JP2000506305A - Thermoplastic elastomer substrate material with tunable dielectric properties and laminates thereof - Google Patents

Abstract

(57) Abstract: A thermoplastic elastomer that can be prepared to have a wide range of dielectric properties according to the needs of individual applications. The material of the present invention is preferably provided in the form of a film, which can be combined with metal layers, supplemental dielectric layers, or other circuit structures to form a laminated structure having desired dielectric properties. is there.

Description

DETAILED DESCRIPTION OF THE INVENTION Thermoplastic elastomer substrate material with tunable dielectric properties and laminates thereof Technical field   The present invention relates to a substrate or a laminated product that can be used as a mount in an electronic device. About. More particularly, the present invention relates to a thermoplastic air-conditioning device having tunable dielectric properties. It relates to a lastomer substrate material or a laminated material. More specifically, the requirements for each application Can be formulated to have a wide range of dielectric constants as desired, preferably It is a thermoplastic elastomer with low dielectric loss. Preferably containing polypropylene And a loss tangent of less than about 0.005, most preferably Preferably less than about 0.003 ethylene-propylene-diene monomer (EPDM) The thermoplastic elastomer material of the present invention having an elastomer component containing , A film or a laminated structure. Background art   Substrate materials for mounting many electronic devices with specific electrical properties are known in the art. It is well known and widely used in many different types of electronic equipment. For example, product Layered products are mainly suitable for substrates such as printed circuits, and conventionally consist of resin-impregnated sheets. , Which are cut into slices or panels and superimposed into layers. Heat this layer And press together to form a solid unit. One side of the laminate obtained in this way Or cover both sides by laminating a metal material, or by a well-known adhesion method. Or to provide a metal layer.   A wide range of polymeric materials are used as substrate or laminate materials in electronic applications. And a great deal of information on its properties is known. For example, Bridson,Plastic s Materials , 4th Edition, 1985, pp. 100-110. These polymers The material is an electrical insulator, i.e., withstands the potential difference between different points of a given piece of material. And only a small current passes, and the wasted energy is low. Polymer material The effect of a capacitor on the capacitance of a capacitor is known as the dielectric constant and is Now it is especially important. Dielectric constant of material ε_rUsed the given material as a dielectric The capacitance of the capacitor and the capacitance of the same capacitor without dielectric It is defined as the ratio of pacitance.   When a polymer material is put into an electric field, its dielectric constant is determined by electronic polarization within its molecular structure. It depends on both the action and the dipole polarization action with neighboring molecules. But Thus, a symmetric or non-polar molecule that experiences only electronic polarization is an electron component. Lower dielectric constant than polar molecules under the influence of both polarization and dipole polarization . Dipolar polarization involves the movement of part or all of a molecule, and thus induces polar molecules. Electrical conductivity depends on the material's "intrinsic viscosity", i.e., the out-of-tune behavior of the dipole .   When a dielectric material is placed in an alternating electric field, its inherent viscosity Losses also occur. This loss was absorbed by the dielectric from the electric field per cycle It is measured as a ratio of energy. The power factor and dielectric loss tangent are By taking into account the delay between the change in activation, which, in turn, When present, the current in the capacitor that induces a potential difference across the capacitor It goes. The angle of induction is called the phase angle Θ, and the term 90-Θ is known as the dielectric loss angle. Have been. The dielectric loss tangent for each material, ie The loss tangent is tan δ.   An important first step in designing electronics to absorb or transmit energy is the The purpose is to select a material for the circuit board. No ideal substrate, no material selected Will depend on the properties required for the intended application. The most important properties of the individual materials are Within its chosen temperature and frequency operating device, its dielectric constant (ε_r) And the loss tangent (tan δ). In general, low loss tangent indicates good energy transfer In short, such materials are useful for designing electronic devices such as antennas. Conversely, Microwave or radar absorbers use dielectric materials with much higher loss tangents. I need. High dielectric constant for low frequency low loss applications such as tapered slot antennas While materials are required, patch antennas require low loss, low dielectric constant materials. dielectric By choosing a material with a low rate, the band of the microstrip patch antenna can be Bandwidth and efficiency can also be increased.   However, the dielectric properties of polymer materials should be considered when designing electronic substrates Not the only problem. Dimensional stability, resistance to temperature, humidity and aging Properties, resistance to chemicals, tensile and structural strength, flexibility, machinability , Impact resistance, strain relief, integrity, adhesion and compliance to cladding, etc. Also, processing considerations are important.   In microstrip antennas, the dielectric properties of the substrate, especially the low loss tangent, are important. is there. Radiator, transmission line feed, microstrip antenna The structure is well known (eg, Bahl et al.,Microstrip Antennas， Artech Hous e, 1980, Pozar and Shaubert, eds.,Microstrip Antennas-The Analysis and D esign of Microstrip Antennas and Arrays , IEEE Press 1995) . In its simplest form, a microstrip patch antenna (MPA) Molded metal fed at one of its edges by a complete microstrip transmission line It may be a metal conductor. This molded transmission line / radiator structure is generally a dielectric Substantially less than 1/4 wavelength at the intended operating frequency of the sheet or antenna (typically A little above the ground plane by a layer that is approximately one-tenth the wavelength or less). Be held. The resonance dimension of the molded radiator patch is generally half the wavelength Selected and therefore the opposite edge (eg, across the feed line) and the underlying contact A pair of radiating slots is provided between the base plate and the base plate. Horizontal or non-radiating dimensions are common And, to some extent, as a function of the desired radiated power. Non-resonant dimension is about 1 wavelength Or more, for example, with a shared feed structure network, It is possible to provide a feed point. Microstrip patch antennas A number of patents and publications, for example, U.S. Pat. No. 4,884 to Shibata et al. 7,089, U.S. Patent No. 5,055,854 to Gustafasson, Aoy U.S. Pat. No. 4,963,891 to agi et al .; U.S. Pat. No. 5,070,340, and Tarot, et al.,New Thechnology to Realize Printed Radiating Elements , Microwave and Optical Technology Letters, v ol. 9, no. 1, May 1995.   In addition to MPA, other types of microstrip antennas include microstrip antennas. There is a lip traveling wave antenna, which is a chain periodic waveguide on a substrate lined with a ground plate. Consists of a body. Microstrip slot antenna is microstrip feeder Include slot cuts in the ground plane perpendicular to the strip conductors of the road.   Desirable antenna features can be obtained with a single microstrip element as described above. High gain, beam scanning, or steering capability can be By combining and arranging the data Can be acquired. Microstrip antenna arrays, for example, Will US Patent No. 4,173,019 to iams and rice granted to Shoemaker Including US Patent No. 4,914,445 and US Patent No. 4,937,585. And many references cited herein.   Use a wide variety of materials as dielectrics for microstrip antennas (Eg, Bahl, et al.,Microstrip Antennas, Pages 317-327 and And references cited in the specification of the present application, Carver and Mink,Microstrip Antenn a Technology , IEEE Trans. Antennas Propaga, vol. AP-29, no. 1,2-24 pages , Jan. 1981). Typical substrate material is polytetrafluoroethylene (PTFE), crystalline materials such as polystyrene, polyethylene and polypropylene Thermoplastic, silicone, polyphenylene oxide (POP), polyester, polyester May contain imides, mica, fiberglass, alumina and beryllia .   After choosing the dielectric material for your particular application, use it to manufacture printed circuit boards. A conventional microstrip antenna can be fabricated by a photochemical etching method It is possible to form the tena structure conveniently. Opposite thin layers of conductive metal, such as copper From the laminate in which the dielectric sheet material attached to the side is the simplest form, the micros A trip antenna assembly is formed. Normally, one conductive layer of the laminate is grounded Form a plate and apply conductive material to the opposite layer by chemical etching or a similar method. Very thin microstrip as a molded conductive patch on a dielectric sheet. Rip radiator and interconnected transmission wiring structure can be formed is there. U.S. Patent No. 4,914,445 to Shoemaker et al .; US Patent No. 4,937,585 to Klaar et al. U.S. Pat. No. 4,833,005 discloses a laminated product for a microstrip antenna. Are described.   As reported in U.S. Patent No. 4,816,836 to Lalezari Effective microstrip antenna laminate structure conforms to curved surfaces, and Must be able to be installed. Microstrip antennas for airplanes Often mounted on curved outer surfaces such as missiles, shells, etc. When mounted on a surface, presence is less noticeable and turbulence is reduced. Generally, the mounting surface is convex Due to its shape, simply deform the antenna assembly and attach directly to the bay Let When the antenna is bent around a small radius curve, the outer convex surface is substantially tight. Must be stretched under tension, so that inflexible materials can crack. You. These cracks eventually lead to deformation and tearing of the copper antenna element, resulting in The antenna is dismantled. The cracks can form in rigid crystalline polymeric materials and foams. This is especially the case.   Lalezari's literature includes antennas, including multilayer PTFE and fiberglass substrates. A method for mounting the antenna and the antenna on a curved surface is described. Described in this patent The antenna structure is a relatively thin dielectric substrate with antenna elements on the surface And a second relatively thin dielectric substrate. As shown in Figure 2 of the Lalezari patent As described above, in order to attach the antenna structure to the bay surface, a thin dielectric substrate material 4 is required. 1b must first be attached to the bay surface as a spacer. Next, yo A thin first dielectric substrate 41a is attached to the spacer 41b. Recorded in Lalezari Due to the method described, PTFE dielectric substrates lack the integrity required for many applications You can see that. In addition, multilayer structures are expensive and difficult to manufacture.   Another desirable feature of antenna dielectric materials is weather resistance. above As a rule, microstrip antennas are generally located on exterior surfaces that are exposed to harsh climatic conditions. Mounting allows the dielectric layer to absorb moisture and poor thermal stability over the operating temperature range Otherwise, antenna characteristics can be significantly affected. Liquid water Very high dielectric constant, antenna is marked by water absorption by foamed dielectric substrate material The tuning is out of order, and finally the substrate is deformed. Conventional foam material absorbs moisture easily The impact resistance is extremely poor, which makes it a desirable antenna substrate or laminated product layer. Maturity is limited.   If weather resistance and toughness are issues, use PTFE as a dielectric substrate suitable for antenna applications. The choice of material is well known to those skilled in the art. PTFE to ceramic or It is also possible to reinforced with glass fibers or to form a fabric laminate. above As such, for some applications, this material is not well suited. PTFE is difficult to extrude Incompatible with many conventional adhesive and antenna materials. In addition, a significant disadvantage is The manufacturing cost of PTFE is high.   Inexpensive and easy to manufacture in a wide variety of stacked configurations without sacrificing critical performance characteristics There is a need for a tunable dielectric substrate material that can be used.   Variability ε_rAnd tanδ, weatherability and toughness, integrity, and workability. Low cost dielectric substrate materials that provide a desirable combination of properties for slave device design Currently not commercially available. Summary of the Invention   The present invention relates to a flexible polymer circuit for mounting electronic devices having tunable dielectric properties. Road substrate material. In one embodiment, the present invention provides that the loss tangent is less than about 0.005. Low dielectric loss thermoplastic elastomer circuit board material or laminate material. The low-loss thermoplastic resin of the present invention The lastomer has a loss tangent of about 0.00 for the resulting thermoplastic elastomer. A polar or non-polar monomer unit, or a mixture thereof, such that it is less than 03. Containing thermoplastic polymer components and polar or non-polar monomer units, especially Excluding the mixture, and an elastomeric polymer component. Thermoplastic elastomers are It can be a rock copolymer, a graft copolymer, or a multi-phase dispersion. The phase dispersion has an olefinic thermoplastic component and is an elastomer of ethylene propylene rubber. Tomer components are preferred. Thermoplastic component containing crystalline polypropylene and ethylene- Thermoplastic containing propylene-diene monomer (EPDM) and elastomer component Plastic elastomers are particularly preferred. The dielectric material of the first embodiment is microscopy. Particularly preferred for use in electronic devices such as trip antennas.   In another embodiment, the dielectric material of the present invention has a loss tangent greater than about 0.005. A high dielectric loss thermoplastic elastomer circuit board material or Is a laminate material. The thermoplastic elastomer of this embodiment of the invention provides results and The loss tangent of the resulting thermoplastic elastomer is greater than about 0.005 and about 0.8. Polar or non-polar monomer units, such as up to 200, or a mixture thereof And a polar or non-polar monomer unit or a mixture thereof. And an elastomer polymer component containing the compound. The dielectric material of this embodiment is Particularly preferred for use as a microwave absorbing material or a radar absorbing material.   The thermoplastic elastomer circuit board material of the present invention is compatible with a wide variety of fillers It is. Add a sufficient amount of filler to the thermoplastic elastomer circuit board material and add about 1 Over a wide range from about 2 to about 35, preferably from about 2 to about 35 It is possible to provide. Filler material such as barium totanate or lead oxide , Doping Or undoped “capacitor grade” ceramics, especially when the Loss dielectric performance has been observed.   The unfilled substrate material of the present invention can be used in a wide variety of other dielectric and metallic materials. Laminates that can be adhered to It is possible to supply with. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 shows the dielectric constant (ε) of the samples of Examples 7 and 11._r) And loss tangent (tanδ) It is a plot of vs. content (%). FIG. 2 shows the dielectric constant (ε) of the samples of Examples 12 to 14._r) And loss tangent (tanδ) vs. Prototype of rate (%). FIG. 3 shows the dielectric constant (ε) of the samples of Examples 15 and 17._r) And loss tangent (tanδ ) Is a plot of vs. content (%). FIG. 4 shows the dielectric constant (ε) of the sample of Example 33._r) And loss tangent (tanδ) vs. content (% ), With tan δ shown in millimeters (mu). FIG. 5 shows the dielectric constant (ε) of the sample of Example 35._r) Vs. time plot. FIG. 6 shows the loss tangent (tan δ) vs. loss of the sample of Example 35. It is a plot of time. FIG. 7 shows the dielectric constant (ε) of the sample of Example 36._r) Change rate (%) vs. exposure time plot It is. Detailed description of the invention   The substrate material of the present invention is a polymer material containing a thermoplastic elastomer. Application "Thermoplastic elastomer" used in the detailed text is the processability of thermoplastic materials (when molten) And the functional performance and properties of conventional thermosetting rubber (when not in a molten state) One class of polymer substance Point.   The low-loss thermoplastic elastomers of the present invention have a predetermined dielectric constant and resulting Provides a loss tangent (tan δ) of less than about 0.005, preferably less than about 0.003. Containing any thermoplastic polymer component and any elastomeric polymer component Is also good. The low loss thermoplastic elastomers of the present invention provide The loss tangent of the elastomer is less than about 0.005, preferably less than about 0.003. Thermoplastics containing polar monomer units, non-polar monomer units, or mixtures thereof A polar polymer unit and a polar monomer unit and a non-polar monomer unit, and The mixture includes an elastomeric polymer component specifically excluded.   Kirk-OthmerEncyclopedcia of Chemical Technology, 4thed., Vol.9 at15 As noted, thermoplastic elastomers generally comprise (a) a block copolymer Or (b) multilayer dispersions, which are classified into two main classes; .   In the case of a block thermoplastic elastomer or a graft thermoplastic elastomer, The hard and elastomer phases are chemically linked by block or graft polymerization. Combined, the structure ABA or (AB)_nWherein A is a hard phase, ie B is a soft or elastomeric phase. For the purpose of the present invention The ABA structure is preferable for its excellent physical properties. Block / graft heat available In the case of plastic elastomers, the rigid polymer end segment is a continuous elastomer. -Form discrete physical regions, called domains, dispersed in the phase. Poly Most of the mer molecules perform the role of physical crosslinking at room temperature and It has hard segments connected by a three-dimensional network. Heat material or dissolve in solvent When solved, this domain loses its strength. The polymer is believed to flow. Upon cooling or evaporation of the solvent, this domain hardens and the three-dimensional network becomes Retain its physical integrity.   In a low loss embodiment of the present invention, the coupling structure is such that the resulting loss tangent is Is less than about 0.005, preferably less than about 0.003. The child component A may be any polar monomer unit, non-polar monomer unit, or a mixture thereof. The elastomeric polymer component B may contain any polar monomer unit or It contains non-polar monomer units and its mixtures are specifically excluded.   As noted above, low dielectric loss polymers are generally non-polar substituents or substantially non-polar Thermoplastic polymer component having a non-polar monomer unit having a hydrophilic substituent and an elastomer Thermoplastic elastomers containing a mer polymer component are preferred for use in the present invention. As used herein, the term “non-polar” refers to the absence or substantial presence of a dipole Refers to a monomer unit that is balanced in vector. In these polymer materials The dielectric properties are primarily the result of electron polarization.   In order to provide a low-loss dielectric material in the present invention, the thermoplastic polymer component A has the following Polar or non-polar monomer units such as styrene, α-methyl Styrene, olefins, halogenated olefins, sulfones, urethanes, Esters, amides, carbonates, and imides, acrylonitrile, And copolymers and mixtures thereof. For example, styrene, α- Non-polar, such as methylstyrene and olefins such as propylene and ethylene Preference is given to monomer units and their copolymers and mixtures. High thermoplasticity The molecular components are polystyrene, poly (α-methylstyrene), and polyolefin. It is preferred to be selected from a class. Polyolefins are preferred, and polypropylene And polyethylene, and copolymers of propylene and ethylene are particularly preferred. New   The elastomeric polymer component B in the low-loss dielectric material of the present invention comprises the following polar monomer Units, such as esters, ethers, and copolymers and mixtures thereof Any of the objects may be included. Elastomer component B comprises the following non-polar monomer units: For example, olefins such as butadiene, isoprene and ethylene-co-butylene , Siloxanes, and isobutylene, and mixtures and copolymers thereof. Any may be included. Elastomer composition of low-loss thermoplastic elastomer of the present invention In minutes, the mixture and copolymer of polar and non-polar monomer units are Unthinkable. Non-butane, isoprene, olefins and siloxanes Polar monomer units, and mixtures and copolymers thereof, are preferred, -Component B comprises polybutadiene, polyisoprene, poly (ethylene-co-butylene) , Poly (ethylene-co-propylene), polydimethylsiloxane, polyisobutylene , Poly (ethylene-co-butylene), and poly (ethylene-co-propylene) It is preferred to be selected from   For example, a thermoplastic resin such as a styrenic block copolymer which is considered to be useful in the present invention. As the lastmer, Union Carbide Chemicals and Plastics, Danbury, CT raton D and Cariflex trade names, as well as Philips Petroleum, Bartlesville, OK Polybutadiene elastomer segment available under the trade name Solprene Or a linear material and / or component having polyisoprene elastomer segments There are branch materials. Poly (ethylene-co-butylene) which is considered useful in the present invention ( EB) Elastomer segments and poly (ethylene-co-propylene) (EP ) Linear styrene block thermoplastic elastomer having elastomer segment EB / EP materials available from Union Carbide under the trade name Kraton G; Great Lakes Termina, an EB material available from Union Carbide under the trade name Elexar l Polybutadiene, also available under the trade name Dynaflex from l and Transport Corp. Is EP material, EB material available under the Tekron trade name from Teknor Apex, and Conce EB materials including silicone oil available under the trade name C-Flex from pt. . Other copolymerized thermoplastic elastomers include Engage from Dow, Midland, MI. And other materials available under the trade name Exact from Exxon, Houston, TX There is.   Block / graft copolymer thermoplastic elastomer that can be used in the present invention Tomers can be synthesized by continuous and sequential polymerization methods well known in the art. Is possible. For example, Kirk OthmerEncyclopedia of Chemical Technology , 4th ed., Vol. 9 at 21-25,Handbook of Polyolefines, Vasilie, Seymour, e See ds. Decker, NY, 1993, pages 943-966.   In a second general class of thermoplastic elastomers, the multilayer material comprises at least one phase Contains materials that are hard at room temperature but become fluid when heated, another phase is rubbery at room temperature Contains soft materials. Thermoplastic elastomers generally contain thermoplastic polymer components and And more of a rubber-like elastomeric polymer component. Usually the two components are fine A well dispersed one-phase or multi-phase system is formed. The rubber aspect is called "dynamic vulcanization" As part of a well-known procedure, it is possible to crosslink during high shear mixing. for example See, for example, U.S. Pat. No. 3,037,954 to Gessler.   In the low loss multiphase structure of the present invention, the thermoplastic polymer component is generally considered to be thermoplastic. Any polar or non-polar monomer units made, and mixtures thereof And copolymers. The resulting loss of multiphase dispersion Tangent less than about 0.005, good The elastomer component is usually thermoplastic and preferably less than about 0.003. Contains any polar or non-polar monomer units considered to be Preferably, the mixture is excluded.   The low-loss multiphase thermoplastic elastomer of the present invention comprises the following polar monomer units or It may contain polar monomer units. Olefins such as propylene and ethylene, Vinyls and their mixtures and copolymers. For the purposes of the present invention, The secondary component is preferably selected from non-polar monomer units, and polyolefins Especially polypropylene and polyethylene, and ethylene monomer units and Copolymers containing pyrene monomer units are preferred. Used as a thermoplastic polymer component Isotactic polypropylene is particularly preferred for use.   The elastomer polymer component of the low-loss multilayer thermoplastic elastomer of the present invention is Crosslinked polar rubber or uncrosslinked polar rubber such as ril rubber, or butyl rubber, natural rubber Rubber, ethylene-propylene rubber (EPR), ethylene-propylene diene rubber (E PDM) and silicone rubber. It may be. Crosslinked or non-crosslinked non-polar rubbers are preferred, EPR and EPDM Is particularly preferred. The elastomer rubber component may be uncrosslinked (raw), Or as part of the dynamic vulcanization process, typical crosslinking agents (eg, phenols And peroxides) may be partially or completely crosslinked.   Preferred crystalline polypropylene thermoplastic for use in the low loss dielectric material of the present invention Polyester having a plastic polymer component and an EPR or EPDM elastomer polymer component. Available from Advanced Elastomer Systems for examples of two-phase thermoplastic elastomers TPR, available from Dexter Ren-Flex, available from Schulman Product Polytrope, available from Teknor Apex Tradename available from Telcar, Ferro Trade name Ferroflex, trade name WRD series or SRD series available from Union Carbide HiFax available from Leeds and Montell USA., Wilmington, DE is there. A crystalline polypropylene thermoplastic polymer composition that can be used in the present invention. Vulcanization formulations containing styrene and EPDM elastomeric polymer components include Adva Santoprene available from nced Elastomer Systems, available from Novacor Available trade names Sarlink 3000, trade names Telprene and Mon available from Teknor Apex HiFax XL available from tell USA. Polypropylene thermoplastic component and Dynamic vulcanizing compounds with butyl rubber elastomer components include Advanced Ela Trade names available from stomer Systems Trefsin and Sarl available from Novacor ink 2000 and others. Polypropylene thermoplastic component usable in the present invention Advanced vulcanizates with natural and natural rubber elastomer components  Vyram available from Elastomer Systems.   The multi-phase thermoplastic elastomers that can be used in the present invention are a wide variety of conventional Can be formulated using the following procedure. Generally, thermoplastic elastomers are hard Mechanical mixing of high-molecular thermoplastic polymer and rubber-like elastomer polymer under high shear Manufactured by extrusion or extrusion, but heatable in the reactor during polymerization In some cases it is possible to produce a plastic elastomer. For example, Legge, Holden  and SchroederThermoplastic Elastomers-A Comprehensive Review,Oxford University Press, 1987,Handbook of Polyolefins,Vasilie, Seymour edition Decke r, NY, 1993, see pages 943-966.   For use in the low loss dielectric material of the present invention, the above-described thermoplastic elastomer is used. Amongstomers, multiphase combinations are preferred. Thermoplastic olefin polymer component Among them, propylene and ethylene are preferred, and crystalline isotactic poly Propylene is particularly preferred. Crosslinked EPDM and uncrosslinked EDPM may It is particularly preferable as a stoma polymer component. Crosslinked EDPM is most preferred. Materials that can be used in the present invention include Snell et al. U.S. Patent Nos. 3,876,454 and 3,470,127, issued to Has been described. Polypropylene thermoplastic component and EDPM elastomer component Relative ratios vary widely depending on the combination of properties desired for a particular application.   Sometimes preferred multi-phase thermoplastic elastomers for use in the present invention are Montell US Trade names HiFax and Union Carbide, available from A of Wilmington, DE, Danbury , CTWRD / SRD, etc. HiFax material is a crosslinked rubber such as EPDM, EPR or butyl Or uncrosslinked rubber and isotactic such as polyethylene or polypropylene It is a blend with olefin plastic. Manufacturer says "thermoplastic olefins Particularly preferred materials for cost and workability reasons, referred to as "uncrosslinked (raw) rubber, Preferably EPR or EPDM, most preferably EPDM, and a crystalline polypropylene. HiFax CA10G, a blend with pyrene. HiF as reported by the manufacturer ax CA10G contains more than about 60% by weight of a polypropylene thermoplastic component and about 40% by weight. EPR / EPDM elastomer component and measured according to ASTM D-2240 Shore Hardness is about 40D and was measured according to ASTM D-636 The tensile strength is about 2200 Psi. The uncrosslinked rubber component is a non-migratory polymer plasticizer CA10G material is reported to have excellent flex fatigue resistance .   Of the pure thermoplastic elastomer used in the low loss material of the present invention The dielectric constant is less than about 3, preferably less than about 2.5, and the loss tangent (tan δ) is preferred. Or less than about 0.003. For these materials, polarization occurs virtually instantaneously. Thus, permittivity and loss tangent are substantially independent of frequency, at least Irrelevant over a wide range of frequencies from about 300 MHz to about 20 GHz . Dielectric properties of polymer materials can be measured using a wide variety of measuring devices However, for the purposes of the present invention, an impedance such as 4291ARF available from Hewlett Packard A dance / material analyzer is preferred.   In another embodiment, the dielectric material of the present invention is greater than about 0.005 and about 0.20. High dielectric loss thermoplastic substrate with loss tangent up to zero. The thermoplastic resin of the present invention Lastomer has a loss tangent of about 0.000 for the resulting thermoplastic elastomer. 5 and up to about 0.200, a polar monomer unit, a non-polar A thermoplastic polymer component containing a monomer unit or a combination thereof, and a polar monomer Unit, a non-polar monomer unit, or an elastomeric polymer component containing a mixture thereof and including. In order to provide dielectric materials with high dielectric loss, polar monomer units must be included. Polymeric components and elastomeric thermoplastic components containing polar monomer units are preferred. No.   However, the dielectric constant and loss tangent of a thermoplastic elastomer From about 1 to about 50, preferably from about 2 to about 35, but at the predetermined level of loss described above. By adding a sufficient amount of filler to maintain the tangent, It is possible to prepare according to. For example, the dielectric properties are tailored to the individual application. As fillers that can be added to the thermoplastic elastomer to adjust, Silicon, aluminum, glass bubbles, barium titanate (BaTiO_Three), Lead oxide (PbO ), Titanium dioxide (TiO_Two) And mixtures thereof. In the present invention, Preferred for use as a filler Is a titanate having a perovskite crystalline structure. Often referred to as "cer grade" ceramic. These titanates, for example, Doped with a wide range of impurities, such as niobium, to tailor dielectric properties to individual applications It is possible to adjust. Particularly preferred for use in the present invention are TAM Available in amorphous or sintered form under the trade name TICON from Ceramics, Niagara Falls, NY Possible solid state reaction powder. Particularly preferred capacitor grade ceramic From TAM Ceramics, TICON COF 40, TICON COF 50, TICON COF-70, TICON CN And materials available under the trade names TAMTRON Y5V183U and Y5V153G.   The filler used in the present invention may also include other polymeric materials. For example, In order to tailor the dielectric and / or physical properties to individual applications, The filled thermoplastic elastomer or the filled thermoplastic elastomer of the present invention Mechanically compounding with tomer to make polymer dispersion in thermoplastic elastomer Is possible. When a polymer filler is used, the thermoplastic elastomer of the present invention can be used. It is easier to control when adjusting the dielectric and / or mechanical properties.   The amount of filler added depends on the dielectric constant and loss tangent required for each application. But up to about 70% by volume, preferably from about 5 to about 60% by volume of thermoplastic elastomer. Stomers are preferred. If the filler content exceeds about 60-70% by volume, the results May adversely affect the physical properties of the resulting material, especially its flexibility and tensile strength There is. Any conventional, such as rolling, extrusion, and dry blending, or a combination thereof Can be blended with the thermoplastic elastomer.   Assess water absorption according to the test procedure outlined in ASTM C272. When the material is exposed to moisture, the added or unadded thermoplastic elastomer The dielectric properties must remain relatively constant.   The dielectric properties of the thermoplastic elastomer, with or without addition, range from about -50 ° C to about 1 ° C. Over a wide range of temperatures up to 00 ° C, preferably from about -30 ° C to about 70 ° C. Must remain relatively constant.   The thermoplastic elastomer selected for use in the present invention surrounds the mandrel. When bent, it is flexible and convex, preferably without breakage or stress whitening. Must conform. Following the test procedures outlined in ASTM D522, When bending around a mandrel, preferably less than about 1 inch (2.5 cm) in diameter, More preferably, around a mandrel less than about 0.5 inch (1.25 cm) in diameter Most preferably, a mand of about 0.125 inch (0.318 cm) diameter when bent When bent around the barrel, the thermoplastic elastomer may break or stress whiten. should not be done. When the material is bent around a mandrel or conforms to a convex surface, The dielectric properties of thermoplastic elastomers with or without additives must remain stable. No.   Additive thermoplastic elastomer or non-additive thermoplastic elastomer used in the present invention It is easy to process into a sheet film using an extruder, and if necessary, Stretching or biaxial stretching is possible. Sheet film may have a wide range of thickness , Its dielectric properties can be tuned for specific applications. The heat of the present invention The plastic elastomer can be easily bent around the roll during web processing Therefore, it is possible to apply a primer, an adhesive or a processing operation on the dielectric material.   As is well known in the art, fiberglass, glass cloth, aluminum cloth, silica, stone It is possible to enhance the physical properties of thermoplastic elastomers by adding It is possible. Thermoplastic to enhance physical properties The amount of filler added to the conductive elastomer also depends on the application, but is well known in the art. As shown, when the filler content is high, the flexibility of the thermoplastic elastomer material and And / or the ultimate tensile strength may vary.   The thermoplastic elastomer used in the present invention may be a corona discharge or other surface treatment To enhance its physical properties. Thermoplastic Eras added Adjust porosity of tomer or additive-free thermoplastic elastomer to adjust dielectric properties It is possible to Methods for increasing porosity include the addition of chemical blowing agents, nitrogen Injection of inert gas such as or carbon, or rice given to Aoyagi et al. As described in U.S. Pat. No. 4,963,891, blending with a plasticizer and subsequent Extraction of plasticizer. Also, as the porosity increases, the dielectric properties increase, The rate can adversely affect the physical properties of the material.   The thermoplastic elastomer of the present invention can be provided in the form of a laminate. The laminate of the present invention may be a single layer, and therefore, is different from a conventional electronic device substrate material. The manufacturing process is simpler in comparison. One or multiple layers of thermoplastic elastomer substrate, Or one layer of thermoplastic elastomer and one or more layers of another dielectric material, For example, gold, silver, copper, aluminum, electrolyte copper, low oxygen content copper, nickel, chromium , One or more layers of metal, such as alloys available under the trade name Inconel, and their alloys It can be bonded to one side or both sides. Metal layer and thermoplastic elast An optional adhesion promoter can be added to the tomer substrate. Shoemaker As described in U.S. Pat. No. 4,937,585 to U.S. Pat. Play or epoxy can play the role of metal layer.   The thickness of the thermoplastic elastomer layer can vary widely depending on the intended use. It may be.   The substrate may be laminated to additional dielectric and / or metal layers to provide specific dielectric properties and In addition, it is possible to provide a laminated structure having physical properties. Further dielectric layers are polar And may be nonpolar and exhibit different crosslink densities and / or dielectric properties. Or may include a different reinforcement or dielectric enhancer as described above. Good. For example, additional dielectric layers include polyolefins, polyamides, polyethers. Even if it is the same as tylene terephthalate, and the thermoplastic elastomer in the substrate It may comprise polar or non-polar thermoplastic elastomers which may be different.   Thermoplastic Elastomer / Metal Laminate Laminates to Additional Reinforcement Layer of Polymeric Material Or on both sides containing polymeric materials that may be the same or different They may be stacked. The thermoplastic elastomer / metal laminate of the present invention further comprises For example, laminated on other reinforcing materials such as circuit board materials such as FR-4, or metal sheets It is possible. The metal layer can be any removable protective sheet on request It is possible to cover. In addition, copper damage inhibitors, anti-ultraviolet agents, antioxidants, etc. May be added to any of the laminate layers.   Of course, the metal layer on the laminate of the present invention can be chemically etched, Processing by any method known in the art, such as It is possible to fabricate electronic circuit structures. Co-pending U.S. Patent Application No. 08 / 609,092 There are several examples in the number, microphones with or without feeder Provide a radistrip antenna radiating patch, ground plane structure, or antenna array A network of radiating patches is included.   Bonding of the metal layer to the thermoplastic elastomer substrate of the present invention is accomplished by a task well known in the art. It can be implemented in any way. For example, Pressure Sensitive Adhesive (PSA) Using Thermoplastic Elastomer Using Any Conventional Laminating System -It can be applied to the substrate, and the metal layer is attached to the PSA by the conventional lamination technology It is possible to Alternatively, a heat press available from Carver or Rucker Can be used to thermally laminate a metal layer to a thermoplastic elastomer substrate. You. For example, the laminate may be between about 10,000 psi (70 MPa) to about 60,000 psi ( Can be manufactured at a temperature of about 350 ° F (175 ° C) under a pressure of 400PMa) It is. Curing times of less than about 10 minutes are preferred. A sputtering method known in the art, The metal layer is applied to the thermoplastic elastomer substrate using stamping or adhesion technology. It is possible to attach. Laminates can be a continuous web or heat laminated Can be manufactured by processing the laminate sheet using the You. Example   The following non-limiting examples illustrate the invention. If there is no valley description, All weight percentages are based on the total weight of the resin plus filler. Example 1   The sample of Example 1 includes a UV stabilizer, a non-crosslinked rubber modified polypropylene formulation, No filler added (ie high ε_rMade from dielectric resin (lacking filler) Was. This resin (natural color, free of colorants) is available from Montell USA, Wilmington, DE From HiFax CA10G. The melting flow rate of this material is ASTM D 1 It is stated in the Montel product literature to be 0.5-0.7 g / 10 min as measured at 328. And its density is reported to be 0.87 g / cc.   Extrude resin using Haake Rheocord single screw extruder And the thickness varies from about 5 mils (0.013 cm) to about 60 mils (0.152 cm) The resulting film was obtained. Single screw diameter is 3/4 inch (1.91 cm) Met. Processing conditions during extrusion were: die temperature 440 ° F (227 ° C), extruder temperature Zone 1 is 325 ° F (163 ° C), Zone 2 is 420 ° F (216 ° C), Zone 3 Was 440 ° F (227 ° C).   Die extrudate (die width: 5 inches (13 cm)) of 2 mil (0.005 cm) polys Cast onto a telfilm carrier and place it on a chromium chill roll and Pass under the backup roll. If the temperature of the cooling roll is 50 ° F (10 ° C).   RF impedance commercially available from Hewlett Packard under the trade name HP 4291A / Material dielectric properties at 905 MHz at room temperature (23 ° C) using material analyzer Sex was tested. This test uses capacitance measurements modified for high frequencies did. Commercially available from Hewlett Packard under the trade name HP 16453A along with a material analyzer The used dielectric test grips were used.   The dielectric properties of the film are shown in Table 1 below. HP reported by Hewlett Packard 4291A Material Analyzer ε_rThe maximum error of the values is about ± 5%. tanδ measured value ≤ 0 reports <0.002 in all tables and 0.002 in all plots I told. Example 2   Filler-free dielectric fill containing partially cross-linked rubber-modified polypropylene A sample of Example 2 was manufactured from the system. This resin (natural color, colorant and UV stabilizer (Not included) is commercially available from Montell USA under the trade name HiFax XL 42D01. Haa The resin is extruded using a ke Rheocord-shaft screw extruder to a thickness of 33 mils ( 0.084 cm). The diameter of the single screw is 3/4 inch ( 1.91 cm) and a 5 inch (12.7 cm) wide die was used. Addition during extrusion The processing conditions are as follows: die temperature 320 ° F (160 ° C), extruder temperature 290 ° F in zone 1 (143 ° C), zone 2 at 310 ° F (154 ° C), and zone 3 at 320 ° F (160 ° F). ° C). Die extrudate is transferred to a 2 mil (0.005 cm) polyester film key. Cast on a chrome chill roll and a silicone backup. Passed under Prowl. The temperature of the chill roll was set to 50 ° F (10 ° C) .   As described in Example 1, the dielectric properties of the film of Example 2 were measured using RF impedance. Measured at 905 MHz with a material / material analyzer. Table 1 shows the results.   Broadband frequency implemented from about 500 MHz to 20 GHz with the film of Example 2 Also tested with 7mm coaxial cable waveguide technology for measurement Was. The film of Example 2 has a uniform ε over this wide frequency range._rShowed a response . Example 3   Induction of carbon black containing partially crosslinked rubber-modified polypropylene resin A sample of Example 3 was manufactured from the conductive film. This resin (black, but ultra-violet No line stability) is commercially available from Montell USA under the trade name HiFax 42D01-Black I have.   Extruding the resin using a 1.5 inch (3.8 cm) single screw extruder , A film about 45 mils (0.114 cm) thick and 14 inches (35.6 cm) wide Obtained. The processing conditions during extrusion were: die temperature 350 ° F (177 ° C), extruder temperature Zone 1 is 300 ° F (149 ° C), Zone 2 is 320 ° F (160 ° C), Zone 3 Was 340 ° F (171 ° C) and Zone 4 was 370 ° F (188 ° C).   The die extrudate is cast on a chrome chill roll and the silicone backup roll Passed below. The temperature of the chill roll was set at 50 ° F (10 ° C).   As described in Example 1, the dielectric properties of the film were measured using RF impedance / material impedance. It was measured at 905 MHz by a narizer. Table 1 shows the results. Examples 4 to 6   In the form of injection molded plaques containing partially crosslinked rubber modified polyolefin resin Samples of Examples 4 to 6 were produced from the filler-free dielectric film. This resin is Natural color with no colorants or UV stabilizers. The plaque is from Montell USA HiFax XL 65A01 (Example 4), HiFax XL 75A01 (Example 5), and HiFax XL 85A 01 (actual It is commercially available under the trade name of Example 6).   As described in Example 1, by RF impedance / material analyzer, 9 The films were tested at 05 MHz and the results are shown in Table 1. Example 7   Solid state, niobium-doped barium titanate ceramic Example 7 by adding to the polymer melt of the HiFax CA10G resin used in Example 1. Was manufactured. This ceramic is available from Tam Ceramics, Inc., Niagara Falls, N. Commercially available from Y under the trade name Ticon COF 70. Ticon COF 70 is 97% by weight Contains barium titanate in excess of, the main impurities SrO (0.7%), Nb_TwoO_Five(0.25%) And SO_Three(0.2%) is described in Tam Ceramic product literature and other Small amounts of impurities are also listed. The general particle size distribution for Ticon COF70 is D50 = The density is described as 1 μ, and the density is described as 5.8 g / cc.   Haake Rheocord System 40 micro with Haake Rheomix Mixer (Type 600) Ticon COF 70 ceramic material using processor controlled torque rheometer Was added to the polymer melt at 210 ° C. 43% by weight (10% by volume) of Ticon COF 70 In addition to the polymer (total volume 48 cc), mix and mix two rotating blades at 40 rpm for 30 minutes The composite was formed by spinning to ensure thorough mixing. After mixing, 2 The composite material is placed between two polyester liners, which are then placed on two 12 "x 12" (30 cm × 30 cm) Placed between stainless steel platens. Cooled spherical double The platen containing the mixture was heated to a Carver Laboratory Press (25 ton hydraulic press, 2518) and the platen was heated to 210 ° C. Maximum hydraulic pressure of 30,000 lbs (1 4,000 kg) and press the sample, about 7 inches in diameter suitable for dielectric property test (18 cm). Spacing inserted between top and bottom release liners The thickness of the film was adjusted with an adjusting plate.   Run at 905 MHz with the RF impedance / material analyzer of Example 1. The dielectric properties of the film of Example 7 were tested, and the results are shown in FIG. Examples 8 to 10   Adding Ticon COF 70 described in Example 7 to HiFax CA10G described in Example 1 Thus, the samples of Examples 8 to 10 were manufactured. Commercially available from Berlyn under the brand name PELL2 2 inches (5 cm) including a die for making two-hole pellets and a water cooling trough ) 33mm APV MP2030TC simultaneous rotation twin screw compounding equipped with pellet making machine Combine Ticon COF 70 and HiFax CA10G with a machine, and the following weight percentage of Ticon C A composite comprising OF 70 was formed: 10% by weight (1.64% by volume) (Example 8), 30 % (6.04% by volume) (Example 9) and 50% by weight (13% by volume) (Example 1) 0). Each composite is fed to a gravimetric feeder that feeds the composite to a twin screw extruder. Was added. The extrudate is sent from a pellet production die (43 ° F, 221 ° C) to a water tank. Finally, the two strands were cut into pellets of a size suitable for extrusion. Haake Rheocord 3/4 inch (1.91 cm) single screw extruder and 5 inch (12.7 cm) ) Using a die (65 mil (0.165 cm) die spacing adjuster) The pellets were extruded into a 20 mil thick film.   The processing conditions were as follows: die temperature 450 ° F. (232 ° C.); ° F (166 ° C), Zone 2 is 425 ° F (218 ° C), Zone 3 is 450 ° F ( 232 ° C). 2 mil die extrudate And cast it on a chrome chill roll. And passed under a silicone backup roll. Chrome cooling roll temperature Was set to 52 ° F (11 ° C).   As described in Example 1, by RF impedance / material analyzer, 9 The dielectric properties of the films of Examples 8 to 10 were measured at 05 MHz and the results are shown in Table 2 below. Show. Measurement of dielectric properties at 5.6 GHz using double split post resonator technology The results are also shown in Table 2. Example 11   The Ticon COF 70 ceramic material described in Example 7 was used in the form of a polymer melt. The sample of Example 11 was prepared by adding the HiFax CA10G resin described in Example 1. did. Adding Ticon COF 70 at 87% by weight (50% by volume) to the polymer melt gives a high A dielectric constant sample was obtained. Ticon COF 70 was heated using the mixing system of Example 7. Degree 4 Added to 10 ° C. (210 ° C.) polymer melt. After adding Ticon COF 70, the result is The resulting melt was mixed at 40 rpm for 30 minutes. The composite was pressed into a film sample using the technique described in Example 7.   This film was applied to the RF impedance / material analyzer as in Example 1. At 905 MHz, and the results are shown in FIG. Example 12   Capacitors etc. marketed by Tam Ceramics under the trade name Tamtron Y5V153G 50% by weight (13% by volume) of the first-grade ceramic composition was heated at a temperature of Add 410 ° F (210 ° C) to the HiFax CA10G resin of Example 1 in the form of a polymer melt. Thus, a sample of Example 12 was manufactured. Tamtron Y5V153G is 85-9 0% by weight of barium titanate and the main impurity barium zirconate (5 to 5%) 10% by weight) and less calcium stannate (1-5% by weight); The density of the material is described in Tam Ceramics product literature as 5.8 g / cc. Jill When konia is added to barium titanate ceramic, it converts to a higher dielectric constant at room temperature. Cheating. The particle size of this ceramic is 5-10μ.   A composite is formed using the pressing technique described in Example 7 and the composite is pressed. As a result, a film sample having dimensions suitable for dielectric measurement was obtained.   As described in Example 1, the film of Example 12 was subjected to RF impedance / material The test was performed at 905 MHz with a sample analyzer and the results are shown in FIG. Examples 13 and 14   Commercially available from Tam Ceramics under the trade name Tamtron Y5Vl53G Capacitor grade ceramic composition 87% by weight (50% by volume) (Example 13) And 91% by weight (60% by volume) (Example 14) using the mixing method of Example 7 The HiFax CA10G tree of Example 1 in the form of a polymer melt at a temperature of 410 ° F (210 ° C) Samples of Examples 13-14 were made by adding to the fat. Example 7 A composite is formed using a pressing technique, and the composite is pressed into a dielectric measurement filter. A lume sample was used.   As described in Example 1, the films of Examples 13-14 were The test was performed at 905 MHz with a material / material analyzer and the results are shown in FIG. Example 15   Uniform, pre-ground powder commercially available from Tam Ceramics under the trade name Tamtron Y5V183U 70% by weight (20% by volume) of the crushed dielectric ceramic was mixed by the mixing method of Example 7. At a temperature of 410 ° F. (210 ° C.), the HiFax CA10G resin described in -In the form of a melt) to produce the sample of Example 15. Tamtron Y5V1 83U is 65-75% by weight lead oxide, 1-5% by weight magnesium oxide, 1-5% % Titanium oxide and <0.1% silicon oxide by weight and a density of 8.0 g / The cc is described in Tam Ceramics product literature. Typical particle sizes are 1. 4μ.   A composite is formed using the pressing technique described in Example 7 and the composite is pressed. This was used as a dielectric measurement film sample.   As described in Example 1, the film of Example 15 was subjected to RF impedance / material The test was performed at 905 MHz by an analyzer, and the results are shown in FIG. Example 16   50% by weight (10% by volume) of the ceramic Tamtron Y5V183U of Example 15 The sample of Example 16 was made by adding to the resin HiFax CA10G of Example 1. This ceramic and resin were blended to form a composite material, and the composite material was prepared according to the methods described in Examples 8 to 10. And pelletized. Using a single screw extruder as described in Examples 8-10 The composite in pellet form was extruded into a 20 mil film.     The film of Example 16 was replaced with RF impedance / material as described in Example 1. Tested at 905 MHz with a sample analyzer and 5.6 GHz as in Example 8. , And the results are shown in Table 2. Example 17   90% by weight (50% by volume) of the ceramic Tamtron Y5V183U of Example 15 The resin of Example 1 at a temperature of 410 ° F. (210 ° C.) by the mixing method described in Example 7. A sample of Example 17 was made by adding to HiFax CA10G.   A composite is formed using the pressing technique described in Example 7 and the composite is pressed. This was used as a dielectric measurement film sample.   The film of Example 17 was subjected to RF impedance / material as described in Example 1. Tested at 905 MHz with an analyzer and at 5.6 GHz as in Example 8. The test was performed, and the results are shown in FIG. Example 18   Commercially available from DuPontde Nemours & Company, Wilmington, DE under the trade name R101. Rutile titanium dioxide with a density of 4.36 g / cc Example 18 was prepared by adding 50% by weight (17% by volume) . R101 is blended with HiFax CA10G to form a composite, and the method described in Examples 8-10 And pelletized. Using the single screw extruder described in Examples 8 to 10, The shaped composite was extruded into a 20 mil (0.051 cm) film.   This film was subjected to RF impedance / material analysis as described in Example 1. 905 MHz, and at 5.6 GHz as in Example 8, The results are shown in Table 2. Example 19   Trade name of WRD-7-507 from Union Carbide Chemicals and Plastics, Danbury, CT Using the rubber-modified thermoplastic elastomer resin commercially available in Made a fee. Using a Haake Rheocord 3/4 "(1.91cm) single screw extruder Containing 38% ethylene propylene rubber ("EPR") in polypropylene Was extruded to obtain a film having a thickness of 20 mils (0.051 cm). Processing conditions are The die temperature was 440 ° F (227 ° C) and the extruder temperature was 400 ° F (204 ° C), Zone 2 at 420 ° F (216 ° C), and Zone 3 at 440 ° F (227 ° C). there were. Die extrudate (5 inch (13 cm) die width) into 2 mil (0.005 cm) poly Cast onto an ester film carrier and place it on a chrome chill roll and It passed under the cone backup roll. Set the temperature of the water-cooled cooling roll to 5 Set to 3 ° F (12 ° C).   This film was subjected to RF impedance / material analysis as described in Example 1. Tested at 905 MHz by Iser and the results are shown in Table 1. Examples 20 to 21   The samples of Examples 20 to 21 were obtained from HiFax CA10G (Example 20) or HiFax 42D01 ( A laminated structure containing copper sputter-deposited on the film of Example 21) is used. For each sample, 45 mils (0.114 cm) thick (Example 20) or 20 mils (0.1 mm). (071 cm) (Example 21). A layered structure in which a copper layer is sputtered on the polymer layer Made. Examples 22 to 23   The samples of Examples 22 to 23 were prepared using HiFax CA10G (Example 22) or HiFax 42D01 (Example 22). A laminated structure including a copper foil on the film of Example 23) is used. On each sample, Glue 1 mil copper foil containing rill pressure sensitive adhesive (1 mil (0.0025 cm) thick) It was produced by laminating the agent on one side of a metal foil. 60 mils thick (0.152 cm) (Example 22) or 28 mil (0.071 cm) (Example 23) Laminate copper foil / PSA on film and make the following layers: Copper foil / PSA / Polymer Was produced. Examples 24 to 25   The samples of Examples 24 to 25 were prepared using HiFax CA10G (Example 24) or HiFax 42D01 (Example 24). A laminated structure including a copper foil on any of the films in Example 25) is used. Each file 1 mil copper foil containing the acrylic pressure sensitive adhesive described in Example 22 Both sides of a 60 mil (Example 24) or 28 mil (Example 25) extruded film Laminate the following layers: Copper foil / PSA / Polymer / PSA / Copper foil Was produced. Examples 26 to 27   The samples of Examples 26 to 27 were obtained from HiFax CA10G (Example 26) or HiFax 42D01 ( Polyester carrier adhered on either one or both sides of Example 27) A laminated structure containing copper sputtered onto the film is used. 5 mils thick (0 . 2 mil (0.0051 cm) containing acrylic pressure sensitive adhesive 180nm copper film sputtered onto polyester film (PET) 60 mils (0.152 cm) thick (Example 26) or 28 mils (0.071 cm) ) The following layers are laminated on one or both sides of the extruded film of (Example 27): PET / copper / PSA / polymer / PSA / copper / PET Was produced. Examples 28 to 29     The samples of Examples 28-29 were HiFax CA10G (Example 28) or HiFax 42D01. (Example 29) A laminated structure including an aluminum foil on one side is used. . A 3 mil aluminum foil sheet (without adhesive) was applied to a 60 mil (0. 152 cm) (Example 28) or 28 mil (0.071 cm) (Example 29) A laminated structure was produced by directly laminating one side of the exposed film by a thermal lamination technique.   Using a Rucker Press (400 tons), aluminum processing using the following processing conditions Layer was completely thermally laminated to the film: cycle residence time: 10 seconds preheating, embossing 20 seconds and cure 6.0 minutes. The zone temperature of the press is zone 1 = 350 ° F (177 ° C), Zone 2 = 350 ° F (177 ° C.), zone 3 = 350 ° F. (177 ° C.), and zone 4 = 350 ° F. (177 ° C.) . The zone pressures were as follows: low pressure = 10,000 psi (70 MPa), high pressure = 60,000 psi (4 00 MPa).   The laminate thus obtained has the following layer structure: Al foil / polymer Had. Examples 30 to 31   The samples of Examples 30 to 31 were prepared using HiFax CA10G (Example 30) or HiFax 42D01 (Example). The laminated structure including aluminum foil on both surfaces of Example 31) is used. 3 mil thickness (0.0076 cm) aluminum foil layer (without adhesive) (0.152 cm) (Example 30) or 28 mil (0.071 cm) (Example 3) Directly laminated on both sides of the extruded film of 1) by the thermal lamination technology of Examples 28 to 29, Layer: a laminated structure having Al foil / polymer / Al foil was produced. Example 32   The sample of Example 32 was prepared by sputtering the laminate of Example 20 using a thermal lamination technique. -The structure including the film of Example 1 adhered to the adhesion surface was adhered. Like this The resulting laminate structure was polymer / sputter deposited copper / polymer. Example 33   Compounding other polymers with the thermoplastic elastomer polymer of the present invention, It is possible to provide dispersions with enhanced properties. For example, KYNAR 2750 P Polyvinyl fluoride marketed by Elf Atochem, Philadelphia, PA under the trade name of VDF Niriden, When added to the thermoplastic elastomer HiFax 42D01 described in Example 2, the resulting Of the mixture used_rRises. As can be seen from FIG. Then, the ε of the compound_rRose from 2.30 to 2.37. Example 34   The flexibility of the films of Examples 1-2 was measured using a command as outlined in ASTM D522. The test was performed by the Mandrel Bend Test. One inch (2.5 cm) Lum splits were placed on test mandrels of various diameters. Test strip The mandrel around the mandrel using a steady pressure and at a uniform speed for less than about 5 seconds. Bent about 180 °. Cracks and stresses that can be seen with the naked eye after removing this film The bleaching phenomenon was examined. Repeat this procedure using successively smaller diameter mandrels. I returned. The minimum diameter tested was 0.125 inches (0.318 cm). Ma Table 3 shows the results of the drel bending test. Example 35   According to the procedure of Example 1, the dielectric constant and loss tangent of the films of Examples 1 and 2 were determined. It was measured at 905 MHz.   Water Absorption Test according to the procedure outlined in ASTM D272 ) Tested the film. At room temperature, the film sample is immersed in water at 23 ° C. for 46 hours. Soak and then blot the entire surface with blotting paper to remove any water on the surface. The weight was measured.   The water increase rate (percent) of a sample of 1 inch × 3 inch (2.5 cm × 8 cm) It was recorded and the dielectric properties were measured again according to the procedure of Example 1.   FIG. 5 shows the dielectric constant (ε) of the water absorption test._rFIG. 6 shows the loss tangent (tan δ) data. Data. Example 36   Example 36 is a trade name of HiFax XL42D0LXL65A01 and XL75A01 from Montell USA. Partially crosslinked, rubber-modified polypropylene resin without filler, sold in A ferroelectric film is used. Extruding the resin using the processing conditions of Example 2 Film.   Non-crosslinked rubber modified polypropylene formulation, filler containing HiFax CA10G of Example 1 An additive-free dielectric film was also made into a film using the processing conditions of Example 1.   A blend of HiFax 42D01 and HiFax CA10G was also filled using the processing conditions of Example 1. I did it.   The following sheets of commercially available dielectric material were also used in this example. F.CELL And closed cell commercially available from Sentinel Corporation under the trade name MICROCELL. Crosslinked polyester foam, CMR Continuous modified rubber closed cell commercially available from Sentinel Corporation under the trade name Rohm Tech, Inc. under the trade name of polyolefin blended film and ROHACELL 71 Commercially available polymethacrylamide foam. Use the procedure described in Example 1. The initial dielectric characteristics of a 2.75 inch x 2.75 inch (7 cm x 7 cm) sample The properties were measured at 905 MHz.   A sample of the above material was subjected to a test with an accelerated test device. This test rig was used by Atlas Water-cooled xenon arc 65WWR or C165 type manufactured by Electric Devices Co. And complies with the standards described in ASTM G-26 Type B and BH. The light source is a controlled radiant flux 0.35W / m at 340nm density^Two650 with borosilicate glass filter It is a xenon arc lamp of 0 watts. After lighting at 63 ° C for 102 minutes, lighting for 18 minutes Repeated cycle exposures of fire and water spray were performed continuously for the duration of the study.   The accelerated exposure protocol treated the dielectric sample for 1000 hours. Low in environmental conditions Equilibrate the sample for at least 72 hours and follow the procedure of Example 1 at 905 MHz. The dielectric properties were measured again. Dielectric constant (ε_r) And the loss tangent (tanδ) Table 4 shows the final values. Dielectric constant (ε_r) Vs. accelerated test exposure time:                     {[(Exposure-initial) / initial] x 100} Is shown in FIG. Example 37   The thermoplastic elastomer of the present invention is used for cost reduction, performance enhancement, or processability. It can be easily blended with a mer. In this embodiment, in order to improve workability, Several polymers with high melt flow index, such as Engage 8200 from Dow and Exact4028 from Exxon A mer has been added to the thermoplastic elastomer of the present invention. Table 5 shows the results.   In Table 5, HFCA10 is HIFAX CA10G and HFXL42 is HIFAX XL42D01. Both heats possible Both plastic elastomer materials are available from Montell USA.  When a polymer filler is added to the thermoplastic elastomer of the present invention, the melt flow index becomes It results in a low formulation. Polymer fillers are somewhat similar to lubricating oils to enhance processability Works without significantly altering the dielectric properties of the first thermoplastic elastomer I do.   The exemplary embodiments described herein in no way limit the scope of the invention. It will be understood that this is not a requirement. In view of the above description, Other modifications, which will be apparent, will be apparent to those skilled in the art. These descriptions clearly disclose the invention. This is to provide a specific example of such an embodiment. Therefore, the present invention is described Or the use of specific elements, dimensions, materials or arrangements contained therein Not limited. All alternative modifications falling within the spirit and scope of the appended claims Corrections and modifications are included in the invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 1/03 610 H05K 1/03 610H (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (KE, LS, MW, SD, SZ, UG), UA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, HU, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO , RU, SD, SE, SG, SI, SK, TJ, TM, TR, TT, UA, UG, UZ, VN. Office box 33427

Claims (1)

[Claims]   1. (A) a thermoplastic elastomer having a loss tangent (tan δ) of less than about 0.005; With stoma,       (B) a sufficient amount of filler material to provide a predetermined dielectric constant of about 1 to about 50; Wherein the doped titanate, the undoped titanate, and mixtures thereof A filler material which is a ceramic material containing at least one of the following: Dielectric material containing.   2. The dielectric material of claim 1, further comprising a polymeric filler.   3. The thermoplastic elastomer,       Polypropylene, polyethylene, and copolymers of ethylene and propylene A thermoplastic polymer component selected from the group consisting of       Crosslinked or uncrosslinked butyl rubber, natural rubber, ethylene propylene rubber (E PR), ethylene-propylene diene rubber (EDPM) and silicone rubber An elastomer component selected from the group consisting of The dielectric material of claim 1 having a multi-phase structure comprising:   4. The thermoplastic polymer component comprises at least polypropylene and polyethylene. Wherein the elastomer component is uncrosslinked or crosslinked ERP and EPD 4. The dielectric material according to claim 3, comprising at least one of M and mixtures thereof. .   5. The thermoplastic component comprises polypropylene, and the elastomer component is cross-linked. 4. The dielectric material according to claim 3, comprising EDPM or uncrosslinked EPDM.   6. A thermoplastic elastomer having a loss tangent (tan δ) of less than about 0.2 A dielectric substrate comprising:       A metal layer on at least one side of the substrate A laminated structure including:   7. The loss tangent of the thermoplastic elastomer is less than about 0.003. 7. The laminated structure according to 6.   8. The metal layer is gold, silver, aluminum, copper, nickel, tin, chromium and 7. The product of claim 6, wherein the product is made of a metal selected from the group consisting of those alloys. Layered structure.   9. The thermoplastic elastomer provides a predetermined dielectric constant of about 1 to about 50. 7. The laminated structure according to claim 6, further comprising a sufficient amount of filler.   10. The thermoplastic elastomer is       Polypropylene, polyethylene, and copolymers of ethylene and propylene A thermoplastic polymer component selected from the group consisting of       Crosslinked or uncrosslinked butyl rubber, natural rubber, ethylene-propylene rubber ( EPR), ethylene-propylene diene rubber (EPDM) and silicone rubber And an elastomer component selected from the group consisting of The laminated structure according to claim 6, comprising:   11. A dielectric substrate having a first surface and a second surface, wherein a loss tangent (tan δ) is approximately A substrate comprising a thermoplastic elastomer that is less than 0.2;       A metal circuit structure on the first surface of the substrate;       A metal layer on the second surface of the substrate; A laminated structure including:   12. (A) a thermoplastic elastomer having a loss tangent (tan δ) of less than about 0.005; Providing a stoma;             (B) the elastomer has a predetermined dielectric constant of about 1 to about 5; Adding a sufficient amount of a filler to provide the filler. A process selected from the group consisting of lamic and polymeric materials; A method for pacing the dielectric properties of a dielectric material, comprising:   13. (A) a thermoplastic elastomer having a loss tangent (tan δ) of less than about 0.2 Providing a substrate comprising the mer,             (B) bonding a metal layer to at least one surface of the substrate; A method of making a dielectric laminate, comprising: