Polyphenylene sulfide compositions and molded articles thereof for laser direct forming processes

Abstract

This document discloses a composition comprising: a. about 30% to about 70% by weight of polyphenylene sulfide; b. more than 0% to about 10% by weight of a polyphenylene sulfide-containing resin; c. about 5% to about 15% by weight of a laser-activated metal compound; and d. about 10% to about 70% by weight of an inorganic filler, wherein the combined weight percentage of all components does not exceed 100% by weight, and all weight percentages are based on the total weight of the composition.

Description

Invention Field

[0001] This disclosure relates to materials containing polyphenylene sulfide, and particularly to polyphenylene sulfide materials for laser direct forming (structuring) applications. Background Technology

[0002] Laser direct forming (LDS) provides a process for applying conductive pathways to the surface of non-conductive materials. This process has been widely used in electronic applications such as antennas and circuits. Compared to conventional methods such as hot stamping and two-shot molding, LDS exhibits many advantages in design capability, cycle time, cost efficiency, device miniaturization, versatility, and functionality. Numerous LDS compounds have been developed based on various polymer resins, including polycarbonate, polyamide, and polyester. Polyphenylene sulfide (PPS) is expected to be a promising base resin for LDS applications, including antennas, due to its cost-effectiveness and well-balanced mechanical, thermal, and dielectric properties. However, the development of PPS-based LDS resins is limited.

[0003] There is still a need in this field for LDS materials based on polyphenylene sulfide. Summary of the Invention

[0004] The above and other deficiencies in the art are satisfied by a thermoplastic composition comprising: about 30% to about 70% by weight of polyphenylene sulfide; about greater than 0% to about 10% by weight of a polyphenylene sulfide-containing resin; about 5% to about 15% by weight of a laser-activated metal compound; and about 10% to about 70% by weight of an inorganic filler. The combined weight percentage of all components does not exceed 100% by weight, and all weight percentages are based on the total weight of the composition.

[0005] The above and other features are illustrated by the following detailed description, examples and claims. Detailed Implementation

[0006] The present disclosure can be more readily understood by referring to the specific embodiments and examples included in the following intended implementation. In the following description and subsequent claims, numerous terms will be used, which have the following meanings.

[0007] Laser-activated semiconductor material (LDS) processes, capable of providing conductive structures on non-conductive plastic surfaces, have been widely used in electronic applications. Compared to conventional methods such as hot stamping and two-shot molding, LDS offers advantages in design capability, cycle time, cost efficiency, miniaturization, versatility, and functionality of a given device. For the fabrication of LDS-capable thermoplastics, a laser-activated (or activatable) component is necessary to release metal seeds after laser treatment. Many LDS thermoplastics have been developed based on various polymer resins such as polycarbonate, polyamide, and polyester. However, progress on polyphenylene sulfide (PPS) as a base thermoplastic resin for LDS materials has been limited. PPS is a cost-effective resin with very balanced mechanical, thermal, and dielectric properties, making it ideal for many LDS-related applications such as antennas and circuits.

[0008] While PPS resins generally possess the properties desired for LDS applications, it remains unclear why they are conventionally considered unsuitable for such applications. Without being bound by any particular theory, theoretically, the sulfides in both the main polymer chain and end groups of PPS resin reduce the activity of laser-activated additives present within the resin. This is particularly evident for copper-based LDS additives. However, the conventional approach of significantly increasing the loading of LDS additives to improve LDS activity in the PPS resin matrix can weaken the mechanical properties of the material and significantly increase costs. The low LDS activity of PPS resins has been an unresolved problem for a considerable period, which explains the lack of mature PPS-based LDS compounds on the market. Attempts have been made to address the activity problem by doping with highly loaded LDS additives; however, this approach significantly degrades mechanical properties and is extremely expensive, making it largely uncommercially viable. Based on our research, the use of high molecular weight PPS resins appears to be a promising approach to solving the LDS activity problem. PPS is a polymer with sulfur in both the main chain and end groups, while LDS processes typically require copper as a seed to initiate the plating (electroplating) process. However, copper and sulfur readily form highly stable compounds, such as copper sulfide, which reduces the activity of LDS additives. Sulfur present on the main chain is not reactive with copper, but end-capping groups derived from synthesis and decomposition during processing react with copper. Following this principle, it makes sense that high-Mw PPS has a relatively low amount of end-capping groups and improves the LDS activity of PPS LDS compounds.

[0009] This article presents robust PPS-based LDS compositions that exhibit strong LDS properties, good flame retardancy, good mechanical properties (especially ductility) and good thermal stability.

[0010] International patent application No. WO 2020130365A1 discloses a polyphenylene sulfide resin composition for laser coating, which includes PPS, LDS additives, and glass fibers. However, these composites include a coating seed-generating promoter and do not incorporate polyphenylene sulfide.

[0011] International patent application No. WO 2015094805A1 discloses a polyarylene sulfide composition comprising polyarylene sulfide, a laser-activated additive, and a fiber filler. This composition does not contain polyphenylene ether.

[0012] International patent application No. WO 2020116769A1 describes a laser direct molding resin composition comprising polyarylene sulfide, LDS additive, and reinforcing filler. This composition does not contain polyphenylene ether.

[0013] Korean Patent Application No. KR 2020070501A discloses an LDS composition comprising a polyarylene sulfide resin, a reinforcing material, and an LDS additive modified with an aminosilane surface. However, the disclosed composition does not specifically provide a combination of polyarylene sulfide and polyphenylene ether. Furthermore, this application does not disclose flame retardancy or high-heat properties.

[0014] International patent application No. WO 2015144630A1 describes thermoplastic compositions comprising a resin matrix, a reinforcing agent, and a laser direct molding additive. However, these compositions do not include polyphenylene sulfide and polyphenylene sulfide blends.

[0015] Therefore, although some PPS compositions have been prepared to have LDS coating properties, this disclosure combines a specific combination of PPS resin, PPO resin, LDS additives and inorganic fillers for flame retardancy, thermal properties, mechanical properties and LDS coating properties.

[0016] Furthermore, articles prepared according to any of the methods described herein are within the scope of this disclosure. For example, articles produced using the materials and methods of this disclosure include those in the electrical field, such as computers, antennas, and lighting articles.

[0017] Before disclosing and describing the compounds, compositions, articles, systems, devices, and / or methods of the present invention, it should be understood that, unless otherwise specified, they are not limited to specific synthetic methods, or, unless otherwise specified, not limited to specific reagents, and therefore variations are naturally possible. It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting.

[0018] This disclosure covers various combinations of elements of this disclosure, such as combinations of elements from dependent claims that depend on the same independent claim.

[0019] Furthermore, it should be understood that, unless otherwise expressly stated, no method listed herein is intended to be construed as requiring its steps to be performed in a particular order. Therefore, where a method claim does not actually describe the order in which its steps are followed, or where the claims or embodiments do not otherwise specifically state that the steps will be limited to a particular order, no order is intended to be inferred in any way. This applies to any possible non-expressive basis of interpretation, including: logical questions concerning the arrangement of steps or the flow of operations; the general meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.

[0020] thermoplastic composition

[0021] This disclosure relates to thermoplastic compositions comprising at least polyphenylene sulfide (PPS), polyphenylene oxide (PPO), laser-activated metal compounds, and inorganic fillers.

[0022] In various aspects, this disclosure provides composite materials that can be used to manufacture laser-activated polyphenylene sulfide (PPS)-based materials. The flame retardancy, heat distortion characteristics, and mechanical properties of these materials have been evaluated. These materials exhibit specific coating properties. Based on PPS, PPO, laser-realizable metal compounds, and filler building blocks, laser-coated thermoplastic compositions with robust LDS performance (specifically, a coating index greater than 0.7), good flame retardancy, high thermal properties (specifically, a heat distortion temperature greater than 270°C at 0.45 MPa according to ISO-75), and balanced mechanical properties have been developed. High viscosity (melt volume flow rate less than 50 cm³ / 10 min under 300°C / 2.16 kg test conditions) has been found. 3 High molecular weight PPS (Mw > 40,000 Daltons and Mn > 9,000, as measured by gel permeation chromatography (GPC)) is crucial for robust LDS activity. Antimony-doped tin oxide has been found to be an effective LDS additive for PPS. The plating performance of the composition was further improved by combining PPS and PPO with a blended LDS additive system. The plating index (PI) of the composition was greater than 0.7, indicating that the developed PPS-based LDS compound exhibited excellent plating performance.

[0023] polyphenylene sulfide

[0024] In various respects, the disclosed compositions may comprise polyaryl sulfides, such as polyphenylene sulfide (PPS). PPS can describe polymers containing an optionally substituted benzene ring linked to (S) and can be used interchangeably with poly(2,6-dimethyl-p-phenylene sulfide). Additionally, the disclosed compositions may comprise specific combinations of PPO resins that provide a balance of specific properties for the composition.

[0025] The PPS polymer has at least 50 mol% repeating units (1) relative to the total number of repeating units in the PPS polymer. In some aspects, the PPS polymer has at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% repeating units relative to the total number of repeating units in the PPS polymer. The repeating unit (1) is represented by the following formula:

[0026]

[0027] Where R 1 The elements at each position are independently selected from alkyl, aryl, alkoxy, aryloxy, alkyl ketone, aryl ketone, fluoroalkyl, fluoroaryl, bromoalkyl, bromoaryl, chloroalkyl, chloroaryl, alkyl sulfone, aryl sulfone, alkylamide, arylamide, alkyl ester, aryl ester, fluorine, chlorine, and bromine; i is an integer from 0 to 4, preferably 0; and t is an integer greater than 50, preferably greater than 100. As used herein, a dashed bond indicates a bond with an atom outside the repeating unit. For example, a dashed bond can be a bond with the same repeating unit, a different repeating unit, or an atom of a non-repeating unit (more specifically, a capping group). PPS polymers may include one or more additional repeating units (1). In such cases, each additional repeating unit may be different from and distinct from one another.

[0028] In various respects, PPS polymers may include metal end-capping agents, including but not limited to sodium end-capping agents. Sodium end-capping agents are represented by a formula consisting of groups selected from the following:

[0029]

[0030] Where M is Na and n is 2. Those skilled in the art will recognize that PPS polymers comprise multiple polymer chains having two ends (terminals). Therefore, such chains can have 0 to 2 end-capping agents. End-capping agents where M is Na are called sodium end-capping agents.

[0031] Polyphenylene sulfide (PPS) can have specific viscosities. In various aspects, PPS can exhibit high viscosity. When tested according to ISO-1133 at 300°C / 2.16 kg, the characteristic of high viscosity can be less than 50 cubic centimeters per 10 minutes (cm³). 3 Melt volume rate ( / 10min.).

[0032] Polyphenylene sulfide (PPS) can have specific molecular weights. In some respects, PPS can have high molecular weights. More specifically, PPS can have a molecular weight greater than 40,000 Daltons. In other respects, PPS can have a molecular weight (Mn) greater than 9,000 Daltons.

[0033] The disclosed polyphenylene sulfide can have specific end-capping groups. Surprisingly, it has been found that PPS polymers end-capped with specific amounts of specific end-capping agents exhibit significantly improved melt stability. For example, those with -SH end-capping groups show improved melt stability at 300°C for 1000 s according to ISO-1133 testing. -1 The lower part is greater than 150cm 3 / 10 minutes, or less than 50cm at 300℃ and 2.16kg. 3 PPS polymers applied for 10 minutes of MVR can result in improved plating performance (i.e., a plating index greater than 0.7 when tested according to the resonant ca method). Due to the significantly improved melt stability, PPS polymers can be advantageously introduced into melt processing technologies.

[0034] Polyphenylene sulfide can be present in the disclosed composition in an amount of about 30% to about 70% by weight based on the total weight of the composition. For example, polyphenylene sulfide can be present in amounts of 30% to 65% by weight, 25% to 70% by weight, 28% to 70% by weight, 40% to 65% by weight, 25% to 75% by weight, 50% to 70% by weight, or 30% to 75% by weight.

[0035] polyphenylene ether

[0036] In various respects, the disclosed compositions may comprise polyphenylene ethers, such as polyphenylene ether (“poly(p-phenylene ether)”) PPO. PPO can describe a polymer containing an optionally substituted benzene ring linked to oxygen (O) and can be used interchangeably with poly(p-phenylene ether) or poly(2,6-dimethyl-p-phenylene ether). Additionally, the disclosed compositions may comprise specific combinations of PPO resins that provide a balance of specific properties for the composition.

[0037] Polyphenylene ether can exist as a polyphenylene ether resin. In other respects, polyphenylene ether can exist as a polyphenylene ether copolymer.

[0038] Certain aspects of the composition include from about 0% to about 10% by weight of polyphenylene ether or polyphenylene ether copolymer. Polyphenylene sulfide can be present in the disclosed composition in an amount from about 30% to about 70% by weight based on the total weight of the composition. For example, polyphenylene sulfide can be present in amounts from 0.01% to 10% by weight, 0.1% to 10% by weight, 1% to 10% by weight, 2% to 10% by weight, 3% to 10% by weight, 0.01% to 8% by weight, 0.1% to 8% by weight, 1% to 8% by weight, 2% to 8% by weight, 3% to 8% by weight, 0.01% to 6% by weight, 0.1% to 6% by weight, 1% to 6% by weight, 2% to 6% by weight, or about 3% to 6% by weight.

[0039] Laser-activated compounds

[0040] The compositions disclosed herein also include laser-activated or laser-direct forming (LDS) additives. The LDS additives are selected to enable the composition to be used in laser-direct forming processes. In an LDS process, a laser beam exposes the LDS additive to the surface of the thermoplastic composition and activates metal atoms from the LDS additive. Therefore, the LDS additive is selected such that metal atoms are activated and exposed upon exposure to the laser beam, and no metal atoms are exposed in areas not exposed to the laser beam. Furthermore, the LDS additive is selected such that, after exposure to the laser beam, the etched areas can be plated to form a conductive structure.

[0041] As used herein, laser-activated additives can refer to additives or reagents that are activated by a physicochemical reaction induced by laser energy (such as a focused laser beam). For example, laser-activated additives can be introduced into thermoplastics. The additive can be activated by a laser beam. The physicochemical reaction forms metal nuclei. These nuclei can act as catalysts for reductive copper plating. In addition to activation, the laser beam can also create a micro-roughened surface on which copper is anchored during the metallization process.

[0042] As used in this article, "capable of plating" means that a substantially uniform metallic plating layer can be deposited onto the material in the laser-etched area. This process differs from laser marking, where the primary result is a change in material color under the effect of energy radiation. A key characteristic of laser marking is the contrast between the mark and the substrate.

[0043] Conversely, for LDS, the goal is to form a metal seed on the laser-etched surface and then form the final metallized layer during the subsequent plating process. The plating coverage and adhesion of the plated layer are key evaluation requirements. Here, color refers to the substrate itself, not discoloration under laser irradiation. Therefore, in addition to enabling the composition to be used in laser direct forming processes, the LDS additives used in this disclosure are selected to help enable the composition to be colored while maintaining its physical properties.

[0044] LDS additives can be configured to allow the formation of conductive pathways via standard electroless plating processes after laser activation. When the LDS additive is exposed to a laser, the elemental metal is released. The laser patterns the circuit onto the component, leaving a rough surface containing embedded metal particles. These particles act as nuclei for crystal growth during subsequent plating processes, such as copper plating. Other electroless plating processes that can be used include, but are not limited to, gold, nickel, silver, zinc, and tin plating.

[0045] Aspects of thermoplastic compositions include laser direct forming (LDS) additives. In some aspects, LDS additives include copper chromate black, basic copper phosphate, tin-antimony tin lime, or combinations thereof. Cassiterite may refer to tin oxide materials. An exemplary copper chromate black LDS additive is Black 1G, available from The Shepherd Color Company. An exemplary basic copper phosphate is Iriotec, available from Merck. TM 8840. An exemplary tin-antimony tin lime (antimony-doped tin oxide) is S-5000, which is available from Ferro.

[0046] In some aspects, LDS additives can be present in the thermoplastic composition in amounts from 0.5 wt% to 20 wt%, or from about 0.5 wt% to about 20 wt%. In other aspects, LDS additives can be present in the thermoplastic composition in amounts from 0.5 wt% to 15 wt%, or from about 0.5 wt% to about 15 wt%, or from 1 wt% to 10 wt%, or from about 1 wt% to about 10 wt%, or from 2 wt% to 12 wt%, or from about 2 wt% to about 12 wt%, or from 2 wt% to 8 wt%, or from about 2 wt% to about 8 wt%, or from 3 wt% to 6 wt%, or from about 3 wt% to about 6 wt%. In various examples, the composition may contain combinations of LDS additives. The amount of LDS additives included is sufficient to coat the traces formed after laser activation without adversely affecting the mechanical properties. In some aspects, for the purposes of this disclosure, titanium dioxide (when present) may be excluded from the amount of LDS present in the thermoplastic composition.

[0047] It is believed that LDS additives contribute to an improved coating index in thermoplastic compositions compared to those without LDS additives.

[0048] As used in this article, the plating index can be defined as the ratio between the average copper thickness of the test sample under specific laser parameters and that of a reference sample. The reference sample used in this article is the commercially available Pocan. TM DP 7102 is a PBT-based LDS. Generally, a plating index greater than 0.7 is desirable.

[0049] The plating index can be determined using the "LPKF method" or "LPKF-LDS method" established by LPKF Laser & Electronics, through a two-step process of laser etching and copper chemical deposition for 45 minutes. In the first step, a molded veneer of the material to be evaluated (e.g., a thermoplastic composition) is laser-etched / structured in LPKF mode, where the laser variables are power, frequency, and speed. Following this step, the laser-structured veneer and a reference rod (reference material, commercially available Pocan from Lanxess) are placed together. TM The DP 7102 was placed in a copper bath until the copper thickness of the reference bar was approximately 5 μm. The cladding and reference bar were then removed, rinsed, and dried. The copper thickness of the reference bar was measured twice on each side using the XRF method (according to ASTM B568 (2014)), and the average was taken at all four points. This was labeled X. ref Then, measure two points for each parameter domain and average the results for each domain. The plating index can be calculated as follows:

[0050]

[0051] Therefore, in some aspects, the thermoplastic composition has a coating index of at least 0.15. In other aspects, the thermoplastic composition has a coating index of at least 0.20, or at least 0.25, or at least 0.30, or at least 0.35, or at least 0.40, or at least 0.45, or at least 0.50, or at least 0.55, or at least 0.60, or at least 0.65, or at least 0.70.

[0052] The LDS additives used in this disclosure may have a core-shell (or specified as core / shell) structure, wherein the core is coated with a laser-activated component (i.e., the shell). The “laser-activated component” is the component that releases metal seeds upon laser activation. The metal seeds can act as catalysts for electroless plating.

[0053] Inorganic packing

[0054] The compositions of the present invention may contain inorganic fillers or reinforcing agents. The specific composition of the filler (if present) may vary, provided that the filler is chemically compatible with the remaining components of the thermoplastic composition.

[0055] Suitable inorganic fillers may include, but are not limited to, metal silicates and silica powders; boron-containing oxides of aluminum (Al), magnesium (Mg), or titanium (Ti); anhydrous or hydrated calcium sulfate; wollastonite; hollow and / or solid glass spheres; kaolin; single-crystal metal or inorganic fibers or “whiskers”; glass fibers (including continuous and chopped fibers, including flat glass fibers); sulfides of molybdenum (Mo) or zinc (Zn); barium compounds; metals and metal oxides; sheet fillers; fiber fillers; short inorganic fibers; reinforced organic fiber fillers formed from organic polymers capable of forming fibers (e.g., polyetheretherketone (PEEK), polyetherimide (PEI), polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS)); and fillers and reinforcing agents such as mica, clay, feldspar, soot, magnesium aluminosilicate, quartz, quartzite, perlite, diatomite, diatomaceous earth, carbon black, etc., or combinations containing at least one of the aforementioned fillers or reinforcing agents. In some aspects, one or more fillers may comprise inorganic materials, which may include clay, titanium dioxide, asbestos fibers, silicate and silica powders, boron powder, calcium carbonate, talc, kaolin, sulfides, barium compounds, metals and metal oxides, wollastonite, glass beads, glass fibers, sheet fillers, fiber fillers, natural fillers and reinforcing materials, as well as reinforcing organic fiber fillers. In some aspects, the composite material may comprise glass fiber fillers. In another aspect, the composite material may contain no or substantially no glass fillers. In one aspect, the composition comprises inorganic fillers selected from glass fibers, glass sheets, talc, clay, mica, wollastonite, titanium dioxide, or combinations thereof. Mineral fillers, such as talc.

[0056] In some instances, the ceramic filler component can be present in amounts from about 10 wt% to about 70 wt%. In other instances, the ceramic filler can be present in amounts from 10 wt% to about 60 wt%, from 10 wt% to about 50 wt%, from 15 wt% to about 50 wt%, from 15 wt% to about 45 wt%, from 20 wt% to about 70 wt%, from 20 wt% to about 65 wt%, from 25 wt% to about 70 wt%, or from 25 wt% to about 60 wt%.

[0057] additive

[0058] The composition may include a variety of additives typically introduced into polymer compositions of this type, provided that one or more additives are selected so as not to significantly adversely affect the desired properties of the thermoplastic composition (e.g., good compatibility). These additives may be mixed at appropriate times during the mixing of the components used to form the composition. The total amount of all additives in the resin composition may be, for example, from 0.001 to 12% by weight, each based on the total weight of the composition. Suitable additives may include UV agents, UV stabilizers, heat stabilizers, antistatic agents, antimicrobial agents, anti-drip agents, radiation stabilizers, pigments, dyes, fibers, fillers, plasticizers, flame retardants, antioxidants, lubricants, wood, glass, and metals, and combinations thereof.

[0059] According to certain aspects, even with high levels of filler (e.g., more than 30% by weight of filler based on the total weight of the polymer composition), the polymer composition can maintain mechanical properties and dielectric strength.

[0060] The composite materials disclosed herein may contain one or more additional fillers. The fillers may be selected to impart additional impact strength and / or provide additional characteristics based on a final selected feature of the polymer composition. In some aspects, the composite material may contain glass fiber fillers. In another aspect, the composite material may contain no or substantially no glass fillers.

[0061] Additional suitable fillers or reinforcing agents may include, for example, mica, clay, feldspar, quartz, quartzite, perlite, diatomite, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, pyrolytic silica, sand, boron nitride powder, borosilicate powder, calcium sulfate, calcium carbonate (such as chalk, limestone, marble, and synthetic precipitated calcium carbonate), talc (including fibrous, modular, acicular, and layered talc), wollastonite, hollow or solid glass spheres, silicate spheres, hollow microspheres (cenospheres), aluminosilicates or (air spheres) (gas spheres), kaolin, silicon carbide whiskers, bauxite, boron carbide, iron, nickel, or copper, etc. The composition includes chopped carbon fibers or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, barite, titanium dioxide, alumina, magnesium oxide, granular or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, flake silicon carbide, flake aluminum diboride, flake aluminum, steel flakes, natural fillers such as wood flour, fibrous cellulose, cotton, sisal, jute, starch, lignin, crushed nut shells, or rice husks, reinforcing organic fiber fillers such as poly(etherketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene, and poly(vinyl alcohol), and combinations comprising at least one of the aforementioned fillers or reinforcing agents. The fillers and reinforcing agents may be coated or surface-treated with, for example, silanes to improve adhesion and dispersion with the polymer matrix. The fillers may generally be used in amounts of 1 to 200 parts by weight based on 100 parts by weight of the total composition.

[0062] The additive composition may include flow modifiers, reinforcing agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet light stabilizers, ultraviolet absorbing additives, plasticizers, lubricants, release agents, antistatic agents, antifogging agents, antimicrobial agents, chain extenders, colorants, mold release agents, flow promoters, flow modifiers, surface effect additives, radiation stabilizers, flame retardants, anti-drip agents, or any combination thereof.

[0063] Heat stabilizer additives include organic phosphites (e.g., triphenyl phosphite, tri-(2,6-dimethylphenyl) phosphite, tri-(mixed mono- and di-nonylphenyl) phosphite, etc.), phosphonates (e.g., dimethylphenyl phosphonate), phosphates (e.g., trimethyl phosphate, etc.), or combinations containing at least one of the aforementioned heat stabilizers. The heat stabilizer may be tris(2,4-di-tert-butylphenyl) phosphate, which can be used as an IRGAPHOS TM 168 obtained. Heat stabilizers are typically used in amounts of 0.01 to 5% by weight based on the total weight of the polymer in the composition.

[0064] There is considerable overlap among plasticizers, lubricants, and mold release agents, including, for example, glyceryl tristearate (GTS), phthalates (e.g., octyl-4,5-epoxy-hexahydrophthalate), tris(octyloxycarbonylethyl)isocyanurate, tristearin, di- or polyfunctional aromatic phosphates (e.g., resorcinol tetraphenyl diphosphate (RDP), hydroquinone bis(diphenyl) phosphate, and bisphenol A bis(diphenyl) phosphate); poly-α-olefins; epoxidized soybean oil; organosilicones, including silicone oils (e.g., poly(dimethyldiphenylsiloxane)); esters, such as fatty acid esters (e.g., alkyl stearyl esters, such as methyl stearate, stearyl stearate, etc.), waxes (e.g., beeswax, lignite wax, paraffin wax, etc.), or combinations comprising at least one of the aforementioned plasticizers, lubricants, and mold release agents. These are typically used in amounts of 0.01 to 5% by weight based on the total weight of the polymer in the composition.

[0065] Light stabilizers, particularly ultraviolet (UV) light absorbing additives, also known as UV stabilizers, include hydroxybenzophenone (e.g., 2-hydroxy-4-n-octyloxybenzophenone), hydroxybenzotriazine, cyanoacrylate, oxaloyl aniline, and benzoxazinone (e.g., 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one, which can be traded under the name CYASORB). TM UV-3638 is commercially available from Cytec Industries Inc., Woodland, NJ; aryl salicylate; hydroxybenzotriazoles (e.g., 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole and 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol, available under the trade name CYASORB. TM 5411 (commercially available from Cytec Industries Inc., Woodland, NJ) or a combination comprising at least one of the aforementioned light stabilizers. The UV stabilizer may be present in an amount of 0.01 to 1% by weight, specifically 0.1 to 0.5% by weight, and more specifically 0.15 to 0.4% by weight, based on the total weight of the polymer in the composition.

[0066] Antioxidant additives include organic phosphites, such as tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and distearyl pentaerythritol diphosphite; alkylated monophenols or polyphenols; alkylation products of polyphenols and dienes, such as tetra[methylene(3,5-di-tert-butyl-4-hydroxycinnamate)]methane; butylation products of p-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylene bisphenols; benzyl compounds; β-(3,5-di-tert-butyl- Esters of 4-hydroxyphenyl)-propionic acid with mono- or polyols; esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with mono- or polyols; esters of thioalkyl or thioaryl compounds, such as distearate thiopropionate, dilaurate thiopropionate, ditridecyl thiodipropionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritolyl-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, or combinations comprising at least one of the aforementioned antioxidants. The antioxidant is used in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of the total composition (excluding any fillers).

[0067] Available flame retardants include organic compounds containing phosphorus, bromine, and / or chlorine. For regulatory reasons, non-brominated and non-chlorinated phosphorus-containing flame retardants may be preferred in certain applications, such as organophosphates and organic compounds containing phosphorus-nitrogen bonds.

[0068] Inorganic flame retardants may also be used, such as C1-16 alkyl sulfonates, such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluorooctane sulfonate, tetraethylammonium perfluorohexane sulfonate, and potassium diphenyl sulfone sulfonate; salts such as Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3; or fluorine anionic complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, and / or Na3AlF6. When present, the inorganic flame retardant salt is present in an amount of 0.01 to 10 parts by weight, more specifically 0.02 to 1 part by weight, based on 100 parts by weight of the total composition (excluding any fillers).

[0069] Anti-drip agents can also be used in compositions, such as fibrillated or non-fibrillated fluoropolymers, like polytetrafluoroethylene (PTFE). Anti-drip agents can be encapsulated from rigid copolymers such as styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is called TSAN. TSAN contains 50% by weight of PTFE and 50% by weight of SAN based on the total weight of the encapsulated fluoropolymer. SAN may contain, for example, 75% by weight of styrene and 25% by weight of acrylonitrile based on the total weight of the copolymer. Based on 100 parts by weight of the total composition (excluding any fillers), the anti-drip agent can be used in amounts from 0.1 to 10 parts by weight.

[0070] The resin composition can be formed using techniques known to those skilled in the art. For example, extrusion and mixing techniques can be used to combine the components of the resin composition.

[0071] The resin compositions of this disclosure can be blended with the aforementioned components through a variety of methods involving close mixing of the materials with any desired additional additives in the formulation. Melt processing methods are generally preferred due to the availability of melt blending equipment in commercial polymer processing facilities. Exemplary examples of equipment for such melt processing methods include co-rotating and counter-rotating extruders, single-screw extruders, co-kneaders, stacked disc processors, and various other types of extrusion equipment. The melting temperature in the methods of this invention is preferably minimized to avoid excessive resin degradation. It is generally desirable to maintain the melt temperature in the molten resin composition at about 230°C to about 350°C, but higher temperatures can be used provided the residence time of the resin in the processing equipment remains short. In some aspects, the melt-processed composition exits the processing equipment, such as an extruder, through a small outlet orifice in the die. The resulting molten resin filament is cooled by passing the filament through a water bath. The cooled filament can be chopped into small pellets for packaging and further processing.

[0072] The composition can be manufactured by various methods, including batch or continuous techniques using kneaders, extruders, mixers, etc. For example, a twin-screw extruder can be used to form the composition as a melt blend. In some aspects, at least some components are added sequentially. For example, a poly(aryl ether) component, one or more polystyrene components, and an impact modifier component can be added to the feed throat of the extruder or to a feed section adjacent to the feed throat, while a filler component can be added to a downstream feed section of the extruder. Alternatively, the sequential addition of components can be accomplished through multiple extrusions. The composition can be prepared by pre-extruding selected components (such as a poly(aryl ether) component, one or more polystyrene components, and an impact modifier component) to produce a granular mixture. A second extrusion can then be used to combine the pre-extruded components with the remaining components. The filler component can be added as part of a masterbatch or directly. The extruder can be a two- or three-bladed twin-screw extruder.

[0073] In one aspect, this disclosure relates to plastic parts, for example, at least partially formed, molded, or formed from the compositions described herein. Plastic parts comprising resin compositions formed by the methods for forming resin compositions disclosed according to the invention are also provided.

[0074] Characteristics and products

[0075] The disclosed compositions exhibit a balance between dielectric and physical properties. These compositions achieve high dielectric constant (Dk), low dielectric constant (DF), high heat distortion temperature (HDT) (e.g., greater than 280°C at 0.45 MPa or greater than 255°C at 1.82 MPa, according to ISO-75), and strong mechanical properties. Furthermore, the disclosed compositions are less dense than comparative compositions, making them more attractive for certain manufacturing specifications.

[0076] In some aspects, the disclosed composite materials can exhibit specific dielectric properties. When measured according to the resonant cavity method, molded articles or panels containing the composite material can exhibit a dissipation factor Df (loss tangent (tanδ), ε” / ε’) of less than 0.005 at frequencies of about 10 to about 120 GHz, or 1 MHz to 100 GHz, or about 1-20 GHz, 1-25 GHz, 1-100 GHz, 50-100 GHz, or 70-90 GHz. In other aspects, when measured according to the resonant cavity method, molded articles or panels containing the composite material can exhibit a dielectric constant Dk of greater than 4 at a frequency of 1.1 GHz.

[0077] The disclosed composition also exhibits high heat resistance, high flowability, and improved ductility. The composition can exhibit high heat resistance, characterized by a heat distortion temperature greater than 270°C at 0.45 MPa or greater than 250°C at 1.8 MPa when tested according to ISO 75. When tested according to ISO-1183, the composition can exhibit a reduced density, i.e., less than 1.7 g / cm³. 3 In addition, the composition exhibits improved ductility, characterized by a notched Izod impact strength greater than 5 KJ / m. 2 .

[0078] The disclosed compositions can exhibit specific laser coating performance as characterized by a plating index. The plating index can be defined as the ratio between the average copper thickness of a test sample obtained under specific laser parameters and that of a reference sample. In some aspects, the reference sample is a commercially available PBT-based LDS product (Pocan DP 7102). Aspects of this disclosure can provide compositions having plating indices, for example, greater than 0.45, greater than 0.5, greater than 0.7, greater than 0.72, and greater than 0.75. Furthermore, the compositions of this disclosure can achieve the disclosed plating index without the presence of plating seed promoters (or plating seed generation promoters) as described in the art (e.g., EP 3699234). Therefore, the disclosed compositions may contain no or substantially no plating seed generation promoters.

[0079] In various respects, this disclosure relates to articles comprising the compositions herein. These compositions can be molded into usable shaped articles by a variety of means, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming. These compositions can be used to manufacture articles requiring materials with good flowability, good impact strength, and good dielectric strength. These compositions can also be used for conductive purposes.

[0080] In various respects, this disclosure provides composite materials that can be used to manufacture phase shifters for base stations, which adjust the incident transmission angle of antennas in the base station. The dielectric properties of these materials, such as dissipation factor Df, were evaluated at frequencies from approximately 10 GHz to 120 GHz. The disclosed compositions can be used as dielectric substrates for phase shifters in 5G base stations.

[0081] The advantageous features of the compositions disclosed herein make them suitable for a range of applications.

[0082] Manufacturing method

[0083] This disclosure also relates to methods for preparing thermoplastic compositions. One or any of the aforementioned components described herein may first be dry-mixed with each other, or with any combination of the aforementioned components, and then fed into an extruder from one or more feeders, or fed into an extruder individually from one or more feeders. Fillers used in this disclosure may also first be processed into a masterbatch and then fed into the extruder. Components may be fed into the extruder from a throat hopper or any side feeder.

[0084] The extruder used in this disclosure may have a single screw, a multi-screw, a meshing co-rotating or counter-rotating screw, a non-meshing co-rotating or counter-rotating screw, a reciprocating screw, a pinned screw, a screened screw, a pinned barrel, a roller, a plunger, a helical rotor, a co-kneader, a stacked disc processor, various other types of extrusion equipment, or include at least one combination of the foregoing.

[0085] The components can also be mixed together and then melt-blended to form a thermoplastic composition. Melt blending of the components involves the use of shear force, tensile force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy, or a combination of at least one of the foregoing forms of force or energy.

[0086] If the resin is a semi-crystalline organic polymer, the barrel temperature on the extruder during compounding can be set to a temperature at which at least a portion of the polymer reaches a temperature greater than or equal to approximately the melt temperature, or if the resin is an amorphous resin, it can be set to the pour point (e.g., the glass transition temperature).

[0087] If desired, mixtures comprising the aforementioned components can undergo multiple blending and molding steps. For example, a thermoplastic composition can first be extruded and molded into granules. The granules can then be fed into a molding machine, where they can be molded into any desired shape or product. Alternatively, a thermoplastic composition derived from a single melt blender can be molded into sheets or wires and subjected to post-extrusion processing, such as annealing, uniaxial or biaxial orientation.

[0088] In the method of this invention, the melting temperature can be maintained as low as possible in some respects to avoid excessive thermal degradation of the components. In some respects, the melting temperature is maintained at about 230°C to about 350°C, but higher temperatures can be used, provided that the residence time of the resin in the processing equipment remains relatively short. In some respects, the melt-processed composition exits the processing equipment, such as an extruder, through a small outlet orifice in a die. The resulting molten resin filament can be cooled by passing the filament through a water bath. The cooled filament can be chopped into pellets for packaging and further processing.

[0089] The method may also include processing the composite material to provide a veneer of the desired thickness. The veneer may be extruded, injection molded, compression molded, or injection compressed, and may have a thickness of approximately 0.5 mm to 6 mm. Other processes may also be applied to the thermoplastic film, including but not limited to lamination, co-extrusion, thermoforming, or hot pressing. In such aspects, additional layers of other materials (e.g., other thermoplastic polymer layers, metal layers, etc.) may be combined with the composite material.

[0090] This disclosure covers various combinations of elements of this disclosure, such as combinations of elements from dependent claims that depend on the same independent claim.

[0091] definition

[0092] It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting. As used in the specification and claims, the term "comprising" may include embodiments "consisting of" and "substantially consisting of". Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Numerous terms will be referenced in this specification and the following claims, and these terms should be defined herein.

[0093] As used in the specification and appended claims, the singular forms “an,” “a,” and “the” include plural references unless the context clearly specifies otherwise. Thus, for example, reference to “thermoplastic polymer component” includes a mixture of two or more thermoplastic polymer components. As used herein, the term “composite” includes blends, mixtures, alloys, reaction products, etc.

[0094] A range may be expressed herein as a range from one value (the first value) to another value (the second value). When such a range is expressed, it includes, in some respects, one or both of the first and second values. Similarly, when a value is expressed as an approximation using the antecedent “about,” it should be understood that the particular value forms the other side. It should also be understood that the endpoints of each range are significant, both relating to and independent of the other endpoint. It should also be understood that many values ​​are disclosed herein, and each value is also disclosed herein as “about” that particular value, in addition to being the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It should also be understood that each unit between two particular units is also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0095] As used herein, the terms “about” and “at or about” mean that the quantity or value under consideration may be a specified value, approximately a specified value, or approximately the same as a specified value. As used herein, it should generally be understood that, unless otherwise specified or inferred, it is a variation of ±10% of the indicated nominal value. This term is intended to convey that similar values ​​facilitate the equivalent results or effects described in the claims. That is, it should be understood that quantities, sizes, formulations, parameters, and other quantities and characteristics are not and need not be precise, but may be approximate and / or larger or smaller as needed, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. Generally, quantities, sizes, formulations, parameters, or other quantities or characteristics are “about” or “approximate”, whether or not explicitly stated otherwise. It should be understood that where “about” is used before a quantitative value, a parameter also includes the specific quantitative value itself, unless otherwise specifically indicated.

[0096] As used herein, the terms “optional” or “optionally” mean that an event or situation subsequently described may or may not occur, and the description includes both cases where the event or situation occurs and cases where it does not occur. For example, the phrase “optional additional process” means that additional processes may or may not be included, and the description includes methods that include and do not include additional processes.

[0097] The components used to prepare the compositions of this disclosure and the compositions themselves used in the methods disclosed herein are disclosed. These and other materials are disclosed herein, and it should be understood that when combinations, subsets, interactions, groups, etc., of these materials are disclosed, while specific references to the individual and collective combinations and arrangements of these compounds are not explicitly disclosed, each is specifically considered and described herein. For example, if a particular compound is disclosed and discussed, and numerous modifications that can be made to many molecules, including that compound, are discussed, then each and every combination and arrangement of that compound and possible modifications is specifically considered, unless specifically indicated to the contrary. Thus, if examples of molecule classes A, B, and C, and molecule classes D, E, and F, and the combination molecule AD are disclosed, then each is considered individually and collectively, even if each is not individually described; AE, AF, BD, BE, BF, CD, CE, and CF are considered disclosed. Similarly, any subsets or combinations of these are also disclosed. Thus, for example, subgroups of AE, BF, and CE are considered disclosed. This concept applies to all aspects of this application, including but not limited to the steps in methods for preparing and using the compositions of this disclosure. Therefore, if there are multiple additional steps that can be executed, it should be understood that each of these additional steps can be performed using any particular aspect or combination of aspects of the methods of this disclosure.

[0098] References to the weight parts of a particular element or component in the description and concluding aspects indicate a weight relationship, expressed in parts by weight, between that element or component and any other element or component in the composition or article. Therefore, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2:5, and are present in this ratio regardless of whether the compound contains any additional components.

[0099] Unless specifically stated to the contrary, the weight percentage of a component is based on the total weight of the formulation or composition including that component.

[0100] The terms “residue” and “structural unit” used when referring to the components of polymers are synonymous throughout this specification.

[0101] Unless otherwise specified, the interchangeable terms “weight percentage,” “wt.%,” and “wt.%” as used herein indicate a weight percentage of a given component based on the total weight of the composition. That is, unless otherwise specified, all weight % values ​​are based on the total weight of the composition. It should be understood that the sum of the weight % values ​​of all components in the disclosed compositions or formulations is 100.

[0102] Unless otherwise stated herein, all testing standards are current and valid at the time of submission of this application.

[0103] As used herein, the terms "number-average molecular weight" or "Mn" are used interchangeably and refer to the statistical average molecular weight of all polymer chains in a sample, defined by the following formula:

[0104]

[0105] Where M i It is the molecular weight of the chain, and N i It is the number of chains with that molecular weight. The M of a polymer (e.g., polycarbonate polymer) n Molecular weight can be determined using methods known to those skilled in the art, such as polycarbonate or polystyrene standards, preferably certified or traceable molecular weight standards.

[0106] As used herein, the terms “weight-average molecular weight” or “Mw” are used interchangeably and are defined by the following formula:

[0107]

[0108] Where M i It is the molecular weight of the chain, and N i This is the number of chains with that molecular weight. (M) n In contrast, when determining the contribution to the average molecular weight, M wThe molecular weight of a given chain has been taken into consideration. Therefore, the larger the molecular weight of a given chain, the better the chain's effect on M. w The greater the contribution, the better. The M of polymers (e.g., polycarbonate polymers) w Molecular weight can be determined using methods known to those skilled in the art, such as polycarbonate or polystyrene standards, preferably certified or traceable molecular weight standards.

[0109] As used herein, the term “polycarbonate” or “multiple polycarbonates” includes copolycarbonate, homopolycarbonate and (co)polyester carbonate.

[0110] As used in this article, the degree of polymerization n describes the number of monomer units (or repeating units) in a given polymer molecule.

[0111] References to the weight parts of a specific element or component in the description and concluding claims indicate a weight relationship, expressed in parts by weight, between that element or component and any other element or component in the composition or article. Therefore, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2:5, and are present in this ratio regardless of whether the compound contains any additional components.

[0112] In one respect, "substantially non-existent" can be less than about 0.5% by weight (wt%). In another respect, "substantially non-existent" can be less than about 0.1% by weight. In yet another respect, "substantially non-existent" can be less than about 0.01% by weight. In yet another respect, "substantially non-existent" can be less than about 100 ppm. In yet another respect, "substantially non-existent" can refer to amounts below detectable levels (if present).

[0113] Each material disclosed herein is commercially available, and / or its production method is known to those skilled in the art.

[0114] It should be understood that the compositions disclosed herein have certain functions. This document discloses certain structural requirements for performing the disclosed functions, and it should be understood that multiple structures exist that can perform the same functions associated with the disclosed structures, and these structures will typically achieve the same results.

[0115] Aspects of this disclosure

[0116] In various respects, this disclosure covers and includes at least the following aspects.

[0117] Aspect 1A. A thermoplastic composition comprising: about 30% to about 70% by weight of polyphenylene sulfide; about greater than 0% to about 10% by weight of a resin containing polyphenylene sulfide; about 5% to about 15% by weight of a laser-activated metal compound; and about 10% to about 70% by weight of an inorganic filler, wherein the combined weight percentage of all components does not exceed 100% by weight, and all weight percentages are based on the total weight of the composition.

[0118] Aspect 1B. A thermoplastic composition comprising essentially the following: about 30% to about 70% by weight of polyphenylene sulfide; about greater than 0% to about 10% by weight of a resin containing polyphenylene sulfide; about 5% to about 15% by weight of a laser-activated metal compound; and about 10% to about 70% by weight of an inorganic filler, wherein the combined weight percentage of all components does not exceed 100% by weight, and all weight percentages are based on the total weight of the composition.

[0119] Aspect 1C. A thermoplastic composition comprising: about 30% to about 70% by weight of polyphenylene sulfide; about greater than 0% to about 10% by weight of a resin containing polyphenylene sulfide; about 5% to about 15% by weight of a laser-activated metal compound; and about 10% to about 70% by weight of an inorganic filler, wherein the combined weight percentage of all components does not exceed 100% by weight, and all weight percentages are based on the total weight of the composition.

[0120] Aspect 2. The thermoplastic composition according to Aspect 1A-C, wherein, when tested according to ISO-1133 at 300°C / 2.16kg, the melt volume rate (MVR) of the polyphenylene sulfide is less than 50 cm³ / 10 min. 3 / 10min).

[0121] Aspect 3. The thermoplastic composition according to aspects 1A-C, wherein the polyphenylene sulfide has a number-average molecular weight Mn greater than 9000 Daltons according to the GPC method.

[0122] Aspect 4. The thermoplastic composition according to aspects 1A-C, wherein the polyphenylene sulfide is a linear polyphenylene sulfide.

[0123] Aspect 5. The thermoplastic composition according to any one of Aspects 1A-4, wherein the resin comprising polyphenylene ether is polyphenylene ether or a polyphenylene ether copolymer.

[0124] Aspect 6. The thermoplastic composition according to any one of Aspects 1A-4, wherein the resin comprising polyphenylene ether is polyphenylene ether or a polyphenylene ether siloxane copolymer.

[0125] Aspect 7. The thermoplastic composition according to any one of Aspects 1A-6, wherein the laser-activated metal compound comprises antimony-doped tin oxide or copper chromite oxide or basic copper phosphate or a combination thereof.

[0126] Aspect 8. The thermoplastic composition according to any one of Aspects 1A-7, wherein the inorganic filler comprises glass fiber, glass flakes, talc, clay, mica, wollastonite, titanium dioxide, or combinations thereof.

[0127] Aspect 9. The thermoplastic composition according to any one of Aspects 1A to 8, wherein the laser-activated metal compound comprises antimony-doped tin oxide, copper chromite, or basic copper phosphate.

[0128] Aspect 10. The thermoplastic composition according to any one of Aspects 1 to 8, wherein the laser-activated metal compound comprises antimony-doped tin oxide.

[0129] Aspect 11. The thermoplastic composition according to any one of Aspects 1A to 9, wherein the composition exhibits a plating index greater than 0.7 according to the LPKF-LDS method.

[0130] Aspect 12. The thermoplastic composition according to any one of Aspects 1A to 11, wherein the thermoplastic composition further comprises at least one additional additive, wherein the at least one additional additive comprises fillers, acid scavengers, anti-drip agents, antioxidants, antistatic agents, chain extenders, colorants, release agents, flow promoters, lubricants, mold release agents, plasticizers, quenchers, flame retardants, UV reflective additives, and combinations thereof.

[0131] Aspect 13. An article formed from a thermoplastic composition according to any one of aspects 1A to 12.

[0132] Aspect 14. The article of manufacture according to aspect 13, wherein the article of manufacture is a component of an electronic device.

[0133] Aspect 15. A thermoplastic composition comprising: about 30% to about 70% by weight of polyphenylene sulfide; 0.01% to about 8% by weight of a resin containing polyphenylene sulfide; about 5% to about 15% by weight of a laser-activated metal compound; and about 10% to about 70% by weight of an inorganic filler, wherein the combined weight percentage of all components does not exceed 100% by weight, and all weight percentages are based on the total weight of the composition.

[0134] Example

[0135] The following examples are provided to provide those skilled in the art with a complete disclosure and description of how to prepare and evaluate the compounds, compositions, articles, devices, and / or methods claimed herein, and are intended to be purely exemplary and not to limit the scope of this disclosure. Efforts have been made to ensure the accuracy of figures (e.g., amounts, temperatures), but some errors and deviations should be taken into account. Unless otherwise stated, parts are parts by weight, temperatures are in °C or ambient temperature, and pressures are at or near atmospheric pressure. Unless otherwise specified, percentages of compositions are expressed in weight percent.

[0136] There are various variations and combinations of mixing conditions, such as component concentration, extruder design, feed rate, screw speed, temperature, pressure, and other mixing ranges and conditions that can be used to optimize the purity and yield of the product obtained from the described process. Only reasonable and routine experiments are required to optimize such process conditions.

[0137] Various PPS resins are prepared from the pure resins shown in Table 1. The polyphenylene resins vary depending on the end-capping groups or melt volume rate.

[0138] Table 1. PPS resins explored.

[0139]

[0140] The other components are shown in Table 2.

[0141] Table 2. Materials and Suppliers.

[0142] describe supplier Product Name Polyphenylene oxide (PPO); intrinsic viscosity 0.4 dl / g SABIC PPO 640 Glass fiber (GF); E-glass, dimensional setting for polyphenylene sulfide Jushi ECS-10-3-584 LDS Additive 1 (LDS1); Copper Chromite Oxide Shephard Black 1G LDS Additive 2 (LDS2); Antimony-doped Tin Oxide Ferro S-5000 <![CDATA[Titanium dioxide (TiO2)]]> Chemours R-350 Polyetheretherketone (PEEK) Victrex 90P Silane; coupling agent to enhance the adhesion between glass fiber and resin Momentive A-186 Antioxidant (AOX1) DOVERPHOS S-9228 Antioxidant (AOX2) BASF <![CDATA[Irganox TM 1010]]> Mold release agent (MR) FACI <![CDATA[Glycolube TM P(ETS)]]>

[0143] The compounding process was performed on a laboratory extruder (Toshiba TEM-37BS). Unless otherwise specified, all thermoplastic resins, fillers, and additives were fed through the extruder throat. Compounding was performed at a screw speed of 300 RPB, an output of 30-40 kg / h, and approximately 50-60% torque. Temperature distribution and molding conditions are shown in Tables 3 and 4.

[0144] Table 3. Temperature distribution used for blending.

[0145]

[0146]

[0147] Table 4. Injection molding conditions.

[0148]

[0149] The PPS LDS formulations are prepared as shown in Table 5.

[0150] Table 5. Formulation of PPS LDS Compositions

[0151]

[0152]

[0153] The dielectric constant (DK) and dissipation factor (DF) at a fixed frequency were measured on a molded sample using a split-pillar dielectric resonator (SPDR) and a network analyzer.

[0154] The plating index is defined as the ratio between the average copper thickness of the test sample under specific laser parameters and that of a reference sample. The reference sample is an LDS specimen based on polybutylene terephthalate (PBT), which can be obtained using Pocan. TM DP 7102 is commercially available. Advantageously, the coating index of the LDS resin needs to be higher than 0.7.

[0155] Table 5 presents the formulations and test results of two groups of PPS LDS compositions. Group 1 (E1 to E3) and Group 2 (E4-E6) include different LDS additives. Within each group, three PPS grades were used as the base resin. As listed in Table 1, the main differences between the three PPS grades lie in their molecular weight and end-capping groups. Polyphenylene sulfide (PPS) grades PPS-3 and PPS-2 have the same end-capping groups, but differ in Mw and Mn. Grades PPS-1 and PPS-2 have similar Mw and Mn, but differ based on the end-capping groups. Therefore, the effectiveness of LDS additives for PPS can be compared between Group 1 and Group 2. Simultaneously, the influence of PPS resins on LDS performance within each group can also be compared.

[0156] Both groups of samples exhibited good laser coating performance, as confirmed by the observed coating index (PI). PI is a comparative value indicating the coating rate of a particular material compared to that of a particular reference material. The second group of samples showed a higher average PI than the first group. However, in terms of the highest PI achieved, the first group outperformed the second. From a practical perspective, the highest PI is more critical for mass production, as it creates a window for achieving maximum production efficiency. The mechanical and thermal properties observed between the first and second groups were also very similar. The first group of samples also exhibited a significantly lower Df value than the second group. Therefore, antimony-doped tin oxide appears to be a more preferable LDS additive for the PPS-based LDS compositions examined in this paper than copper chromate.

[0157] PPS with higher melt viscosity (characterized by high Mw and high Mn from a synthetic perspective) exhibits better LDS activity than low-viscosity PPS. In both groups, PPS-3 achieved a PI 50% higher than PPS-2 and PPS-1. Therefore, for PPS-based LDS compositions, a PPS base resin with a viscosity similar to or higher than PPS-3 is preferable. The low LDS activity of PPS resins has been an unresolved problem for a considerable period, which explains the lack of mature PPS-based LDS compounds on the market. Attempts have been made to address the activity problem by doping with highly loaded LDS additives; however, this approach significantly degrades mechanical properties and is extremely expensive, making it largely uncommercially viable. Our research suggests that using high molecular weight PPS resins is a promising approach to solving the LDS activity problem. PPS is a polymer with sulfur in both the main chain and end groups, while LDS processes typically require copper as a seed to initiate the plating process. However, copper and sulfur readily form highly stable compounds, such as copper sulfide, which reduces the activity of LDS additives. The sulfur present in the main chain is not reactive with copper, but the end-capping groups derived from synthesis and decomposition during processing react with copper.

[0158] Given these results, it appears that higher molecular weight PPS, with a relatively low amount of end-capping groups, improves the LDS activity of PPS-based LDS compositions. Conversely, comparing the PI between PPS-2 and PPS-1 (which have different end-capping groups), PPS-1 exhibits slightly better LDS performance than PPS-2 in both LDS groups 1 and 2. PPS-2 includes -SH as an end-capping group, while PPS-1 is characterized by -SNa as an end-capping group. Therefore, it is uncertain whether the -SH and -SNa end-capping groups result in different LDS plating properties. Instead, they appear to behave similarly. Based on the results of groups 1 and 2, it is found that the LDS activity of PPS-based resins can be improved by including high molecular weight PPS and suitable LDS additives.

[0159] Nevertheless, the plating index values ​​presented in Table 5 are not as robust as the current industry standard requiring a plating index of at least 0.7. Further investigations were conducted to optimize LDS plating performance. Formulations E7 to E10, prepared from PPS-3 and including PPO, were prepared. Different LDS additives were also introduced into these samples to determine which performed best.

[0160] Table 6. Formulations of PPS-LDS compositions with PPS-3 (high MW)

[0161]

[0162]

[0163] Table 6 presents the formulations and results of the improved PPS LDS compositions. Samples E7 and E8 comprise high-Mw PPS (PPS-3) and ATO (antimony-doped tin oxide), as these formulations performed best in groups 1 and 2 of Table 5. Here, the concentration of ATO in PPS was increased to further improve LDS activity (increase the plating index). The concentration of ATO in PPS can be readily defined as the weight ratio between ATO and ATO plus PPS. In E1 of Table 5, the ATO concentration was 5 / (5+53.6) = 8.5%, and for E7 and E8, the concentrations were 9.9% and 12.3%, respectively. Comparing the average PI and optimal PI of E1, E7, and E8, it appears that higher ATO loading can effectively increase plating performance. However, ATO is a relatively expensive raw material and contributes to increased composition density, which is generally undesirable from a production perspective.

[0164] To address this issue, PPO was introduced into the formulation. PPO exhibits significantly higher LDS activity than PPS and also possesses specific compatibility with PPS, allowing it to replace a portion of the PPS volume and achieve higher overall coating performance under the same ATO load. PPO also has a much lower density than PPS, thus facilitating density control of the final compound. A comparison of samples E7 and E9 demonstrates the advantages of incorporating PPO. Under the same ATO load, the average coating index increased from 0.45 to 0.57. Secondly, the density decreased from 1.73 to 1.68.

[0165] Furthermore, as shown in E10, adding 0.5% copper oxide chromite to E9 further increased the plating index to 0.72. This indicates that the use of hybrid or mixed LDS additive systems can synergistically improve the plating index. By reviewing the detailed plating data, we found that copper oxide chromite contributes to plating in both very high-energy and low-energy laser windows, thereby improving overall plating performance. All plating adhesion values ​​for the examples listed in Table 6 are 5B, indicating very strong adhesion between the plating metal layer and the material.

[0166] The above description is intended to be illustrative and not restrictive. For example, the above embodiments (or one or more aspects thereof) may be used in combination with each other. Other embodiments may be used by those skilled in the art after reviewing the above description. An abstract is provided to allow the reader to quickly determine the nature of the technical disclosure. It should be understood at the time of submission that it is not intended to interpret or limit the scope or meaning of the claims. Furthermore, in the above detailed description, various features may be grouped together to simplify the disclosure. This should not be construed as meaning that any unclaimed disclosed feature is necessary for any claim. Rather, the subject matter of the invention may lie in fewer than all features of a particular disclosed embodiment. Therefore, the following claims are hereby introduced into the detailed description as embodiments or implementations, wherein each claim exists independently as a separate embodiment, and these embodiments are contemplated to be able to be combined with each other in various combinations or arrangements. The scope of this disclosure should be determined by reference to the full scope of the appended claims together with their equivalents.

[0167] It will be apparent to those skilled in the art that various modifications and variations can be made to this disclosure without departing from its scope or spirit. Other embodiments of this disclosure will be apparent to those skilled in the art upon consideration of the specification and practice disclosed herein. The specification and examples are intended to be illustrative only, and the true scope and spirit of this disclosure are indicated by the appended claims.

[0168] The patentable scope of this disclosure is defined by the claims and may include other embodiments that would occur to those skilled in the art. These other embodiments are intended to be within the scope of the claims if they have structural elements that are not different from the literal language of the claims, or if they include equivalent structural elements that are not substantially different from the literal language of the claims. It should be understood that the compositions disclosed herein have certain functions. This document discloses certain structural requirements for performing the disclosed functions, and it should be understood that there are multiple structures that can perform the same functions associated with the disclosed structures, and these structures will typically achieve the same results.

Claims

1. A thermoplastic composition comprising: a. 30 to 70 weight percent of a polyphenylene sulfide, wherein the polyphenylene sulfide has a melt volume rate of less than 50 cc / 10 minutes when tested according to ISO-1133 at a temperature of 300 °C and a load of 2.16 kg; b. greater than 0 to 10 weight percent of a resin comprising a polyphenylene ether; c. 5 to 15 weight percent of a laser activatable metal compound, wherein the laser activatable metal compound consists of antimony-doped tin oxide; and d. 10 to 70 weight percent of an inorganic filler comprising glass fibers, wherein the composition exhibits a plating index of at least 0.7, wherein the plating index is measured according to the LPKF method, wherein the combined weight percent values of all components do not exceed 100 weight percent, and all weight percent values are based on the total weight of the composition.

2. The thermoplastic composition of claim 1, wherein the polyphenylene sulfide has a number average molecular weight, Mn, of greater than 9000 Daltons as determined according to the GPC method.

3. The thermoplastic composition of claim 1, wherein the polyphenylene sulfide is a linear polyphenylene sulfide.

4. The thermoplastic composition of claim 1, wherein the resin comprising a polyphenylene ether is a polyphenylene ether or a polyphenylene ether copolymer.

5. The thermoplastic composition of claim 1, wherein the resin comprising a polyphenylene ether is a polyphenylene ether or a polyphenylene ether siloxane copolymer.

6. The thermoplastic composition of claim 1, wherein the laser activatable metal compound comprises antimony-doped tin oxide, and one or more of copper chromite oxide or basic copper phosphate.

7. The thermoplastic composition of claim 1, wherein the weight ratio between the antimony-doped tin oxide and the antimony-doped tin oxide plus the polyphenylene sulfide is equal to or greater than 8.5%.

8. The thermoplastic composition of claim 1, wherein the weight ratio between the antimony-doped tin oxide and the antimony-doped tin oxide plus the polyphenylene sulfide is equal to or higher than 9.9%.

9. The thermoplastic composition of any one of claims 1 to 8, wherein the thermoplastic composition further comprises at least one additional additive, wherein the at least one additional additive comprises a filler, an acid scavenger, an anti-dripping agent, an antioxidant, an antistatic agent, a chain extender, a colorant, a mold release agent, a flowability promoter, a lubricant, a mold lubricant, a plasticizer, a quenching agent, a flame retardant, a UV reflecting additive, or a combination thereof.

10. An article formed from the thermoplastic composition of any one of claims 1 to 8.

11. The article of claim 10, wherein the article is a component of an electronic device.

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