween.
  • the sheet was taken from the bath after electrolysis for 10 seconds. In this condition the sheet was wet exclusively in the exposed areas which showed a pale gray color.
  • the sheet was then washed with water, dried and finally wiped with a sponge impregnated with an aqueous solution (concentration 0.2 percent) of a blue dye (C.I. acid blue 54) to obtain a blue negative image.
  • the optical density of the image was 0.57.
  • Example 2 17 Example 3 in this example, a percent aqueous solution of photographic gelatin was coated onto the photosensitive layer in Example 1, and cooled and dried to obtain gelatin layer 1.9 microns thick after drying. The photosensitive layer was successively subjected to imagewise exposure at ca. 10,000 lux for 8 seconds with a light source as in Example 1.
  • composition of the electrolytic bath employed was as follows:
  • the sample was washed with hot water after electrolytic treatment as in Example 1. After drying, the sample was coated with an aqueous solution of formalin to harden the gelatin image and dipped into an aqueous solution of CI. acid blue 54 as in Example 1. Then the aqueous solution of Color Index acid blue 54.
  • a transfer process as shown in Example 3 provided a dark blue transferred image. it was found that the gelatin layer was totally insoluble in hot water in the area subjected to maximum exposure.
  • Example 5 The procedure of Example 4 was repeated except that the electrolytic bath had further added thereto 0.2 parts of Compound I. The results obtained were comparable to those of Example 4.
  • Example 6 I in this example the photosensitive layer was dyesensitized by adding a dye solution of the following composition to the photosensitive composition of Example l at the solvent dilution thereof.
  • the following table also indicates the resulting sensitivity to white light (tungsten lamp, color temperature ca. 3,000K). The amounts in this table are with respect to 100 g of zinc oxide.
  • Gelatin (Photographic grade) 5 parts Compound-l 0.5 parts Compound-4 0.1 parts Distilled water 100 parts The thickness after drying of the gelatin layer was 2.0
  • the electrolytic bath employed was as follows:
  • the temperature of the warm water capable used generally ranges between about 30C. and about 98C.
  • the sample was further treated with formalin to harden the gelatin image and dipped into an Photosensitive layer No. 3 was further provided with a gelatin layer as shown in Example 4 and subjected to imagewise exposure through a negative photographic film placed in a photographic enlarger (enlarger for 35 mm film produced by Fuji Photo Film.) The exposure was carried out for 3.5 seconds with maximum luminance at the exposed surface of lux.
  • Electrolytic treatment similar to that in example 4 provided a satisfactory positive gelatin image.
  • Example 1 The procedure of Example 1 was repeated using an electrolytic bath of the following composition:
  • Example 1 The procedure of Example 1 was repeated using an electrolytic bath of the following composition:
  • Example II 6 parts Polymer-3 Compound-2 0.3 parts Cobalt chloride hexahydrate 9 parts Distilled water 100 parts
  • the procedure of Example I provided results comparable to those obtained in Example 1.
  • the following composition was kneaded for 20 hours in a porcelain ball mill.
  • the white paste thus prepared was diluted with toluene to an appropriate viscosity, then coated onto the copper surface of a laminated plate for printed circuits (Matsushita Electric Co.) composed of an epoxy resin support plate and copper layer provided thereon.
  • the coating thickness was 16 microns after drying.
  • the photosensitive layer thus prepared was further coated with the following composition:
  • the electrolytic bath employed was as follows:
  • the photosensitive element thus prepared was subjected to imagewise exposure through a negative original for printed circuits, electrolytic treatment, washing with hot water (45C) and hardening with formalin as shown in Example 4, and further washed with ligroin to remove the bare photosensitive layer in unhardened areas.
  • the element was then dipped into an acidic solution of ferric chloride (40 Be) for 15 minutes at 45C, then washed with water.
  • a sharp printed circuit was obtained by strongly wiping the hardened areas with benzene to remove the photosensitive layer and the hardened image provided thereon.
  • Example 1 l The procedure of Example 10 was repeated except that the laminated printed circuit plate was further provided with a vacuum-evaporated aluminum layer of 750 angstroms on the copper layer to obtain a sharp printed circuit comparable to that obtained in Example l0.
  • the aluminum layer could be eliminated by washing with a 1N sodium hydroxide solution. Insertion of the aluminum layer between the photosensitive layer and the copper layer reduced the necessary exposure time to /2 /'s that in Example 10.
  • composition was separately coated on a sheet of polyethylene terephthalate previously irradiated with ultraviolet light (thickness: 120 microns):
  • the coating layer was first set by cooling and then dried by exposing it to warm air.
  • the gelatin layer was swollen in a 0.1N sodium hydroxide solution at 15C and tightly pressed against the surface of the xerographic plate holding the toner image thereon.
  • Example 13 The following composition was coated onto a sheet of polyethylene terephthalate of 120 microns thick which had been previously irradiated with ultraviolet light to obtain a coating thickness of 3 microns after drying:
  • Example 14 The following composition was coated onto a sheet of polyethylene terephthalate (thickness 60 microns) previously subjected to ultraviolet irradiation so as to provide a dry thickness of 2 microns:
  • Example I 5 The photosensitive layer of Example 1 was subjected to imagewise exposure through a line positive image. Separately, a sheet of thin Japanese paper was dipped into the following solution kept at 28C.
  • the thus treated paper sheet showed satisfactory performance as a stencil master (mimeographic 22
  • Example 18 A composition consisting of Gelatin 5 parts Red pigment (brilliant Carmine 613) l part Compound-2 0.3 part Urea 0.8 part Ferric chloride 0.01 part Distilled water 100 parts was coated to a thickness of 4 microns as a dry layer on a polyethylene terephthalate film to prepare a laser sensitive recording material.
  • the recording material thus obtained was exposed to an argon ion laser light modified by a signal and treated with warm water at a temperature of 40C to obtain a red gelatin image.
  • Example 19 The following compositions were heated at 40C to form a uniform solution.
  • An epoxy resin-zinc laminate plate for letter press printing plate use was coated with the white photosensitive paste shown in Example 10. After drying, the plate was further coated with the composition shown in Example 10 in a thickness as shown in Example 10.
  • the photosensitive element thus prepared was subjected to imagewise exposure, washing with warm water (45C), and hardening with formalin as shown in Example 4, and further treated with ligroin to remove the photosensitive layer present in the unexposed portions thereof. Then the plate was dipped into an etching solution (Itoh Chemical Co.) containing ferric chloride at 45C for 15 minutes to dissolve zinc present in the unhardened areas. After washing with water, the photosensitive layer in the hardened areas was removed to gether with the hardened image by means of wiping with benzene to provide a zinc letterpress plate.
  • etching solution Itoh Chemical Co.
  • thickness of the layer was 7 microns.
  • the film was then immersed in 0.05N aqueous potassium hydroxide solution at 15C for 2 seconds and dried. By the treatment with alkali the layer was hardened and rendered insoluble in warm water (60C).
  • the above-mentioned pro Obs were carried out under a subdued light excluding ultra-violet radiation.
  • the film thus formed was exposed in contact with a transparent original to a light from a high pressure mercury lamp of W at a distance of 35 cm. for 3 minutes. Then the film was washed with warm water of 60C. The exposed portions of the layer were washed out, while the unexposed portions were remained. The film was immersed in a mixed solvent of acetone and water (1:1) by volume) to remove carbontetrabromide present in the unexposed portions.
  • a process for forming an image in a system including a recording layer comprising imagewise forming first and second portions in said system by forming a water insoluble first portion in or on said recording layer by reacting a hydrophilic macromolecular substance (A) containing primary amino radicals, a metal ion (B) selected from the group consisting of ions of metallic atoms belonging to groups 6A, 7A, 8, 1B, and 2B of the periodic table of the IUPAC Comptes Rondus XXIII Conference, 1965, a compound (D) represented by the following general formula:
  • metal ion is selected from the group consisting of chromium, manganese, iron cobalt, nickel, coppen zincf palladium, silver, cadmium, mercury and gold.
  • An imaging process as in claim 1 where said recording layer is a photosensitive element said process including the steps of projecting a light image onto said photosensitive element comprising an electroconductive support and a photoconductive layer provided thereon and selectively passing an electric current through the exposed areas of said photoconductive layer in an aqueous solution optionally containing at least one component of said substance (A), ion (B), and compound (D) at a point no earlier than simultaneously with said exposure, the remaining components (if any) of said system being present in at least one outer layer provided on said photoconductive layer, the medium adjacent the surface of the light exposed areas of said photoconductive layer being maintained at a pH value not less than 8 by said electric current to thereby enable the components of said system to react and form a water insoluble image at the light exposed areas.
  • a process as in claim 23 including providing said recording layer with an additional component which raises the temperature of said surrounding medium when it absorbs light, said heat image forming step ineluding scanning said recording layer with a modulated laser beam, the beam being so modulated that when an image portion is to be formed in said recording layer, the intensity of the beam is made sufiicient to elevate the temperature so that said component (C decomposes to thereby water insolubilize said recording layer at said image portion.

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  • Printing Plates And Materials Therefor (AREA)
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  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US00214141A 1970-12-30 1971-12-30 Imaging process Expired - Lifetime US3839028A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066453A (en) * 1973-05-02 1978-01-03 Hoechst Aktiengesellschaft Process for the preparation of printing forms
US4255238A (en) * 1978-06-19 1981-03-10 Commissariat A. L'energie Atomique Method of control for an electrolytic display cell and especially a cell of the metal halide type and a circuit for the application of said method
US5217839A (en) * 1990-01-16 1993-06-08 Nippon Zeon Co., Ltd. Preparation process of toner
US5240335A (en) * 1991-05-09 1993-08-31 Eastman Kodak Company Braille printing apparatus
US6436605B1 (en) 1999-07-12 2002-08-20 International Business Machines Corporation Plasma resistant composition and use thereof
US20040222304A1 (en) * 2001-04-11 2004-11-11 Matthew Adams Method and apparatus for on-demand marking or etching of metal
US20050145122A1 (en) * 2003-09-24 2005-07-07 Matthew Adams Use of a UV-curable thermal ribbon in conjunction with a porous substrate to form a durable, on-demand electro-chemical stencil
US20060127581A1 (en) * 2003-12-11 2006-06-15 Aspens Glenn D Method for on-demand direct item marking via a screen printing process
US20090242236A1 (en) * 2005-09-13 2009-10-01 Fyson John R Method of forming conductive tracks
US20120177817A1 (en) * 2006-12-21 2012-07-12 Fujifilm Corporation Method for producing a conductive film

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3332857A (en) * 1964-03-31 1967-07-25 Hogan Faximile Corp Electrolytic recording medium
US3632484A (en) * 1970-01-27 1972-01-04 Robert Doughty Richards Electrolytic facsimile-recording process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3332857A (en) * 1964-03-31 1967-07-25 Hogan Faximile Corp Electrolytic recording medium
US3632484A (en) * 1970-01-27 1972-01-04 Robert Doughty Richards Electrolytic facsimile-recording process

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066453A (en) * 1973-05-02 1978-01-03 Hoechst Aktiengesellschaft Process for the preparation of printing forms
US4255238A (en) * 1978-06-19 1981-03-10 Commissariat A. L'energie Atomique Method of control for an electrolytic display cell and especially a cell of the metal halide type and a circuit for the application of said method
US5217839A (en) * 1990-01-16 1993-06-08 Nippon Zeon Co., Ltd. Preparation process of toner
US5240335A (en) * 1991-05-09 1993-08-31 Eastman Kodak Company Braille printing apparatus
US6436605B1 (en) 1999-07-12 2002-08-20 International Business Machines Corporation Plasma resistant composition and use thereof
US20040222304A1 (en) * 2001-04-11 2004-11-11 Matthew Adams Method and apparatus for on-demand marking or etching of metal
US20050145122A1 (en) * 2003-09-24 2005-07-07 Matthew Adams Use of a UV-curable thermal ribbon in conjunction with a porous substrate to form a durable, on-demand electro-chemical stencil
US20060127581A1 (en) * 2003-12-11 2006-06-15 Aspens Glenn D Method for on-demand direct item marking via a screen printing process
US20090242236A1 (en) * 2005-09-13 2009-10-01 Fyson John R Method of forming conductive tracks
US20120177817A1 (en) * 2006-12-21 2012-07-12 Fujifilm Corporation Method for producing a conductive film
EP2096648A4 (en) * 2006-12-21 2013-01-23 Fujifilm Corp CONDUCTIVE FILM AND METHOD FOR MANUFACTURING THE SAME

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DE2165665A1 (de) 1972-07-13
JPS4917741B1 (enExample) 1974-05-02

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