WO1998026431A1

WO1998026431A1 - Cyclic olefin polymer composites having a high dielectric constant

Info

Publication number: WO1998026431A1
Application number: PCT/US1997/017960
Authority: WO
Inventors: Lak M. Walpita; William M. Pleban
Original assignee: Hoechst Celanese Corporation
Priority date: 1996-12-13
Filing date: 1997-10-06
Publication date: 1998-06-18

Abstract

Polymeric compositions having a high dielectric constant and low loss tangent are made from a cyclic olefin polymer, a ceramic having a high dielectric constant and a low loss tangent, and optionally an added reinforcing filler. The preferred ceramic is strontium titanate. The compositions have a dielectric constant of at least about 4. When mica, alumina, or magnesium titanate is used as an added reinforcing filler, the coefficient of thermal expansion diminishes significantly.

Description

CYCLIC OLEFIN POLYMER COMPOSITES HAVING A HIGH DIELECTRIC CONSTANT

Related Applications

The invention disclosed in this patent application is related to that disclosed in U.S. patent Applications No. 08/646,207, filed May 7, 1 996, and 08/563,801 , filed November 28, 1 995.

Field of the Invention

This invention relates generally to the field of materials having a high dielectric constant, and more particularly to composite materials comprising cyclic olefin polymer and ceramic fillers that have high dielectric constants and low loss tangents.

Background of the Invention

New materials with high dielectric constants and low loss tangents are needed in the electronics industry for use at high frequencies and as a means to enable further miniaturization. These materials are particularly useful if they can be made into thin films, sheets, plaques, and other molded shapes, so that they can be used as circuit boards at microwave frequencies, high energy density capacitors, filters, antennas, buried components, and multichip modules. These have a variety of end uses, as for example in wireless communications. Many ceramic materials have the desired high dielectric constant and low dielectric loss, but they are not readily made into thin films and sheets. Ceramic materials that have been fabricated into films and shaped articles are also generally brittle. One approach to making films and sheets with the desired properties is to utilize a composite comprising a polymeric matrix and a ceramic filler having a high dielectric constant. This approach is difficult because the composites need high levels of the ceramic filler in order to achieve the desired high dielectric constant while retaining rheological properties that make the composites suitable for extrusion or molding. The composites must also be stable to changes in ambient moisture (humidity) and temperature. Resistance to elevated temperatures, as well as high mechanical strength, impact resistance and chemical resistance are also all desirable. Finally, in many applications, flat substrates made from these materials will need to be made into laminates with copper and/or other materials. Several high dielectric constant materials based on polymers combined with ceramics are known. For example, numerous patents are assigned to Rogers Corporation that teach composites of fluoropolymers, preferably poly(tetrafluoroethylene) (PTFE), and ceramic materials for use as high dielectric materials, as for example U.S. Patent No. 4,335, 1 80, 5,358,775 and 5,552,210. Rogers Corporation sells a composite of PTFE and a ceramic filler for use as a high dielectric film. However, it is generally difficult to make thin films and other shaped articles of PTFE containing a filler.

Other examples of high dielectric composite materials are disclosed in U.S. Patent No. 5, 1 54,973, which describes generally composites that can be based on any of several different polymers and any of several different ceramic materials. German patent publication DE 3,242,657, describes a composite of BaTiθ3 in poly(ethylene terephthalate). Japanese patent publication JP 5,307,91 1 describes the utility of using a metal-coated ceramic powder (e.g. BaTiOs) in an epoxy substrate. The metal coating increases the permittivity (dielectric strength). Japanese patent publication JP 57,853 describes composites of poly(phenylene oxide) and TiO₂. Finally, Japanese patent publication JP 98,069 discloses composites of BaTiO3 in polyphenylene sulfide; a low molecular weight heat resistant oil is added to the polymer composite to improve its processability in the melt. A high dielectric composite in which the matrix polymer is an epoxy resin based on bisphenol F epoxy and an organic amino curing agent and in which the filler is barium titanate at a 34 volume % level has been described (S. Asai, et al., IEEE Transactions on Components, Hybrids and Manufacturing Technology, Vol. 1 6, No. 5, August, 1 993, pp. 499-504). This composite was easy to process before the epoxy resins set because of the low viscosity of the epoxy prepolymer, and dielectric constants up to about 20 and loss tangents of about 0.01 65 - 0.0173 were observed with this composite.

Finally composites based on polyphenylene sulfide and ceramic fillers is disclosed in pending, commonly assigned U. S. patent application, Serial No. 08/, filed.

High dielectric constant/low loss tangent composites have now been found that utilize a thermoplastic polymer and a filler, and that are easy to fabricate without complex processing.

Summary of the Invention

Polymeric compositions having a high dielectric constant are made by combining a cyclic olefin polymer and a ceramic having a high dielectric constant. The ceramic is one or more of the following: strontium titanate (SrTiθ3), barium neodymium titanate, or barium strontium titanate/magnesium zirconate. The ceramic is included in an amount that is sufficient to yield a composition that has a dielectric constant of at least about 4.0 at 1 GHz of frequency. These polymeric compositions are useful for making electronic components, such as antennas, for use at high frequencies because the composites have both a high dielectric constant and a low loss tangent. Objects from these composites also have very low Coefficient of Thermal Expansion ("CTE") .

Laminates that have a high dielectric constant and low loss tangent may also be made from these compositions. Such laminates include at least one flat substrate of the polymeric composition described above, which contains a cyclic olefin polymer and one or more of SrTiOs, barium neodymium titanate, or barium strontium titanate/magnesium zirconate. For example, a layer of copper or other metal may be laminated or coated onto one or both sides of the sheet of the polymeric composition by a suitable process, resulting in a laminated structure which has a dielectric constant of at least about 4.0 at a frequency of 1 .0 GHz.

A method of making a laminate that has a high dielectric constant includes the following steps:

(a) compounding a cyclic olefin polymer and a sufficient amount of one or more ceramics selected from the group consisting of strontium titanate, barium neodymium titanate, and barium strontium titanate/magnesium zirconate to yield a polymeric composition having a dielectric constant of at least about 4.0 at a frequency of 1 .0 GHz; (b) shaping the polymeric composition into a flat substrate; and (c) applying copper or other metal onto one or both surfaces of the substrate to yield a laminated structure. By "shaping" is meant any process for making a polymer into a fabricated product, such as a sheet, film or three-dimensional object. Such processes include extrusion, injection molding, calendaring, compression molding, and the like.

The polymeric compositions described above may optionally also include other fillers, which are included as reinforcing fillers or for other purposes, such as for lubrication for molding or to modify the electrical properties. Fillers that are preferred include glass fiber, mica, alumina, magnesium titanate, calcium titanate and titanium dioxide. For example, mica leads to improved physical properties and also further reduces the coefficient of thermal expansion, resulting in reduced warpage in laminates made using these compositions. Mica reduces the CTE in the plane of a flat substrate or laminate, and to a lesser extent, reduces the CTE perpendicular to the plane.

Detailed Description of the Invention

The combination of a suitable cyclic olefin polymer and one or more of the ceramics from the group that includes SrTiθ3, barium neodymium titanate, and barium strontium titanate/magnesium zirconate yields a composition that is excellent for making substrates having a high dielectric constant for use in electronic circuits at high frequencies (above about 500 MHz) . High dielectric constant is useful for further miniaturization of the circuits. The loss tangent (also known as dielectric loss, dielectric loss factor, or dissipation factor) is low, which is beneficial and often necessary to reduce noise and to minimize signal loss. In fact, the loss tangents obtained on some of these compositions are lower than those for most other polymeric composites. The compositions comprising a cyclic olefin polymer and a ceramic or other filler having a high dielectric constant are also referred to herein as "high dielectric composites" and "high dielectric constant composites". Cyclic olefin polymers are well known materials. They may be homopolymers or copolymers of cyclic olefin monomers such as, for example, norbornene, tetracyclododecene, bicyclo[2,2, 1 ]hept-2-ene, 1 -methylbicyclo[2,2, 1 ]hept-2-ene, hexacyclo[6,6, 1 ,1³'⁶,1 ¹⁰'¹³,0²'⁷,0⁹ ]-4-heptadecene, and the like. If it is a copolymer, preferably the comonomer is an acyclic olefin such as, for example, ethylene, propylene, butylene, pentene isomers and the like. Many such suitable cyclic olefin copolymers ("COC") are known. They are described, for example, in U.S. Patents 5,087,677; U. S. 5,422,409; 5,324,801 ; 5,331 ,057; 4,943,61 1 ; 5,304,596 and EP 608903. An illustrative COC composition useful in the practice of this invention is a copolymer of norbornene and ethylene described in the above-mentioned U.S. patent 5,087,677. It is also commercially available under the trade name TOPAS^® from Hoechst Celanese Corporation, Somerville, New Jersey. The three preferred ceramic materials that are blended with the cyclic olefin polymer are all commercially available or readily synthesized by methods known in the art. For example, the metal titanates can be made by sintering the metal oxides (e.g., oxides of Sr, Ba, Nd, Zr and/or Mg) and Ti0₂ in the stoichiometric ratio needed to obtain the desired product. See for example "Ceramic Dielectrics And Capacitors," by J.M. Herbert, Gordon and Breach Science Publishers, New York, 1 985, for more details on synthetic methods. The ratio of Ba and Nd, or Mg, Ba, Zr and Sr, in the mixed metal titanates can be optimized to achieve the desired loss tangent and dielectric constant. Strontium titanate is available from several manufacturers. Strontium titanate and barium neodymium titanate are both available from Tarn Ceramics, Niagara Falls, NY, and are sold as TICON™55 and COG900MW respectively. The commercial barium neodymium titanate has a Ba:Nd atomic ratio of about 1 , with a small amount of Bi ( < 10% compared with Ba or Nd) and enough Ti to balance the titanate stoichiometry. This material has a dielectric constant of about 92 and a loss tangent of about 0.001 at 1 .0 GHz. A preferred barium strontium titanate/magnesium zirconate can be made by sintering about 68% by weight BaTiθ3, about 28% by weight SrTiθ3, and about 3% MgZrθ3, or by sintering a mixture of the oxides.

Strontium titanate (SrTiOs) is the preferred high dielectric ceramic. It is readily compounded with the cyclic olefin polymer to yield high dielectric compositions that are readily fabricated into shaped articles by such conventional methods as injection molding and extrusion of films or sheets. It is preferably used as a powder having an average particle size in the range of about 0.2 microns to about 10 microns, preferably about 1 to about 2 microns. Larger or smaller particle sizes can also be used, depending on the size and shape of the article to be fabricated. The electrical properties are easily fine-tuned for specific applications by adjusting the amount of SrTiU3. The loss tangent is low at all levels of SrTiθ3, generally not exceeding 0.003 at a frequency of 1 .0 GHz. In fact in some samples it is as low as 0.0005 at 1 GHz, which appears to be a surprisingly very low number for a polymer-based composition. Furthermore, because of the ease of mixing and injection molding these compositions, specific compositions can be made that give reproducible dielectric constants. Thus, for example, a composition containing about 30% of SrTiθ3 in a cyclic olefin polymer on a volume basis has a dielectric constant of about 7.44. The concentration of the SrTiOs in cyclic olefin polymer for any application depends on the desired dielectric constant, with concentrations typically ranging from about 10% to about 70% , on a volume basis, with preferred ranges being about 20% to about 70% , or about 30% to about 70% , depending on the specific application. Thus, compositions having a dielectric constant of at least about 6, at least about 10, or other values are readily made for specific applications.

The composites of ceramics (e.g. SrTiOs) and the cyclic olefin polymer have good tensile properties, because the ceramic filler acts as a reinforcing filler. However, other fillers, such as glass fiber, can also be added to further reinforce the filled cyclic olefin polymer or for other purposes, such as lubrication for molding or to modify the electrical properties. These fillers are added at levels such that the cyclic olefin polymer has a total content of fillers, including the ceramic, in the range of about 10% to about 70% by volume. When other fillers are included with the high dielectric ceramic (e.g. SrTiO3>, the ceramic may be used at a level of as low as about 2% by volume.

Solid or reinforcing fillers that may be used include carbon, wollastonite, mica, talc, silicates, silica, clay. poly(tetrafluoroethylene), thermotropic liquid crystalline polymer, polyphenylene sulfide, alumina, glass, rock wool, silicon carbide, diamond, fused quartz, aluminum nitride, beryllium oxide, boron nitride, and magnesium titanate, all in either particle or fiber form, including mixtures of more than one filler. Antioxidants, mold lubricants, and sizing and coupling agents may also be added. The use of some of these other additives (e.g. carbon) may be limited by their detrimental effect on the loss tangent or dielectric constant. Glass fiber is a desirable filler for obtaining further reinforcement. Mica, magnesium titanate, and alumina are preferred for applications in which a low coefficient of thermal expansion and low temperature coefficient of dielectric constant are desired such as, for example, laminates.

The high dielectric polymer compositions are made by standard methods for making compounds of polymers and fillers. These methods typically involve mixing the filler and polymer at a temperature high enough to melt the polymer. Compounding of the polymer and ceramic filler in a twin screw extruder is the preferred method. The polymeric compositions may be readily made into shaped articles such as, for example, films, sheets, plaques, discs, and other flat shapes which are particularly useful as substrates in electronics (e.g. printed circuit boards) . Three dimensional shapes may also be made. The polymers may be shaped by many processes, such as extrusion, injection molding, and compression molding. Films and sheets typically may be made by injection molding or extrusion processes. Such techniques are well known to those skilled in the art. Laminates having a high dielectric constant and low loss tangent may also be readily made from these polymer compositions. Such laminates are particularly useful in making rf circuits, such as antennas, filters, couplers, splitters, and the like. The metal may be laminated onto the filled cyclic olefin polymer sheet by the use of an adhesive or by heating the polymer composition to the melt temperature while the metal film or foil is pressed against the polymeric sheet. Alternatively, the metal film or foil may be laminated onto a freshly extruded sheet of the polymer composition while the sheet is still in a molten or softened state by co-feeding the metal film or foil with the polymer composition sheet as it emerges from the die of the extruder and passing the metal film or foil and polymer sheet through an apparatus that applies pressure, such as a set of rollers. Another method of making a laminate directly from molten polymer is to place the metal film or foil against the inner walls of a mold and then feed molten polymer composition into the mold under pressure in an injection molding process. The pressure of the molding process results in a laminate with good adhesion after the polymer cools and hardens. The preferred method is application of the metal foil or film under heat and pressure to a preformed polymer substrate. Such methods are well known to those skilled in the art. The dielectric laminates may be stacked and interconnected so that multiple layers are present. The layers may have different dielectric constants and different thickness, to form substrates for multichip modules and circuit boards.

As stated previously, the cyclic olefin polymer and the high dielectric constant ceramic filler may be compounded with mica, alumina, and/or magnesium titanate filler. Such compounding may be done in the melt phase, in either one step or two steps (i.e. sequentially) . A twin screw extruder is preferred. Compounding of mica and/or alumina and the high dielectric ceramic with the polymer at the same time is the simplest and most economical method and is preferred. The mica and/or alumina and high dielectric constant ceramic filler (e.g. SrTiOs) are typically included in combined amounts in the range of about 10% to about 70% by volume, with the amount of high dielectric ceramic being as low as about 2% by volume.

The high dielectric composites and laminates formed therefrom have many uses. Some of them are, for example, in printed circuit boards that are useable at microwave frequencies, high energy density capacitors, filters, antennas, buried components, and multichip modules. An application for which these materials are particularly useful is printed circuit antennas, such as microstrip, dipole, and patch antennas, for wireless equipment. These kinds of antennas are typically flat because the substrate is a ceramic, and their emitted signals and response to received signals are therefore directional. These materials may easily be made in curved or other shaped forms so that the directionality of the antenna response (either transmitting or receiving) can be modified as desired. Other applications include printed (stripline or microstrip) rf and microwave circuit elements, such as transmission lines, inductors, capacitors, filters, (e.g. low pass filters, high pass filters, band pass filters, and band stop filters), signal couplers, branch line couplers, power splitters, signal splitters, impedance transformers, half wave and quarter wave transformers, and impedance matching circuits.

The invention is further illustrated by the following non-limiting examples. Examples

Example 1. Composite of a cyclic olefin copolymer and strontium titanate: In a Brabender twin screw extruder, TOPAS™ brand COC (from Hoechst Celanese Corporation; 70% by volume) and TITCON55™ strontium titanate, purchased from Tarn Ceramics, Inc., 451 1 Hyde Park Boulevard, Niagara Falls, NY 14305 (average particle size: 1 -2μm as measured using a Fisher sub-sieve sizer; 30% by volume) were compounded for about 5 minutes and then extruded. The die temperature of the extruder was 280° C and the screw speed was 1 50 rpm. The compounded product was extruded into water and then pelletized. The pellets were then injection molded into 1 /16 inch thick, 3 inch squares, as well as 1 /8 inch thick 2.5 inch diameter discs, using a BOY30M injection molding machine (from Dr. BOY-GMBH, Fernthal, Germany) at the melt temperature of 280-290° C. The dielectric constant and loss tangent of the discs were measured at 1 GHz by the Resonant Cavity Perturbation Method, according to ASTM D2520, Test Method B. The electric field inside the cavity was parallel to the length of the test sample. The dielectric constant and loss tangent of the composition was 7.44 and 0.0005 respectively. This value for loss tangent is surprisingly and uniquely low for polymer compositions.

In order to determine the CTE, thermomechanical analysis ("TMA") was used. TMA was run using a Perkin-Elmer 7 Series Thermal Analysis System. Expansion (in mm) was plotted against temperature (in °C) as the sample was heated. CTE was determined from the slope of the TMA traces between 30°C and the T_g of the COC (around 175°C). The CTE in that temperature range was found to be about 3.826 x 10^~5 mm/(mm»K). This is a substantially low number, as will be obvious to those skilled in the art.

Example 2. Composite of a cyclic olefin copolymer, mica and strontium titanate: A composition containing TOPAS brand COC (60% by volume), mica (32% by volume) and TICON55^™ strontium titanate (8% by volume) were mixed in a HBI 90 Mixer (a Haake Buckler Company product) at 280°C, and 100 rpm over 10 minutes. The mica was the L-140 brand mica from KMG Minerals, Inc., Kings Mountain, North Carolina 28086. The mica was in the form of platelets having an average particle size of about 70 μm. Discs (1 /8 inch thick and 2 inch diameter) were made by compression molding in a TMP^™ vacuum press made by Technical machine Products, Cleveland, Ohio, at 203° C. The dielectric constant and loss tangent of the disc was measured at 2 GHz by the ASTM method described above, over a temperature range -20 to 100°C. There was virtually no variation in the dielectric constant over that temperature range within experimental error. Dielectric constant was found to be between 4.45 and 4.48.

It is to be understood that the above-described embodiments of the invention are illustrative only and that modification throughout may occur to one skilled in the art. Accordingly, this invention is not to be regarded as limited to the embodiments described herein.

Claims

ClaimsWhat is claimed is:

1 . A polymeric composition having high dielectric constant comprising a cyclic olefin polymer and a high dielectric ceramic wherein said high dielectric ceramic is selected from the group consisting of SrTiU3, barium neodymium titanate, and barium strontium titanate/magnesium zirconate, and further wherein said high dielectric ceramic is present in sufficient quantity such that said composition has a dielectric constant of at least about 4.0 at a frequency of 1 .0 Ghz.

2. The polymeric composition recited in Claim 1 , wherein said composition has a loss tangent of not more than about 0.003 at a frequency of 1 GHz.

3. The polymeric composition recited in Claim 1 , wherein said composition has a loss tangent of not more than about 0.002 at a frequency of 1 GHz.

4. The polymeric composition recited in Claim 1 , wherein said composition has a loss tangent of not more than about 0.001 at a frequency of 1 GHz.

5. The polymeric composition recited in Claim 1 , wherein said high dielectric ceramic is present in an amount of about 10% to about 70% by volume.

6. The polymeric composition recited in Claim 1 , wherein said high dielectric ceramic is SrTiU3.

7. The polymeric composition recited in Claim 1 , wherein said high dielectric ceramic is barium neodymium titanate.

8. The polymeric composition recited in Claim 1 , wherein said cyclic olefin polymer is a homopolymer of a cyclic olefin monomer.

9. The polymeric composition recited in Claim 1 , wherein said cyclic olefin polymer is a copolymer of a cyclic olefin monomer and an acyclic olefin.

10. The polymeric composition recited in Claim 8 or 9, wherein said cyclic olefin monomer is selected from the group consisting of norbornene, tetracyclododecene, bicyclo[2,2, 1 ]hept-2-ene, 1 - methylbicyclo[2,2,1 ]hept-2-ene and hexacyclo[6,6,1 , 1³'⁶, 1 ¹⁰'¹³,0²'⁷,0⁹'¹⁴]-4-heptadecene.

1 1 . The polymeric composition recited in claim 10, wherein said cyclic olefin monomer is norbornene.

1 2. The polymeric composition of Claim 9, wherein said acyclic olefin is selected from the group consisting of ethylene, propylene, butylene and pentene.

13. The polymeric composition recited in Claim 1 2, wherein said acyclic olefin is ethylene.

14. The polymeric composition recited in Claim 9, wherein said copolymer is a copolymer of norbornene and ethylene.

1 5. The polymeric composition recited in Claim 1 , wherein said composition further comprises a solid or reinforcing filler.

1 6. The polymeric composition recited in Claim 1 5, wherein said solid or reinforcing filler is selected from the group consisting of carbon, wollastonite, mica, talc, silicates, silica, clay, poly(tetrafluoroethylene), thermotropic liquid crystal polymer, polyphenylene sulfide, alumina, glass, rock wool, silicon carbide, diamond, fused quartz, aluminum nitride, beryllium oxide, boron nitride, magnesium titanate, calcium titinate, titinium dioxide and mixtures thereof, wherein said fillers are particles, fibers, or mixtures thereof.

17. The polymeric composition recited in Claim 1 5, wherein said ceramic and said solid or reinforcing filler together comprise about 10% to about 70% by volume of said composition.

18. The polymeric composition recited in Claim 1 6, wherein said solid or reinforcing filler is mica.

1 9. A high dielectric constant laminate comprising:

(a) a flat substrate comprising a polymeric composition having a high dielectric constant, said substrate having two surfaces, said polymeric composition comprising a cyclic olefin polymer and a high dielectric ceramic selected from the group consisting of SrTiO3, barium neodymium titanate, and barium strontium titanate/magnesium zirconate; and

(b) at least one layer of metal adhering to at least one surface of said substrate; wherein said laminate has a dielectric constant of at least about 4.0 at 1 .0 GHz frequency.

20. A high dielectric laminate as recited in Claim 1 9, wherein said metal is copper.

21 . A high dielectric constant laminate as recited in Claim 1 9, wherein said high dielectric ceramic is SrTiO3.

22. A high dielectric constant laminate as recited in Claim 1 9, said laminate having a loss tangent of not more than about 0.003 at a frequency of 1 GHz.

23. A high dielectric constant laminate as recited in Claim 1 9, wherein said polymeric composition having a high dielectric constant comprises SrTiU3 at a level of about 10% to about 70% by volume.

24. A high dielectric constant laminate as recited in Claim 1 9, wherein said polymeric composition also comprises a solid or reinforcing filler selected from the group consisting of carbon, wollastonite, mica, talc, silicates, silica, clay, poly(tetrafluoroethylene), thermotropic liquid crystal polymer, polyphenylene sulfide, alumina, glass, rock wool, silicon carbide. diamond, fused quartz, aluminum nitride, beryllium oxide, boron nitride, magnesium titanate, calcium titanate, titanium dioxide and mixtures thereof, wherein said fillers are particles, fibers, or mixtures thereof.

25. A high dielectric constant laminate as recited in Claim 24, wherein said solid or reinforcing filler is mica.

26. A high dielectric constant laminate as recited in Claim 19, said laminate comprising said substrate and two layers of copper, wherein one layer of copper adheres to each of said surfaces of said substrate, said polymeric composition comprising about 90% to about 30% by volume of a cyclic olefin polymer and about 10% to about 70% by volume of SrTiθ3 and an optional solid or reinforcing filler, selected from the group consisting of carbon, wollastonite, mica, talc, silicates, silica, clay, poly(tetrafluoroethylene), thermotropic liquid crystal polymer, polyphenylene sulfide, alumina, glass, rock wool, silicon carbide, diamond, fused quartz, aluminum nitride, beryllium oxide, boron nitride, magnesium titanate, calcium titanate, titanium dioxide and mixtures thereof, wherein said fillers are particles, fibers, or mixtures thereof, said high dielectric constant laminate having a dielectric constant of at least about 4.0 at a frequency of 1 GHz and a loss tangent of not more than about 0.003 at a frequency of 1 GHz.

27. A high dielectric constant laminate as recited in Claim 27, wherein said solid or reinforcing filler is selected from the group consisting of mica, alumina, magnesium titanate, and mixtures thereof.

28. A method of making a laminate having a high dielectric constant, comprising the steps of:

(a) compounding a cyclic olefin polymer, an optional solid or reinforcing filler, and a sufficient amount of a ceramic having a high dielectric constant selected from the group consisting of SrTiθ3, barium neodymium titanate, and barium strontium titanate/magnesium zirconate to yield a polymeric composition having a dielectric constant of at least about 4.0 at 1 GHz; (b) shaping said polymeric composition into a flat substrate, said substrate having two surfaces; and

(c) applying metal to one or both surfaces of said substrate.

29. The method as recited in Claim 28, wherein said ceramic having a high dielectric constant is SrTiOs, said metal is copper, and said optional solid or reinforcing filler is selected from the group consisting of carbon, wollastonite, mica, talc, silicates, silica, clay, poly(tetrafluoroethylene), thermotropic liquid crystal polymer, polyphenylene sulfide, alumina, glass, rock wool, silicon carbide, diamond, fused quartz, aluminum nitride, beryllium oxide, boron nitride, magnesium titanate, calcium titanate, titanium dioxide and mixtures thereof, wherein said fillers are particles, fibers, or mixtures thereof.

30. The method as recited in Claim 30, wherein about 10% to about 70% by volume of SrTiU3 and said optional solid or reinforcing filler, and about 90% to about 30% by volume of cyclic olefin polymer, are compounded to yield a polymeric composition having a dielectric constant of at least about 4.0 at a frequency of 1 GHz.