Thermoplastic compositions, laser weldable parts, and articles thereof

Abstract

A thermoplastic composition comprises: a poly(arylene ether) composition comprising a poly(arylene ether) and optionally, a poly(arylene ether siloxane); one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, an organophosphorus flame retardant present in an amount effective to provide at least 0.9 wt% phosphorus, based on the total weight of the thermoplastic composition; wherein a sample of the composition has a laser transmittance of greater than 10% at a wavelength of 980 nm and a sample thickness of 2.0 mm, a UL94 5VA rating at a thickness of 2.0 mm, a UL94 5VB rating at a thickness of 2.0 mm, and a UL94 rating of V0 at a thickness of 1.5 mm or less, and an f1 rating according to the UL746C standard, and wherein the composition comprises 0 to 1000 ppm carbon black. The thermoplastic compositions are suitable for laser welding.

Description

THERMOPLASTIC COMPOSITIONS, LASER WELDABLE PARTS, AND ARTICLESTHEREOFCROSS-REFERENCE TO RELATED APPLICATIONThis application claims priority to EP Application No. 24188239.8, filed July 12, 2024, the contents of which are incorporated herein by reference in their entirety.BACKGROUND

[0001] This disclosure relates to thermoplastic compositions, methods of manufacture, laser weldable parts, and articles thereof.

[0002] Laser welding for thermoplastics is a joining process that uses a laser beam to melt and fuse together two or more thermoplastic components. Laser welding is a fast process, capable of producing a bond (“weld”) between two parts in less time than the time needed to bond parts using adhesives, for example. This high-speed capability makes it suitable for high- volume production environments, improving overall manufacturing efficiency. For example, when attempting to join two thermoplastic articles, near-infrared (NIR) laser- welding requires one of the polymer articles to be at least partially transparent to laser light, and the other to absorb a significant amount of the laser light. Otherwise, the joining of the two materials by laser transmission welding is either impossible or restricted to slow scan speeds, thus decreasing the efficiency of the part assembly cycle time.

[0003] Poly(arylene ethers) can improve dielectric performance, heat resistance, flame resistance and moisture absorption of materials, making them particularly well suited for a variety of applications, including electronic applications. It is desirable for the thermoplastic compositions in such applications to have good weatherability, i.e., ability to withstand exposure to various environmental conditions over time without significant degradation. UV radiation from sunlight is a primary cause of weathering in thermoplastics. It can lead to degradation of the polymer chains, resulting in changes to the material’s mechanical properties, color fading, surface cracking, and overall deterioration. To enhance the weatherability of thermoplastics, conventional compositions incorporate additives such as UV stabilizers, antioxidants, and other weathering agents into the polymer matrix. Although these additives help to mitigate the effects of UV radiation, temperature extremes, moisture, and chemical exposure, the additives can also have an adverse effect on the laser transmittance of the material.

[0004] There accordingly remains a need in the art for poly(arylene ether) compositions that have good weatherability and a high laser transmittance.BRIEF DESCRIPTION

[0005] The above-described and other deficiencies of the art are met by a thermoplastic composition comprising: a poly (arylene ether) composition comprising a poly (arylene ether) and optionally, a poly(arylene ether siloxane); one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, an organophosphorus flame retardant present in an amount effective to provide at least 0.9 wt% phosphorus, based on the total weight of the thermoplastic composition; optionally, a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene; and optionally a colorant composition comprising an organic dye; optionally, an additive composition; wherein a sample of the composition has a laser transmittance of greater than 10% at a wavelength of 980 nm and a sample thickness of 2.0 mm, a UL94 5VA rating at a thickness of 2.0 mm, a UL94 5VB rating at a thickness of 2.0 mm, and a UL94 rating of V0 at a thickness of 1.5 mm or less, and an fl rating according to the UL746C standard, and wherein the composition comprises 0 to 1000 ppm carbon black. Althenatively, the thermoplastic composition can include a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene.

[0006] In an aspect, a weldable part comprises the above-described thermoplastic composition.

[0007] In another aspect , a method for forming the weldable part comprises molding, extruding, or shaping the above-described thermoplastic composition to form the weldable part.

[0008] In yet another aspect , a welded article comprises the above-described weldable part.

[0009] In still another aspect , a method for forming the above-described welded article comprises welding the above-described weldable part to another thermoplastic part to provide the welded article.

[0010] The above described and other features are exemplified by the following detailed description.DETAILED DESCRIPTION

[0011] Component parts can be joined to form an article using laser welding. Laser welding can produce high-strength, hermetic seals with minimal distortion and heat-affected zones, making it suitable for a wide range of applications in industries such as automotive, aerospace, electronics, medical devices, and consumer goods. For example, the high-speed andautomated nature of laser welding make it suitable for mass production in the automotive sector for joining thermoplastic components such as interior trim panels, instrument panels, and bumpers. Laser welding is also used in electronics manufacturing for joining thermoplastic components to create small, precise welds without damaging sensitive electronic components. Laser welding typically requires the transmission of laser energy through a laser-weldable part to ensure proper energy absorption at the interface for effective bonding. As such, the laser weldable part should be manufactured from a composition with high laser transmittance. It is also desirable for the thermoplastic compositions in such applications to have good weatherability, i.e., ability to withstand exposure to various environmental conditions over time without significant degradation.

[0012] Carbon black is often added to conventional composition to improve UV resistance and weatherability. It acts as a UV stabilizer by absorbing UV radiation, which can otherwise degrade the polymer material. However, carbon black absorbs wavelengths in the near infrared range, thus preventing energy from the laser irradiation from reaching the interface between the parts to be laser welded. Pigments, which are additives conferring color, but without dissolving in the host material, either block or scatter light in the infrared region of the UV spectrum, but without absorbing the UV light and thus do not promote weatherability.

[0013] The inventors have discovered poly(arylene ether) compositions that can have the desired combination of weatherability and high laser transmittance, thus making it suitable for preparing laser- weldable parts and articles. The poly (arylene ether) composition includes a poly (arylene ether), one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, organophosphorus flame retardant, and other optional components. The poly(arylene ether) compositions are substantially free of carbon black and have a laser transmittance of greater than 10% at a wavelength of 980 nm and a sample thickness of 2.0 mm, a UL94 5VA rating at a thickness of 2.0 mm, a UL94 5VB rating at a thickness of 2.0 mm, and a UL94 rating of V0 at a thickness of 1.5 mm or less, and an fl rating according to the UL746C standard. Without being bound by theory, it is believed that the thermoplastic compositions described herein achieve relatively high laser transmittance by controlling the size of the rubber domains in the composition to be relatively small, compared to prior art compositions. In particular specific hydrogenated block copolymers within a specific molecular weight and amount of rigid (e.g., styrene) to soft (i.e., rubber) blocks is used to maintain the desired small rubber domain size in the composition. It is believed that high laser transmittance is not achievable without controlling these factors.

[0014] The poly(arylene ether) is derived from monomers including a monohydric phenol, or a monohydric phenol and a dihydric phenol. The monohydric phenol can have the following formula (1)wherein Z1is independently at each occurrence is halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and Z2is independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atom.

[0015] In some aspects, the poly(arylene ether) includes repeating units derived from a monohydric phenol having the formula (la)wherein Qlais C1-C12 primary or secondary alkyl or cycloalkyl, preferably C1-C12 primary alkyl, more preferably Ci-Ce primary alkyl, even more preferably methyl; Qlbis halogen, C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, preferably C1-C12 alkyl or C3-C12 cycloalkyl, more preferably Ci-Ce alkyl, even more preferably methyl. Each occurrence of Q2is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, preferably hydrogen; and e is 1 to 200, preferably 1 to 100; and y is 1 or 2, preferably 2. For example, Qlais methyl or cyclohexyl, and Qlbis halogen, unsubstituted C1-C12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-C12 aryl.

[0016] Exemplary monohydric phenols include 2,6-dimethylphenol, 2-methylphenol, 2,5-dimethylphenol, 2-allyl-6-methylphenol, 2,3,6-trimethylphenol, 2-methyl-6-phenyl phenol, 2-cyclohexyl-6-methylphenol, or a combination thereof. For example, the monohydric phenol can include 2,6-dimethylphenol.

[0017] In addition to repeating units derived from a monohydric phenol, the monomers can comprise a dihydric phenol. The poly (arylene ether) can have the structure of formula (2)wherein each occurrence of Q1and Q2independently comprises halogen, unsubstituted or substituted C1-15 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q3and Q4independently comprises hydrogen, halogen, unsubstituted or substituted C1-C15 primary or secondary hydrocarbyl, C1-C12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y have an average value, and are each independently 0-30, or 0-20, preferably 0-15, still more preferably 0-10, even more preferably 0-8, provided that the sum of x and y is at least 2, preferably at least 3, more preferably at least 4.

[0018] In Formula (2), L can be of formula (3)wherein each occurrence of R3, R4, R5, and R6independently comprises hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; w is 0 or 1; and Y iswherein each occurrence of R7independently comprises hydrogen or C1-12 hydrocarbyl, each occurrence of R8and R9independently comprises hydrogen, C1-12 hydrocarbyl, or R8and R9together form a C4-12 cyclohydrocarbylene with the carbon atom. In an aspect in formula (3), each of R3, R4, R5, and R6independently comprises hydrogen, halogen, unsubstituted or substituted C1-6 primary or secondary hydrocarbyl; and w is 0 or 1. In an aspect of formula (3), R3, R4, R5, and R6independently comprise hydrogen, halogen, or C1-C12 alkyl, more preferably hydrogen or Ci-Ce alkyl; and w is 0 or 1, preferably 1. When w is 0, the two aryl groups are connected by a single bond. For example, the dihydric phenol includes 2,2-bis(3,5-dimethyl-4- hydroxyphenol)propane. In a specific aspect, the monohydric phenol comprises 2,6-dimethyl phenol, 2,3,6-trimethyl phenol, or a combination thereof, and the dihydric phenol comprises 2,2- bis(3,5-dimethyl-4-hydroxyphenyl)propane.

[0019] In another aspect, L in formula (2) can be of formula (4)wherein E is 6-100, or 11-80, or 11-60; and each occurrence of R independently comprises an unsubstituted or substituted C1-13 alkyl, C1-13 alkoxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-i4 aryl, Ce-io aryloxy, C7-13 arylalkylene, or C7-13 alkylarylene. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. Further in formula (4), each p and q are independently 0 or 1; R1is a divalent C2-8 aliphatic group, and each occurrence of M independently comprises halogen, cyano, nitro, Ci-s alkylthio, C1-8 alkyl, C1-8 alkoxy, C2-8 alkenyl, C2-8 alkenyloxy, C3-8 cycloalkyl, C3-8 cycloalkoxy, Ce-io aryl, Ce-io aryloxy, C7-12 aralkyl, C7-12 aralkoxy, C7-12 alkylaryl, or C7-12 alkylaryloxy, wherein each n independently comprises 0, 1, 2, 3, or 4. Preferably in formula 4, E is 5-60; each occurrence of R independently comprises C1-6 alkyl, C3-6 cycloalkyl, or Ce-i4 aryl, more preferably methyl; p and q are each 1 ; R1is a divalent C2-8 aliphatic group, M is halogen, cyano, C1-4 alkyl, CM alkoxy, Ce-io aryl, C7-12 aralkyl, or C7-12 alkylaryl, more preferably methyl or methoxy; and each n independently comprises 0, 1, or 2.

[0020] For example, L of Formula (2) can be derived from the dihydric phenol of formula (4a)wherein n is, on average, 5 to 100, specifically 10 to 60.

[0021] Poly(arylene ethers), for example, poly(phenylene ether), which optionally can be in the form of a copolymer of two or more monomers, for example a terpolymer, and the raw materials used to produce the poly(arylene ethers) can be, or can be formed from, renewable, sustainable, bio-circular, circular, lower carbon footprint feedstocks, upcycled, and / or postconsumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”) .

[0022] Poly(arylene ethers) made from renewable sources can include, for example, a bio-content or PCR content of up to about 99.9%, about 1-99%, 5- 95%, 55-99%, or 80-99%, 1- 50%, 1-25%, 1-15%, 1-10%, or 1-5%, based, e.g., on the monomer source. The poly(arylene ether) can be, e.g., an oligomer with as few as two repeating units to ultra-high molecular weight poly(arylene ethers). The weight average molecular weight of the poly(arylene ethers) in one non-limiting embodiment can range from 600 to 200,000 g / mol, as determined by gel permeation chromatography. In another non-limiting embodiment, the poly(arylene ethers) can have an intrinsic viscosity of up to 1.5 deciliters per gram (dl / g) as measured at 25°C in chloroform. Poly(arylene ethers) made from renewable sources can include material made by a mass balance approach and certified by regulatory bodies such as, for example, the ISCC Plus.

[0023] Poly(arylene ethers) in one embodiment can be prepared by oxidative polymerization of monomers in the presence of a polymerization catalyst in the presence of oxygen. Any of the components used in the polymerization reaction or their synthetic precursors, or the solvents used in the process, can be bio-sourced, bio-circular, or renewable raw materials. Such components and precursors include monomers (e.g., monohydric phenol, dihydric phenol and other comonomers), reagents, solvents, catalysts (e.g., a metal source, a secondary alkylene diamine ligand, a tertiary monoamine, and optionally a secondary monoamine or alternatively enzyme catalysts), gases (e.g., oxygen gas), or any combinations thereof. In some aspects, reaction components used in the polymerization of poly (arylene ethers) can be from sources as listed in the EU Renewable Energy Directive Annex IX.

[0024] Poly(arylene ethers) can be further processed, such as by redistribution, or any chemical derivatization, such as post-polymerization end-group capping or coupling, to make other materials that can transfer the sustainability characteristic to the new material. Such reagents and / or their synthetic precursors can be sustainable, bio-sourced, bio-circular, orrenewable raw materials, upcycled, and / or post-consumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”), to produce a poly(arylene ether).

[0025] Biosourced and sustainable materials can be derived from biomass sources or industrial sources such as waste (e.g., municipal waste). Biomass is a renewable organic material that comes from organic matter. Lignocellulosic biomass, the most abundant type of biomass and includes a wide variety of different biomass types including grasses, wood, energy crops, and agricultural and municipal wastes, is mostly composed of cellulose, hemicellulose, and lignin. Depolymerization of lignin, which is a phenolic polymer, can provide phenol. Solvents used in the production of monomers, such as methanol and acetone can be obtained from syngas, which is a product of the gasification of biomass.

[0026] Poly (arylene ether), such as a recycled poly (arylene ether) comprising an open- or closed-loop post-consumer recycled (“PCR”) poly(arylene ether), an open- or closed-loop post-industrial recycled (“PIR”) poly(arylene ether), or upcycled polyphenylene ether or a combination thereof can be used, provided that the desired property or combination of properties can be achieved. As used herein, the term “post-consumer recycle poly(arylene ether)” refers to a poly(arylene ether) that has reached the intended user or consumer and which has been collected or reclaimed after utilization by the end-user or consumer. Thus, for example, it is understood that that the term refers to a poly(arylene ether) material in whole or in part that would have otherwise been disposed of as waste, but has instead been collected and recovered (reclaimed) as a material input, in lieu of a virgin material, for a recycling or manufacturing process. PCR-poly(arylene ether) is inclusive of material that has been reprocessed from collected or reclaimed material by means of a manufacturing process, (including e.g., purification, sorting, and pretreating) and made into a product or into a component for incorporation into a product. Such recycled poly(arylene ether)s can be further processed, for example, into the form of powders, ground materials, flakes, pellets, or other form. As used herein, the term “post-industrial recycled poly(arylene ether)” refers to a poly(arylene ether) polymer or polymers that have never reached the end user and that is production waste arising during polymerization reactions, during further processing, or during manufacturing the resin or an article and includes materials such as, but not limited to, sprues from injection molding, startup material from injection molding or extrusion, extrusion scrap, molding scrap, edge trims from extruded sheets or films, and the like, including materials diverted from the waste stream during a manufacturing process for an article.

[0027] The poly(arylene ethers) and the poly(arylene ether siloxanes) can have an intrinsic viscosity of 0.25 to 1.5 deciliter per gram measured by Ubbelohde viscometer at 25 °Cin chloroform. Within that range the intrinsic viscosity can be at least 0.2, at least 0.25, at least 0.3, or at least 0.37 dl / g and up to 1.4, up to 1.2, up to 1.0, 0.8, up to 0.6, or up to 0.55 dl / g as measured at 25 °C in chloroform. A range for the intrinsic viscosity can include any of the foregoing limits.

[0028] The poly(arylene ether) and optionally, the poly(arylene ether siloxane) are present from at least 60 wt%, based on the total thermoplastic composition. Within that range, the poly(arylene ethers) can be present from at least 65 wt%, at least 70 wt%, or at least 75 wt% and up to 95 wt%, up to 90 wt%, or up to 85wt%, each based on the total thermoplastic composition. A range can include any combination of the foregoing limits. The poly(arylene ether siloxane) can be present in an amount effective to provide up to 2.0 wt%, up to 1.5 wt%, or up to 1.0 wt% siloxane units, based on the total thermoplastic composition.

[0029] The poly(arylene ether) having phenolic terminal groups can be formed by polymerization of monomers, for example, including a monohydric phenol, a dihydric phenol, or a combination thereof, by continuous addition of oxygen to a reaction mixture including the monomers, optionally a solvent, and a polymerization catalyst. The molecular oxygen (O2) can be provided as air or pure oxygen. The polymerization catalyst can be a metal complex, i.e. a metal catalyst, including a transition metal cation, including cations from Group VIB, VIIB, VIIIB, or IB of the periodic table, or a combination thereof. The catalyst can include a metal cation such as chromium, manganese, cobalt, copper, or combination thereof and an anion such as chloride, bromide, iodide, sulfate, acetate, propionate, butyrate, laurate, palmitate, benzoate, or a combination of one or more of these anions, and optionally one or more charge-neutral ligands such as water, amines, phosphines, CO, or the like. Alternatively, a metal or metal oxide and an inorganic acid, organic acid, or an aqueous solution of such an acid can be combined to form a corresponding metal salt or hydrate in situ. For example, cuprous oxide and hydrobromic acid can be combined to generate cuprous bromide in situ.

[0030] Exemplary amine ligands can be, for example, a monoamine, an alkylene diamine, or a combination thereof. Monoamines include dialkylmonoamines (such as di-n- butylamine) and trialkylmonoamines (such as N,N-dimethylbutylamine).

[0031] In addition to the poly(arylene ether), the thermoplastic compositions include a hydrogenated block copolymer of an alkenyl aromatic monomer comprising styrene and a conjugated diene. The alkenyl aromatic monomer used to prepare the hydrogenated block copolymer can have the structurewherein R1and R2each independently represent a hydrogen atom, a Ci-Cs alkyl group, or a C2-C8 alkenyl group; R3and R7each independently represent a hydrogen atom or a Ci-Cs alkyl group; and R4, R5, and R6each independently represent a hydrogen atom, a Ci-Cs alkyl group, or a C2-C8 alkenyl group, or R4and R5are taken together with the central aromatic ring to form a naphthyl group, or R5and R6are taken together with the central aromatic ring to form a naphthyl group. Specific alkenyl aromatic monomers include, for example, styrene, methylstyrenes such as alpha-methylstyrene and p-methylstyrene, and t-butylstyrenes such as 3- t-butylstyrene and 4-t-butylstyrene. In some aspects, the alkenyl aromatic monomer is styrene.

[0032] The conjugated diene used to prepare the hydrogenated block copolymer can be a C4-C20 conjugated diene. Suitable conjugated dienes include, for example, 1,3-butadiene, 2-methyl-l,3-butadiene, 2-chloro- 1,3-butadiene, 2, 3-dimethyl- 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and combinations thereof. In some aspects, the conjugated diene is 1,3-butadiene, 2-methyl- 1,3-butadiene, or a combination thereof. In some aspects, the conjugated diene is 1,3- butadiene.

[0033] The hydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene, in which the aliphatic unsaturated group content in the block (B) is at least partially reduced by hydrogenation. In some aspects, the aliphatic unsaturation in the (B) block is reduced by at least 50 percent, or at least 70 percent. The arrangement of blocks (A) and (B) includes a linear structure, a grafted structure, and a radial teleblock structure with or without a branched chain. Linear block copolymers include tapered linear structures and non-tapered linear structures. In some aspects, the hydrogenated block copolymer has a tapered linear structure. In some aspects, the hydrogenated block copolymer has a non-tapered linear structure. In some aspects, the hydrogenated block copolymer comprises a (B) block that comprises random incorporation of alkenyl aromatic monomer. Linear block copolymer structures include diblock (A-B block), triblock (A-B-A block or B-A-B block), tetrablock (A-B-A-B block), and pentablock (A-B-A-B-A block or B-A-B-A-B block) structures as well as linear structures containing 6 or more blocks in total of (A) and (B), wherein the molecular weight of each (A)block can be the same as or different from that of other (A) blocks, and the molecular weight of each (B) block can be the same as or different from that of other (B) blocks. In some aspects, the hydrogenated block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof.

[0034] In some aspects, the hydrogenated block copolymer consists of blocks derived from the alkenyl aromatic compound and the conjugated diene. It does not include grafts formed from these or any other monomers. It also consists of carbon and hydrogen atoms and therefore excludes heteroatoms. In other aspects, the hydrogenated block copolymer includes the residue of one or more acid functionalizing agents, such as maleic anhydride.

[0035] Methods for preparing hydrogenated block copolymers are known in the art and many hydrogenated block copolymers are commercially available. Illustrative commercially available hydrogenated block copolymers include the polystyrene-poly(ethylene-butylene)- polystyrene triblock copolymers available from Kraton Performance Polymers Inc. as KRATON™ G1641 (having about 33 wt% polystyrene), G1650 (having about 30 wt% polystyrene), G1651 (having about 33 wt% polystyrene), and G1654 (having about 31 wt% polystyrene). Mixtures of two of more hydrogenated block copolymers can be used.

[0036] In some aspects, the hydrogenated block copolymer has a weight average molecular weight of 150,000-400,000 g / mol, or 200,000-350,000 g / mole. In such aspects, the hydrogenated block copolymer is present in an amount effective to provide up to 3.8 wt% styrene to the total thermoplastic composition. Within that range, the hydrogenated block copolymer can be present in an amount effective to provide up to 3.5 wt%, up to 3.0 wt%, up to 2.5 wt%, up to 2.0 wt%, up to 1.8 wt%, up to 1.75 wt%, at least 1.0 wt%, at least 1.2 wt%, at least 1.4 wt%, or at least 1.5 wt% styrene to the total thermoplastic composition.

[0037] In some aspects, the hydrogenated block copolymer is a combination of two or more hydrogenated block copolymers having an average weight average molecular weight of 100,000-220,000 g / mol. In such aspects, the hydrogenated block copolymer is present in an amount effective to provide up to 3.8 wt% styrene to the total thermoplastic composition. Within that range, the hydrogenated block copolymer can be present in an amount effective to provide up to 3.5 wt%, up to 3.0 wt%, up to 2.5 wt%, up to 2.0 wt%, up to 1.8 wt%, up to 1.75 wt%, at least 1.0 wt%, at least 1.2 wt%, at least 1.4 wt%, or at least 1.5 wt% styrene to the total thermoplastic composition.

[0038] In some aspects, the hydrogenated block copolymer has a weight average molecular weight of 30,000-150, OOOg / mol, or 30,000-120,000 g / mole. In such aspects, the hydrogenated block copolymer is present in an amount effective to provide up to 3.8 wt%styrene to the total thermoplastic composition. Within that range, the hydrogenated block copolymer can be present in an amount effective to provide up to 3.5 wt%, up to 3.0 wt%, up to 2.5 wt%, up to 2.0 wt%, up to 1.8 wt%, up to 1.75 wt%, at least 1.0 wt%, at least 1.2 wt%, at least 1.4 wt%, or at least 1.5 wt% styrene to the total thermoplastic composition.

[0039] In some aspects, the hydrogenated block copolymer comprises a graft copolymer having a weight average molecular weight of 30,000- 150, OOOg / mol, or 30,000-120,000 g / mole. In such aspects, the hydrogenated block copolymer is present in an amount effective to provide up to 3.8 wt% styrene to the total thermoplastic composition. Within that range, the hydrogenated block copolymer can be present in an amount effective to provide up to 3.5 wt%, up to 3.0 wt%, up to 2.5 wt%, up to 2.0 wt%, up to 1.8 wt%, up to 1.75 wt%, at least 1.0 wt%, at least 1.2 wt%, at least 1.4 wt%, or at least 1.5 wt% styrene to the total thermoplastic composition.

[0040] In the foregoing aspects, the hydrogenated block copolymer can have a styrene content of at least 20 wt%, or at least 25 wt%, based on the total weight of the hydrogenated block copolymer. Within that range, the hydrogenated block copolymer can have a styrene content of up to 60 wt%, or up to 50 wt%, or up to 40 wt%, based on the total weight of the hydrogenated block copolymer.

[0041] In addition to the poly(arylene ether), the composition can optionally include polystyrene comprising at least 90 wt% of repeating units derived from polymerization of styrene. In some aspects, the polystyrene comprises at least 95 wt%, or at least 98 wt%, of repeating units derived from polymerization of styrene. In some aspects, the polystyrene is a styrene homopolymer. The styrene homopolymer can be atactic, isotactic, or syndiotactic. The polystyrene can have a number average molecular weight of about 10,000 to about 200,000 g / mol, specifically about 30,000 to about 100,000 g / mol. The polystyrene can be absent or present. The polystyrene can be present up to 3 wt% based on the total weight of the composition. Within that range, polystyrene can be present up to 2.5 wt%, or up to 2.0 wt%, based on the total weight of the thermoplastic composition. In this aspect, the composition can include a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene, e.g., a homopolystyrene.

[0042] The polystyrene comprising at least 90 wt% of repeating units derived from polymerization of styrene can be minimized in the thermoplastic compositions. Polystyrene can be present up to 3 wt% based on the total weight of the composition. Within that range, polystyrene can be present up to 2.5 wt%, or up to 2.0 wt%, based on the total weight of thethermoplastic composition, or no polystyrene comprising at least 90 wt% of repeating units derived from polymerization of styrene can be present.

[0043] Rubber-modified polystyrenes are sometimes referred to as “high-impact polystyrenes” or “HIPS.” Although HIPS has better impact resistance than a polystyrene including at least 90 wt% of repeating units derived from polymerization of styrene, it is flammable and burns readily. Given the desired flame test performance of the thermoplastic compositions, rubber-modified polystyrenes are preferably minimized or excluded. In some aspects, the thermoplastic compositions can include rubber-modified polystyrene in an amount of less than 10 wt%, less than 5 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or less than 0.01 wt% based on the total thermoplastic composition. In some aspects, the composition is free of rubber-modified polystyrene.

[0044] The thermoplastic compositions include an organophosphorus flame retardant. Organophosphorus flame retardants can include aromatic organophosphorus compounds that have at least one organic aromatic group, the aromatic group can be a substituted or unsubstituted C3-30 group containing one or more of a monocyclic or polycyclic aromatic moiety (which can optionally contain with up to three heteroatoms (N, O, P, S, or Si)) and optionally further containing one or more nonaromatic moieties, for example alkyl, alkenyl, alkynyl, or cycloalkyl. The aromatic moiety of the aromatic group can be directly bonded to the phosphorus-containing group, or bonded via another moiety, for example an alkylene group. The aromatic moiety of the aromatic group can be directly bonded to the phosphorus-containing group, or bonded via another moiety, for example an alkylene group. In an aspect the aromatic group is the same as an aromatic group of the polycarbonate backbone, such as a bisphenol group (e.g., bisphenol A), a monoarylene group (e.g., a 1,3-phenylene or a 1,4-phenylene), or a combination comprising at least one of the foregoing.

[0045] The phosphorus-containing group can be a phosphate (P(=O)(OR)3), phosphite (P(OR)3), phosphonate (RP(=O)(OR)2), phosphinate (R2P(=O)(OR)), phosphine oxide (R3P(=O)), or phosphine (R3P), wherein each R in the foregoing phosphorus-containing groups can be the same or different, provided that at least one R is an aromatic group. A combination of different phosphorus-containing groups can be used. The aromatic group can be directly or indirectly bonded to the phosphorus, or to an oxygen of the phosphorus-containing group (i.e., an ester).

[0046] In an aspect the aromatic organophosphorus compound is a monomeric phosphate. Representative monomeric aromatic phosphates are of the formula (GO)3P=O, wherein each G is independently an alkyl, cycloalkyl, aryl, alkylarylene, or arylalkylene grouphaving up to 30 carbon atoms, provided that at least one G is an aromatic group. Two of the G groups can be joined together to provide a cyclic group. In some aspects G corresponds to a monomer used to form the polycarbonate, e.g., resorcinol. Exemplary phosphates include phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p- tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and the like. A specific aromatic phosphate is one in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like.

[0047] Di- or polyfunctional aromatic organophosphorus compounds are also useful, for example, compounds of the formulaswherein each G1is independently a C1-30 hydrocarbyl; each G2is independently a C1-30 hydrocarbyl or hydrocarbyloxy; Xais as defined in formula (3) or formula (4); each X is independently a bromine or chlorine; m is 0 to 4, and n is 1 to 30. In a specific aspect, Xais a single bond, methylene, isopropylidene, or 3,3,5-trimethylcyclohexylidene. Specific aromatic organophosphorus compounds are inclusive of acid esters of formula (9)wherein each R16is independently Ci-8 alkyl, C5-6 cycloalkyl, C6-20 aryl, or C7-12 arylalkylene, each optionally substituted by C1-12 alkyl, specifically by C M alkyl and X is a mono- or polynuclear aromatic Ce-30 moiety or a linear or branched C2-30 aliphatic radical, which can be OH- substituted and can contain up to 8 ether bonds, provided that at least one R16or X is an aromatic group; each n is independently 0 or 1 ; and q is from 0.5 to 30. In some aspects each R16is independently C1-4 alkyl, naphthyl, phenyl(Ci-4)alkylene, aryl groups optionally substituted by C1-4 alkyl; each X is a mono- or poly-nuclear aromatic Ce-30 moiety, each n is 1; and q is from 0.5 to 30. In some aspects each R16is aromatic, e.g., phenyl; each X is a mono- or poly-nuclear aromatic Ce-30 moiety, including a moiety derived from formula (2); n is one; and q is from 0.8 to 15. In other aspects, each R16is phenyl; X is cresyl, xylenyl, propylphenyl, or butylphenyl,one of the following divalent groupsor a combination comprising one or more of the foregoing; n is 1; and q is from 1 to 5, or from 1 to 2. In some aspects at least one R16or X corresponds to a monomer used to form the polycarbonate, e.g., bisphenol A, resorcinol, or the like. Aromatic organophosphorus compounds of this type include the bis(diphenyl) phosphate of hydroquinone, resorcinol bis(diphenyl phosphate) (RDP), and bisphenol A bis(diphenyl) phosphate (BPADP), and their oligomeric and polymeric counterparts.

[0048] The organophosphorus flame retardant containing a phosphorus-nitrogen bond can be a phosphazene, phosphonitrilic chloride, phosphorus ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, or tris(aziridinyl) phosphine oxide. These flameretardant additives are commercially available. In an aspect, the organophosphorus flame retardant containing a phosphorus-nitrogen bond is a phosphazene or cyclic phosphazene of the formulaswherein wl is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each Rwis independently a C1-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene group. In the foregoing groups at least one hydrogen atom of these groups can be substituted with a group having an N, S, O, or F atom, or an amino group. For example, each Rwcan be a substituted or unsubstituted phenoxy, an amino, or a polyoxyalkylene group. Any given Rwcan further be a crosslink to another phosphazene group. Exemplary crosslinks include bisphenol groups, for example bisphenol A groups. Examples include phenoxy cyclotriphosphazene, octaphenoxy cyclotetraphosphazene decaphenoxy cyclopentaphosphazene, and the like. In an aspect, the phosphazene has a structure represented by the formula

[0049] Commercially available phenoxyphosphazenes having the aforementioned structures are LY202 manufactured and distributed by Lanyin Chemical Co., Ltd, FP-110 manufactured and distributed by Fushimi Pharmaceutical Co., Ltd, and SPB-100 manufactured and distributed by Otsuka Chemical Co., Ltd.

[0050] The organophosphorus flame retardant can include an oxaphosphorinoxide of the Formula (23) below.

[0051] In Formula (23), the phosphorous atom and one oxygen atom are part of a cyclic structure, for example, a five or six membered ring and q is at least two. Each Ar is independently Ce-is aryl, preferably benzene, which is optionally substituted with a Ci-is hydrocarbyl group, or a Ci-ishydrocarbyloxy group (e.g., -O-hydrocarbyl). When n and p are each 0 and m is 1 (“mono-DOPO” type compounds), then R2is hydrogen, Ci-Cis alkyl, C3-10 cycloalkyl, (C1-6 alkyl)C3-io cycloalkyl, Ce-is aryl, (C1-6 alkyl)Ce-i8 aryl, C3-12 heteroaryl, or (C1-6 alkyl)C3 i2 heteroaryl. In the foregoing groups at least one hydrogen atom of these groups can be substituted with a group having an N, S, O, or F atom. As used herein, “(C1-6 alkyl)C3-io cycloalkyl” refers to a cycloalkyl group attached to an alkylene group, “(C1-6 alkyl)Ce-i8 aryl” refers to an aryl group attached to an alkylene group, and “(C1-6 alkyl)C3-i2 heteroaryl” refers to a heteroaryl group attached to an alkylene group. In any of the alkyl or cycloalkyl groups of R2, any carbon-carbon single bond is optionally replaced by a carbon-carbon double or triple bond, and any methylene is optionally replaced by O, S, S(=O), C(=O), P(=O), or NR10, wherein R10is hydrogen or C1-6 alkyl, and any methylene is optionally substituted with a group having an N, S, O, or F atom.

[0052] In Formula (23), when n and p are each 1 or more and m is 0 (“Di-DOPO” type compounds), then X is Ci-Cis alkylidene, C3-10 cycloalkylidene, Ce-is arylene, C3-12 heteroarylene, a group derived from Formula (3), or a group represented by -L^X’-L2-. The L1and L2linker groups are each independently a single bond, Ci-Cis alkylidene, or a C3-10 cycloalkylidene, where any carbon-carbon single bond is optionally replaced by a carbon-carbon double or triple bond, and any methylene is optionally replaced by O, S, S(=O), C(=O), P(=O), or NR10, wherein R10is hydrogen or C1-6 alkyl, and any methylene is optionally substituted witha group having an N, S, 0, or F atom. X’ is Ci-Cis alkylidene, C3-10 cycloalkylidene, Ce-is arylene, C3-12 heteroarylene, or a group derived from Formula (3).

[0053] Specific examples of an oxaphosphorinoxide include 9,10-dihydro-9-oxo-10- phosphaphenanthrene-10-oxide, commercially available as from SANKO CO., LTD., under the trade name Sanko-HCA, 3-(6-oxidodibenzo[c,e][l,2]oxaphosphinin-6-yl)propenamide, and 6- [(l-oxido-2,6,7-trioxa-l-phosphabicyclo[2.2.2.]oct-4-yl)methoxy-6-oxide (23c, “DOPO- PEPA”). An exemplary Di-DOPO compound is HTP-6123G, commercially available from GUIZHOU YUANYI MINING GROUP CO.

[0054] The organophosphorus flame retardant can present in an amount effective to provide at least 0.9 wt% phosphorus, or 0.9- 1.6 wt% phosphorus, based on the total thermoplastic composition.

[0055] A colorant composition comprising an organic dye can be present. Although carbon black is often added to conventional compositions to improve UV resistance and weatherability, it acts as a UV stabilizer by absorbing UV radiation, which can otherwise degrade the polymer material. However, carbon black absorbs wavelengths in the near infrared range, thus preventing energy from the laser irradiation from reaching the interface between the parts to be laser welded. Pigments, which are additives conferring color, but without dissolving in the host material, either block or scatter light in the infrared region of the UV spectrum, but without absorbing the UV light and thus do not promote weatherability. Organic dyes include coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red or the like; lanthanide complexes; hydrocarbon and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillation dyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substituted poly (C2-8) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazonium dyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes, perinone dyes; bis-benzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes; thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores such as anti-stokes shift dyes which absorb in the near infrared wavelength and emit in the visible wavelength, or the like; luminescent dyes such as 7-amino-4- methylcoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin; 2-(4-biphenylyl)-5-(4-t- butylphenyl)-l,3,4-oxadiazole; 2,5-bis-(4-biphenylyl)-oxazole; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 3,5,3"",5""-tetra-t-butyl-p-quinquephenyl; 2,5-diphenylfuran; 2,5- diphenyloxazole; 4,4'-diphenylstilbene; 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; l,l'-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4',5,5'- dibenzothiatricarbocyanine iodide; 7-dimethylamino-l-methyl-4-methoxy-8-azaquinolone-2; 7- dimethylamino-4-methylquinolone-2; 2-(4-(4-dimethylaminophenyl)-l,3-butadienyl)-3- ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate; 2- (l-naphthyl)-5-phenyloxazole; 2,2'-p-phenylen-bis(5-phenyloxazole); rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, or the like; or a combination thereof. In some aspects, the colorant composition includes at least two organic dyes. In some aspects, the colorant composition includes a cyan organic dye and a red organic dye, or a green organic dye and a magenta organic dye, or a blue organic dye and a yellow organic dye. The organic dyes can be present from 0.1-1 wt%, 0.2-0.8 wt%, 0.3-0.5 wt%, based on the total thermoplastic composition.

[0056] Colorants such as pigment can also be present. Pigments, which are additives conferring color, but without dissolving in the host material, can either block or scatter light in the infrared region of the UV spectrum, but without absorbing the UV light and thus do not promote weatherability. As such, pigments other than carbon black can be present in small amounts provided that the weatherability is not significantly affected. Pigments can include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxides, iron oxides, or the like; sulfides such as zinc sulfides, or the like; aluminates; sodium sulfo-silicates sulfates, chromates, or the like; zinc ferrites; ultramarine blue; organic pigments such as azos, di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids, flavanthrones, isoindolinones, tetrachloroisoindolinones, anthraquinones, enthrones, dioxazines, phthalocyanines, and azo lakes; Pigment Red 101, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and Pigment Brown 24; or a combination thereof. In some aspects, white pigments including zinc oxide and / or zinc sulfide can be present in small amounts, e.g., 0.5 wt% or less, or 0.3 wt% or less, based on the total thermoplastic composition. In some aspects, the thermoplastic compositions are substantially free of pigments. As used herein, “substantially free of pigments” means less than 5000 ppm, less than 3000 ppm, or less than 1000 ppm pigment other than carbon black. In some aspects, the thermoplastic compositions exclude pigments other than carbon black. In some aspects, the thermoplastic compositions exclude carbon black and pigments other than carbon black.

[0057] An additive composition can be used, comprising one or more additives selected to achieve a desired property, with the proviso that the additive(s) are also selected so as to notsignificantly adversely affect a desired property (i.e., weatherability and laser transmittance) of molded samples of the thermoplastic composition. The additive composition or individual additives can be mixed at a suitable time during the mixing of the components for forming the composition. The additive can be soluble or non-soluble in poly(arylene ether). The additive composition can include an impact modifier, flow modifier, a reinforcing agent (e.g., glass fibers), antioxidant, heat stabilizer, light stabilizer, plasticizer, lubricant, release agent (such as a mold release agent), antistatic agent, anti-fog agent, antimicrobial agent, surface effect additive, radiation stabilizer, or a combination thereof. In general, additives are used in amounts generally known to be effective. For example, the total amount of the additive composition can be 0.001 to 10.0 wt%, or 0.01 to 5 wt%, or 0.01 to 1 wt%, each based on the total weight of the composition.

[0058] Anti-drip agents can also be used in the compositions, for example a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The antidrip agent can be encapsulated by a rigid copolymer, for example styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. TSAN comprises 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN can comprise, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer. In some aspects, the thermoplastic compositions can exclude anti-drip agents. The thermoplastic compositions can minimize or eliminate conventional anti-drip agents, in particular fluorinated anti-drip agents. In some aspects, the fluorinated anti-drip agent is present in an amount effective to provide 0.15 wt% or less fluorine to the total thermoplastic composition. In some aspects, a fluorinated anti-drip agent is excluded from the thermoplastic compositions.

[0059] The thermoplastic compositions include: a poly(arylene ether) composition comprising a poly(arylene ether) and optionally, a poly(arylene ether siloxane); one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, an organophosphorus flame retardant present in an amount effective to provide at least 0.9 wt% phosphorus, based on the total weight of the thermoplastic composition; optionally, a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene; and optionally a colorant composition comprising an organic dye; optionally, an additive composition; and wherein the composition comprises 0 to 1000 ppm carbon black. In some aspects, the one or more hydrogenated block copolymers, e.g., styrene-ethylene-butadiene-styrene copolymers (SEBS), comprise an average weight average molecular weight of 220,000-400,000 g / mol and wherein the one or more hydrogenated block copolymers, e.g., SEBS, are present in an amount effective to provide 1.8 wt% styrene or less,based on the total thermoplastic composition. In some aspects, the one or more hydrogenated block copolymers, e.g., SEBS, comprise an average weight average molecular weight of 100,000-220,000 g / mol and wherein the one or more hydrogenated block copolymers are present in an amount effective to provide 3.8 wt% styrene or less, based on the total thermoplastic composition. In some aspects, the one or more hydrogenated block copolymers comprise a graft copolymer, e.g., SEBS, and wherein the one or more hydrogenated block copolymers are present in an amount effective to provide 3.8 wt% styrene or less, based on the total thermoplastic composition. In some aspects, the a poly(arylene ether) and a poly(arylene ether siloxane) are present, and the poly(arylene ether siloxane) is present in an amount effective to provide 1.5 wt% siloxane units or less, based on the total weight of the thermoplastic composition; and the one or more hydrogenated block copolymers, e.g., SEBS, comprise an average weight average molecular weight of 100,000-220,000 g / mol and are present in an amount effective to provide 3.8 wt% styrene or less, based on the total thermoplastic composition. Without being bound by theory, it is believed that the foregoing thermoplastic compositions achieve high laser transmittance by controlling the size of the rubber domain to be relatively small, compared to prior art compositions. In particular, specific types of SEBS(s) within a specific molecular weight and rigid to soft blocks ratio is used to maintain the desired small rubber domain size in the composition. The foregoing compositions have not only high laser transmittance, but a good combination of other properties as well.

[0060] The thermoplastic compositions can have a combination of good weatherability and good transmission. Good weatherability is evidenced by an fl rating according to the UL 746C test. Materials considered suitable for outdoor use have been subjected to ultraviolet (UV) light exposure and water immersion. UV exposure is performed by using either a twin-enclosed carbon weatherometer for 720 hours, or a xenon-arc weatherometer for 1000 hours. Water immersion testing is performed for 7 days at 70°C. Specimens are tested before and after exposure for flammability, mechanical impact, and mechanical strength. Materials whose properties are not significantly degraded in any of these areas are considered to have passed and are suitable for outdoor use. In some aspects, samples of the thermoplastic compositions retain greater than 70% of the Izod notched impact resistance after ultraviolet (UV) light exposure and water immersion as compared with the Izod notched impact resistance before ultraviolet (UV) light exposure and water immersion. Within this range, samples can retain at least 75%, at least 80%, at least 85%, or at least 90% of the Izod notched impact resistance.

[0061] Laser transmittance refers to the percentage of laser light that passes through a material without being absorbed or scattered. It is a measure of how effectively a material allowslaser energy to pass through it. The laser transmittance is calculated by dividing the intensity of light transmitted through the material by the intensity of the incident laser beam times 100%. Samples of the thermoplastic compositions can have a laser transmittance of greater than 10% at a wavelength of 980 nm and a sample thickness of 2.0 mm. Within that range, samples of the thermoplastic compositions can have a laser transmittance of greater than 20%, at least 25%, at least 30%, at least 35%, at least 40%, or at least 45%, at a wavelength of 980 nm and a sample thickness of 2.0 mm.

[0062] The thermoplastic compositions can include low levels of halogens. In some aspects, the thermoplastic compositions include a calculated added bromine and chlorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added halogen content of the polycarbonate composition is about 1500 ppm or less; or the calculated added bromine, chlorine, and fluorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added bromine, chlorine, and fluorine content of the polycarbonate composition is about 1500 ppm or less.

[0063] The thermoplastic compositions can have ultra-low halogen content. As used herein, “ultra-low chlorine, bromine, or fluorine content” is defined as having a bromine, chlorine, or fluorine content of less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, based on the total parts by weight of the composition. Preferably, the thermoplastic composition has a combined bromine, chlorine, and fluorine content of less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, based on the total parts by weight of the composition.

[0064] The thermoplastic compositions can be manufactured by methods generally available in the art. For example, one method of manufacturing a thermoplastic composition comprises melt blending the components of the composition. More particularly, the powdered thermoplastic polymer components and other optional additives (including stabilizer packages, e.g., antioxidants, heat stabilizers, mold release agents, and the like) are first blended, in a HENSCHEL-Mixer® high speed mixer. Other low shear processes such as hand mixing can also accomplish this blending. The blend is then fed into the throat of an extruder via a hopper. Alternatively, one or more of the components can be incorporated into the composition by feeding directly into the extruder at the throat and / or downstream through a side stuffer. Alternatively, any desired additives can also be compounded into a master batch, in particular the white pigment, and combined with the remaining polymeric components at any point in the process. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate is immediately quenched in a water batch and pelletized.Such pellets can be used for subsequent molding, shaping, or forming. In specific embodiments, a method of manufacturing a thermoplastic composition comprises melting any of the abovedescribed compositions to form the laser-weldable composition.

[0065] Shaped, formed, or molded laser weldable parts comprising the compositions are also provided. In one embodiment, a laser weldable part is formed by extruding, casting, blow molding, or injection molding a melt of the thermoplastic composition. The laser weldable parts can be in the form of a film or sheet. The laser weldable parts can both be prepared from the disclosed thermoplastic compositions.

[0066] In some aspects, a weldable part is made from the disclosed thermoplastic compositions and the other weldable part is made from an auxiliary thermoplastic composition that is known in the art to be suitable for welding. The other thermoplastic part can comprise a wide variety of thermoplastic polymer compositions that have been rendered laser absorbing by means known to those of skill in the art including the use of additives and / or colorants such as but not limited to carbon black. Exemplary auxiliary thermoplastic compositions include polyacetals, poly(Ci-6 alkyljacrylates, polyacrylamides, polyamides, , polyamideimides, poly anhydrides, polyarylates, polyarylene ethers, polyarylene sulfides, polyarylene sulfones, polybenzothiazoles, polybenzoxazoles, polycarbonates, polyesters, polyetheretherketones, poly etherimides, polyetherketoneketones, polyetherketones, polyethersulfones, polyimides (including copolymers such as polyimide-siloxane copolymers), poly(Ci-6 alkyljmethacrylates, polymethacrylamides, polynorbornenes, polyolefins, poly oxadiazoles, polyoxymethylenes, polyphthalides, poly silazanes, polysiloxanes, polystyrenes, polysulfides, poly sulfonamides, poly sulfonates, polysulfones, poly thioesters, polytriazines, polyureas, polyurethanes, polyvinyl alcohols, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinyl ketones, polyvinyl thioethers, polyvinylidene fluorides, or the like, or a combination thereof.

[0067] A process for welding a laser weldable part comprising the above compositions to another thermoplastic part to provide an article comprises physically contacting at least a portion of a surface of the laser weldable part with at least a portion of a surface of the other thermoplastic part, applying laser radiation to the laser weldable part, wherein the radiation passes through the laser weldable part and the radiation is absorbed by the other thermoplastic part and sufficient heat is generated to weld the laser weldable part to the other thermoplastic part.

[0068] The laser welded articles include automotive, electrical, and electronic components. Because the laser-weldable parts have weatherability, articles can include any article for an application where weatherability is desired, e.g., outdoor applications, where theparts and articles are exposed to sunlight, rain, wind, temperature variations, and other environmental factors. In a particular aspects, the article comprises a photovoltaic microinverter, an optimizer, a junction box, a housing for an electrical component, or an automotive air conditioner electrical housing.

[0069] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLES

[0070] The materials shown in Table 1 were used.Table 1

[0071] The various formulations were prepared by direct dry-blending of the raw materials and pre-blended and then extruded using a twin-screw extruder. The composition was melt-kneaded, extruded, cooled through a water bath and pelletized. A typical extrusion profile is listed in Table 2. An Engel 45 molding machine was used to mold the test parts for standard physical property testing. The parameters are provided in Table 3. Sample preparation and testing methods are described in Table 4.Table 2.Table 3.Table 4.

[0072] Weatherability was assessed by testing flammability, impact, and mechanical strength after exposure to UV light and immersion testing according to the UL746C standard (“Polymeric Materials, Use in Electrical Equipment Evaluations”). UV exposure was performed by using either a twin-enclosed carbon weatherometer for 720 hours, or a xenon-arc weatherometer for 1000 hours. Specimens were tested before and after exposure to UV light and immersion in water for flammability, mechanical impact, and mechanical strength. Materials whose properties are not significantly degraded in any of these areas are considered to have passed and are suitable for outdoor use. An “fl” rating indicates that the material has met both UV and water immersion requirements. An “f2”rating indicates that the material has met either UV or water immersion requirements.

[0073] The Izod notched impact resistance was measured before the samples were exposed to UV light and water immersion pursuant to the UL746C standard (see “Nil, 23 °C”) and then measured after the samples were exposed to UV light and immersed in water. The value “Nil, weathering” is Nil, 23 °C divided by the Nil value obtained after exposure to UV light and water immersion pursuant to the UL746C standard times 100%. A value of greater than 70% is desired.

[0074] Flammability tests were performed on samples at a thickness of 1.5 mm, 1.0 mm, and 0.75 mm in accordance with the Underwriter’s Laboratory (UL) UL 94 standard (“Vertical Burning Flame Test”). In some cases, a second set of 5 bars was tested to give an indication of the robustness of the rating. In this report the following definitions are used as shown in Table 5. Total flame-out-times for all 5 bars (FOT = tl + t2) were determined. V-ratings were obtained for every set of 5 bars.

[0075] Flammability properties were also measured on bars 125 mm long by 13 mm wide by 2 mm thick, and on 150 millimeter x 150 millimeter plaques having a thickness of 2 millimeter according to Underwriter’s Laboratory Bulletin 94 “Tests for Flammability of Plastic Materials, UL 94”, 500 W (125 mm) Vertical Burning Flame Test. Results are expressed as performance class 5VA for 6 plaques and performance class 5VB for 10 bars. Table 5.Examples 1-15

[0076] Tables 6-7 show the compositions for the following comparative examples and examples. Comparative examples are indicated with an asterisk. “Percent styrene” refers to the wt% of styrene provided by the hydrogenated block copolymers (i.e., SEBS copolymers).Table 6.Table 7.

[0077] As shown in Tables 6-7, the comparative examples (Examples 1-3) failed to permit any laser transmittance at a wavelength of 980 nm. Improvements to laser transmittance were realized for Examples 4-15 with removal of the inorganic filler (11.5% to 50% transmittance). The representative examples (Examples 4-15) passed all flammability tests and provided comparable tensile and impact strength properties as the comparative examples. A combination of high molecular weight SEBS and low molecular weight SEBS realized a good balance of a relatively high laser transmittance, high impact strength and good flame retardancy, as shown in examples 6. SEBS-3 is maleic anhydride grafted, which can result in smaller sized SEBS domains in the resin matrix attributable to the reaction between the maleic anhydride and the resin matrix. This explains example 11 having higher laser transmittance than the examples with SEBS-2. Poly (arylene ether siloxane) acts as flame retardant synergist in examples 8 to 10, and benefits to better flame retardancy. In addition, the polyphenylene ether compositions of Examples 4-15 provided laser transmittance and impact strength retention after weathering. Examples 4-15 provided compositions with comparable flame retardancy, heat resistance,mechanical strength, and impact strength to the comparative Examples 1-3 with inorganic fillers and carbon black.

[0078] This disclosure further encompasses the following aspects.

[0079] Aspect 1. A thermoplastic composition comprising: a poly(arylene ether) composition comprising a poly(arylene ether) and optionally, a poly(arylene ether siloxane); one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, an organophosphorus flame retardant present in an amount effective to provide at least 0.9 wt% phosphorus, based on the total weight of the thermoplastic composition; optionally, a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene; and optionally a colorant composition comprising an organic dye; optionally, an additive composition; wherein a sample of the composition has a laser transmittance of greater than 10% at a wavelength of 980 nm and a sample thickness of 2.0 mm, a UL94 5VA rating at a thickness of 2.0 mm, a UL94 5VB rating at a thickness of 2.0 mm, and a UL94 rating of V0 at a thickness of 1.5 mm or less, and an fl rating according to the UL746C standard, and wherein the composition comprises 0 to 1000 ppm carbon black. In another aspect, a polystyrene comprising at least 90 wt% of repeating units derived from polymerization of styrene is present in this composition.

[0080] Aspect 2. The thermoplastic composition of aspect 1 comprising less than 100 ppm, or less than 50 ppm carbon black, based on the total thermoplastic composition.

[0081] Aspect 3. The thermoplastic composition of any one of the preceding aspects wherein the organophosphorus flame retardant is present in an amount effective to provide 1.6 wt% or less phosphorus, based on the total thermoplastic composition.

[0082] Aspect 4. The thermoplastic composition of any one of the preceding aspects, wherein the hydrogenated block copolymer is present in an amount effective to provide less than 3.8 wt% styrene, based on the total thermoplastic composition.

[0083] Aspect 5. The thermoplastic composition of any one of the preceding aspects, wherein the one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene comprises an average weight average molecular weight of 100,000-220,000 g / mol.

[0084] Aspect 6. The thermoplastic composition of any one of the preceding aspects, wherein the one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene comprises an average weight average molecular weight of 100,000-220,000 g / mol and the one or more hydrogenated blockcopolymers are present in an amount effective to provide less than 3.8 wt% styrene, based on the total thermoplastic composition.

[0085] Aspect 7. The thermoplastic composition of any one of the preceding aspects, wherein the one or more hydrogenated block copolymers comprise graft-modified hydrogenated block copolymer.

[0086] Aspect 8. The thermoplastic composition of any one of the preceding aspects, wherein the poly(arylene ether siloxane) is present in an amount effective to provide 1.5 wt% or less siloxane units, based on the total thermoplastic composition.

[0087] Aspect 9. The thermoplastic composition of any one of the preceding aspects, wherein the organophosphorus flame retardant comprises the formulawherein R16, R17, R18and R19are each independently Ci-8 alkyl, C5-6 cycloalkyl, C6-20 aryl, or C7- 12 arylalkylene, each optionally substituted by C1-12 alkyl, and X is a mono- or poly-nuclear aromatic Ce-30 moiety or a linear or branched C2-30 aliphatic radical, each of which is optionally OH-substituted and optionally contain up to 8 ether bonds, provided that at least one of R16, R17, R18, R19, and X is aromatic, n is each independently 0 or 1, and q is from 0.5 to 30, and preferably wherein each of R16, R17, R18, and R19is phenyl, X is of the formulacombination thereof, each n is 1, and q is 1 to 5.

[0088] Aspect 10. A laser weldable part comprising the thermoplastic composition of any one of the preceding aspects.

[0089] Aspect 11. A method for forming the weldable part of aspect 10 comprising molding, extruding, or shaping the thermoplastic composition of any one of the preceding aspects to form the laser weldable part.

[0090] Aspect 12. A laser welded article comprising the laser weldable part of aspect 10.

[0091] Aspect 13. The laser welded article of aspect 12, wherein the article comprises a photovoltaic micro-invertor, an optimizer, a junction box, a housing for an electrical component, or an automotive air conditioner electrical housing.

[0092] Aspect 14. A method for forming a laser welded article comprising welding the laser weldable part of aspect 10 to another thermoplastic part to provide the laser welded article.

[0093] Aspect 15. The method of aspect 14, wherein the thermoplastic part is a laser weldable part according to aspect 10.

[0094] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, which are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0095] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25 wt%, or, more specifically, 5 wt% to 20 wt%”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt% to 25 wt%,” etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and / or” unless clearly stated otherwise. Reference throughout the specification to “some embodiments,” “an embodiment,” and so forth, means that a particular element described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements can be combined in any suitable manner in the various embodiments. A “combination thereof’ is open and includes any combination comprising at least one of the listed components or properties optionally together with a like or equivalent component or property not listed.

[0096] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0097] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflictswith a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0098] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dashthat is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group.

[0099] As used herein, the term “hydrocarbyl,” whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen unless it is specifically identified as “substituted hydrocarbyl.” The hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. When the hydrocarbyl residue is described as substituted, it can contain heteroatoms in addition to carbon and hydrogen. The term "alkyl" means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carboncarbon double bond (e.g., ethenyl (-HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-), or propylene (-(CH2)3-)). “Cycloalkylene” means a divalent cyclic alkylene group, -CnFfcn-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carboncarbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present. The prefix “hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a C1-9 alkoxy, aCi-9 haloalkoxy, a nitro (-NO2), a cyano (-CN), a C1-6 alkyl sulfonyl (-S(=O)2-alkyl), a C6-12 aryl sulfonyl (-S(=O)2-aryl)a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a C6-12 aryl, a C7-13 arylalkylene, a C4-12 heterocycloalkyl, and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents. For example -CH2CH2CN is a C2 alkyl group substituted with a nitrile.[000100] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

CLAIMSWhat is claimed is:

1. A thermoplastic composition comprising: a poly(arylene ether) composition comprising a poly(arylene ether) and optionally, a poly (arylene ether siloxane); one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, an organophosphorus flame retardant present in an amount effective to provide at least 0.9 wt% phosphorus, based on the total weight of the thermoplastic composition; optionally, a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene; and optionally a colorant composition comprising an organic dye; optionally, an additive composition; wherein a sample of the composition has a laser transmittance of greater than 10% at a wavelength of 980 nm and a sample thickness of 2.0 mm, a UL945VA rating at a thickness of 2.0 mm, a UL945VB rating at a thickness of 2.0 mm, and a UL94 rating of V0 at a thickness of 1.5 mm or less, and an fl rating according to the UL746C standard, and wherein the composition comprises 0 to 1000 ppm carbon black.

2. The thermoplastic composition of claim 1 comprising less than 100 ppm, or less than 50 ppm carbon black, based on the total thermoplastic composition.

3. The thermoplastic composition of any one of the preceding claims wherein the organophosphorus flame retardant is present in an amount effective to provide 1.6 wt% or less phosphorus, based on the total thermoplastic composition.

4. The thermoplastic composition of any one of the preceding claims, wherein the hydrogenated block copolymer is present in an amount effective to provide less than 3.8 wt% styrene, based on the total weight of the thermoplastic composition.

5. The thermoplastic composition of any one of the preceding claims, wherein the one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprisingstyrene and a conjugated diene comprises an average weight average molecular weight of 100,000-220,000 g / mol.

6. The thermoplastic composition of any one of the preceding claims, wherein the one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene comprises an average weight average molecular weight of 100,000-220,000 g / mol and the one or more hydrogenated block copolymers are present in an amount effective to provide less than 3.8 wt% styrene, based on the total thermoplastic composition.

7. The thermoplastic composition of any one of the preceding claims, wherein the one or more hydrogenated block copolymers comprise graft-modified hydrogenated block copolymer.

8. The thermoplastic composition of any one of the preceding claims, wherein the organophosphorus flame retardant comprises the formulawhereinR16, R17, R18and R19are each independently Ci-8 alkyl, Cs-6 cycloalkyl, Ce -20 aryl, or C7 -12 arylalkylene, each optionally substituted by C1-12 alkyl, andX is a mono- or poly-nuclear aromatic Ce-30 moiety or a linear or branched C2-30 aliphatic radical, each of which is optionally OH-substituted and optionally contain up to 8 ether bonds, provided that at least one of R16, R17, R18, R19, and X is aromatic, n is each independently 0 or 1, and q is from 0.5 to 30, and preferably wherein each of R16, R17, R18, and R19is phenyl,X is of the formulacombination thereof,each n is 1 , and q is 1 to 5.

9. The thermoplastic composition of any one of the preceding claims wherein the poly(arylene ether siloxane) is present in an amount effective to provide 1.5 wt% or less siloxane units, based on the total thermoplastic composition.

10. A laser weldable part comprising the thermoplastic composition of any one of the preceding claims.

11. A method for forming the weldable part of claim 10 comprising molding, extruding, or shaping the thermoplastic composition of any one of the preceding claims to form the laser weldable part.

12. A laser welded article comprising the laser weldable part of claim 10.

13. The laser welded article of claim 12, wherein the article comprises a photovoltaic micro-invertor, an optimizer, a junction box, a housing for an electrical component, or an automotive air conditioner electrical housing.

14. A method for forming a laser welded article comprising welding the laser weldable part of claim 10 to another thermoplastic part to provide the laser welded article.

15. The method of claim 14, wherein the thermoplastic part is a laser weldable part according to claim 10.

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