US3745002A - Method of preparing a printing master by xerography - Google Patents

Method of preparing a printing master by xerography Download PDF

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Publication number
US3745002A
US3745002A US00075364A US3745002DA US3745002A US 3745002 A US3745002 A US 3745002A US 00075364 A US00075364 A US 00075364A US 3745002D A US3745002D A US 3745002DA US 3745002 A US3745002 A US 3745002A
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United States
Prior art keywords
coating
photoconductive
toner
resin binder
isocyanate
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Expired - Lifetime
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US00075364A
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English (en)
Inventor
S Honjo
Y Tamai
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • G03G13/32—Relief printing plates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0592—Macromolecular compounds characterised by their structure or by their chemical properties, e.g. block polymers, reticulated polymers, molecular weight, acidity
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0926—Colouring agents for toner particles characterised by physical or chemical properties

Definitions

  • R 4 tCl aims ABSTRACT BF HE DKSCLOSURE image with a toner comprising a masked polyisocyanate compound; heating the developed plate to an elevated temperature sufiicient to regenerate the isocyanate thus causing a reaction between the resin binder in the photoconductive coating and the polyisocyanate whereby the resin binder is completely cured and becomes insoluble in organic solvents, and finally removing the photoconductive coating at the areas where no toner deposition occurred and thus exposing the metal substrate.
  • This invention relates to a new method of xerography, and especially, to a method of preparing a printing master by xerography.
  • Xerography in its most common manner of practice, comprises imparting a uniform charge on a photoconductive insulating layer provided on an electrically conductive support under a subdued light by means of corona discharge, exposing said layer to a light image to be reproduced to form an electrostatic latent image, and finally applying a toner material onto said latent image having an electrostatic charge of desired polarity to render the image visible.
  • the obtained toner image may be permanently fixed directly on the photoconductive layer or may be transferred onto a suitable transfer member.
  • a new application has been developed by utilizing a chemically active toner material which can react with an ingredient contained in the photoconductive layer. A typical example of such application is disclosed in Japan patent publication No. 13,470/63, or in US. Pat. No.
  • the typical combination of materials has been polysiloxane resin binder in the photoconductive coating and aluminum oxide, or aluminum salts of organic acids as toner, in which case, however, the silicone" resins not only exhibited an insufiicient adhesion to a variety of metal substrates, but were difiicult to form a photoconductor coating of a high light sensitivity.
  • the hardened coating showed a poor resistance to 1 chemical reagents used for etchant. Due to these shortcomings the process has not yet been commercialized.
  • the principal object of the present inven-' tion is to provide a new combination of resinous binder above described shortcomings, and thus to provide a s 370 and toner material which can overcome or improve the ans-m2 ice new method of preparing a printing master by xerography.
  • Such object has proved to be accomplished by forming on a metal substrate photoconductive insulating coating comprising an intimate mixture of a photoconductive powder and an electrically insulating resin binder con taining chemically active functional groups which can react with isocyanate groups, providing an electrostatic latent image, developing this image with a toner com prising a masked polyisocyanate compound which is sometimes referred to as isocyanate generator, heating the developed plate to an elevated temperature sufficient to regenerate the isocyanate thus causing a reaction between the resin binder and the toner material, whereby the resin binder is completely cured and becomes insoluble in organic solvents, and finally removing the photoconductive coating only at the areas where no toner deposition occurred thus exposing the metal substrate.
  • FIG. 1 illustrates a cross-sectional view of an electrophotographic material having on its photoconductive coating a toner image.
  • the recording material 1 comprises a conductive substrate 11 and a photoconductive insulating coating 12 provided on H.
  • the substrate ll. comprises metals in this invention, including zinc, mag nesium, aluminum, copper, and etc.
  • the photoconductive coating 12 comprises an intimate mixture of a finelydivided photoconductor such as zinc oxide, cadmium sulfide, titanium dioxide, lead oxide, or other calcogenite compounds of zinc, cadmium and lead, and a resinous binder.
  • the coating may contain as minor ingredient spectrural sensitizers for the photoconductor, or chemical sensitizers.
  • the resinous binder used must contain such functional groups as to be able of reacting with an isocyanate group. Such groups are primary and secondary hydroxyl and amino radicals.
  • Suitable resinous materials include various types of alkyd (drying and non-drying oil modified, phenolformaldehyde resin modified, styrene or acrylester modified, rosin modified, and etc.), epoxyesters, (for example, epoxyester of dehydrated caster oil fatty acid) epoxides, vinyl polymers containing monomers having; hydroxyl groups (for example, polyvinylbutyral, copolymers, of terpolym'ers comprising a monomer selected from styrene, alkylacrylates, alkylmethacryl a-tes, vinyl chloride, vinyl acetate, or ethylene, and comonomet selected .from hydroxyalkylacrylate, hydroxyalkylmethac'rylate, and allyl alcohol; the polymer may also "cont
  • the photoconductive coating 12 normally comprises 40 to 80 volume percents of a photoconductive powder in its total volume and its coating thickness lies between several and several ten microns.
  • the electrophotographic coating is uniformly charged in a subdued light, then exposed to an image of light and shadow to be reproduced whereby the light-struck area loses the surface charge, and thus an electrostatic latent image is formed.
  • the exposed coating is subjected to a development operation by using a toner comprising polyisocyanate generator to convert the latent image into a material image.
  • a toner comprising polyisocyanate generator
  • Any known development method may be employed, among which the liquid development or electrophoretic development can give a developed image of highest quality.
  • the development image is designated as 21 in FIG. 1.
  • An isocyanate generator which is a quite important material characterizing the present process is a'compound in which the isocyanate group is temporarily blocked or or masked by a suitable component attached to the isocyanate below a certain temperature above which the As for isocyanate compounds, aromatic isocyanates are preferred because of their high reactivities.
  • the isocyanate generator is suitably pulverized to prepare a toner for drydeveloping operations such as magnetic brush, cascade, or powder cloud development; or it may be dissolved in a suitable organic solvent, then the resulting solution is dispersed in an electrically insulating, nonpolar liquid which cannot dissolve the generator; the resulting dispersion may be used in liquid development.
  • the dispersioncarrier liquid may be isoparafiinic, normal paraflinic or cyclo aliphatic hydrocarbons, halogenated hydrocarbons, etc.
  • the resulting dispersion has proved to exhibit stable elec trophoretic properties for a long period of time.
  • Coloring agents or other charge control agents may also be added to the masked isocyanate. The colored toner makes it easy to judge the developed image quality with the unaided eyes.
  • FIG. 2 shows the cross-sectional view of the electrop v photographic material in the state after the developed toner image 21 is impregnated into the photoconductivej coating 12 and then the polyisocyanate is regenerated by heating whereby the resinous binder in 12 is completely cured at the toner-deposited areas.
  • 13 and 14 designate the cured and uncured regions of the coating, respectively.
  • the impregnation of the toner image 12 can be accomplished either by heating the material to an temperature above the melting point but below the dissociating point of the isocyanate generator, or by exposing the material to a solvent vapor of the generator.
  • the suitable range of temperature for toner impregnation is 140 to 170 C.
  • the curing reaction is carried out at 170 to 180 C. with the same product, and under such elevated temperatures a reaction counterpart having a low reactivity such as secondary hydroxyl group can even enter into condensation reaction with the regenerated isocyanate rather rapidly.
  • the uncured region is removed by a suitable solvent including esters, ketones, aromatic hydrocarbons, etc.
  • a suitable solvent including esters, ketones, aromatic hydrocarbons, etc.
  • chlorinated hydrocarbons, or chlorofluorinated designates the exposed substrate metal.
  • the exposed substrate has been etched by a suitable etching solution such as an aqueous ferric chloride solution, or other acidic etching baths.
  • a suitable etching solution such as an aqueous ferric chloride solution, or other acidic etching baths.
  • One way carry out additional operations to improve the image quality of the developed image.
  • Representative examples of such additional operations are pre-bathing of the latent image bearing material and the rinsing of the developed material prior to the removing operation of the uncured coating.
  • the former serves to decrease background, while the latter, in addition to the decrease of background, improves the uniformity of the developed image.
  • the plate still held a thin film of the developer which was rinsed with an isoparaffinic solvent Isopar E (manufactured by Esso Standard Oil Co.). Then the plate was dried by applying a warm air of about 40 C. Next, the plate was left in an air oven kept at C. for 10 minutes, then the temperature was raised to C. Underthis condition the platewas kept for 10 minutes. "magma curingreaction completed. The plate was inimersed in toluol with mild stirring whereby the tonerdeposited area remained unchanged but at the background 65 area the photoconductive coating slowly dissolved or.
  • Isopar E isoparaffinic solvent
  • EXAMPLE n 7 An electrophotographic material was prepared in a similar manner as was describedin Example I except that an 'epoxyester of dehydrated castor oil fatty acid having an oil length of 40% was used in place of the styrenated alkydresin.
  • V V A cascade developing material was prepared by mixing nitrocellulose coated silica granulesand'a finely-divided Desmodur AP Stable of 20 micron mean diameter. With the use of these materials a similar satisfactory result was obtained.
  • EXAMPLE III To a zinc plate there was applied a layer comprising 100 parts by weight of photoconductive zinc oxide, 20 parts by weight of copolymer containing 60% of butyl methacrylate, 25% of styrene, 13% of hydroxyethylacrylate and 2% of acrylic acid, and 5 parts by weight of acrylic ester modified alkyd resin (hydroxyl value 30).
  • the electrophotographic material thus formed was treated in a similar manner as described in Example I except that a mixture of 50 parts of toluol and 50 parts of ethyl acetate was used in place of the toluol. A similar result as Example I was obtained.
  • a method of producing an etch resist pattern by Xerography comprising; forming on a metal substrate an inorganic photoconductive insulating coating comprising an intimate mixture of a photoconductive powder and an electrically insulating resin binder containing chemically active functional groups which can react with isocyanate groups, providing an electrostatic latent image on said coating, developing said latent image with a toner comprising a masked polyisocyanate compound, impregnating the inner portion of the photocondnctive coating with the developed toner material, heating the developed plate to an elevated temperature sufiicient to regenerate the isocyanate thus causing a reaction between the resin binder in the photoconductive coating and said polyisocyanate whereby the resin binder is completely cured and becomes insoluble in organic solvents, and finally removing the photoconductive coating at the areas where no toner deposition occurred and thus exposing the metal substrate.
  • said resin binder is alkyd resin, epoxyester of dehydrated castor oil fatty acid, vinyl copolymer containing hydroxyalkyl acrylate, hydroxyalkyl methacrylate or allyl alcohol, or a compatible combination thereof.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Developing Agents For Electrophotography (AREA)
US00075364A 1969-09-30 1970-09-25 Method of preparing a printing master by xerography Expired - Lifetime US3745002A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44078025A JPS4827362B1 (enExample) 1969-09-30 1969-09-30

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US3745002A true US3745002A (en) 1973-07-10

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US00075364A Expired - Lifetime US3745002A (en) 1969-09-30 1970-09-25 Method of preparing a printing master by xerography

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US (1) US3745002A (enExample)
JP (1) JPS4827362B1 (enExample)
BE (1) BE756595A (enExample)
DE (1) DE2048204C3 (enExample)
FR (1) FR2068748B1 (enExample)
GB (1) GB1314109A (enExample)
NL (1) NL7014086A (enExample)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042450A (en) * 1971-04-23 1977-08-16 Igor Danilovich Voitovich Method for the production of films having the desired configuration
US4066453A (en) * 1973-05-02 1978-01-03 Hoechst Aktiengesellschaft Process for the preparation of printing forms
WO1981000310A1 (en) * 1979-07-16 1981-02-05 Minnesota Mining & Mfg Plating resist with improved resistance to extraneous plating
US4308333A (en) * 1976-03-13 1981-12-29 Konishiroku Photo Industry Co., Ltd. Cadmium sulfide-type photoconductor with an isocyanate film
US4357403A (en) * 1979-08-08 1982-11-02 Konishiroku Photo Industry Co., Ltd. Photoconductive plate for printing and a method for the preparation of a printing plate by heating
US4705696A (en) * 1984-09-27 1987-11-10 Olin Hunt Specialty Products Inc. Method of making a lithographic printing plate, printing plates made by the method, and the use of such printing plates to make lithographic prints
US5612156A (en) * 1988-06-27 1997-03-18 Ishihara Sangyo Kaisha, Ltd. Electrophotographic photosensitive element and a process for manufacturing an offset printing master from the element
US5888689A (en) * 1996-07-26 1999-03-30 Agfa-Gevaert, N.V. Method for producing cross-linked fixed toner images

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2556386C2 (de) * 1975-12-15 1985-02-28 Hoechst Ag, 6230 Frankfurt Verfahren zur Herstellung von Druckformen und/oder metallisierten Bildern
DE2724851C2 (de) * 1977-06-02 1979-08-23 Du Pont De Nemours (Deutschland) Gmbh, 4000 Duesseldorf Verfahren zur Nachbehandlung von photopolymerisierbaren Druckplatten für den Flexodruck
JPS54144203A (en) * 1978-05-01 1979-11-10 Fuji Yakuhin Kogyo Kk Method of making flat printing plate
ES8502909A1 (es) * 1982-09-24 1985-02-01 Coulter Systems Corp Un metodo electrofotografico para fabricar una placa impresora
EP0104626A1 (en) * 1982-09-24 1984-04-04 Coulter Systems Corporation Opaque contact print copy and method of making same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042450A (en) * 1971-04-23 1977-08-16 Igor Danilovich Voitovich Method for the production of films having the desired configuration
US4066453A (en) * 1973-05-02 1978-01-03 Hoechst Aktiengesellschaft Process for the preparation of printing forms
US4308333A (en) * 1976-03-13 1981-12-29 Konishiroku Photo Industry Co., Ltd. Cadmium sulfide-type photoconductor with an isocyanate film
WO1981000310A1 (en) * 1979-07-16 1981-02-05 Minnesota Mining & Mfg Plating resist with improved resistance to extraneous plating
US4357403A (en) * 1979-08-08 1982-11-02 Konishiroku Photo Industry Co., Ltd. Photoconductive plate for printing and a method for the preparation of a printing plate by heating
US4705696A (en) * 1984-09-27 1987-11-10 Olin Hunt Specialty Products Inc. Method of making a lithographic printing plate, printing plates made by the method, and the use of such printing plates to make lithographic prints
US5612156A (en) * 1988-06-27 1997-03-18 Ishihara Sangyo Kaisha, Ltd. Electrophotographic photosensitive element and a process for manufacturing an offset printing master from the element
US5888689A (en) * 1996-07-26 1999-03-30 Agfa-Gevaert, N.V. Method for producing cross-linked fixed toner images

Also Published As

Publication number Publication date
DE2048204B2 (de) 1974-12-12
NL7014086A (enExample) 1971-04-01
FR2068748A1 (enExample) 1971-09-03
BE756595A (fr) 1971-03-01
DE2048204A1 (de) 1971-04-15
GB1314109A (en) 1973-04-18
DE2048204C3 (de) 1975-07-31
FR2068748B1 (enExample) 1973-01-12
JPS4827362B1 (enExample) 1973-08-22

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