EP0147642A2 - Elektroerosionsdruckmaterial mit Schutzschicht - Google Patents

Elektroerosionsdruckmaterial mit Schutzschicht Download PDF

Info

Publication number
EP0147642A2
EP0147642A2 EP84114277A EP84114277A EP0147642A2 EP 0147642 A2 EP0147642 A2 EP 0147642A2 EP 84114277 A EP84114277 A EP 84114277A EP 84114277 A EP84114277 A EP 84114277A EP 0147642 A2 EP0147642 A2 EP 0147642A2
Authority
EP
European Patent Office
Prior art keywords
recording material
electroerosion
titanium
conductive
overlayer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP84114277A
Other languages
English (en)
French (fr)
Other versions
EP0147642A3 (en
EP0147642B1 (de
Inventor
Krishna Gandhi Sachdev
Keith Samuel Pennington
Mitchell Simmons Cohen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Business Machines Corp
Original Assignee
International Business Machines Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Publication of EP0147642A2 publication Critical patent/EP0147642A2/de
Publication of EP0147642A3 publication Critical patent/EP0147642A3/en
Application granted granted Critical
Publication of EP0147642B1 publication Critical patent/EP0147642B1/de
Expired legal-status Critical Current

Links

Images

Classifications

    • 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
    • B41M5/24—Ablative recording, e.g. by burning marks; Spark recording
    • B41M5/245—Electroerosion or spark recording

Definitions

  • the present invention relates to improvements in protective coatings for electroerosion print media.
  • the surface which is locally eroded or removed during writing to provide such indicia on the recording material is a thin film of conductive material, usually a vacuum deposited aluminum layer, which vaporizes in response to the high localized temperature associated with sparking (arcing) initiated by applying an electric current to a stylus, more generally to multiple styli, typically tungsten wire in a printing head, . having electrical contact between the surface of the thin conductive film and the tip of the stylus.
  • Electroerosion printing is effected when the stylus, styli or print head sweep across the surface of the recording medium. Electrical writing signals are fed to the stylus, styli or print head to provide controlled electrical pulses which generate sparks accompanied by high local temperatures at the surface of the recording material causing a selective disruption and evaporation of the aluminum film in areas of the recording material. The locations from which material has been removed correspond to the indicia or images which are to be recorded.
  • U.S. Patent 2,983,220 discloses a lithographic coating on an electroerosion recording sheet.
  • the coating may be a copolymer binder system containing zinc oxide and zinc sulfide.
  • a layer containing a conductive material, such as graphite, is disclosed in U.S. Patent 3,048,515, Dalton et al.
  • High temperature lubricants comprising graphite in oil are also known as disclosed in U.S. Patent 3,242,075, Hunter.
  • U .S. Patent 3,514,325 discloses an electroerosion recording material in which a surface layer of crosslinked binder containing conductive particles such as zinc oxide is placed on top of a thin aluminum layer.
  • U.S. Patent 4,305,082 Kusakawa et al, describes an electroerosion recording paper in which a resistance layer may be provided over a thin conductive aluminum film.
  • U.S. Patent 3,002,854 relates to a process involving treatment of a solid surface with titanium organic compositions to improve adhesion with other surfaces.
  • U.S. Patent 3,082,117, Schilly relates to coated films, particularly to organic based films such as polyethylene terephthalate, having a continuous coating of a heat-sealable thermoplastic organic polymeric coating which involves applying a continuous coating of a solution of a titanium organic compound from the group consisting of hydrolyzable organic titanium esters and reac- ' tion products of acetylacetone with an alkyl titanate.
  • U.S. Patent 3,951,882, A.H. Markhart et al relates to dielectric coating compositions containing an organophilic clay pigment prepared by treatment of clay with an organotitanium compound.
  • One object of the present invention is to provide an electroerosion recording material having a multilayer structure with an abrasion resistant overcoating.
  • Another object of the present invention is to provide electroerosion recording materials having a multilayer structure with an abrasion resistant overcoating comprising one or more solid lubricants in a polymeric matrix modified by the addition of one or more organotitanium reagents.
  • Still another object of the present invention is to provide compositions for such abrasion resistant overcoatings in the fabrication of electroerosion recording materials which provide coatings of improved wear resistance and which have improved shelf-life.
  • Yet a further object of the present invention is to provide improved electroerosion recording materials having a thin, uniform overcoating which is continuous and highly adherent to a metal surface, and which does not flake off during storage and handling.
  • a further object of the present invention is to provide electroerosion recording materials of improved resistance to stylus scratching by use of an abrasion resistant overcoating which is fast drying, has high mechanical strength, even at a low organic binder content, and which prevents stylus fouling during the electroerosion printing process.
  • a further object of the present invention is to provide abrasion resistant overcoatings which also exhibit improved contrast when used to produce direct negatives by electroerosion printing.
  • a polymer film e.g., a dark graphite/polymer film, modified (cross- linked) with an organotitanium reagent, can serve to block light that otherwise may be partially transmitted through the thin conductive film e.g., a thin aluminum film.
  • Another object of the present invention is to provide, in a preferred embodiment, a continuous, crosslinked and conductive or resistive protective abrasion resistant overcoating for electroerosion recording media which has a low concentration of organic polymer vehicle for dispersing a solid particulate lubricant.
  • the low binder content allows application of a relatively thicker layer over a conductive metal surface, e.g., aluminum, without adversely affecting print quality.
  • Another object of the present invention is to provide an electroerosion recording material as above described which further comprises a thin hard base layer of an organic polymer which is preferably crosslinked and preferably contains a particulate material.
  • the above objects of the present invention are achieved by the use of very small proportions of an organotitanium reagent which provides a crosslinked overcoating of excellent properties which does not require the use of substantial amounts of crosslinking agent as are required in the prior art and which can be cured in situ.
  • the invention provides an electroerosion recording material comprising a non-conductive support, an electroerodible conductive layer; and an abrasion resistant overlayer which comprises a crosslinked polymer matrix formed by interaction of a hydroxyl group-containing polymer with one or more organo-titanium reagents.
  • Fig. 1 of the drawings 1 indicates the support, e.g., a polyester.
  • the optional hard base layer of the present invention formed thereon is represented by numeral 2 and is shown between the support 1 and the conductive film 3.
  • the abrasion resistant overcoating of the present invention 4 is shown deposited thereon.
  • a direct negative is shown formed after electroerosion printing wherein imaged regions 5 are shown where the conductive layer 3 'and the abrasion resistant overcoating 4 have been removed following electroerosion printing. Also shown are unwritten areas 6. If desired, the abrasion resistance overcoating may be totally removed, but this is not necessary for direct negative use.
  • Fig. 3 shows a direct offset master formed per the present invention where unwritten areas 6 as shown in Fig. 2 have been removed in a conventional manner, for example, by immersion in a solvent such as isopropanol, N-butanol, FPC (from Graphic Arts Co.), etc.
  • a solvent such as isopropanol, N-butanol, FPC (from Graphic Arts Co.), etc.
  • immersion is at room temperature and the abrasion resistant top coat is merely remove ⁇ by swabbing the same.
  • the electroerosion print material of the present invention comprises a support with a conductive layer thereon and an abrasion resistant overcoating or overlayer which has been formed by in situ crosslinking a polymer binder with an organotitanium reagent.
  • overcoating In the present application the terms “overcoating”, “overlayer” or “protective layer” are used interchangeably to describe the topmost layer of the electroerosion print material of the present invention.
  • the support is the same as typically used in the prior art, e.g., paper, polymers such as polyethylene terephthalate, Riston, Kapton, polycarbonates, polypropylenes, polyethylenes, polyesters and the like.
  • the thickness of the support is not limited in any fashion so long as sufficient strength is provided for the end use contemplated. Typically, thicknesses will be on the order of about 1 mil to 5 mils.
  • the support may be opaque or light transparent or transmissive.
  • the resulting product can be used as a photomask or direct negative medium for the development of photosensitive materials, e.g., in the production of offset lithography masters, circuit boards, etc.
  • the electroerosion electrodes have been energized and the overlayer and conductive film burned off, light windows are provided through the transparent backing so that the material is rendered selectively light transmissive and may then be used in direct-photonegative or like applications.
  • the conductive film typically aluminum, is usually deposited by the conventional techniques of sputtering or vacuum evaporation on the base layer. While not limitative, it preferably is about 200-1,000 Angstroms thick and has a resistivity of about 0.5 to about 5 ohms per square centimeter. Other conductive films such as magnesium are also useful per the present invention.
  • the optional, thin, hard polymeric base layer may or may not be crosslinked. It should have a sufficiently high tensile strength and a sufficiently high softening temperature so that it reduces plastic deformation of the support during electroerosion so that scratching of the conductive film is minimized.
  • hard supports e.g., polycarbonates
  • the base layer provides superior results when it is present.
  • the base layer contains an inorganic filler. Crosslinking the base layer is preferred since this generally provides a harder base layer, reducing the chance of generating a soft residue during electroerosion which might adhere to the electroerosion styli and inhibit writing.
  • the most preferred thin, hard base layers are harder than polyethylene terephthalate, a currently preferred support material, exhibit a high Tg, e.g., equal to or greater than 130°C, have a hardness of 20 to 30 or more (Knoops hardness), show an elongation at break of about 4 to 7% (Tensile Instron) or more, and have a contact angle with water of equal to or greater than about 75°, i.e., they are hydrophobic.
  • the base layer should be white, transparent or translucent; obviously, in this case if a particulate material is present to create roughness, the same must be white, transparent or translucent.
  • the base layer is typically formed from solvent castable polymeric/oligomeric materials containing residual reactive sites such as free hydroxyl, epoxy, olefinic, acetylenic, a, P-unsaturated carbonyl moities, etc., which can be crosslinked by suitable reagents using heat and/or radiation to accelerate the curing process. With these materials, crosslinking can also be accomplished by thermal or radiation-induced processcs without the addition of another crosslinking agent.
  • Inorganic fillers such as SiO 2 , CaCO 3 , Ti0 2 and calcium silicate, etc., generally of a particle size ranging from 0.5 ⁇ m to 10 ⁇ m can be incorporated by the usual techniques of grinding or milling together with, e.g., the binder, the urethane solvent such as a methyl ethyl ketone (MEK)-toluene mixture, and a suitable dispersing agent such as Multron R221-75, a saturated polyester resin from Mobay Chemical Co.
  • the binder the urethane solvent such as a methyl ethyl ketone (MEK)-toluene mixture
  • MEK methyl ethyl ketone
  • suitable dispersing agent such as Multron R221-75, a saturated polyester resin from Mobay Chemical Co.
  • Other useful solvents and proportions are the same as for overlayer formation later discussed.
  • the urethane forming reactions of the above described binders and urethane prepolymers can be catalyzed by conventional organometallic reagents such as stannous oleate, stannous octoate, dibutyl-tin dioctoate, dibutyl-tin dilaurate, calcium or cobalt naphthenate, also tertiary amines, etc. Further acceleration of the crosslinking reaction can be achieved by thermal treatment of the coatings.
  • Crosslinked polymer coatings with beneficial properties can be obtained by the use of radiation (UV) curable acrylated polyurethane oligomers of the type "UVITHANE 783" and “UVITHANE 788” available from Thiokol Chemical Div.
  • UV curable acrylated polyurethane oligomers of the type "UVITHANE 783" and “UVITHANE 788” available from Thiokol Chemical Div.
  • Inorganic fillers such as silica can be dispersed by the conventional techniques prior to coating.
  • Highly crosslinked films can also be obtained by thermal or radiation-induced copolymerization/ co-crosslinking of the above UV curable urethane oligomers with added multifunctional monomers such as pentaerythritol triacrylate (PETA) and trimethylol-propane triacrylate (TMPTA) available from Celanese Corporation.
  • PETA pentaerythritol triacrylate
  • TMPTA trimethylol-propane triacrylate
  • Desired crosslinked films with or without inorganic fillers can also be formed by thermal, microwave, or UV curing of coatings cast from blends of acrylated cellulosic derivatives and UV curable urethane oligomers described above.
  • base coat formulations were typically formed at NCO:OH ratio of about 0.5 to about 1, more preferably 0.7 to 0.8.
  • the particulate solid filler when used, is typically used in an amount of from about 3 to about 40 weight percent, more preferably from 5 to 25 weight percent, based on the weight of organics present.
  • Talysurf Traces of typical filled films show a peak to valley ratio on the order of 1 to 2 microns.
  • the base layer has a thickness of from about 2 to about 10 mm.
  • crosslinked, preferably pigmented, films as the hard base layer can also be obtained by the use of organotitanium reagents as crosslinkers for the polymer-binder of the base layer.
  • organotitanium reagents as crosslinkers for the polymer-binder of the base layer.
  • one such system would comprise amorphous silica in cellulose derivatives such as cellulose acetate butyrate, ethyl cellulose or other binders with available hydroxyl groups for crosslinking reactions with organotitanium reagents as later described.
  • proportions, processing conditions, etc. are essentially the same as for the abrasion-resistant topcoat layer which will now be discussed.
  • a superior electroerosion recording material is generated when the aluminized structure described above is overcoated with an abrasion resistant topcoat layer which preferably comprises a conductive lubricant such as graphite, MoS 2 , CaF 2 , etc., most preferably graphite, in a hydroxyl group containing polymeric matrix which has been modified/cross- linked through the use of an organotitanium reagent, such as a titanium chelate or a titanium ester, which yields abrasion-resistant topcoats of superior lubricity, better adhesion to the underlying conductive layer, excellent hardness and excellent flake off resistance.
  • a conductive lubricant such as graphite, MoS 2 , CaF 2 , etc.
  • an organotitanium reagent such as a titanium chelate or a titanium ester
  • the preferred materials are titanium esters of the formula Ti(OR) 4 where R is a hydrocarbon group having from 1 to 12 carbon atoms, more preferably from 3 to 12 carbon atoms and most preferably from 3 to 6 carbon atoms, with preferred examples of R being n-propyl, i-propyl, n-butyl, t-butyl, and pentyl.
  • R can be a methyl or ethyl group, but this is not preferred since in this situation the titanium esters gel the hydroxyl group containing binder extremely rapidly and, to be useful on a practical basis, a gelling retarder is necessary.
  • the R groups may be the same or different in the titanium esters, but for practical purposes (ease of manufacture) they are generally the same.
  • the preferred titanium chelates used per the present invention are cyclic complexes formed by the reaction of titanium alkoxides with organic ligands having two or more atoms which simultaneously serve as donor sites for titanium.
  • organic ligands include 1, 3-diketones, p-ketoesters, and p-hydroxylamines.
  • Titanium chelates can be represented by the following general structure: where X represents a functional group containing oxygen or nitrogen, Y represents a 2 or 3 carbon atom chain and R represents a 3 to 5 hydrocarbon chain joined with oxygen through a secondary or tertiary carbon atom.
  • the amines may be primary, secondary or tertiary.
  • the total number of carbon atoms in X and Y (which are derived from the organic ligand) when carbon atoms are present (they would not be present in the case of a primary amino group or a hydroxy group) is preferably from 2 to 12.
  • titanium chelates are: titanium acetylacetonate, titanium triethanolamine chelate, titanium lactic acid chelate, titanium ethyl acetoacetate, octylene glycol titanate, etc.
  • titanate esters are: tetra-n-butyltitanate, tetraethylene-glycol titanate, tetraisopropyl titanate, tetrakis(2-ethylhexyl) titanate, etc.
  • the organic titanium reagents including titanium esters and titanium chelates can be freely selected from those which will react with the polyhydroxy organic binders to yield a hard, non-tacky polymer film after a conventional thermal cure which causes evaporation of the casting solvent(s) and provides the desired solvent-resistant coating.
  • reagents are employed to favorably modify the adhesion, solubility and mechanical characteristics of the protective overcoating to obtain thermally stable coatings. They are processable with a wide variety of hydroxyl group-containing polymers, and eliminate any problems of phase-incompatibility commonly encountered with prior art coating systems.
  • organotitanium reagents are commercially available from E.I. du Pont de Nemours & Co., Inc., Pigments Department, under the trade name "TYZOR” Organic Titanates.
  • the organotitanium compositions for the protective coatings applicable according to this invention are most preferably formed of dispersions of a lubricant such as graphite in polymeric systems having available hydroxy groups such as cellulose derivatives such as ethyl cellulose, cellulose acetate butyrate, hydroxypropylcellulose, hydroxyethylcellulose, nitrocellulose, cellulose acetate, or materials such as polyvinyl acetal resins, polyvinyl alcohol, etc., in an alcoholic solvent such as isopropanol, to which titanium acetylacetonate or an alternate related reagent is added in an amount of about 1 to about 20% by weight of the binder, preferably 5 to 10% by weight of the binder.
  • a lubricant such as graphite in polymeric systems having available hydroxy groups
  • cellulose derivatives such as ethyl cellulose, cellulose acetate butyrate, hydroxypropylcellulose, hydroxyethylcellulose, nitrocellulose, cellulose a
  • organotitanium reagents of the present invention could be used at very low proportions as compared to conventional crosslinking agents to provide the abrasion-resistant topcoat of the present invention. They are applied by conventional deposition techniques such as dip coating, spin coating or web coating.
  • solvents may also be used such as butyl acetate- isopropanol, methyl-ethyl-ketone-tetrahydrofuran, toluene-isopropanol-ethyl lactate, etc.
  • the preferred solvents are tetrahydrofuran-isopropanol, toluene-butyl acetate-butanol or isopropanol alone.
  • the solvent for the abrasion resistant topcoat is not critical so long as it does not cause gelation upon addition of organotitanium reagents prior to coating application. While not to be construed as limitative, we have found that an amount of solvent sufficient to provide a viscosity on the order of about 500 to about 600 cps (Brookfield Viscometer) is quite acceptable.
  • the cellulose derivatives such as cellulose acetate butyrate (CAB), ethyl cellulose, nitrocellulose and cellulose acetate preferably used are available from Eastman Chemicals. These materials have a hydroxy equivalent weight of about 300 to about 400. Several grades with varying hydroxyl contents from 0.33 to 1.0 hydroxyl groups per anhydroglucuse unit can be employed.
  • Most preferred materials include ethyl cellulose, and nitrocellulose with about 0.75 hydroxyl groups per anhydroglucose unit.
  • the titanium reagent modified film is typically formed by adding the organotitanium reagent, e.g., titanium acetylacetonate, to a preformed dispersion of solid lubricant in the desired hydroxyl group-containing polymer in a suitable solvent and after thorough mixing and, if necessary, dilution, the film is cast by any conventional technique onto the conductive surface of the composite structure, whereafter the same is subjected to a dry/cure cycle, typically at a temperature of about 100° to about 110°C for about 5 to about 15 minutes when a plastic support such as Mylar® is employed.
  • organotitanium reagent e.g., titanium acetylacetonate
  • the atmosphere of the dry/cure cycle is not important and is typically air.
  • the pressure is typically ambient.
  • the abrasion resistant overcoat layer of the present invention most desirably contains one or more conductive or resistive solid particulate lubricants such as graphite.
  • the general class of laminar solids may be employed as such lubricants. Examples include MoS 2 , WS 2 , TaS 2 and CaF 2 with graphite being preferred. Other compounds may be considered such as ZnO, TiO 2 , AgI, PbO, Pb(OH) 2 , PbC0 3 , PbO, etc., since they have all been shown to be lubricants.
  • soft metal particles such as Sn, Cu, Zn, Ag, Pb, Au, Bi and Al are expected to be useful in the present invention.
  • colloidal graphite suspensions in cellulosic binders in the presence of organotitanium crosslinking agents are preferred from the viewpoint of lubricity, abrasion resistance, dispersion quality and film uniformity.
  • the lubricating agent most preferably has a particle size equal to or less than 1 ⁇ m and when the same is graphite, it most preferably has a size of from about 200 angstroms to 1 micron, more preferably 200 angstroms to 500 angstroms.
  • ELECTRO-DAG 154 comprises graphite dispersed in a cellulose derivative such as ethyl cellulose and isopropanol as a solvent. It comprises about 20 weight percent solid (20 weight percent of which is binder and 80 weight percent of which is graphite), balance solvent.
  • the most preferred protective lubricant coating formulations of the present invention are formed by thoroughly mixing the titanium reagents into such graphite dispersions followed by appropriate dilution with a suitable solvent(s) so as to adjust the viscosity or the desired dry thickness of the coating.
  • the total organic binder content including the dispersion vehicle and the organic titanium reagent should preferably be maintained at a relatively lov) level for reasons of possible fouling concern due to organic debris generated during the electroerosion printing process which may adhere to the print head and interfere with the electroerosion printing process.
  • the resulting electroerosion recording material is subjected to electroerosion printing in a conventional manner, whereupon application of an electrical pulse to a stylus results in an arc or spark between the stylus and the conductive layer causing local removal of, e.g., aluminum which is selectively eroded along with the abrasion resistant top coat layer to expose the support or base layer when used.
  • An offset or direct master per the present invention can be used in a conventional manner for offset lithographic printing with conventional oleophilic inks. In a similar fashion, it is used as direct negative in a conventional manner.
  • a special advantage of the approach of the present invention as compared "tb the use of an urethane crosslinked matrix formed using polyfunctional isocyanates as crosslinking agents for polymeric systems with free hydroxyl groups and other approaches in the prior art is that the organotitanium reagents are relatively less toxic, require no catalyst or initiator and effective modification of film properties can be achieved by adding as little as about 1 to about 5 percent of the organotitanium reagent with respect to the organic binder in coating formulations prior to application.
  • a brief thermal curing cycle at temperatures as low as about 50 to 100°C suffices to form uniform, non-tacky and abrasion resistant films.
  • abrasion resistant topcoat compositions according to the present invention is that coherent, uniform thin films can be obtained at very low organic binder contents relative to graphite or alternative solid lubricants.
  • a low binder content in the overlayer is advantageous since in this case the debris generated during electroerosion printing or writing is relatively non-adherent and does not cake around the styli which would otherwise interfere with the printing process.
  • An overcoat composition with a slightly higher -.rganic binder content can be formed by adding 1 part of a, 4 weight percent solution of CAB to the above composition and the same can be applied to the electroconductive aluminum layer to obtain a continuous, uniform and abrasion resistant layer.

Landscapes

  • Paints Or Removers (AREA)
  • Photographic Developing Apparatuses (AREA)
EP19840114277 1983-12-30 1984-11-27 Elektroerosionsdruckmaterial mit Schutzschicht Expired EP0147642B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US56729983A 1983-12-30 1983-12-30
US567299 1983-12-30

Publications (3)

Publication Number Publication Date
EP0147642A2 true EP0147642A2 (de) 1985-07-10
EP0147642A3 EP0147642A3 (en) 1987-02-25
EP0147642B1 EP0147642B1 (de) 1989-02-01

Family

ID=24266592

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19840114277 Expired EP0147642B1 (de) 1983-12-30 1984-11-27 Elektroerosionsdruckmaterial mit Schutzschicht

Country Status (4)

Country Link
EP (1) EP0147642B1 (de)
JP (1) JPS60147389A (de)
CA (1) CA1221833A (de)
DE (1) DE3476530D1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0158826A3 (en) * 1984-04-05 1988-01-07 International Business Machines Corporation Electroerosion recording materials with new hydrophilic protective coating
EP0379673A3 (en) * 1989-01-23 1990-09-19 International Business Machines Corporation Electroerosion recording medium of improved corrosion resistance
EP0490051A1 (de) * 1990-12-07 1992-06-17 International Business Machines Corporation Verbesserte Elektroerosion-Druckplatten
WO2005049662A1 (en) * 2003-11-17 2005-06-02 Sun Chemical Corporation Reactive hydroxylated and carboxylated polymers for use as adhesion promoters

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983221A (en) * 1955-11-28 1961-05-09 Timefax Corp Planographic printing plates
JPS59124889A (ja) * 1982-12-30 1984-07-19 インタ−ナショナル　ビジネス　マシ−ンズ　コ−ポレ−ション 放電記録材
JPS59124888A (ja) * 1982-12-30 1984-07-19 インタ−ナショナル　ビジネス　マシ−ンズ　コ−ポレ−ション 放電記録材

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0158826A3 (en) * 1984-04-05 1988-01-07 International Business Machines Corporation Electroerosion recording materials with new hydrophilic protective coating
EP0379673A3 (en) * 1989-01-23 1990-09-19 International Business Machines Corporation Electroerosion recording medium of improved corrosion resistance
EP0490051A1 (de) * 1990-12-07 1992-06-17 International Business Machines Corporation Verbesserte Elektroerosion-Druckplatten
US5176947A (en) * 1990-12-07 1993-01-05 International Business Machines Corporation Electroerosion printing plates
WO2005049662A1 (en) * 2003-11-17 2005-06-02 Sun Chemical Corporation Reactive hydroxylated and carboxylated polymers for use as adhesion promoters
CN1906219B (zh) * 2003-11-17 2010-04-28 太阳化学公司 用作粘合促进剂的活性羟基化和羧基化聚合物
US9034958B2 (en) 2003-11-17 2015-05-19 Sun Chemical Corporation Reactive hydroxylated and carboxylated polymers for use as adhesion promoters
US9279034B2 (en) 2003-11-17 2016-03-08 Sun Chemical Corporation Reactive hydroxylated and carboxylated polymers for use as adhesion promoters
US10059795B2 (en) 2003-11-17 2018-08-28 Sun Chemical Corporation Reactive hydroxylated and carboxylated polymers for use as adhesion promoters
US10676563B2 (en) 2003-11-17 2020-06-09 Sun Chemical Corporation Reactive hydroxylated and carboxylated polymers for use as adhesion promoters
US11780955B2 (en) 2003-11-17 2023-10-10 Sun Chemical Corporation Reactive hydroxylated and carboxylated polymers for use as adhesion promoters

Also Published As

Publication number Publication date
EP0147642A3 (en) 1987-02-25
DE3476530D1 (en) 1989-03-09
JPS60147389A (ja) 1985-08-03
EP0147642B1 (de) 1989-02-01
CA1221833A (en) 1987-05-19

Similar Documents

Publication Publication Date Title
EP0158826B1 (de) Hydrophile Schutzschichten für Elektroerosionsdruckmaterial
US4894279A (en) Electroerosion print media having protective coatings modified with organotitanium reagents
US4554562A (en) Scratch resistant recording materials for electroerosion printing not requiring a lubricant overcoat
US4596733A (en) Electroerosion recording material with polyorganosiloxane overlayer
US4567490A (en) Electroerosion recording medium of improved lubricity
EP0147642B1 (de) Elektroerosionsdruckmaterial mit Schutzschicht
EP0158276B1 (de) Elektroerosionsaufzeichnungsmaterial
EP0113005A1 (de) Aufzeichnungsmaterialien für Elektroerosion und Verwendungsverfahren
US4830909A (en) Scratch resistant recording materials for electroerosion printing comprising cross-linked polymer base layer
CA1221832A (en) Method for making direct negatives and direct masters by electroerosion recording and products formed thereby
US20010035105A1 (en) Lithographic plate materials and method for making lithographic plates using the same
EP0490051A1 (de) Verbesserte Elektroerosion-Druckplatten
KR0171630B1 (ko) 열 전사용 기록 시이트
US5084331A (en) Electroerosion recording medium of improved corrosion resistance
EP1457352B1 (de) Wärmeempfindliches Aufzeichnungsmaterial
EP0379673B1 (de) Elektroerosions-Aufzeichnungsmaterial mit verbesserter Korrosionsbeständigkeit
JP2000238450A (ja) 直描型水なし平版印刷版原版の製造方法
JPH0752295B2 (ja) 静電記録シ−ト
JP3060351B2 (ja) レーザー製版用版シート
JP4216706B2 (ja) 記録体の製版方法
JPH05270153A (ja) 感熱記録媒体

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19841214

AK Designated contracting states

Designated state(s): DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB

17Q First examination report despatched

Effective date: 19880314

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 3476530

Country of ref document: DE

Date of ref document: 19890309

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: FR

Ref legal event code: GC

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19991102

Year of fee payment: 16

Ref country code: FR

Payment date: 19991102

Year of fee payment: 16

Ref country code: DE

Payment date: 19991102

Year of fee payment: 16

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001127

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20001127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST