Methods for creating electrical circuits in filled organic polymers

Abstract

An electrical circuit is created on the surface of an organic polymer. An electrical circuit 2 is created on a support 11 and a polymerizable composition 30A is brought into contact with the support and the circuit. The polymerizable composition is polymerized while in contact with the support and the electrical circuit to create a solid organic polymer 30. The electrical circuit 2 is adhered to and partially embedded in the surface of the solid organic polymer 30. After the polymerization step the support can be removed to expose the electrical circuit on the surface of the solid organic polymer.

Description

[Technical field]

[0001] The present invention relates to a method for producing electrical circuits on the surface of an organic polymer. [Background technology]

[0002] Hard surfacing materials are found in residential, commercial and institutional buildings. One such filled organic polymer product is manufactured and sold by DuPont under the Corian® brand name. Walls, ceilings, floors, countertops, tabletops and other surfaces are often made from or using such materials. Electrical components are often attached to or adjacent to these surfaces, most often by some type of mechanical attachment. To power these electrical components, electrical circuits must be installed. This is also done mechanically by running power lines behind or through the surfacing material to where they are needed. The mechanical installation of electrical components and electrical circuits is time consuming and expensive. The surfacing material often must be post-processed to create channels or other openings to accommodate the electrical components. This is often done on-site as part of the installation process. This method is expensive and time consuming.

[0003] US Patent No. 7,543,956 and US Patent Publication No. 2018-0162026 describe techniques for incorporating light emitting diodes into polymeric materials. US Patent No. 7,543,956 describes a method for embedding light emitting diodes and associated circuitry into polymeric hard surface materials. The diodes and associated circuitry are mounted on a sacrificial scaffold. A polymerizable material is poured around the circuitry, thereby encapsulating and embedding the circuitry. The polymerizable material is then polymerized. Mechanical methods such as polishing, grinding, drilling, screwing, and pin insertion are required to access the encapsulated electrical conductors.

[0004] US Patent Publication No. 2018-0162026 describes a method for applying electrical circuits to a transparent or translucent thermoplastic polymer that functions as a light guide. A decorative film is applied to a transfer sheet and the electrical circuit is printed onto the decorative sheet. Other functional components, such as LEDs, are then assembled onto the electrical circuit. A heat-softened thermoplastic polymer is then molded around the resulting assembly to encapsulate the electrical circuit and functional components. After the molten thermoplastic polymer is solidified, the transfer sheet is removed to reveal the decorative surface. Summary of the Invention [Means for solving the problem]

[0005] The present invention in one aspect is a method for producing an electrical circuit in a polymeric material, the method comprising: a) creating an electrical circuit on a surface of a support; b) contacting the substrate and the electrical circuit with a polymerizable composition comprising at least one organic polymer precursor; and then c) polymerizing the at least one organic polymer precursor while the polymerizable composition is in contact with the support and the electrical circuitry to produce a solid polymer layer comprising an organic polymer produced by polymerization of the at least one organic polymer precursor, the solid polymer layer having the electrical circuitry adhered to and at least partially embedded in its surface.

[0006] In certain embodiments, the method further comprises, after step c), a step d) of removing the support from the electrical circuitry and the solid polymer layer to expose the electrical circuitry.

[0007] In a particular aspect, the present invention is a method for producing an electrical circuit in a filled polymeric material, the method comprising: a) creating an electrical circuit on a surface of a support; b) contacting the substrate and the electrical circuitry with a polymerizable composition comprising: (i) one or more polymerizable materials comprising at least one acrylate monomer; and (ii) at least one particulate filler; and then c) polymerizing a polymerizable material of the polymerizable composition while the polymerizable composition is in contact with the support and the electrical circuitry to produce a filled, solid polymer layer comprising an acrylate polymer produced by polymerization of at least one acrylate monomer, the filled, solid polymer layer having the electrical circuitry adhered to and at least partially embedded in its surface.

[0008] The method of this particular aspect, in some embodiments, further comprises, after step c), step d) of removing the support from the electrical circuitry and the filled solid, electrically insulating acrylate polymer layer to expose the electrical circuitry.

[0009] The present invention also provides a) a solid polymeric material; b) an exposed electrical circuit adhered to and at least partially embedded in at least one surface of a solid, electrically insulating polymeric material.

[0010] In a particular embodiment, the present invention provides a method for producing a method for the treatment of a cancer a) a solid, filled acrylate polymer, the solid, filled acrylate polymer comprising 55-95% by weight of filler particles, the solid, filled acrylate polymer having a Vicat softening temperature (ISO 306, test condition B / 50N) of at least 75° C., a viscosity of at least 1×10 10 a solid filled acrylate polymer having a volume resistivity of ohms / cm and a Rockwell M scale hardness of at least 80; b) an exposed electrical circuitry adhered to and embedded in at least one surface of a solid, electrically insulating polymeric material. [Brief description of the drawings]

[0011] [Figure 1] FIG. 2 is a top view of a transfer sheet having an applied printed circuit used to produce a charged polymeric material according to the method of the present invention. [Diagram 2]FIG. 1 is a schematic diagram of a process for producing a charged polymeric material in accordance with the present invention. [Figure 3-3A] FIG. 3 is an isometric view of a charged polymeric material made in accordance with the present invention, and FIG. 3A is a cross-sectional side view of a charged polymeric material made in accordance with the present invention taken along line 3A-3A of FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The support is any material or combination of materials capable of generating an electrical circuit and that is sufficiently stable (mechanically, thermally, chemically and otherwise) under the conditions of steps (b) and (c) of the method that the electrical circuit can be transferred intact to the surface of the polymer layer. In some embodiments, the support is separable from the electrical circuit and the polymer layer after the polymerization step. In other embodiments, the support is not separable and remains with the product after the polymerization step. The support material can be rigid or flexible. The support material can consist of or include one or more functional components (in addition to the electrical circuit), such as, for example, decorative or protective films, that remain in the product after the polymerization step.

[0013] Rigid supports can be made, for example, from various metals, wood and wood products, such as plywood, particle board, and strand board, stone, engineered stone products (such as filled organic polymers as described herein), organic polymer structural panels that may be reinforced or cellular, organic polymer board stock, including board stock made from melt-processable organic polymers, such as expanded polystyrene, cardboard, gypsum, plaster, wallboard, concrete, and cement. Such rigid supports can be all or part of the mold or form in which or on which the polymerizable composition is contacted with the support and electrical circuitry and / or in which or on which the polymerizable composition is polymerized to form a solid organic polymer. In such embodiments, the support can be, for example, the bottom, side, or top surface of the mold or form whose surface is contacted with the polymerizable composition during step b) of the method of the present invention.

[0014] Flexible supports can be made, for example, from metal or organic polymer sheets, or paper products such as wallpaper, newsprint, kraft paper, or cardboard. The thickness of such sheets can be, for example, from 12.7 μm to 2540 μm (0.5 to 100 mils), with preferred thicknesses being up to 635 μm (25 mils) or up to 254 μm (10 mils).

[0015] A preferred support material is a transfer sheet, i.e., a flexible sheet that can be separated from the electrical circuit and polymer layer after the polymerization step. Organic polymers that are chemically, thermally and mechanically stable under the conditions of the polymerization step c) are useful as the constituent material of the transfer sheet. Examples of such organic polymers include, but are not limited to, polyimides, polyesters (including polyethylene terephthalate), polycarbonates, acrylics, styrene-based polymers (including copolymers), phenolic resins, and various polyolefins. The transfer sheet can be a single layer or multilayer structure, and the transfer sheet (or any of its constituent layers) can be, for example, a cast, meltblown, extruded film or sheet, or a plexifilament (such as DuPont's Tyvek® plexifilament sheet), and the transfer sheet (or any of its constituent layers) can be uniaxially or biaxially oriented or unoriented.

[0016] The transfer sheet can be surface treated in various ways that may be beneficial for the side that carries the electrical circuit. For example, the transfer sheet can be treated to enhance the adhesion of the electrical circuit. This can be done chemically by including an adhesion promoter in the sheet, or by corona discharge, plasma, UV or other treatment methods. Conversely, the transfer sheet can be surface treated to facilitate release from the electrical circuit and / or the polymer layer formed in step c) of the process. For example, a slip agent or other low surface energy material can be applied to the surface of the transfer sheet that carries the electrical circuit. Other surface treatments can include, for example, antistatic treatments.

[0017] Specific examples of suitable transfer sheets include those sold under the trade names Melinex® and Mylar®, both available from DuPont Teijin Films. The thickness of the transfer sheet can be, for example, from 12.7 μm to 2540 μm (0.5 to 100 mils), with preferred thicknesses being up to 635 μm (25 mils) or up to 254 μm (10 mils).

[0018] Electrical circuits typically include one or more components made from conductive materials such as graphite, carbon black, various metals such as silver, gold, aluminum, copper, platinum, iron, bronze, and brass, and conductive polymers such as poly(3,4-ethylenedioxythiophene).

[0019] Referring to FIG. 1, an electrical circuit transfer sheet 10 includes a support 11, which as shown is a flexible polymeric film, having an electrical circuit 2 printed or created on one surface thereof.

[0020] The electrical circuit is generated on the surface of the support using any convenient method. The electrical circuit thus generated can cover part or all of the transfer sheet. A convenient method is a printing method in which an ink having the desired electrical properties (conductive, resistive, dielectric, phosphor, etc.) is applied to the surface of the support. "Ink" is used in the context of the present invention to include both inks and pastes. Suitable printing methods and inks are well known in the art. For example, inkjet, stencil, screen, 3D, and transfer printing methods are useful. Conductive inks include one or more conductive materials as described above, and they are typically suspensions of particles of conductive material in a liquid carrier. Useful inks are commercially available. Examples of suitable inks include BQ221, BQ242, 7102, 7105, 8144, and CB028 carbon conductive materials, 4816N, 4922N, 4929N, 5000, 5021, 5025, 5028, 5029, 5064, 5065, 5069, 5504N, 5815, 7713, 7723, 9145, and 9169 silver conductive materials, 5870, 5874, and 5876. Examples of such inks include silver / silver chloride conductive material, 5524 silver / carbon conductive material, BQ321 platinum and BQ331 gold conductive materials, 7164 semi-transparent conductor material, 3571, 5018, 5018A, 5018G, 5036, and 8153 dielectric materials, and LuxPrint® 8150B, 8150L, ​​8152B, 8152K, and 8154L electroluminescent materials (all sold by DuPont Microcircuit Materials, Research Triangle Park, North Carolina, USA). Such inks are applied to a substrate in a preselected pattern and dried and / or cured as necessary to produce a circuit.

[0021] Other suitable methods for producing electrical circuits include photolithography and the so-called "pick-and-place" method.

[0022] The thickness of the electrical circuit of the support may be, for example, at least 1 μm, at least 5 μm, at least 10 μm, at least 15 μm, or at least 20 μm, and for example, up to 200 μm, up to 150 μm, up to 100 μm, or up to 50 μm, the preferred thickness depending on the electrical properties required for the various components of the electrical circuit. The thickness may be uniform or non-uniform.

[0023] In certain embodiments, the electrical circuit produced on the substrate includes a plated copper structure produced by printing a layer of conductive ink on the substrate to form a conductive ink pattern, and then plating copper onto all or a portion of the conductive ink pattern, as described, for example, in U.S. Patent Application Publication Nos. 2021-0249168, 2021-0249169, and 2021-0249902. This produces a multi-layer circuit having a layer of conductive ink and a layer of copper. As described therein, there may be an intervening layer of electroless metal.

[0024] The electrical circuit, in some embodiments, simply functions as a conductor to conduct power from a power source to one or more functional electrical components present in or external to the electrical circuit on the support. The electrical circuit may include one or more functional electrical components, which may be passive or active, limited only by the requirement that the electrical circuit be generated on the support and then transferred to the solid polymeric material, as described herein. The electrical circuit may include one or more current conductors, dielectric elements, resistive elements, capacitors, inductors, transformers, transistors (such as bipolar junction transistors, MOSFETs, FETs, and JEFTs), phosphor elements, and / or diodes (such as Zener diodes, photodiodes, Schottky diodes, and / or light emitting diodes). The electrical circuit may include one or more integrated circuits, application specific integrated circuits (ASICs), microcontrollers, and thin chip or flexible hybrid versions thereof. For example, as shown in Figures 1 and 3, all or part of the electrical circuitry may be a spiral structure, such as an Archimedes spiral or a rectangular shape, the opposite end of which may be coupled with an external capacitor to form a tank circuit, as described in US Patent Publications 2021-0249168 and 2021-0249902. Such a spiral structure or other circuitry may function as an antenna. The circuitry may be or include a capacitive sensing circuitry, a display circuitry, an audio circuitry, an accelerometer, a magnetometer, and / or a wireless (inductive) circuitry (such as a charging circuitry including a Q1 charging circuit). The circuitry may be a 3D printed circuit. An important advantage of the present invention is that it allows electronic circuits to be embedded in solid, electrically insulating polymeric materials, providing some protection to sensitive electrical components.

[0025] A polymerizable composition comprising at least one organic polymer precursor is applied to the surface of the transfer sheet and contacted with the electrical circuitry. By "polymer precursor" is meant one or more materials that react with other molecules of the same material and / or with other polymer precursors present in the polymerizable composition to produce an organic polymer.

[0026] One useful class of polymer precursors includes ethylenically unsaturated monomers, particularly those that are polymerizable at temperatures up to 180° C. Examples of ethylenically unsaturated monomers include alpha olefins (such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc.), vinyl aromatic monomers such as styrene, divinylbenzene, and vinyl naphthylene, vinyl acetate, vinyl chloride, vinylidene chloride, and preferably acrylate monomers. The term "acrylate monomer" is used herein to refer to monomers having one or more acrylate or methacrylate groups, such as acrylic acid, methacrylic acid, acrylic acid esters, e.g., methyl acrylate, ethyl acrylate, t-butyl acrylate, n-butyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, hydroxyethyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol penta / hexamethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerin triacrylate, glycerin trimethacrylate, and the like.

[0027] Other useful polymer precursors include precursors to polyisocyanate-based polymers that include one or more polyisocyanates and may include one or more curing agents, such as water, one or more polyols, one or more alkanolamines, one or more primary and / or secondary amine-containing compounds, etc.

[0028] Still other useful polymer precursors include vinyl ester resins, unsaturated polyester resins, phenolic resins, epoxy resins, and their hardeners.

[0029] The polymerizable composition may include various other ingredients as necessary or desired. Examples of such ingredients include, for example, polymerization catalysts, free radical initiators, chain transfer agents, crosslinking agents, interfacial coupling agents, colorants, antioxidants, biocides, UV absorbers, pigments, preservatives, and the like. Free radical initiators include various peroxides or azo compounds or combinations thereof. Free radicals can be generated by applying heat, UV light, activators / accelerators, or combinations thereof.

[0030] Particulate fillers are preferably present in the polymerizable composition. As used herein, "filler" refers to any material that is solid at room temperature and atmospheric pressure and insoluble in the various components of the polymerizable composition under the conditions encountered in the process of the present invention (including the polymerization step). Mineral and / or ceramic fillers are preferred. These include alumina trihydrate, porcelain, glass, quartz, quartz rock, gypsum, sand, silica, travertine, wollastonite, calcium carbonate, talc, feldspar, chert, chalcedony, alabaster, agate, various titanates, barium sulfate, lithopone, china clay, magnesite, mica, iron oxide, silicon dioxide, and various siennas. Such filler particles may have a d50 particle size, as determined by sieving methods, of 0.1 microns to 100 microns, more preferably 7 microns to 100 microns, and most preferably 10 microns to 50 microns.

[0031] The filler particles may be or include modified filler particles, for example, as described in US Pat. No. 9,338,295.

[0032] Other useful fillers include macroscopic decorative particles known in the industry as "crunchies". Crunchies are various filled or unfilled, colored or dyed chips of polymers such as ABS resins, cellulose esters, cellulose ethers, epoxy resins, polyethylene, ethylene copolymers, melamine resins, phenolic resins, polyacetals, polyacrylics, polydiene, polyesters, polyisobutylene, polypropylene, polystyrene, urea / formaldehyde resins, polyureas, polyurethanes, polyvinyl chloride, polyvinylidene chloride, polyvinyl esters, etc. Further examples of macroscopic decorative particles are chopped fibers, natural stone particles, plastic particles, glass particles, mirror particles, mica, and metal flakes.

[0033] The filler, in some embodiments, constitutes 20-95%, preferably 55-95%, of the total weight of the polymerizable composition and the solid polymer layer formed therefrom. The portion of the filler that is a decorative particle can, for example, constitute 1-25% of the total weight of the polymerizable composition and the solid polymer layer formed therefrom.

[0034] Particularly preferred polymerizable compositions include methyl methacrylate, preferably with a poly(methyl methacrylate) polymer dissolved therein. Crosslinking monomers having two or more acrylate and / or methacrylate groups, such as ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate, may be present. Such polymerizable compositions preferably include 55-95% by weight, based on the weight of the polymerizable composition, of one or more fillers, preferably one or more of alumina trihydrate, porcelain, and quartz, any of which may be modified with functional materials, particularly pigments, as described in U.S. Pat. No. 9,338,295. A free radical initiator, particularly a peroxy compound, is preferably present in an effective amount. Examples of peroxide free radical initiators include, for example, peroxymaleate esters as described in U.S. Pat. No. 3,234,194, metal salts of maleic acid hemiperesters as described in U.S. Pat. No. 3,362,942, hemiperesters of maleic acid as described in U.S. Pat. No. 3,450,088, lauroyl peroxide, benzoyl peroxide, t-butyl perbenoate and t-butyl peroxypivalate. Such preferred polymerizable compositions may include amine compounds such as trialkylamines, benzylamines, p-anisidine, 2,4,6-trimethylaniline, N-methyl p-toluidine, N,N-dimethyl p-toluidine, N,N-diethyl p-anisidine and N,N-dimethyl 2,5-dimethoxyaniline as described in U.S. Pat. No. 3,234,194. In addition, such preferred polymerizable compositions may include up to 1 weight percent water, up to 1 weight percent calcium hydroxide, and an effective amount of an accelerator. Mercapto compounds such as ethylene glycol dimercapto methacrylate are useful accelerators.

[0035] In a particularly preferred process, a syrup is formed that includes poly(methyl methacrylate) dissolved in methyl methacrylate. The syrup is mixed with a filler to form a slurry. A curing package is mixed with the slurry simultaneously with or after mixing of the filler and the syrup, and immediately prior to contacting the resulting polymerizable composition with the substrate and electrical circuitry. The curing package includes a free radical initiator and preferably an accelerator such as ethylene glycol dimercapto methacrylate or an amine compound as described above. The free radical initiator can be or include a metal salt of maleic acid hemiperester, which can be formed in situ by mixing maleic acid hemiperester acid with an alkali metal or alkaline earth metal base such as calcium oxide to neutralize the acid groups and form the salt. Thus, a particularly preferred curing package includes maleic acid hemiperester acid, an alkali metal and / or alkaline earth metal base such as calcium oxide, and an accelerator such as ethylene glycol dimercapto methylate.

[0036] The polymerizable composition is contacted with the support and the electrical circuitry. This step can be carried out, for example, by pouring or spraying the polymerizable composition onto the support and the electrical circuitry, or by placing the polymerizable composition in a container such as a mold or form and placing the electrical circuitry with its support on top of the polymerizable composition, as shown in Figure 2. During this step, the polymerizable composition is preferably in direct contact with the electrical circuitry, particularly without any intervening insulating material (such as wire insulation) between the electrical circuitry and the polymerizable composition.

[0037] The support is arranged so that the electrical circuit faces the polymerizable composition, for example, the electrical circuit faces up if the polymerizable composition is applied over the support and the electrical circuit, or faces down if the support and the electrical circuit are applied over the polymerizable composition. In the embodiment shown in FIG. 2, the electrical circuit is thus in direct contact with and covered by the polymerizable composition. The opposite side of the support is generally not covered by the polymerizable composition and remains open. This allows the support to be removed, if necessary, after the polymerizable composition has been polymerized.

[0038] 2, an electrical circuit transfer sheet 10 including electrical circuitry 2 present (such as by printing) on ​​the top surface of a support 11 (as shown) is placed at the bottom of a mold or trough 20. In Figures 2 and 3, the thickness of electrical circuitry 2 is greatly exaggerated for illustrative purposes. A polymerizable composition 30A is dispensed into the mold or trough 20 and contacts the top surfaces of the support 11 and electrical circuitry 2.

[0039] Another useful method of contacting the polymerizable composition with the support and electrical circuitry is to introduce the polymerizable composition into a mold or trough, or onto a form, belt or other supporting device, thereby creating an exposed surface, and place the support, with the electrical circuitry facing downwards, on the exposed surface of the polymerizable composition. This method is adaptable to continuous production by using a moving mold, trough, form, belt or other supporting device to continuously feed the electrical circuitry and its support onto the exposed surface of the polymerizable composition. The support and electrical surface are preferably applied to the top surface of the polymerizable composition. An advantage of this method is that it creates a good quality "show" surface on the opposite side of the electrical circuitry.

[0040] Another particularly useful method of contacting the polymerizable composition with the substrate and the electrical circuitry is to place the substrate with the electrical circuitry facing up on a moving platform and continuously pour or spray the polymerizable composition onto the moving substrate, such that continuous production is also possible.

[0041] The organic polymer precursor is then polymerized while the polymerizable composition is in contact with the support and the electrical circuitry. The polymerization conditions are selected with the particular polymer precursor. In addition, the polymerization conditions, particularly the temperature conditions, are such that the support and the electrical circuitry retain their physical dimensions and do not distort, melt, or otherwise thermally degrade. The preferred polymerizable compositions described above can polymerize spontaneously when formed at a temperature of 10-30°C without the addition of further heat. The polymerization temperature (including any exothermic temperature rise that may occur during the polymerization process) preferably does not exceed 180°C, more preferably does not exceed 150°C. Cooling can be applied to control the temperature rise due to the exotherm. Pressure conditions can vary widely, as long as the polymerizable composition remains in contact with the support and the electrical circuitry throughout the polymerization process.

[0042] Returning to FIG. 2, after optional leveling and gauging steps that determine the thickness of the resulting organic polymer layer 30, the polymerizable composition 30A is cured to form a solid organic polymer layer 30.

[0043] Polymerization is continued until the polymerizable composition is transformed into a solid polymer layer. The polymer layer includes an organic polymer produced in the polymerization of at least one organic polymer precursor. The electrical circuit is adhered to the surface of the solid organic polymer layer and at least partially embedded in the solid organic polymer layer, as shown in Figures 2 and 3A. In embodiments in which the support is subsequently removed, the electrical circuit is exposed, i.e., uncovered and open to the atmosphere.

[0044] 3 and 3A show an electrically charged polymeric material 1 of the present invention. The electrically charged polymeric material 1 includes a solid organic polymer layer 3 having an electrical circuit 2 adhered to a surface of the polymer layer and at least partially embedded in the polymer layer.

[0045] The solid organic polymer layer preferably has a Vicat softening temperature (ISO 306, test condition B / 50N) of at least 25° C. The Vicat softening temperature is preferably at least 50° C., at least 75° C., or at least 100° C. The organic polymer component of the organic polymer layer preferably has a glass transition temperature, as measured by dynamic mechanical analysis (DMA), of at least 25° C., preferably at least 50° C., at least 75° C., or at least 100° C. If crystalline or semi-crystalline, the organic polymer component of the organic polymer layer may have a crystalline melting point, as measured by differential scanning calorimetry, of at least 25° C., preferably at least 50° C., at least 75° C., or at least 100° C.

[0046] The solid organic polymer layer, in some embodiments, is electrically insulating, having a volume resistivity, measured according to ATSM D257, of at least 1×10 10 ohms / cm, and preferably the volume resistivity is at least 1×10 12 Ohms / cm, or at least 1×10 14 In other embodiments, the solid organic polymer layer is conductive and / or semiconductive, with a volume resistivity of 1×10 10 Less than ohms / cm (e.g., 1×10 8 ~9.9×10 9 The electrical conductivity of the polymerizable composition and the resulting solid organic polymer layer can optionally include conductive fillers such as metals, graphite, carbon black, and the like to enhance their electrical conductivity.

[0047] The solid organic polymer can have a dielectric constant of at least 2, preferably at least 3 (vacuum=1), measured according to ASTM D150-18. The polymerizable composition and the resulting solid organic polymer layer can optionally include particles of dielectric materials, such as calcium oxide, silicon dioxide, alumina, and fumed silica, to increase their dielectric constant. For example, fillers modified with such dielectric particles, such as those produced according to the process described in U.S. Pat. No. 9,338,295, can be present in the polymerizable composition and the resulting solid organic polymer.

[0048] The solid organic polymer layer, in some embodiments, has a Mohs scale hardness (ASTM C1895) of at least 3, preferably at least 3.5, and / or a Rockwell M hardness (ASTM D785) of at least 80, especially 85-95.

[0049] The organic polymer present in the solid organic polymer layer may be a thermoplastic or a thermoset material. The organic polymer may be linear, branched, or crosslinked.

[0050] The thickness of the solid organic polymer layer may be, for example, from 1 mm to 50.8 mm or more. Preferred thicknesses for products useful as hard facing materials are at least 3 mm, preferably at least 6 mm, up to 50.8 mm, preferably up to 25.4 mm or up to 20 mm.

[0051] After the polymerization step, the solid organic polymer layer and electrical circuitry are, in some embodiments, separated from the support, as shown in Figure 2. In the preferred case where the support is a transfer sheet, this is typically accomplished by simply peeling the transfer sheet from the product. If the support is all or part of a mold or form, the separation step is accomplished by removing the product from the mold or form.

[0052] After the support is removed, the electrical circuitry is exposed and it may be desirable to apply one or more layers of another material over the circuitry to sandwich the electrical circuitry. This can be done in a variety of ways.

[0053] In some embodiments, a second layer of polymerizable composition is applied to the exposed electrical circuitry and polymerized as before, thereby producing a sandwich structure in which the electrical circuitry forms the intermediate layer. The second layer of polymerizable composition, and the resulting solid organic polymer layer, can be the same or different from the layer to which the electrical circuitry was applied.

[0054] In addition, various other protective and / or functional layers can be applied over the exposed electrical circuitry using mechanical, adhesive, thermal, or other means. For example, a layer of preformed solid organic polymer layer, which may be the same or different as that carrying the exposed electrical circuitry, can be applied over the electrical circuitry to form such a sandwich structure. The organic layers can be bonded using methods that do not compromise the integrity of the electrical circuitry, such as mechanical or adhesive methods. When the organic layer is or includes a polymer of methyl methacrylate (which may include a filler material as described above), a suitable method of bonding the organic polymer layer is to use an adhesive system that includes a methyl methacrylate monomer and a free radical initiator. Such an adhesive system can be a two-part adhesive system with the monomer and initiator packaged separately, the parts being combined to produce a curable adhesive. Such adhesive systems are commonly used to bond separate portions of organic polymer sheets during installation of the product to form, for example, countertops, walls, or other hard surfaces. This method is a convenient way to provide electrical circuitry between the seams of such installations.

[0055] Alternatively, an adhesive, including those just described, can be applied over the exposed electrical circuitry and cured to create a protective layer.

[0056] The product of the invention ("charged polymeric material") is a solid organic polymer having an electrical circuit adhered to at least one surface thereof, the surface of the electrical circuit being exposed. The electrical circuit is preferably embedded in the organic polymer, the exposed surface being approximately flush (e.g., no more than 20 μm, particularly no more than 5 μm, or no more than 2 μm higher or lower) with adjacent surfaces of the organic polymer. The solid organic polymer is preferably substantially non-porous, with a void volume of no more than 5%, more preferably no more than 1%, and a bulk density of no more than 1 g / cm. 3 More preferably, 2 g / cm 3 Exceeds.

[0057] Charged polymeric materials are useful in many applications and in the creation of a number of devices.

[0058] One application is in pre-wired walls, floors, ceilings, table tops, counter tops, and other building surfaces. In such applications, the electrical circuitry can function as a power line that delivers low voltage DC current (such as 30V or less) and / or typical utility AC current (such as 110V / 60Hz or 230V / 50Hz power) from a power source through the building surface. Such pre-wired building surfaces can, for example, deliver power to electrical equipment connected (permanently or temporarily) to the pre-wired building surface or adjacent to the pre-wired building surface. This provides a method of installing wiring in a building by simply installing the building surface, without the need for separate wiring at the location where the pre-wired building surface is installed.

[0059] Another application is functional building surfaces, i.e. building surfaces with embedded electric or electronic devices. Examples of such embedded electric or electronic devices include charging devices, card readers such as credit and bank card readers, lighting, displays, heating devices, capacitive sensing devices, accelerometers, magnetometers, and / or wireless (inductive) circuits (charging circuits, transmitters and receivers, Q1 charging circuit, etc.), many others, and components of any of the above.

[0060] Various connectors, ports, and the like can be provided on the charged polymeric material as needed or as is convenient for connecting to power sources, to other charged polymeric materials of the present invention, and / or to various functional devices. These can optionally be provided during the manufacturing process of the charged polymeric material or can be provided later. EXAMPLES

[0061] The following examples are offered to illustrate the invention but are not intended to limit its scope. All parts and percentages are by weight unless otherwise indicated.

[0062] Example 1 The electrical circuit is printed onto a 125 μm heat stabilized, corona treated poly(ethylene terephthalate) transfer film (Melinex® ST505 from Tekra, LLC) using silver conductive ink (DuPont Microcircuit Materials 5000) and a TF-226 pattern, 325ss mesh, 1.1 wire, 30 angle screen. The printing pressure is 35 psi (241 kPa), the flood is 25.4 μm, and the line speed is 10.16 cm / sec. Drying is performed at a temperature of 130° C. The print thickness is approximately 10 μm.

[0063] The printed transfer film is placed in the bottom of a box mold with the printed circuit facing up. A polymerizable composition including methyl methacrylate, dissolved poly(methyl methacrylate), a peroxy free radical initiator, 55-80 weight percent based on the total weight of alumina trihydrate particles, and ethylene glycol dimercaptoacetate is poured over the transfer film and in contact with the printed electrical circuit to form a layer approximately 12.7 mm thick covering the printed electrical circuit. The polymerizable composition is then cured in the box mold at a temperature of approximately 130° C. to produce a filled, solid polymer suitable for use as a hard surface material. The polymer is removed from the box along with the electrical circuit and transfer sheet and allowed to cool to approximately room temperature. The transfer sheet is then peeled away, leaving the entire electrical circuit adhered to the surface of the organic polymer. Upon inspection, the electrical circuit is found to be embedded in the organic polymer with its top surface exposed. Electrical testing confirms that the electrical circuit functions as designed.

[0064] Example 2 Example 1 is repeated, this time replacing the silver conductive ink with a carbon conductive ink (Dupont Microcircuit Materials 7102). The pressure is increased to 42 psi (290 kPa) and the line speed is reduced to 7.6 cm / sec. The print thickness is 12.6 μm. The transfer sheet is removed leaving the entire electrical circuit with the organic polymer partially embedded therein and with the surface exposed. Electrical testing confirms that the electrical circuit functions as designed.

[0065] Example 3 Example 1 is repeated again using a transfer film with an LED circuit printed on it. The LEDs are arranged in a striped pattern of 16 columns and 10 rows. There are 4 alternating rows of blue and green LEDs. When the transfer sheet is removed, the entire electrical circuit including the LEDs remains with the organic polymer, partially embedded within it and with the surface exposed. When current is applied to the circuit, the LEDs all function normally.

Claims

1. 1. A method for producing an electrical circuit in a polymeric material, comprising: a) creating an electrical circuit on a surface of a substrate; b) contacting said substrate and said electrical circuit with a polymerizable composition comprising at least one organic polymer precursor; and then c) polymerizing the at least one organic polymer precursor while the polymerizable composition is in contact with the substrate and the electrical circuit to produce a solid polymer layer comprising an organic polymer produced by the polymerization of the at least one organic polymer precursor; The solid organic polymer layer has the electrical circuitry adhered to and at least partially embedded in its surface.

2. The polymerizable composition comprises (i) at least one acrylate monomer; (ii) at least one particulate filler; The method of claim 1, wherein the particulate filler comprises 55 to 95 weight percent of the polymerizable composition.

3. 1. A method for creating an electrical circuit in a filled polymeric material, comprising: a) creating an electrical circuit on a surface of a substrate; b) (i) one or more polymerizable materials comprising at least one acrylate monomer; and (ii) at least one particulate filler. contacting the substrate and the electrical circuit with a polymerizable composition comprising: c) polymerizing the polymerizable material of the polymerizable composition while the polymerizable composition is in contact with the substrate and the electrical circuit to produce a filled solid polymer layer comprising an acrylate polymer produced by the polymerization of the at least one acrylate monomer; The filled solid polymer layer has the electrical circuit adhered to and at least partially embedded in its surface.

4. After step c), 4. The method of claim 3, further comprising step d) removing the support from the electrical circuitry and the filled solid acrylate polymer layer to expose the electrical circuitry.

5. The method of claim 3 , wherein the acrylate monomer comprises methyl methacrylate.

6. The method of any one of claims 3 to 5, wherein the particulate filler comprises alumina trihydrate.

7. a) a solid polymeric material; b) an exposed electrical circuit adhered to and embedded in at least one surface of said solid polymeric material.

8. a) a solid filled acrylate polymer, the solid filled acrylate polymer comprising 55 to 95 wt. % filler particles, the solid filled acrylate polymer having a Vicat softening temperature (ISO 306, test condition B / 50N) of at least 75°C, a viscosity of at least 1 x 10 10 a solid, filled acrylate polymer having a volume resistivity of ohms / cm and a Rockwell M scale hardness of at least 80; b) an exposed electrical circuit adhered to and embedded in at least one surface of said solid polymeric material; 1. An electrically charged polymeric material comprising:

9. 9. The charged polymeric material of claim 8, wherein the filler particles comprise decorative particles, the decorative particles comprising 1 to 25 percent of the total weight of the solid, filled acrylate polymer.

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