EP0147642B1 - Matériel pour l'enregistrement par électroérosion avec couche protectrice - Google Patents

Matériel pour l'enregistrement par électroérosion avec couche protectrice Download PDF

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Publication number
EP0147642B1
EP0147642B1 EP19840114277 EP84114277A EP0147642B1 EP 0147642 B1 EP0147642 B1 EP 0147642B1 EP 19840114277 EP19840114277 EP 19840114277 EP 84114277 A EP84114277 A EP 84114277A EP 0147642 B1 EP0147642 B1 EP 0147642B1
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EP
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Prior art keywords
recording material
electroerosion
titanium
electroerosion recording
binder
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EP19840114277
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German (de)
English (en)
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EP0147642A2 (fr
EP0147642A3 (en
Inventor
Krishna Gandhi Sachdev
Keith Samuel Pennington
Mitchell Simmons Cohen
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International Business Machines Corp
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International Business Machines Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/24—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.
  • Electroerosion printing is a well known technique for producing markings such as letters, numbers, symbols, patterns, such as circuit patterns, or other legible or coated indicia, on a recording material. This is typically performed by computer-output controlled printing which involves removal of an aluminum layer from selected areas of the recording material as the result of spark initiation.
  • 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.
  • sparking arcing
  • 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.
  • Electroerosion recording materials and printing processes are useful to directly produce human readable images, photomasks, etc.
  • Special paper and polymer substrates have been employed which are coated with a black organic underlayer and then the electroerodable conductive layer, typically a metal film such as a vapor deposited aluminum film, is deposited.
  • the electroerodable conductive layer typically a metal film such as a vapor deposited aluminum film.
  • EP-A-113005 which belongs to the prior art as defined in Article 54(3)(4) EPC, describes electroerosion recording media suitable for high resolution printing to produce high quality "direct negatives" and short run “offset masters”.
  • 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 reaction 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 (crosslinked) 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 lasyer 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.
  • 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. Typically, immersion is at room temperature and the abrasion resistant top coat is merely removed by swabbing the same.
  • 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 removed 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 electroerosion print material comprises a support with a hard, abrasion resistant polymer-inorganic particulate film matrix thereon which is crosslinked, a thin conductive electroerodable film such as aluminum thereon and an abrasion resistant overcoating or protective overlayer comprising one or more conductive or resistive particulate solid lubricants (lubricants) in a hydroxyl group-containing binder modified through incorporation of one or more organotitanium reagents.
  • lubricants conductive or resistive particulate solid lubricants
  • 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 25-127 11m (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 major characteristic which the thin conductive electroerodable film (hereafter often merely a conductive film for brevity) must exhibit is that upon application of an electrical pulse from an electrode or stylus during electroerosion printing, the same is lifted off or eroded from the base layer along with the protective abrasion-resistant overcoat. If this criterion is met, any conductive material can be used in the present invention so long as image discrimination is provided for those uses where such is necessary.
  • 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 20-100 nm (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.
  • crosslinking firmly fixes the filler in place, reducing the chance of filler dislodgement and adherence to the electroerosion styli.
  • a crosslinked base layer improves the corrosion resistance of the conductive film due to its good passivating properties, thus increasing shelf life and performance reliability.
  • 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 moieties, 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 processes without the addition of another crosslinking agent.
  • Urethane crosslinked cellulosic coatings with and without roughness causing particulate material are formed from cellulose derivatives and aromatic or aliphatic polyisocyanates in the presence of suitable dispesing agents, catalysts and wetting agents well known to those skilled in the polyurethane art.
  • suitable cellulose derived materials include: cellulose acetate butyrate (CAB), ethyl cellulose (EC), nitrocellulose, cellulose acetate and cellulose diacetate, etc.
  • Alternate materials containing unsubstituted hydroxyl groups for reaction with polyisocyanates to form crosslinked polyurethanes are: polyvinyl butyral, polyvinyl formal Bakelite phenoxy resins, phenolic resins e.g., novolaks (which have a slight color), epoxies such as Eponois and polyether glycols such as "Teracol” (from DuPont), and poly(styrylallyl alcohol).
  • Typical polyisocyanates that react with available -OH groups of cellulosic binders or alternate systems include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate-based systems such as Desmodur N-75 (aliphatic prepolymer, Mobay Chemical Co.) and Mondur Resins such as CB-60 and CB-75, and Mondur HC.
  • Melamine crosslinking agents can also be employed to obtain thermoset coatings with the above binders.
  • Inorganic fillers such as Si0 2 , CaC0 3 , Ti0 2 and calcium silicate, etc., generally of a particle size ranging from 0.5 pm to 10 urn 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
  • 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.
  • Drying/airing is usually at about 90 to about 110°C for about 5 to about 15 minutes in air. Greater or lesser times/temperatures can be used, if desired.
  • 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/crosslinked 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
  • organotitanium reagents used per the present invention are not unduly limited so long as they can crosslink the hydroxyl group containing binder to provide an abrasion-resistant overcoat.
  • 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 ⁇ -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 hydroxyl groups such as cellulose derivatives such as ethyl cellulose, cellulose acetate butyrate, hydroxypropylcellulose, hydroxyethylcellulose, nitrocellulose, cellulose acetate, or materials such as polyvinyl acetal resins, p7olyvinyl 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 hydroxyl groups
  • cellulose derivatives such as ethyl cellulose, cellulose acetate butyrate, hydroxypropylcellulose, hydroxyethylcellulose, nitro
  • 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.
  • volatile non-reactive solvents can be used to form layers per the present invention to reduce the solids content and permit the coating of very thin layers on the conductive surface.
  • Classes of suitable solvents include, but are not limited to, aromatic solvents, such as toluene and xylene; ketones, such as methylethylketone and isophorone; acetates, such as ethyl acetate and butyl acetate; alcoholic solvents such as ethanol, isopropanol, butanol and tetrahydrofuran, etc.
  • 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 thickness of the protective layer is not limited in any special fashion so long as it is sufficiently thick to provide a uniform coverage of the conductive film, provides protection against abrasion and will not flake off during handling and the electroerosion printing process. Also, it should not substantially reduce print quality or printed spot resolution capability.
  • 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, Ti0 2 , Agl, 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 AI 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 pm and when the same is graphite, it most preferably has a size of from about 20 nm (200 angstroms) to 1 micron, more preferably 20 nm to 50 nm (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 low 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 to 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.
  • the CAB solution in THF and toluene was first prepared, and it was combined with the silica along with the dispersant and ball milled for 12-16 hours to form a homogeneous MILL BASE.
  • the final coating composition was obtained by mixing the various ingredients described below in the following proportions:
  • This composition was coated by web coating onto a 51 ⁇ m (2 mil) thick polyester substrate to a dry coating thickness of 5 ⁇ m (200 microinches) after drying/curing at 100-110°C for 5-10 minutes.
  • a layer of aluminum at a thickness of about 35 nm (350 Angstroms) deposited by a conventional technique of sputter evaporation or vacuum evaporation.
  • composition was used to form an abrasion resistant coating on the aluminum surface of the composite structure described above. All parts are by weight unless otherwise indicated.
  • the titanium acetylacetonate was used in the form of a 75 weight percent solution in IPA. It was commercially available under the trade name TYZOR AA, available from E. I. du Pont de Nemours & Co., Inc.
  • the above composition was applied by conventional web coating to the electroconductive aluminum layer and dried at 100-110°C for 10-15 minutes.
  • the final dry thickness of the coating was from 50-400 nm (500-4,000 angstroms), typically 70 nm (700 angstroms).
  • An overcoat composition with a slightly higher organic 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.
  • An aluminized structure having a 40 nm (400 Angstrom) thick aluminum layer with a hard intermediate layer interposed between the polyester support and the aluminum layer was prepared as described in Example 1.
  • the tetraisopropyl titanate is available from E. I. du Pont de Nemours & Co., Inc. under the trade name TYZOR O TPT.
  • Example 2 An alternate underlayer comprising a silica-titanium chelate crosslinked ethyl cellulose matrix was formed on a polyester support as was used in Example 1 from the following composition. All parts are by weight.
  • the ethyl cellulose was first dissolved in the solvent mixture, combined with the silica powder and then ball milled for 16 hours to form the desired mill base. Prior to coating, to the mill base there was added a solution of two parts of TYZOR AA in 10.0 parts of IPA. After thorough mixing, the formulation was applied to the 51 pm (two mil) thick polyester substrate on a continuous film casting apparatus with a controlled drying/curing cycle set at 100-110°C for 10-15 minutes to obtain a dry coating thickness for the resulting base layer between 5.1-6.4 ⁇ m (200-250 microinches).
  • the lubricant protective layer was formed on the aluminum surface from the following composition where all parts are by weight.
  • the CAB solution was prepared using an IPA-toluene mixture and combined with the colloidal graphite suspension, whereafter one part each of IPA and toluene were added. The mixture was then ball milled for sixteen hours. Prior to coating application, the dispersion was combined with the remainder of the solvents and the TYZOR AA, applied to the aluminum surface and dried/cured as described in Example 2. The thickness was as per Example 2.
  • Example 2 Using the aluminized structure of Example 1, an overlayer of the following constituents was formed on the surface of the aluminum. All parts are by weight.
  • Example 1 The solution of the novolak resin in the solvent mixture was combined with the carbon black and the mixture was ball milled for 16 hours. Prior to coating application the resin-carbon black dispersion was diluted with 300 parts of a 1:1:1 volume mixture of THF-toluene-ethanol and combined with 5.0 parts of the tetraisopropyl titanate (TYZOR TPT) and applied and dried/cured as in Example 1. The thickness was as in Example 1.

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Claims (14)

1. Matériau d'enregistrement par électroérosion comprenant:
un support non-conducteur,
une couche conductrice électroérodable; et
une surcouche résistante à l'abrasion constituée d'une matrice polymère réticulée formée par l'interaction d'un polymère contenant des groupements hydroxyle avec un ou plusieurs réactifs d'organo- titane.
2. Matériau d'enregistrement par électroérosion selon la revendication 1, comprenant en outre une couche polymère dure entre ledit support non-conducteur et ladite couche conductrice électroérodable.
3. Matériau d'enregistrement par électroérosion selon les revendications 1 ou 2, dans lequel ladite surcouche résistant à l'abrasion comprend de plus un lubrifiant solide particulaire conducteur ou résistif.
4. Matériau d'enregistrement par électroérosion selon la revendication 3, dans lequel ladite couche de polymère dure et mince contient de plus des particules de charge solides.
5. Matériau d'enregistrement par électroérosion selon la revendication 4, dans lequel le matériau particulaire est dispersé dans une matrice polymère réticulée.
6. Matériau d'enregistrement par électroérosion selon l'une quelconque des revendications 1 à 5, dans lequel la surcouche comprend du graphite et un lianat de cellulose qui a été réticulé par lesdits réactifs d'organo-titane.
7. Matériau d'enregistrement par électroérosion selon la revendication 3, dans lequel le lubrifiant de la surcouche est choisi dans le groupe constitué du graphite, du noir de carbone, du MoS2 et du ZnO conducteur, et la matrice polymère réticulée comprend le produit réactionnel d'un élément ou plus choisi dans le groupe constitué de l'acétate butyrate de cellulose, de la cellulose éthylique, de la nitrocellulose ou de l'acétate de cellulose, l'un des éléments ou plus étant choisi(s) dans le groupe constitué des esters de titane et des chélates de titane.
8. Matériau d'enregistrement par électroérqsion selon les revendications 1 à 7, dans lequel le réactif d'organotitane est choisi dans le groupe constitué des tetraalkyltitanates de formule Ti(OR)4 ou R est un radical hydrocarbure ayant de 3 à 12 atomes de carbone.
9. Matériau d'enregistrement par électroérosion selon les revendications 1 à 7, dans lequel ledit réactif d'organo-titane est un ester de titane choisi dans le groupe constitué du titanate de tétraisopropyl, du tétra- n-butyl titanate, du tetrakis (2-éthyl-hexyl) titanate et du tétraéthylène glycol titanate.
10. Matériau d'enregistrement par électroérosion selon les revendications 1 à 7, dans lequel le réactif d'organo-titane est un chélate de titane choisi dans le groupe constitué de l'acétylacétonate de titane, du triéthanolamine chélate de titane et du chélate d'acide lactique de titane.
11. Matériau d'enregistrement par électroérosion selon les revendications 1 à 10, dans lequel la surcouche est formée en mélangeant environ 5 à 20% en poids du réactif d'organo-titane avec une dispersion préformée de solvant, de liant et de graphite, par rapport au poids du constituant de liaison.
12. Matériau d'enregistrement par électroérosion selon les revendications 1 à 11, dans lequel la surcouche est séchée et cuite jusqu'à une épaisseur sèche finale d'environ 0,05 um à 0,6 um.
13. Matériau d'enregistrement par électroérosion selon les revendications 1 à 12, dans lequel la surcouche est formée d'une composition comprenant environ 20 à 40% en poids de liant polymère, environ 60 à 80% en poids de lubrifiant, par rapport au poids du liant plus celui du lubrifiant, et de 5 à 20% en poids dudit réactif d'organo-titane, par rapport au poids du liant.
14. Matériau d'enregistrement par électroérosion selon les revendications 1 à 13, dans lequel la couche dure entre le support non conducteur et la couche conductrice électroérodable est formée d'une composition qui comprend de la silice et un dérivé de la cellulose qui a été modifié en le soumettant à une cycle de sèchage/cuisson vers environ 100 à 110°C pendant à peu près 10 à 15 minutes en présence d'un réactif d'organo-titane pour fournir une épaisseur finale à sec comprise entre 2 et 10 pm environ.
EP19840114277 1983-12-30 1984-11-27 Matériel pour l'enregistrement par électroérosion avec couche protectrice Expired EP0147642B1 (fr)

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US56729983A 1983-12-30 1983-12-30
US567299 1983-12-30

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EP0147642A2 EP0147642A2 (fr) 1985-07-10
EP0147642A3 EP0147642A3 (en) 1987-02-25
EP0147642B1 true EP0147642B1 (fr) 1989-02-01

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JP (1) JPS60147389A (fr)
CA (1) CA1221833A (fr)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4617579A (en) * 1984-04-05 1986-10-14 International Business Machines Corporation Hydrophilic protective coatings for electroerosion printing
EP0379673B1 (fr) * 1989-01-23 1994-04-13 International Business Machines Corporation Elément pour l'enregistrement par électro-érosion avec une résistance modifiée à la corrosion
US5176947A (en) * 1990-12-07 1993-01-05 International Business Machines Corporation Electroerosion printing plates
EP1689793B1 (fr) 2003-11-17 2023-03-15 Sun Chemical Corporation Polymeres carboxyles et hydroxyles reactifs utilisables en tant que promoteurs d'adhesion

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Publication number Priority date Publication date Assignee Title
US2983221A (en) * 1955-11-28 1961-05-09 Timefax Corp Planographic printing plates
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
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

Also Published As

Publication number Publication date
JPS60147389A (ja) 1985-08-03
EP0147642A2 (fr) 1985-07-10
CA1221833A (fr) 1987-05-19
DE3476530D1 (en) 1989-03-09
EP0147642A3 (en) 1987-02-25

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