EP0264037B1 - UV-härtbare dielektrische Zusammensetzungen - Google Patents

UV-härtbare dielektrische Zusammensetzungen Download PDF

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Publication number
EP0264037B1
EP0264037B1 EP87114441A EP87114441A EP0264037B1 EP 0264037 B1 EP0264037 B1 EP 0264037B1 EP 87114441 A EP87114441 A EP 87114441A EP 87114441 A EP87114441 A EP 87114441A EP 0264037 B1 EP0264037 B1 EP 0264037B1
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EP
European Patent Office
Prior art keywords
composition
acrylated
adhesion
oligomer
curable
Prior art date
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Expired - Lifetime
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EP87114441A
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English (en)
French (fr)
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EP0264037A3 (en
EP0264037A2 (de
Inventor
Christina Nicholson Lazaridis
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of EP0264037A2 publication Critical patent/EP0264037A2/de
Publication of EP0264037A3 publication Critical patent/EP0264037A3/en
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins

Definitions

  • the invention is directed to novel UV-curable dielectric compositions and especially to such compositions for use in membrane touch switches.
  • the membrane touch switch is a normally open, low-voltage, pressure-sensitive device currently being used in a wide variety of applications, including appliances, electronic games, keyboards, and instrumentation. It is usually fabricated as a three-layer sandwich with the conductive traces printed on the inner sides of the top and bottom layers which are separated by a spazcer sheet. Pressure applied to the top layer establishes momentary electrical contact between the top and bottom layers through punched openings in the spacer sheet. Both flexible and rigid switches are available. The former are typically printed over a flexible polyester base, while the latter use a printed circuit board bottom panel.
  • the dielectric be screen-printable, and either thermally curable or UV light curable. Faster cures which can be obtained with the latter make it the more cost-effective approach, and the wide availability of UV curing units makes this a practical route.
  • the dielectric must be compatible with the conductive ink, and must meet certain performance standards. It must cure to a flexible, abrasion-resistant film, free of pinholes with good adhesion to the substrate and to the conductive ink. Crossover applications also require that the conductive ink have good adhesion to the dielectric, and, frequently, good adhesion of the dielectric to itself is also specified. Electrical requirements call for a low dielectric constant, high insulation resistance, and high breakdown voltage. The physical and electrical properties must not degrade under a variety of environmental conditions.
  • dielectric failure can lead to either electrical or physical breakdown of the switch. Both materials vendors and switch manufacturers rigorously test components under fresh and accelerated aging conditions to decrease the probability of this occurrence. Electrical failure implies that shorting has occurred because of pinholes, the presence of conductive impurities in the formulation, dielectric failure under load, or other stressful environmental conditions. Physical failures originate from blistering, softening, or cracking, any of which can occur during the manufacturing process or during use. Blistering may be due to incompatibility of the dielectric with the conductor or the substrate, as well as from moisture susceptibility. Softening can occur under high humidity conditions or with solvent from a conductor ink, and cracking can result from the inherent brittleness of a cured composition. All of these problems can be prevented with appropriately formulated inks.
  • polyester films are the most widely used in touch switches, polycarbonate and polyimide films are occasionally encountered.
  • Each film manufacturer typically offers several grades of each product, with different surface characteristics due to variable processing techiques and/or surface pretreatments.
  • the films may also be given a heat treatment to reduce shrinkage in later curing steps.
  • both Mylar®EL 500 and 500D (7) polyester films show evidence of rough surfaces, due to slip pretreatment to allow easy handling of these films, while Melinex®O (6) polyester film has an extremely smooth surface.
  • the Mylar®500D polyester film has much smaller particulates than the Mylar®EL 500 polyester film, giving it a clear appearance, while the Mylar®EL 500 has a cloudy apperance.
  • the Melinex®O polyester film is also very clear, but suffers from poor handleability and tends to stick to itself. As might be predicted adhesion to these surfaces is quite variable and indirectly related to surface smoothness - the Melinex®O polyester film generally giving the poorest values. Since membrane switch manufacturers often select their substrates not for microscopic structure but for reasons of cost, dimensional stability and visual appearance, the physical surface characteristics are frequently overlooked, yet may be critical to the performance of an ink from the standpoint of adhesion.
  • the invention is therefore directed in its primary aspect to an improved screen printable dielectric composition having superior adhesion to a wide variety of substrates which is a printable dielectric composition comprising
  • the invention is directed to membrane touch switches comprising upper and lower flexible layers having facing electrically conductive areas separated by an adherent spacer layer of the above-described composition.
  • the invention is directed to membrane touch switches comprising upper and lower flexible layers having facing electrically conductive areas separated by an adherent spacer layer and having electrically conductive traces leading therefrom encapsulated within a layer of the above-described composition.
  • the invention is directed to a membrane touch switch comprising upper and lower flexible layers at least one of which layers has a plurality of overlying electrically conductive areas each separated from the other by a layer of the above-described composition.
  • the mose widely accepted criterion for measuring the adhesion of membrane switch materials is the tape test described by ASTM D3359-78, Method B.
  • ASTM D3359-78, Method B For films under 5 mils thickness, it requires that a 10 by 10 grid pattern be made with a sharp cutting instrument through the cured ink to the surface of the substrate.
  • a device for this purpose is available from the Gardner/Neotec Instrument Division of Pacific Scientific.
  • a pressure-sensitive tape, such as 3M Scotch® (10) Brand 810, is applied over the grid pattern and then removed with a continuous, nonjerking motion.
  • the adhesion is rated from 0B to 5B, the highest rating representing no ink removal.
  • polymeric inks need to be toughened so that the applied forces are absorbed or dissipated in the vicinity of the cuts and are thus prevented from traveling to the ink-substrate interface.
  • One way of doing this is to increase the degree of crosslinking. Yet this technique can be counterproductive in that the resulting composition may become too brittle for a touch switch ink.
  • Another method is to rubber-toughen the formulation with elastomeric inclusions, a technique widely used in epoxy chemistry.
  • rigid filler particles such as alumina, silica and glass spheres. Recent studies reported have combined these last two approaches in epoxy systems to give hybrid-particulate composites. In these systems dispersed rubbery particles enhance the extent of localized plastic shear deformations around the crack tip, while the rigid particles increase crack resistance by a crack-pinning mechanism.
  • the improved adhesion is attributed both to a rubber-toughening mechanism and to crack-pinning of the filler.
  • the rigid filler particles were found to contribute much less to the overall toughness (and, thus, adhesion) since the analogous compositions without the elastomeric inclusions give very poor crosshatch adhesion.
  • the invention is therefore directed to a novel UV-curable dielectric composition having excellent adhesion to a wide variety of polyester surfaces which contains both elastomeric and rigid fillers.
  • Such elastomeric fillers might be added to dielectric compositions in a variety of ways; for example, micron size core-shell polymers such as those disclosed by Burk in U.S. Patent 3,313,748 were blended with the dielectric. Another approach was to blend elastomeric polymers such as polyisoprene in the formulation. While both of these technical approaches were effective to some extent by far the most effective technique has been that of choosing monomers and oligomers which contribute both elastomeric and nonelastomeric character to the final composition.
  • rubber fillers are incorporated into the composition by means of both an acrylated rubber modified epoxy resin oligomer and acrylated polybutadiene oligomer.
  • the rheology of the system is then adjusted by the use of alkyl acrylates.
  • a mixture of mono- and di-functional alkyl acrylates is particularly preferred for this purpose.
  • the composition of the filler which can be used in the invention is quite critical. Only talc and mica have been found to be effective to attain the high degree of adhesion afforded by the composition of the invention.
  • inorganic fillers have been tested for use as an adhesion agent for the composition of the invention. (See Examples 3-14 infra.) However, the only materials which have been found to be generally effective are talc and mica.
  • talc and mica The purity of the talc and mica does not seem to be critical and ordinary commercial grades of these materials are satisfactory for use in the invention. Unlike talc which has a single theoretical chemical composition (3MgO.4SiO2.H2O), mica occurs as several different forms of aluminum silicate of which muscovite and phlogopite have appreciable commercial usage. Either of these is suitable for use in he invention. Mixtures of talc and mica can be used without disadvantage.
  • At least 25% wt. of the talc and/or mica are required to obtain the deisred level of adhesion for the compositions of the invention. However, more than about 35% wt. of these adhesive agents is detrimental in that the cured composition may become too inflexible.
  • the talc and mica used in accordance with the invention may be treated with a silane coupling agent to effect bonding of the filler to the organic polymer constituents of the liquid curable component. This mainly improves the aging qualities of the composition, especially under environmental stress conditions.
  • Typical silane coupling agents have the structure R-Si( ⁇ OR ⁇ )3 in which R is an organo functional group which reacts with the organic polymer and OR ⁇ is an hydrolyzable group which hydrolyzes to yield (R-Si( ⁇ OH)3 which condenses with -Si-OH groups on substrates to yield an -Si-O-Si-bond.
  • the various silanes contain different kinds of organofunctional groups.
  • Available silane coupling agents include amino-functional silane, methacrylate-functional cationic silane, polyamino-functional silane, mercapto-functional silane, vinyl-functional silane and chloroalkyl-functional silane.
  • An essential ingredient of the curable liquid component of the invention and the primary rubbery material is the acrylated rubber-modified epoxy resin oligomer.
  • These materials are prepared by reacting the epoxide moieties of a polyepoxide with the acid moieties of an unsaturated monocarboxylic acid and a liquid carboxyl-terminated homopolymer or copolymer of a conjugated diene. The preparation of these materials is described in US 3,892,819 to Najvar and in U.S. 3,928,491 to Waters.
  • a preferred oligomer of this type is the reaction product of a bisphenol A-derived epoxy resin with acrylic acid and a carboxyl-terminated butadiene/acrylonitrile copolymer.
  • the acrylated rubber-modified epoxy resin oligomer should constitute 20-50% wt. of the curable liquid component and preferably 35-45% wt.
  • a second essential ingredient of the curable liquid component (b) and the secondary rubbery material is the acrylated polydiene oligomer.
  • These materials are acrylates, normally diacrylates, of low molecular weight liquid conjugated diene/oligomers having a moleuclar weight of 2-4,000. A molecular weight of 3,000 has been particularly effective. Vinyl content of the oligomers is on the order of 15-30% wt., 20-25% wt. vinyl content being preferred. Acrylated oligomers of either butadiene or isoprene can be used in this application.
  • the polydiene oligomer should be 5-25% wt. of the curable liquid component (b) and is preferably used in a lesser amount than the epoxy resin oligomer. From 7 to 20% wt., preferably 7,5 to 15% wt. of the acrylated polydiene, particularly polybutadiene, is especially preferred.
  • Alkyl acrylates in some instances constitute a major part of the curable liquid component of the invention.
  • the alkyl acrylates must be liquid at room temperature. Both mono- and multi-functional acrylates can be used in the invention.
  • the amount of tri- and higher functionality acrylates must be limited to 10% wt. or less of the curable liquid component in order to avoid excessive crosslinking and shrinkage of the composition. It is therefore preferred to employ only mono- and di-functional liquid alkyl acrylates in an amount of 35-80% wt., preferably 35-75% wt. of the total curable liquid component. From 40 to 60% wt. is still further preferred.
  • Suitable alkyl acrylates include but are not limited to acrylates and the corresponding methacrylates listed below: allyl acrylate tetrahydrofurfuryl acrylate triethyleneglycol diacrylate ethyleneglycol diacrylate polyethyleneglycol diacrylate 1,3-butyleneglycol diacrylate 1,4-butanediol diacrylate diethyleneglycol diacrylate 1,6-hexanediol diacrylate neopentylglycol diacrylate 2-(2-ethoxyethoxy)ethyl acrylate tetraethyleneglycol diacrylate pentaerythritol tetraacrylate 2-phenoxyethyl acrylate ethoxylated bisphenol A diacrylate trimethylolpropane triacrylate glycidyl acrylate isodecyl acrylate dipentaerythritol monohydroxypenta acrylate pentaerythritol triacrylate 2-
  • momofunctional acrylates it is preferred that they be of higher molecular weight and therefore of lower volatility.
  • the alkyl moiety of the acrylate can be substituted with virtually any inert, organic group so long as the resultant acrylate remains liquid at room temperature and is miscible in the above-described acrylated polydiene oligomers.
  • a preferred alkyl acrylate combination is dicyclopentenyloxyethyl acrylate and tripropyleneglycol diacrylate. (See Examples 1 and 2).
  • composition of the invention may also contain various secondary materials to add to or enhance its properties such as elastomeric polymers, 0,1-10% wt. photoinitiator to render the compositon UV curable, up to 5% wt. inert pigments (soluble or insoluble) and 0,1-2,0% by weight various printing aids such as leveling agents, anti-foam agents and thickeners.
  • secondary materials such as elastomeric polymers, 0,1-10% wt. photoinitiator to render the compositon UV curable, up to 5% wt. inert pigments (soluble or insoluble) and 0,1-2,0% by weight various printing aids such as leveling agents, anti-foam agents and thickeners.
  • the %ual amounts of the additives are based on the total composition as claimed in Claim 1 of the present application.
  • compositions of the invention are not difficult to formulate in that simple low energy mixing is sufficient to facilitate solution. While it is necessary that the compositions form stable admixtures, it is not necessary that the compositions be completely soluble in each other. In fact, some immiscibility of these blends was anticipated, which, upon UV curing, would lead to microscopic phase separation and, hence, to a multiple phase structure.
  • Polyester film substrates employed for adhesion testing are commercially available 127 ⁇ m (5 mil) thick films. The several grades evaluated are specified in the examples.
  • the polyimide substrate is also commercially available 127 ⁇ m (5 mil) thick film sold under the tradename Kapton® (3) by the Du Pont Company.
  • the polycarbonate film is commercially available, 127 ⁇ m (5 mil) thick, from General Electric under the tradename Lexan® (4) .
  • the polymeric silver conductive ink is commercially available as product 5007 (9) from the Du Pont Company.
  • Adhesion results reported refer to crosshatch adheson run according to ASTM D3359-78, using Method B, in which a lattice pattern of 11 cuts in each direction is made in the dielectric to the substrate, pressure-sensitive tape is applied over the lattice and then removed, and the adhesion rated according to the degree of removal, according to he following scale:
  • Example 21 a composition was formulated identical to Example 1 except that the rigid filler was omitted altogether.
  • a UV curable mixture was made from 26.09% wt. of an acrylated rubber-modified epoxy resin, 7.34% wt. of an acrylated polybutadiene oligomer, 26.22% wt. of dicyclopentenyloxyethyl acrylate, 6.52% wt. of tripropyleneglycol diacrylate, 0.17% of a predispersed copper phthalocyanine pigment in trimethylolpropane triacrylate (20:80), 2.44% wt. of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.69% wt. of 2,2-diethoxyacetophenone, 0.53% wt. of a silicone printing aid, and 30.0% wt. talc. After printing and curing, this composition gave excellent crosshatch adhesion over a broad spectrum of substrates, as shown in Table II.
  • Example 1 is repeated, except that mica is used in place of talc. After printing and curing, this composition also gave excellent crosshatch adhesion over a broad spectrum of substrates, as shown in Table II.
  • Example 1 is repeated, except that talc is replaced by other filler candidates, as shown in Table II. These compositions do not show the excellent adhesion to a wide spectrum of substrates shown in Examples 1 and 2, in which talc and mica were used.
  • Example 1 is repeated, except that the acrylated rubber-modified epoxy resin is replaced by an acrylated epoxy resin. This composition does not show the excellent adhesion to a wide spectrum of substrates shown by Example 1.
  • Example 1 is repeated, except that the acrylated rubber-modified epoxy resin is replaced by an acrylated aromatic urethane resin. This composition does not shown the excellent adhesion to a wide spectrum of substrates shown by Example 1.
  • Example 1 is repeated, except that the acrylated polybutadiene oligomer is replaced by an equivalent amount of tripropylene glycol diacrylate. This composition does not show the excellent adhesion to a wide spectrum of substrates shown by Example 1.
  • Example 1 is repeated, except that the acrylated polybutadiene oligomer and the dicyclopentenyloxyethyl acrylate are both replaced by an equivalent amount of tripropylene glycol diacrylate. This compostion does not show the excellent adhesion to a wide spectrum of substrates shown by Example 1.
  • Example 1 is repeated, except that the dicyclopentenyloxyethyl acrylate is replaced by an equivalent amount of tripropylene glyco diacrylate. This composition does not show the excellent adhesion to a wide spectrum of substrates shown by Example 1.
  • Example 1 is repeated, except that the acrylated polybutadiene oligomer and the tripropylene glycol diacrylate are both replaced by dicyclopentenyloxyethyl acrylate. This composition does not show the excellent adhesion to a wide variety of substrates shown by Example 1.
  • Example 1 is repeated except that the talc was omitted from the composition. This composition did not shown adequate adhesion to the wide variety of substrates as did the corresonding talc containing compositions of Examples 1 and 2.
  • a UV curable mixture was made from 13.30% wt. of an acryalted rubber-modified epoxy resin, 13.23% wt. of an acrylated polybutadiene oligomer, 36.33% wt. of dicyclopentenyloxyethyl acrylate, 3.31% wt. of tripropyleneglycol diacrylate, 0.17% of a predispersed copper phthalocyanine pigment in trimethylolpropane triacrylate (20:80), 2.44% wt. of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.69% wt. of 2,2-diethoxyacetophenone, 0.53% wt. of a silicone printing aid, and 30.0% wt. talc. After printing and curing, this compostion gave excellent crosshatch adhesion over a broad spectrum of substrates, as shown in Table II.
  • a UV curable mixture was made from 38.94% wt. of an acrylated rubber-modified epoxy resin, 3.31% wt. of an acrylated polybutadiene oligomer, 14.23% wt. of dicyclopentenyloxyethyl acrylate, 9.73% wt. of tripropyleneglycol diacrylate, 0.17% of a predispersed copper phthalocyanine pigment in trimethylolpropane triacrylate (20:80), 2.44% wt. of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.69% wt. of 2,2-diethoxyacetophenone, 0.53% wt. of a silicone printing aid, and 30.0% wt. talc. After printing and curing, this composition did not give the excellent crosshatch adhesion over a broad spectrum of substrates, as shown in Table II.
  • a UV curable mixture was made from 38.94% wt. of an acrylated rubber-modified epoxy resin, 3.31% wt. of an acrylated polybutadiene oligomer, 10.72% wt. of dicyclopentenyloxyethyl acrylate, 13.23% wt. of tripropyleneglycol diacrylate, 0.17% of a predispersed copper phthalocyanine pigment in trimethylolpropane triacrylate (20:80), 2.44% wt. of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.69% wt. of 2,2-diethoxyacetophenone, 0.53% wt. of a silicone printing aid, and 30.0% wt. talc. After printing and curing, this composition also did not give excellent crosshatch adhesion over a broad spectrum of substrates, as shown in Table II.
  • Example 1 The composition of Example 1, which is the best mode of the invention, has quite excellent performance properties. These are shown in Table III which follows.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Epoxy Resins (AREA)
  • Switch Cases, Indication, And Locking (AREA)
  • Inorganic Insulating Materials (AREA)
  • Organic Insulating Materials (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (10)

  1. Druckfähige dielektrische Zusammensetzung, umfassend
    (a) 25-35 Gew.-% feine Teilchen eines anorganischen Haftmittels, ausgewählt aus Talkum, Glimmer und deren Mischungen, dispergiert in
    (b) 75-65 Gew.-% einer aushärtbaren flüssigen Zusammensetzung, umfassend:
    (1) 20-50 Gew.-° eines mit acryliertem Kautschuk modifizierten Epoxy-Harz-Oligomers;
    (2) 5-25 Gew.-% eines acrylierten Polydien-Oligomers; und
    (3) 35-75 Gew.-% Alkylacrylat, das bei Raumtemperatur flüssig sein muß.
  2. Druckfähige dielektrische Zusammensetzung, umfassend
    (a) 25-35 Gew.-% feine Teilchen eines anorganischen Haftmittels, ausgewählt aus Talkum, Glimmer und deren Mischungen, dispergiert in
    (b) 75-65 Gew.-% einer aushärtbaren flüssigen Zusammensetzung, umfassend:
    (1) 20-50 Gew.-% eines mit acryliertem Kautschuk modifizierten Epoxy-Harz-Oligomers;
    (2) 5-25 Gew.-% eines acrylierten Polydien-Oligomers;
    (3) 35-60 Gew.-% monofunktionelles Alkylacrylat; und
    (4) 5-15 Gew.-% difunktionelles Alkylacrylat,
    worin (3) und (4) bei Raumtemperatur flüssig sein müssen.
  3. Zusammensetzung nach Anspruch 2, worin die Mengen-Anteile der Komponenten in der aushärtbaren flüssigen Zusammensetzung die folgenden sind:
    (1) 35-45 Gew.-%;
    (2) 7,5-15 Gew.-%;
    (3) 35-45 Gew.-%; und
    (4) 7,5-15 Gew.-%.
  4. Zusammensetzung nach Anspruch 1, enthaltend bis zu 5 Gew.-% an inerten Pigmenten.
  5. Zusammensetzung nach Anspruch 1, die durch UV aushärtbar ist und 0,1 bis 10 Gew.-% eines Photoinitiators enthält.
  6. Zusammensetzung nach Anspruch 1, worin die anorganischen Teilchen mit einem Silan-Kupplungsmittel behandelt werden.
  7. Zusammensetzung nach Anspruch 1, zusätzlich enthaltend 0,1 bis 2,0 Gew.-% eines Druckhilfsmittels.
  8. Membran-Berührungsschalter, umfassend jeweils eine obere und eine untere biegsame Schicht mit einander zugewandten elektrisch leitfähigen Bereichen, die durch eine anhaftende Abstandshalter-Schicht der Zusammensetzung des Anspruchs 1 voneinander getrennt sind.
  9. Membran-Berührungsschalter, umfassend jeweils eine obere und eine untere biegsame Schicht mit einander zugewandten elektrisch leitfähigen Bereichen, die durch eine anhaftende Abstandshalter-Schicht von einander getrennt sind und aus dieser herausführende elektrisch leitfähige Spuren aufweisen, die im Inneren einer Schicht aus der Zusammensetzung des Anspruchs 1 verkapselt sind.
  10. Membran-Berührungsschalter, umfassend jeweils eine obere und eine untere biegsame Schicht aus einem dielektrischen Polymer, von denen wenigstens eine Schicht eine Mehrzahl einander überlagernder, elektrisch leitfähiger Bereiche aufweist, die jeweils durch eine Schicht der Zusammensetzung des Anspruchs 1 voneinander getrennt sind.
EP87114441A 1986-10-07 1987-10-03 UV-härtbare dielektrische Zusammensetzungen Expired - Lifetime EP0264037B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US91632986A 1986-10-07 1986-10-07
US916329 1986-10-07

Publications (3)

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EP0264037A2 EP0264037A2 (de) 1988-04-20
EP0264037A3 EP0264037A3 (en) 1990-03-07
EP0264037B1 true EP0264037B1 (de) 1993-01-20

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EP87114441A Expired - Lifetime EP0264037B1 (de) 1986-10-07 1987-10-03 UV-härtbare dielektrische Zusammensetzungen

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EP (1) EP0264037B1 (de)
JP (1) JPH0697569B2 (de)
KR (1) KR910001806B1 (de)
DE (1) DE3783703T2 (de)
DK (1) DK522887A (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100209819B1 (ko) * 1993-10-18 1999-07-15 사또 아끼오 광기록매체, 광기록매체의 표면에 프린팅하는 방법및 자외선경화형잉크
JP5662754B2 (ja) * 2010-09-28 2015-02-04 住友理工株式会社 誘電材料、その製造方法、それを用いたトランスデューサ

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US3892819A (en) * 1973-03-21 1975-07-01 Dow Chemical Co Impact resistant vinyl ester resin and process for making same
JPS54123160A (en) * 1978-03-17 1979-09-25 Ube Ind Ltd Photo-setting composition

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Publication number Publication date
DE3783703D1 (de) 1993-03-04
EP0264037A3 (en) 1990-03-07
EP0264037A2 (de) 1988-04-20
DK522887D0 (da) 1987-10-06
JPH0697569B2 (ja) 1994-11-30
KR880005639A (ko) 1988-06-29
DK522887A (da) 1988-04-08
JPS63105407A (ja) 1988-05-10
DE3783703T2 (de) 1993-06-24
KR910001806B1 (ko) 1991-03-26

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