Laminated foam articles and related methods and battery packs for electric vehicles

Abstract

The present invention provides a laminated foam article comprising a foam core and a fiber-reinforced skin bonded to opposing major surfaces of the foam core. The foam core comprises specific amounts of poly(phenylene ether), polystyrene or rubber-modified polystyrene, or a combination thereof, a block copolymer comprising a polystyrene block and a polybutadiene block, or a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof, and an organophosphate flame retardant. The fiber-reinforced skin comprises specific amounts of reinforcing fibers and a thermoplastic skin composition. Also described are a method for manufacturing the laminated foam article and a battery pack including the laminated foam article.

Description

[Technical Field]

[0001] The present invention relates to laminated foam articles and related methods and battery packs for electric vehicles.

[0002] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of European Patent Application Publication No. 22212521.3, filed December 9, 2022, the entire contents of which are incorporated herein by reference. [Background technology]

[0003] Poly(phenylene ether) foams exhibit excellent heat resistance and flame retardancy, making them suitable for a wide variety of applications, including automotive, rail transport, air transport, and 5G communications equipment. However, for some applications, the flexural strength and flexural modulus of poly(phenylene ether) foams are insufficient. To improve these flexural properties, a laminated foam product is known, in which a poly(phenylene ether) foam sheet is sandwiched between two fiber-reinforced thermoplastic skins. See, for example, Japanese Patent Application Publication No. H10-44282 to Fushimi, published February 17, 1998; U.S. Patent Application Publication No. 2010 / 0261000A1 to Jones, published October 14, 2010; Japanese Patent Application Publication No. 2014-208417 to Kuwahara et al., published November 6, 2014; Japanese Patent Application Publication No. 2017-106041 to Konno et al., published June 15, 2017; and Chinese Patent Application Publication No. 109867942W (A of W) to Zhai et al., published June 11, 2019. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-44282 [Patent Document 2] US Patent Application Publication No. 2010 / 0261000A1 [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-208417 [Patent Document 4] Japanese Patent Application Laid-Open No. 2017-106041 [Patent Document 5] Chinese Patent Application Publication No. 109867942A Summary of the Invention [Problem to be solved by the invention]

[0005] However, there is a further need for poly(phenylene ether) based laminated foam articles that exhibit improved flexural properties while maintaining excellent heat resistance and flame retardancy. [Means for solving the problem]

[0006] In one embodiment, the laminated foam article has a thickness of 2 to 40 millimeters (mm) and a density of 0.06 to 0.24 grams per centimeter as measured by ASTM D1622-14. 3 (g / cm 3), and first and second fiber reinforced skins adhered to opposing major surfaces of the foam core, the foam core comprising a foam composition comprising, based on the total weight of the foam composition, 40 to 79 weight percent poly(phenylene ether), 10 to 48 weight percent polystyrene, rubber-modified polystyrene, or a combination thereof, 1 to 10 weight percent block copolymer comprising a polystyrene block and a polybutadiene block, a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof, and 10 to 25 weight percent organophosphate flame retardant, wherein the sum of the weight percents of the poly(phenylene ether), polystyrene or rubber-modified polystyrene, or a combination thereof, the block copolymer, and the organophosphate flame retardant is 95 to 100. % by weight, wherein the first and second fiber-reinforced skins independently have a thickness of 0.2 to 2 mm and independently comprise, based on the total weight of the fiber-reinforced skins, 35 to 65 weight percent reinforcing fibers selected from the group consisting of glass fiber, carbon fiber, basalt fiber, poly(p-phenylene terephthalamide) fiber, and combinations thereof; and 35 to 65 weight percent thermoplastic skin composition, wherein the thermoplastic skin composition of the first and second fiber-reinforced skins independently comprises, based on the total weight of the thermoplastic skin composition, 22 to 65 weight percent thermoplastic resin selected from the group consisting of poly(phenylene ether), poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof, wherein the thermoplastic resin has a viscosity of 0.28 to 0.01 mm as measured in chloroform at 25°C using an Ubbelohde viscometer.a thermoplastic resin having an intrinsic viscosity of 5 dL / g, 14 to 26 weight percent of polystyrene, rubber-modified polystyrene, or a combination thereof, 14 to 40 weight percent of an organic phosphoric acid flame retardant, 4 to 12 weight percent of a hydrogenated hydrocarbon resin, and 3 to 12 weight percent of a maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, wherein, independently, for each of the first and second fiber-reinforced thermoplastic skin compositions, the sum of the weight percents of the thermoplastic resin, polystyrene or rubber-modified polystyrene, or a combination thereof, the organic phosphoric acid flame retardant, the hydrogenated hydrocarbon resin, and the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer is 95 to 100 weight percent.

[0007] Another embodiment is a method of making a laminated foam article, the method comprising the steps of thermally laminating first and second prepregs to opposite major surfaces of a foam core to form a laminated foam article comprising a foam core and first and second fiber reinforced skins respectively adhered to opposite major surfaces of the foam core, the foam core having a thickness of 2 to 40 mm and a density of 0.06 to 0.24 g / cm as measured by ASTM D1622-14. 3and the foam core comprises a foam composition comprising, based on the total weight of the foam composition, 40 to 79 wt. % of poly(phenylene ether), 10 to 48 wt. % of polystyrene, rubber-modified polystyrene, or a combination thereof, 1 to 10 wt. % of a block copolymer comprising a polystyrene block and a polybutadiene block, a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof, and 10 to 25 wt. % of an organophosphate flame retardant, wherein the sum of the wt. % of the poly(phenylene ether), the polystyrene or rubber-modified polystyrene, or a combination thereof, the block copolymer, and the organophosphate flame retardant is 95 to 100 wt. %. the first and second fiber-reinforced skins independently have a thickness of 0.2 to 2 mm and independently comprise 35 to 65 weight percent reinforcing fibers selected from the group consisting of glass fiber, carbon fiber, basalt fiber, poly(p-phenylene terephthalamide) fiber, and combinations thereof; and 35 to 65 weight percent thermoplastic skin composition, the thermoplastic skin composition of the first and second fiber-reinforced skins independently comprising 22 to 65 weight percent thermoplastic resin selected from the group consisting of poly(phenylene ether), poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof, based on the total weight of the thermoplastic skin composition, the thermoplastic resin having a viscosity of 0.28 to 0.01 as measured by an Ubbelohde viscometer in chloroform at 25°C.a thermoplastic resin having an intrinsic viscosity of 5 dL / g, 14 to 26 wt. % of polystyrene, rubber-modified polystyrene, or a combination thereof, 14 to 40 wt. % of an organic phosphoric acid flame retardant, 4 to 12 wt. % of a hydrogenated hydrocarbon resin, and 3 to 12 wt. % of a maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, wherein, independently, for the thermoplastic skin compositions of the first and second fiber reinforced skins, the sum of the wt. % of the thermoplastic resin, polystyrene or rubber-modified polystyrene, or a combination thereof, the organic phosphoric acid flame retardant, the hydrogenated hydrocarbon resin, and the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer is 95 to 100 wt. %.

[0008] These and other embodiments are described in further detail below. [Brief explanation of the drawings]

[0009] In the drawings, like elements are numbered alike in the several views.

[0010] [Figure 1] 1 is a schematic diagram showing a laminated foam article. [Figure 2] 1 is a schematic diagram showing an apparatus for producing a prepreg, which is a precursor to a fiber-reinforced skin of a laminated foamed article. [Figure 3] 1 is a schematic diagram showing an apparatus for producing a laminated foam article from a foam core and two prepregs. DETAILED DESCRIPTION OF THE INVENTION

[0011] The inventors of the present invention have found that a laminated foamed article manufactured by combining a specific poly(phenylene ether) foam with a specific poly(phenylene ether) fiber-reinforced thermoplastic skin can improve flexural properties while maintaining excellent heat resistance and flame retardancy.

[0012] That is, one embodiment is a laminated foam article, the laminated foam article having a thickness of 2 to 40 mm and a density of 0.06 to 0.24 g / cm as measured by ASTM D1622-14. 3and first and second fiber reinforced skins adhered to opposite major surfaces of the foam core, wherein the foam core comprises a foam composition comprising, based on the total weight of the foam composition, 40 to 79 weight percent poly(phenylene ether), 10 to 48 weight percent polystyrene, rubber-modified polystyrene, or a combination thereof, 1 to 10 weight percent block copolymer comprising a polystyrene block and a polybutadiene block, a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof, and 10 to 25 weight percent organophosphate flame retardant, wherein the sum of the weight percents of the poly(phenylene ether), polystyrene or rubber-modified polystyrene, or a combination thereof, the block copolymer, and the organophosphate flame retardant is 95 to 100% by weight, the first and second fiber-reinforced skins independently having a thickness of 0.2 to 2 mm and independently comprising, based on the total weight of the fiber-reinforced skins, 35 to 65% by weight of reinforcing fibers selected from the group consisting of glass fiber, carbon fiber, basalt fiber, poly(p-phenylene terephthalamide) fiber, and combinations thereof; and 35 to 65% by weight of a thermoplastic skin composition, the thermoplastic skin composition of the first and second fiber-reinforced skins independently comprising, based on the total weight of the thermoplastic skin composition, 22 to 65% by weight of a thermoplastic resin selected from the group consisting of poly(phenylene ether), poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof, the thermoplastic resin having a viscosity of 0.28 to 0.01 psi, as measured in chloroform at 25°C using an Ubbelohde viscometer.a thermoplastic resin having an intrinsic viscosity of 5 dL / g, 14 to 26 weight percent of polystyrene, rubber-modified polystyrene, or a combination thereof, 14 to 40 weight percent of an organic phosphoric acid flame retardant, 4 to 12 weight percent of a hydrogenated hydrocarbon resin, and 3 to 12 weight percent of a maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, wherein, independently, for each of the first and second fiber-reinforced thermoplastic skin compositions, the sum of the weight percents of the thermoplastic resin, polystyrene or rubber-modified polystyrene, or a combination thereof, the organic phosphoric acid flame retardant, the hydrogenated hydrocarbon resin, and the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer is 95 to 100 weight percent.

[0013] FIG. 1 is a schematic diagram of a laminated foam article 10 including a foam core 11, a first fiber reinforced skin 12, and a second fiber reinforced skin 13.

[0014] The laminated foam is produced by laminating first and second fiber-reinforced skins to opposite major surfaces of a foam core. The foam core has a thickness of 2 to 40 mm. Within this range, the thickness can be 4 to 20 mm or 4 to 16 mm. Additionally, the foam core has a density of 0.06 to 0.24 g / cm3 as measured by ASTM D1622-14. 3 Within this range, the density ranges from 0.06 to 0.20 g / cm 3 or 0.08 to 0.16 g / cm 3 It can be said that:

[0015] The foam core comprises a foam composition comprising, based on the total weight of the foam composition, 40 to 79 wt. % of poly(phenylene ether), 10 to 48 wt. % of polystyrene, rubber-modified polystyrene, or a combination thereof, 1 to 10 wt. % of a block copolymer comprising a polystyrene block and a polybutadiene block, a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof, and 10 to 25 wt. % of an organophosphate flame retardant, wherein the sum of the wt. % of the poly(phenylene ether), polystyrene or rubber-modified polystyrene, or a combination thereof, the block copolymer, and the organophosphate flame retardant is 95 to 100 wt. %.

[0016] The foam composition includes a poly(phenylene ether). Generally, a poly(phenylene ether) is a polymer containing repeating structural units represented by the following structural formula: [ka] where Z for each occurrence 1 are independently halogen, unsubstituted or substituted C1-C 12 Hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1-C 12 Hydrocarbylthio, C1-C 12 Hydrocarbyloxy, or C2-C 12 halohydrocarbyloxy (where the halogen and oxygen atoms are separated by at least two carbon atoms), and each occurrence of Z 2 are independently hydrogen, halogen, unsubstituted or substituted C1-C 12 Hydrocarbyl (provided that the hydrocarbyl group is not tertiary hydrocarbyl), C1-C 12 Hydrocarbylthio, C1-C 12 Hydrocarbyloxy, or C2-C 12and halohydrocarbyloxy (where the halogen and oxygen atoms are separated by at least two carbon atoms). As used herein, the term "hydrocarbyl," whether used alone or as a prefix, suffix, or part of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also include combinations of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon groups. However, when a hydrocarbyl residue is described as substituted, it may optionally contain heteroatoms in addition to the carbon and hydrogen that make up the substituent residue. That is, when stated as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or can contain heteroatoms within the backbone of the hydrocarbyl residue. As an example, Z 1 may be a di-n-butylaminomethyl group formed by reacting a terminal 3,5-dimethyl-1,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst.

[0017] Poly(phenylene ether)s can include molecules with aminoalkyl-containing end groups (typically ortho to the hydroxyl group). Also frequently present are tetramethyldiphenoquinone (TMDQ) end groups, typically derived from reaction mixtures containing 2,6-dimethylphenol (in which the tetramethyldiphenoquinone by-product is present). Poly(phenylene ether)s can be in the form of homopolymers, copolymers, graft copolymers, ionomers, or block copolymers, as well as combinations thereof.

[0018] In some embodiments, the poly(phenylene ether) present in the foam composition has an intrinsic viscosity of 0.42 to 0.50 dL / g as measured by an Ubbelohde viscometer in chloroform at 25° C. In some embodiments, the poly(phenylene ether) present in the foam composition comprises poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured by an Ubbelohde viscometer in chloroform at 25° C.

[0019] The foam composition comprises poly(phenylene ether) in an amount of 40 to 70 weight percent, based on the total weight of the foam composition. Within this range, the amount of poly(phenylene ether) can be 40 to 65 weight percent, 40 to 60 weight percent, or 45 to 55 weight percent.

[0020] In addition to poly(phenylene ether), the foam composition includes polystyrene, rubber-modified polystyrene, or a combination thereof. As used herein, the term "polystyrene" refers to a homopolymer of styrene. The polystyrene can be atactic, syndiotactic, or isotactic. In some embodiments, the polystyrene is atactic. The rubber-modified polystyrene (sometimes referred to as high impact polystyrene or HIPS) comprises 80 to 98 wt. % polystyrene and 2 to 20 wt. % polybutadiene, based on the weight of the rubber-modified polystyrene. Within the range of 80 to 98 wt. %, the amount of polystyrene can be 82 to 96 wt. % or 84 to 94 wt. Within the range of 2 to 20 wt. %, the amount of polybutadiene can be 4 to 18 wt. % or 6 to 16 wt. %. In some embodiments, the polybutadiene contains 85 to 100% cis double bonds and 0 to 15% trans double bonds, where the sum of cis and trans double bonds is 100 mole percent (%). Within the 85 to 100% range, the amount of cis double bonds can be 90 to 100% or 95 to 100% (the remainder being trans double bonds). In some embodiments, the polystyrene, rubber-modified polystyrene, or combination thereof comprises rubber-modified polystyrene.

[0021] The foam composition includes polystyrene, rubber-modified polystyrene, or a combination thereof in an amount of 10 to 48 weight percent, based on the total weight of the foam composition. Within this range, the amount of polystyrene, rubber-modified polystyrene, or a combination thereof is 15 to 40 weight percent or 25 to 30 weight percent.

[0022] In addition to the poly(phenylene ether) and polystyrene, rubber-modified polystyrene, or a combination thereof, the foam composition may include a block copolymer comprising a polystyrene block and a polybutadiene block, a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof. The block copolymer comprising a polystyrene block and a polybutadiene block includes at least one polystyrene block and at least one polybutadiene block. In some embodiments, it is a diblock copolymer comprising one polystyrene block and one polybutadiene block. In other embodiments, it is a triblock copolymer comprising two polystyrene blocks and one polybutadiene block. In the block copolymer comprising a polystyrene block and a polybutadiene block, one or more of the polybutadiene blocks are not hydrogenated. The block copolymer comprising a polystyrene block and a polybutadiene block may include 15 to 50% by weight polystyrene and 50 to 85% by weight polybutadiene, based on the weight of the block copolymer comprising a polystyrene block and a polybutadiene block. Within the range of 15 to 50 wt%, the polystyrene content can be 20 to 40 wt% or 25 to 35 wt%. Within the range of 50 to 85 wt%, the amount of polybutadiene can be 60 to 80 wt% or 65 to 75 wt%.

[0023] In block copolymers comprising a polystyrene block and a hydrogenated polybutadiene block, one or more polybutadiene blocks are hydrogenated and may be referred to as poly(ethylene-butylene) blocks. Block copolymers comprising a polystyrene block and a hydrogenated polybutadiene block comprise at least one polystyrene block and at least one hydrogenated polybutadiene block. In some embodiments, this is a diblock copolymer comprising one polystyrene block and one hydrogenated polybutadiene block. In other embodiments, this is a triblock copolymer comprising two polystyrene blocks and one hydrogenated polybutadiene block.

[0024] A block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block can comprise 15 to 50% by weight of polystyrene and 50 to 85% by weight of poly(ethylene-butylene), based on the weight of the block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block. Within the range of 15 to 50% by weight, the polystyrene content can be 20 to 40% by weight or 25 to 35% by weight. Within the range of 50 to 85% by weight, the amount of poly(ethylene-butylene) can be 60 to 80% by weight or 65 to 75% by weight.

[0025] In some embodiments, the block copolymer comprising a polystyrene block and a polybutadiene block, the block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof comprises a block copolymer comprising a polystyrene block and a polybutadiene block. In some embodiments, the block copolymer comprising a polystyrene block and a polybutadiene block, the block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof comprises a polystyrene-polybutadiene-polystyrene triblock copolymer having a polystyrene content of 20 to 40 wt. % and a polybutadiene content of 60 to 80 wt. % based on the weight of the polystyrene-polybutadiene-polystyrene triblock copolymer.

[0026] The foam composition includes a block copolymer including a polystyrene block and a polybutadiene block, a block copolymer including a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof, in an amount of 1 to 10 weight percent, based on the total weight of the foam composition. Within this range, the amount can be 1 to 6 weight percent or 1 to 4 weight percent.

[0027] In addition to the poly(phenylene ether), polystyrene or rubber-modified polystyrene or a combination thereof, and a block copolymer containing a polystyrene block and a polybutadiene block or a block copolymer containing a polystyrene block and a hydrogenated polybutadiene block, the foam composition also contains an organic phosphate flame retardant. Representative organic phosphate flame retardants include phosphate esters containing phenyl groups, substituted phenyl groups, or combinations of phenyl groups and substituted phenyl groups, bisaryl phosphate esters based on resorcinol (e.g., resorcinol bis(diphenyl phosphate)), and those based on bisphenols (e.g., bisphenol A bis(diphenyl phosphate)). In some embodiments, the organophosphate flame retardant is selected from the group consisting of tris(alkylphenyl)phosphate (e.g., CAS Registry Number 89492-23-9 or CAS Registry Number 78-33-1), resorcinol bis(diphenyl phosphate) (CAS Registry Number 57583-54-7), bisphenol A bis(diphenyl phosphate) (CAS Registry Number 181028-79-5), triphenyl phosphate (CAS Registry Number 115-86-6), tris(isopropylphenyl)phosphate (e.g., CAS Registry Number 68937-41-7), t-butylphenyl diphenyl phosphate (CAS Registry Number 56803-37-3), bis(t-butylphenyl)phenyl phosphate (CAS Registry Number 65652-41-7), tris(t-butylphenyl)phosphate (CAS Registry Number 78-33-1), and combinations thereof. In some embodiments, the organophosphate flame retardant comprises resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), or a combination thereof. In some embodiments, the organophosphate flame retardant comprises resorcinol bis(diphenyl phosphate).

[0028] The foam composition includes the organophosphate flame retardant in an amount of 10 to 25 weight percent, based on the total weight of the foam composition. Within this range, the amount of organophosphate flame retardant can be 12 to 22 weight percent or 14 to 20 weight percent.

[0029] In the foam composition, the sum of the weight percent of the poly(phenylene ether), polystyrene or rubber-modified polystyrene or combination thereof, block copolymer, and organophosphate flame retardant is 95 to 100 weight percent, based on the total weight of the foam composition. Within this range, the sum can be 97 to 100 weight percent, 98 to 100 weight percent, or 98.5 to 100 weight percent.

[0030] In some embodiments, the foam composition comprises 45 to 55 wt. % poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured by Ubbelohde viscometer in chloroform at 25° C., 25 to 35 wt. % rubber-modified polystyrene, 1 to 5 wt. % polystyrene-polybutadiene-polystyrene triblock copolymer, and 12 to 22 wt. % organophosphate flame retardant.

[0031] In addition to the foam core, the laminated foam article includes first and second fiber-reinforced skins adhered to opposite major surfaces of the foam core. The first and second fiber-reinforced skins independently have thicknesses of 0.2 to 2 mm. While the thickness of the first and second fiber-reinforced skins can be measured after they are adhered to the foam core, the thicknesses shown are for the first and second fiber-reinforced skins prior to adhesion to the foam core. Within the 0.2 to 2 mm range, the first and second fiber-reinforced skins can independently have thicknesses of 0.3 to 1.5 mm or 0.3 to 1 mm. For simplicity, the terms "first fiber-reinforced skin" and "second fiber-reinforced skin" are used to refer to the fiber-reinforced skins both before and after lamination to the foam core. When it is necessary to distinguish between the fiber-reinforced skins prior to lamination and the fiber-reinforced skins after lamination, the fiber-reinforced skins prior to lamination can be referred to as "prepreg."

[0032] The first and second fiber-reinforced skins independently comprise a skin composition including, based on the total weight of each of the first and second fiber-reinforced skins, 35 to 65 weight percent reinforcing fibers selected from the group consisting of glass fiber, carbon fiber, basalt fiber, poly(p-phenylene terephthalamide) fiber, and combinations thereof, and 35 to 65 weight percent thermoplastic skin composition. Within the 35 to 65 weight percent range, the amount of reinforcing fibers can independently be 40 to 60 weight percent or 45 to 55 weight percent for the first and second fiber-reinforced skins. Within the 35 to 65 weight percent range, the amount of thermoplastic skin composition can independently be 40 to 60 weight percent or 45 to 55 weight percent for the first and second fiber-reinforced skins.

[0033] The reinforcing fibers of the first and second fiber-reinforced skins are selected from the group consisting of glass fiber, carbon fiber, basalt fiber, poly(p-phenylene terephthalamide) fiber, and combinations thereof. In some embodiments, the reinforcing fibers are glass fiber, carbon fiber, and combinations thereof. In some embodiments, the reinforcing fibers include glass fiber. The reinforcing fibers can be provided in the form of a fiber fabric (woven, nonwoven, etc.). In some embodiments, the reinforcing fibers are provided in the form of a glass fiber fabric. The reinforcing fibers can have a diameter of 4 to 40 micrometers (μm) or 6 to 20 μm. The reinforcing fibers can have a length of 1 to 1000 mm or 5 to 500 mm (micrometers), or, particularly in the case of a woven fiber fabric, the fibers can be essentially continuous.

[0034] The thermoplastic skin compositions of the first and second fiber reinforced skins (sometimes referred to herein as the first and second thermoplastic skin compositions) independently comprise: a thermoplastic resin selected from the group consisting of poly(phenylene ether), poly(phenylene ether)-polysiloxane block copolymers, and combinations thereof, wherein the thermoplastic resin has an intrinsic viscosity of 0.28 to 0.5 dL / g as measured in chloroform at 25°C using an Ubbelohde viscometer; polystyrene or rubber-modified polystyrene, or a combination thereof; an organic phosphate flame retardant; a hydrogenated hydrocarbon resin; and a maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0035] The first and second thermoplastic skin compositions each comprise a thermoplastic resin selected from the group consisting of poly(phenylene ether), poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof, wherein the thermoplastic resin has an intrinsic viscosity of 0.28 to 0.5 dL / g or 0.28 to 0.43 dL / g as measured by an Ubbelohde viscometer in chloroform at 25°C. Poly(phenylene ether) is generally described above in the foam composition section. As used herein, the term "poly(phenylene ether)-polysiloxane block copolymer" refers to a block copolymer comprising at least one poly(phenylene ether) block and at least one polysiloxane block. In some embodiments, the poly(phenylene ether)-polysiloxane block copolymer is prepared by oxidative copolymerization. In this method, the poly(phenylene ether)-polysiloxane block copolymer is the product of a process comprising the oxidative copolymerization of a monomer mixture comprising a monohydric phenol and a hydroxyaryl-terminated polysiloxane. In some embodiments, the monomer mixture comprises 70 to 99 parts by weight of the monohydric phenol and 1 to 30 parts by weight of the hydroxyaryl-terminated polysiloxane, based on the total weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane. The hydroxyaryl-diterminated polysiloxane can comprise a plurality of repeating units represented by the following structural formula: [ka] where R for each occurrence 8 are independently hydrogen, C1 to C 12 Hydrocarbyl, or C1-C 12 and the two terminal units are represented by the following structural formula: [ka] In the formula, Y is hydrogen, C1 to C 12 Hydrocarbyl, C1-C 12 hydrocarbyloxy, or halogen, and each occurrence of R 9 are independently hydrogen, C1 to C 12 Hydrocarbyl, or C1-C 12 In more specific embodiments, each occurrence of R is halohydrocarbyl. 8 and R 9 is methyl and Y is methoxyl. In some embodiments, the monohydric phenol comprises 2,6-dimethylphenol and the hydroxyaryl-terminated polysiloxane has the following structural formula: [ka] where n is, on average, 5 to 100, more specifically, 30 to 60. The oxidative copolymerization process produces poly(phenylene ether)-polysiloxane block copolymers as the desired product, with poly(phenylene ether) (without incorporated polysiloxane blocks) as a by-product. Separation of the poly(phenylene ether) from the poly(phenylene ether)-polysiloxane block copolymer is not necessary. Thus, the poly(phenylene ether)-polysiloxane block copolymer can be used as a "reaction product" containing both poly(phenylene ether) and poly(phenylene ether)-polysiloxane block copolymer. Certain isolation procedures, such as precipitation from isopropanol, can render the reaction product substantially free of residual hydroxyaryl-terminated polysiloxane starting material. In other words, such isolation procedures can ensure that the polysiloxane in the reaction product is essentially entirely in the form of poly(phenylene ether)-polysiloxane block copolymer. Detailed methods for preparing poly(phenylene ether)-polysiloxane block copolymers are described in U.S. Pat. No. 8,017,697 to Carrillo et al. and U.S. Patent Application Publication No. 2012 / 0329961 A1 to Carrillo et al.

[0036] The thermoplastic resin has an intrinsic viscosity of 0.28 to 0.5 dL / g as measured by an Ubbelohde viscometer in chloroform at 25° C. Within this range, the intrinsic viscosity can be 0.28 to 0.43 dL / g, 0.3 to 0.43 dL / g, or 0.33 to 0.43 dL / g. In some embodiments, the thermoplastic resin comprises poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.45 dL / g or 0.35 to 0.45 dL / g as measured by an Ubbelohde viscometer in chloroform at 25° C. In some embodiments, the thermoplastic resin is comprised of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.45 dL / g or 0.35 to 0.45 dL / g as measured by an Ubbelohde viscometer in chloroform at 25° C.

[0037] The first and second thermoplastic skin compositions independently comprise a thermoplastic resin in an amount of 25 to 65 weight percent, based on the total weight of each of the first and second thermoplastic skin compositions. Within this range, the amount of thermoplastic resin can independently be 30 to 60 weight percent, 35 to 55 weight percent, or 37 to 50 weight percent for the first and second thermoplastic skin compositions.

[0038] In addition to the thermoplastic resin, the first and second thermoplastic skin compositions include polystyrene or rubber-modified polystyrene or a combination thereof. Polystyrene and rubber-modified polystyrene are generally described above in the foam composition section. In some embodiments, the first and second thermoplastic skin compositions independently include a rubber-modified polystyrene comprising 80 to 98 wt. % polystyrene and 2 to 20 wt. % polybutadiene. Within the 80 to 98 wt. % range, the amount of polystyrene can be 82 to 96 wt. % or 84 to 94 wt. Within the 2 to 20 wt. % range, the amount of polybutadiene can be 4 to 18 wt. % or 6 to 16 wt. %.

[0039] The first and second thermoplastic skin compositions independently comprise polystyrene or rubber-modified polystyrene or a combination thereof in an amount of 14 to 26 weight percent, based on the total weight of each of the first and second thermoplastic skin compositions. Within this range, the amount of polystyrene or rubber-modified polystyrene or a combination thereof can be 16 to 24 weight percent.

[0040] In addition to the thermoplastic resin and polystyrene or rubber-modified polystyrene or a combination thereof, the first and second thermoplastic skin compositions each include an organophosphate flame retardant. Organophosphate flame retardants are generally described above in the foam composition section. In some embodiments, the organophosphate flame retardant used in the first and second thermoplastic skin compositions is resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), or a combination thereof. In some embodiments, the organophosphate flame retardant includes bisphenol A bis(diphenyl phosphate).

[0041] The first and second thermoplastic skin compositions independently comprise an organophosphate flame retardant in an amount of 14 to 40 weight percent, based on the total weight of each of the first and second thermoplastic skin compositions. Within this range, the amount of organophosphate flame retardant can be 15 to 37 weight percent, 20 to 35 weight percent, or 20 to 30 weight percent.

[0042] In addition to the thermoplastic resin, polystyrene or rubber-modified polystyrene or a combination thereof, and an organophosphate flame retardant, the first and second thermoplastic skin compositions each include a hydrogenated hydrocarbon resin. As used herein, the term "hydrogenated hydrocarbon resin" refers to a C6 to C8 20 This refers to a hydrogenated homopolymer or copolymer of an olefin. Examples include hydrogenated copolymers of two or more of styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and indene. In some embodiments, the hydrogenated hydrocarbon resin has a softening point of 105 to 145°C as measured by ASTM E28-18. Within this range, the softening point can be 115 to 135°C or 120 to 130°C. Suitable hydrogenated hydrocarbon resins include, for example, Alcon™ P-115, Alcon™ P-125, and Alcon™ P-140, manufactured by Arakawa Chemical Industries, Ltd. In some embodiments, the hydrogenated hydrocarbon resin has a number average molecular weight of 400 to 4,000 g / mol, 700 to 2500 g / mol, or 800 to 1500 g / mol as measured by gel permeation chromatography using a polyethylene standard.

[0043] The first and second thermoplastic skin compositions independently comprise the hydrogenated hydrocarbon resin in an amount of 4 to 12 weight percent, based on the total weight of each of the first and second thermoplastic skin compositions. Within this range, the amount of hydrogenated hydrocarbon resin can be 5 to 12 weight percent or 5 to 11 weight percent.

[0044] In addition to the thermoplastic resin, polystyrene or rubber-modified polystyrene or a combination thereof, the organophosphate flame retardant, and the hydrogenated hydrocarbon resin, the first and second thermoplastic skin compositions each include a maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer. As used herein, the term "maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer" refers to the reaction product of a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer in which maleic anhydride is grafted onto the poly(ethylene-butylene) midblock. In some embodiments, the maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45 wt. % and a bound maleic anhydride content of 0.5 to 4 wt. %, based on the total weight of the maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer. Within the range of 15 to 45 wt%, the polystyrene content can be 20 to 40 wt% or 25 to 35 wt%. Within the range of 0.5 to 4 wt%, the bound maleic anhydride content can be 0.8 to 3 wt% or 1 to 2.5 wt%. Suitable maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers include, for example, KRATON™ FG1901 and KRATON™ FG1924 manufactured by Kraton Corporation.

[0045] The first and second thermoplastic skin compositions independently comprise the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer in an amount of 3 to 12 weight percent, based on the total weight of each of the first and second thermoplastic skin compositions. Within this range, the amount of the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer can be 3 to 11 weight percent or 4 to 10 weight percent.

[0046] For each of the first and second thermoplastic skin compositions, the sum of the weight percent values ​​of the thermoplastic resin, polystyrene or rubber-modified polystyrene or a combination thereof, organophosphate flame retardant, hydrogenated hydrocarbon resin, and maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer is 95 to 100 weight percent, 96 to 100 weight percent, 97 to 100 weight percent, or 98 to 100 weight percent.

[0047] In some embodiments, the first and second thermoplastic skin compositions comprise 0 to 1 wt. %, 0 to 0.5 wt. %, 0 to 0.1 wt. %, or 0 wt. % of a block copolymer comprising a polystyrene block and a polybutadiene block, based on the total weight of each of the first and second thermoplastic skin compositions.

[0048] In some embodiments, the first and second thermoplastic skin compositions comprise 0 to 1 wt. %, 0 to 0.5 wt. %, 0 to 0.1 wt. %, or 0 wt. % homopolystyrene, based on the total weight of each of the first and second thermoplastic skin compositions.

[0049] In a more specific embodiment of the laminated foam article, the reinforcing fibers are in the form of woven glass fibers, and the thermoplastic skin compositions of the first and second fiber reinforced skins independently comprise 30 to 50 wt. % thermoplastic resin, 16 to 24 wt. % rubber-modified polystyrene, 20 to 35 wt. % organophosphate flame retardant, 5 to 12 wt. % hydrogenated hydrocarbon resin, and 3 to 11 wt. % maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, wherein the thermoplastic resin is The rubber-modified polystyrene comprises 80 to 95 wt. % polystyrene and 5 to 20 wt. % polybutadiene, based on the total weight of the rubber-modified polystyrene; and the hydrogenated hydrocarbon resin is a hydrogenated poly(C6-C8) having a number average molecular weight of 400 to 4,000 g / mol, as measured by gel permeation chromatography using polyethylene standards. 20 olefin), wherein the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45 wt.% and a bound maleic anhydride content of 0.5 to 4 wt.%, based on the total weight of the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer. In a variation of this more specific embodiment, the foam composition comprises 45 to 55 wt.% poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured by an Ubbelohde viscometer in chloroform at 25°C, 25 to 35 wt.% rubber-modified polystyrene, 1 to 5 wt.% block copolymer comprising a polystyrene block and a polybutadiene block (i.e., a non-hydrogenated block copolymer), and 12 to 22 wt.% organophosphate flame retardant.

[0050] The present invention includes a method for producing a laminated foam article. As previously mentioned, the terms "first fiber reinforced skin" and "second fiber reinforced skin" are used to refer to the fiber reinforced skin both before and after lamination to a foam core. When it is necessary to distinguish between the pre-lamination fiber reinforced skin and the post-lamination fiber reinforced skin, the pre-lamination fiber reinforced skin can be referred to as a "prepreg." The method for producing a laminated foam article includes thermally laminating first and second prepregs to opposite major surfaces of a foam core to produce a laminated foam article comprising a foam core and first and second fiber reinforced skins (made from the first and second prepregs, respectively) adhered to opposite major surfaces of the foam core, the foam core having a thickness of 2 to 40 mm and a density of 0.06 to 0.24 g / cm as measured by ASTM D1622-14. 3and the foam core comprises a foam composition comprising, based on the total weight of the foam composition, 40 to 79 wt. % of poly(phenylene ether), 10 to 48 wt. % of polystyrene, rubber-modified polystyrene, or a combination thereof, 1 to 10 wt. % of a block copolymer comprising a polystyrene block and a polybutadiene block, a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof, and 10 to 25 wt. % of an organophosphate flame retardant, wherein the sum of the wt. % of the poly(phenylene ether), polystyrene or rubber-modified polystyrene, or a combination thereof, the block copolymer, and the organophosphate flame retardant is 95 to 100 wt. %. The first and second prepregs independently have a thickness of 0.2 to 2 mm and independently comprise 35 to 65 weight percent reinforcing fibers selected from the group consisting of glass fiber, carbon fiber, basalt fiber, poly(p-phenylene terephthalamide) fiber, and combinations thereof, and 35 to 65 weight percent thermoplastic skin composition, wherein the thermoplastic skin composition of the first and second prepregs independently comprises 22 to 65 weight percent thermoplastic resin selected from the group consisting of poly(phenylene ether), poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof, based on the total weight of the thermoplastic skin composition, wherein the thermoplastic resin has a viscosity of 0.28 to 0.5 dL / g or 0.28 to 0.5 dL / g as measured in chloroform at 25°C using an Ubbelohde viscometer.a thermoplastic resin having an intrinsic viscosity of 43 dL / g, 14 to 26% by weight of polystyrene or rubber-modified polystyrene or a combination thereof, 14 to 40% by weight of an organic phosphoric acid flame retardant, 4 to 12% by weight of a hydrogenated hydrocarbon resin, and 3 to 12% by weight of a maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, wherein, independently, for each of the thermoplastic skin compositions of the first and second prepregs, the sum of the weight percentages of the thermoplastic resin, polystyrene or rubber-modified polystyrene or a combination thereof, the organic phosphoric acid flame retardant, the hydrogenated hydrocarbon resin, and the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer is 95 to 100% by weight.

[0051] 2 is a schematic diagram of an apparatus for producing a prepreg, which may be the first prepreg and / or the second prepreg. The prepreg production apparatus 100 includes a fiber fabric roll 110 from which a fiber fabric monolayer 120 is unwound. The fiber fabric monolayer 120 is preheated with an infrared heater 140 and then laminated with two layers of thermoplastic film 160 to form a prepreg. The thermoplastic film monolayer 160 is unwound from a thermoplastic film roll 150 and laminated to the fiber fabric monolayer 120 in a heated double-belt press, which includes two heated steel belts 170, to form a prepreg 180.

[0052] 3 is a schematic diagram of an apparatus for producing a laminated foam article from a foam core and two prepregs. The laminate production apparatus 200 converts a foam sheet 210 into a laminated foam article 230 by laminating two prepregs 180. More specifically, the foam sheet 210 and two prepregs 180 (i.e., the first and second prepregs) are preheated with an infrared heater 140 and then laminated with two heated steel belts 170 to form the laminated foam article 230.

[0053] All of the various statements made above regarding the laminated foam article also apply to the method of manufacturing the laminated foam article. For example, in some embodiments of the method, the reinforcing fibers of the first and second prepregs are in the form of a woven fiber fabric. As another example, in some embodiments of the method, the reinforcing fibers are in the form of a woven glass fiber fabric.

[0054] In some embodiments of the method, the step of thermally laminating the first and second prepregs to opposite major surfaces of the foam core includes contacting the first and second prepregs, respectively, to opposite major surfaces of the foam core to form a sandwich structure (the two prepregs are outer layers in contact with the inner foam core but are not yet bonded), and exposing the sandwich structure to a temperature of 250 to 290°C and a pressure of 0.8 to 3.2 megapascals (MPa) for 5 to 50 seconds to bond the first and second prepregs to the foam core, thereby forming a laminated foam article. Within the range of 250 to 290°C, the temperature can be 260 to 280°C. Within the range of 0.8 to 3.2 MPa, the pressure can be 1 to 3 MPa or 1 to 2 MPa. Within the range of 5 to 50 seconds, the time can be 10 to 30 seconds or 10 to 20 seconds.

[0055] In some embodiments of the process, the foam composition comprises 45 to 55 wt. % poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured by an Ubbelohde viscometer in chloroform at 25° C., 25 to 35 wt. % rubber-modified polystyrene, 1 to 5 wt. % block copolymer comprising a polystyrene block and a polybutadiene block (i.e., a non-hydrogenated block copolymer), and 12 to 22 wt. % organophosphate flame retardant.

[0056] In some embodiments of the process, the thermoplastic resin of the first and second fiber reinforced skins is poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.45 dL / g as measured by an Ubbelohde viscometer in chloroform at 25° C. Within this range, the intrinsic viscosity can be 0.35 to 0.45 dL / g.

[0057] In some embodiments of the process, the hydrogenated hydrocarbon resin is a hydrogenated poly(C6-C8) having a softening point of 105 to 145°C as measured by ASTM E28-18. 20 Within this range, the softening point may be from 115 to 135°C or from 120 to 130°C.

[0058] In some embodiments of the process, the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers of the first and second thermoplastic skin compositions independently have a polystyrene content of 15 to 45 weight percent and a bound maleic anhydride content of 0.5 to 4 weight percent, based on the total weight of the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer. Within the 15 to 45 weight percent range, the polystyrene content can be 20 to 40 weight percent or 25 to 35 weight percent. Within the 0.5 to 4 weight percent range, the bound maleic anhydride content can be 0.8 to 3 weight percent or 1 to 2.5 weight percent.

[0059] In a more specific embodiment of the process, the reinforcing fibers are in the form of a woven glass fabric, and the thermoplastic skin compositions of the first and second fiber reinforced skins independently comprise 30 to 50 wt. % thermoplastic resin, 16 to 24 wt. % rubber-modified polystyrene, 20 to 35 wt. % organophosphate flame retardant, 5 to 12 wt. % hydrogenated hydrocarbon resin, and 3 to 11 wt. % maleic anhydride grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, the thermoplastic resin being The rubber-modified polystyrene comprises 80 to 95 wt. % polystyrene and 5 to 20 wt. % polybutadiene, based on the total weight of the rubber-modified polystyrene; and the hydrogenated hydrocarbon resin is a hydrogenated poly(C6-C8) having a number average molecular weight of 400 to 4,000 g / mol, as measured by gel permeation chromatography using polyethylene standards. 20 olefin), wherein the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45 wt. % and a bound maleic anhydride content of 0.5 to 4 wt. % based on the total weight of the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer. In a variation of this more specific embodiment, the foam composition comprises 45 to 55 wt. % poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured by an Ubbelohde viscometer in chloroform at 25° C., 25 to 35 wt. % rubber-modified polystyrene, 1 to 5 wt. % block copolymer comprising a polystyrene block and a polybutadiene block (i.e., a non-hydrogenated block copolymer), and 12 to 22 wt. % organophosphate flame retardant.

[0060] In some embodiments, the thermoplastic skin composition of the first and second fiber reinforced skins comprises 0 to 1 wt. % of a block copolymer comprising a polystyrene block and a polybutadiene block, hi some embodiments, the thermoplastic skin composition of the first and second fiber reinforced skins comprises 0 to 1 wt. % of homopolystyrenes.

[0061] The present invention includes an electric vehicle battery pack including a battery and any of the various laminated foam articles described herein. The term "electric vehicle battery pack" includes articles in which the laminated foam article is present inside the battery or in association with the battery, but external to the battery. In an electric vehicle battery pack, the laminated foam article can provide one or more of physical protection for the battery, thermal protection for the battery, and flame retardancy for the battery.

[0062] This specification uses examples to disclose the invention, including the best mode, but also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are within the scope of the claims if they have structural elements that do not differ from the claim language, or if they contain equivalent structural elements that do not change substantially from the claim language.

[0063] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety, except that if a term in this application contradicts or conflicts with a term in an incorporated reference, the term in this application will take precedence over the conflicting term from the incorporated reference.

[0064] All ranges disclosed herein are inclusive of their endpoints, and the endpoints are independently combinable with each other. Each range disclosed herein is intended to disclose every point or subrange within the disclosed range.

[0065] The use of the terms "a," "an," "the," and similar referents in the text describing the present invention (particularly in the claims that follow) should be construed to include both the singular and the plural unless the text indicates otherwise or unless clearly contradicted by context. It should be further noted that the use of the terms "first," "second," etc. in the text does not denote any order, quantity, or importance, but rather is used to distinguish one element from another. The modifier "about" used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of a particular quantity). [Example]

[0066] The present invention is further illustrated by the following non-limiting examples.

[0067] The ingredients used in these examples are summarized in Table 1.

[0068] [Table 1]

[0069] The composition of the pre-foamed material (referred to as Resin A) is summarized in Table 2. Component amounts are expressed as weight percent of the total weight of the composition. This composition was compounded in a 36 mm twin-screw extruder operated at feed-to-die barrel temperatures of 200, 230, 260, 260, 280, 280, 280, 285, and 275°C, with a die temperature of 275°C. The extrudate was cooled and pelletized, then dried at 100°C for 3 hours before being used for sheet extrusion.

[0070] [Table 2]

[0071] Sheet extrusion of Resin A was carried out in a sheet extruder operated at barrel temperatures of 200, 240, 260, 270, 280, 280, 260, and 250° C. and a die temperature of 245° C. The finished cooled sheet had a thickness of 5.5 mm.

[0072] The extruded sheet of Resin A was expanded using a Jinhe Technology CLJ600 mold press. After preheating the machine to 150°C, the extruded sheet of Resin A was placed in the machine cavity, and the mold cavity was sealed using a hydraulic device. Supercritical carbon dioxide was injected into the cavity, and the cavity was maintained at 150°C and 15 MPa for 60 minutes. After 60 minutes, the pressure was quickly released through the exhaust port, opening the cavity. The expanded sheet was quickly transferred to an air-operated flat press molder equipped with upper and lower 30 mm thick steel plates, where it was cooled and molded to a thickness of 8 mm and a density of 0.12 g / cm3 as measured by ASTM D1622-14. 3 A flat foamed sheet having a density of 1000 MPa was obtained.

[0073] Table 3 summarizes the compositions of materials represented by Resins B to H (which are extruded into thin sheets and then combined with glass fiber fabric to make prepregs). The amounts of components are expressed as mass % of the total mass of the composition.

[0074] [Table 3]

[0075] [Table 4]

[0076] To form the prepreg, resins B through H were first compressed into a 0.2 mm thick film using a double steel press. Two compressed films were then laminated to opposite major surfaces of a 0.5 mm thick glass fiber fabric to form the prepreg. The apparatus shown schematically in Figure 2 was used for this process. The heat and pressure module of the apparatus was maintained at a temperature of 270°C, and a pressure of 1.6 MPa was applied to the sample moving through it. The resulting prepreg had a thickness of 0.5 mm and a weight of 1200 g / m. 2 and contained 50 mass % of glass fiber fabric and 50 mass % of one of resins B to H relative to the total mass of the prepreg.

[0077] Table 4 summarizes the properties of each prepreg. For property testing, 1-mm prepregs were prepared by laminating two 0.5-mm-thick prepregs prepared as described above. Prepregs A through G were each prepared by laminating two layers of prepregs 1 through 7. Flexural strength (in MPa) and flexural modulus (in gigapascals (GPa)) were determined in accordance with ASTM D790-17 using bar specimens with a thickness (i.e., minimum dimension) equivalent to the prepreg thickness. Flame retardancy of the prepregs was determined in accordance with Underwriter's Laboratory Bulletin 94 "Tests for Flammability of Plastic Materials, UL 94," a 20-mm vertical flame test. The specimens were 125 mm long, 13 mm wide, and 1 mm thick (i.e., the prepreg thickness). Prior to testing, the specimens were conditioned at 23°C and 50% relative humidity for at least 48 hours. The specimens were oriented so that the cross-section of the sample faced the flame. A set of five combustion specimens was tested for each type of prepreg (laminated foam article). For each specimen, the time it took for the specimen to self-extinguish after the flame was removed was recorded (first afterflame time, t1). The specimen was then re-exposed to the flame and the time it took for the specimen to self-extinguish after the flame was removed was recorded (second afterflame time, t2), as well as the time it remained glowing after the flame was applied (afterglow time, t3). To qualify for a V-0 rating, the afterflame times t1 and t2 for each individual specimen must be 10 seconds or less, the total afterflame time for all five specimens (t1 + t2 for all five specimens) must be 50 seconds or less, the second afterflame time + afterglow time (t2 + t3) for each individual specimen must be 30 seconds or less, there must be no afterflame or afterglow to the holding clamp, and there must be no indicator cotton ignition by burning particles or drips.To qualify for a V-1 rating, the afterflame times t1 and t2 for each individual specimen must be 30 seconds or less, the total afterflame time for all five specimens (t1 + t2 for all five specimens) must be 250 seconds or less, the second afterflame time plus the afterglow time (t2 + t3) for each individual specimen must be 60 seconds or less, there must be no afterflame or afterglow to the holding clamp, and there must be no indicator cotton ignition due to burning particles or droplets.To qualify for a V-2 rating, the afterflame times t1 and t2 for each individual specimen must be 30 seconds or less, the total afterflame time for all five specimens (t1 + t2 for all five specimens) must be 250 seconds or less, the second afterflame time plus the afterglow time (t2 + t3) for each individual specimen must be 60 seconds or less, there must be no afterflame or afterglow to the holding clamp, but there may be indicator cotton ignition due to burning particles or droplets. Compositions that did not achieve a V-2 rating were considered failures. The results in Table 4 show that prepregs D through F, prepared from thermoplastic skin compositions E through H, respectively, exhibited superior flexural strength values, superior flexural modulus values, and superior flame retardancy compared to prepregs A through C, prepared from thermoplastic skin compositions B through D, respectively.

[0078] [Table 5]

[0079] [Table 6]

[0080] To form the laminated foam, one layer of each of prepregs 1-7 was laminated to each of the two major surfaces on either side of the foamed resin A sheet. The apparatus shown diagrammatically in Figure 3 was used for this process. The equipment's spaced heat and pressure modules were maintained at a temperature of 270°C with a steel belt spacing of 7.5 mm. The resulting laminated foam had a thickness of 7.5 mm and a weight of 2160 g / m². 2and contained 35.7 mass % of glass fiber fabric and 64.3 mass % of a combination of resin A and one of resins B to H relative to the total mass of the laminated foamed article.

[0081] The properties of the laminated foam are summarized in Table 5. Flexural strength values ​​(expressed in units of MPa) and flexural modulus values ​​(expressed in units of GPa) were determined according to ASTM D790-17 using bar specimens having a thickness (i.e., smallest dimension) corresponding to the thickness of the laminated foam.

[0082] Flame retardancy was determined according to Underwriter's Laboratory Bulletin 94, "Tests for Flammability of Plastic Materials, UL 94," a 20 mm vertical flame test. Specimens were 125 mm long, 13 mm wide, and 7.5 mm thick (i.e., the thickness of the laminated foam). Prior to testing, specimens were conditioned at 23°C and 50% relative humidity for at least 48 hours. Specimens were oriented so that the cross section of the specimen (including the exposed foam) was exposed to the flame. A set of five flame specimens was tested for each type of laminated foam. For each specimen, the time it took for the specimen to self-extinguish after the flame was removed from the specimen (first afterflame time, t1) was recorded. The time it took for the specimen to self-extinguish after the flame was removed from the specimen (second afterflame time, t2) and the time it remained glowing after the flame were recorded. To qualify for a V-0 rating, the afterflame times t1 and t2 for each individual specimen must be 10 seconds or less, the total afterflame time for all five specimens (t1 + t2 for all five specimens) must be 50 seconds or less, the second afterflame time plus the afterglow time (t2 + t3) for each individual specimen must be 30 seconds or less, there must be no afterflame or afterglow to the holding clamp, and there must be no indicator cotton ignition by burning particles or droplets.To qualify for a V-1 rating, the afterflame times t1 and t2 for each individual specimen must be 30 seconds or less, the total afterflame time for all five specimens (t1 + t2 for all five specimens) must be 250 seconds or less, the second afterflame time plus the afterglow time (t2 + t3) for each individual specimen must be 60 seconds or less, there must be no afterflame or afterglow to the holding clamp, and there must be no indicator cotton ignition by burning particles or droplets. To qualify for a V-2 rating, the afterflame times t1 and t2 for each individual specimen must be 30 seconds or less, the total afterflame time for all five specimens (t1 + t2 for all five specimens) must be 250 seconds or less, the second afterflame time + afterglow time (t2 + t3) for each individual specimen must be 60 seconds or less, and there must be no afterflame or afterglow up to the holding clamp, although indicator cotton ignition by burning particles or drips may occur.Compositions that failed to achieve a V-2 rating were considered failures.

[0083] The results in Table 5 show that the laminated foamed articles of Examples 1 to 4, which were prepared using prepregs 4 to 7 (prepared from thermoplastic skin compositions E to H, respectively), exhibited superior flexural strength values, superior flexural modulus values, and excellent flame retardancy, compared to the laminated foamed articles of Comparative Examples 1 to 3, which were prepared using prepregs 1 to 3 (prepared from thermoplastic skin compositions B to D, respectively).

[0084] [Table 7]

[0085] [Table 8]

[0086] The present invention includes at least the following aspects.

[0087] Aspect 1: A laminated foam article, the laminated foam having a thickness of 2 to 40 mm and a modulus of elasticity of 0.06 to 0.24 g / cm as measured by ASTM D1622-14. 3and first and second fiber reinforced skins adhered to opposing major surfaces of the foam core, the foam core comprising a foam composition comprising, based on the total weight of the foam composition, 40 to 79 weight percent poly(phenylene ether), 10 to 48 weight percent polystyrene, rubber-modified polystyrene, or a combination thereof, 1 to 10 weight percent block copolymer comprising a polystyrene block and a polybutadiene block, a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof, and 10 to 25 weight percent organophosphate flame retardant, wherein the sum of the weight percents of the poly(phenylene ether), polystyrene or rubber-modified polystyrene, or a combination thereof, the block copolymer, and the organophosphate flame retardant is 95 to 100. % by weight, wherein the first and second fiber-reinforced skins independently have a thickness of 0.2 to 2 mm and independently comprise, based on the total weight of the fiber-reinforced skins, 35 to 65 weight percent reinforcing fibers selected from the group consisting of glass fiber, carbon fiber, basalt fiber, poly(p-phenylene terephthalamide) fiber, and combinations thereof; and 35 to 65 weight percent thermoplastic skin composition, wherein the thermoplastic skin composition of the first and second fiber-reinforced skins independently comprises, based on the total weight of the thermoplastic skin composition, 22 to 65 weight percent thermoplastic resin selected from the group consisting of poly(phenylene ether), poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof, wherein the thermoplastic resin has a viscosity of 0.28 to 0.5 dL / g or 0.28 to 0.5 dL / g as measured in chloroform at 25°C using an Ubbelohde viscometer.a thermoplastic resin having an intrinsic viscosity of 43 dL / g, 14 to 26% by weight of polystyrene or rubber-modified polystyrene or a combination thereof, 14 to 40% by weight of an organic phosphoric acid flame retardant, 4 to 12% by weight of a hydrogenated hydrocarbon resin, and 3 to 12% by weight of a maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, wherein, independently, for each of the first and second fiber-reinforced thermoplastic skin compositions, the sum of the weight percentages of the thermoplastic resin, polystyrene or rubber-modified polystyrene or a combination thereof, the organic phosphoric acid flame retardant, the hydrogenated hydrocarbon resin, and the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer is 95 to 100% by weight.

[0088] Embodiment 2: The laminated foam article of Embodiment 1, wherein the foam composition comprises 45 to 55 weight percent poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured by Ubbelohde viscometer in chloroform at 25° C.; 25 to 35 weight percent rubber-modified polystyrene; 1 to 5 weight percent polystyrene-polybutadiene-polystyrene triblock copolymer; and 12 to 22 weight percent organophosphate flame retardant.

[0089] Embodiment 3: The laminated foam article of embodiment 1 or 2, wherein the thermoplastic resin is poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.45 dL / g as measured by an Ubbelohde viscometer in chloroform at 25° C.

[0090] Aspect 4: The laminated foam of any of Aspects 1-3, wherein the hydrogenated hydrocarbon resin is a hydrogenated poly(C6-C6) having a softening point of 105 to 145°C as measured by ASTM E28-18. 20 olefins).

[0091] Embodiment 5: The laminated foam of any of Embodiments 1-4, wherein the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45 wt. % and a bound maleic anhydride content of 0.5 to 4 wt. %, based on the total weight of the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0092]

[0020] Aspect 6. The laminated foam article of Aspect 1, wherein the reinforcing fibers are in the form of a woven glass fabric; and wherein the thermoplastic skin compositions of the first and second fiber reinforced skins independently comprise: 30 to 50 wt. % thermoplastic resin; 16 to 24 wt. % rubber-modified polystyrene; 20 to 35 wt. % organophosphate flame retardant; 5 to 12 wt. % hydrogenated hydrocarbon resin; and 3 to 11 wt. % maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer; The rubber-modified polystyrene comprises 80 to 95 wt. % polystyrene and 5 to 20 wt. % polybutadiene, based on the total weight of the rubber-modified polystyrene; and the hydrogenated hydrocarbon resin is a hydrogenated poly(C6-C8) having a number average molecular weight of 400 to 4,000 g / mol, as measured by gel permeation chromatography using polyethylene standards. 20 olefin), and the maleic anhydride grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45 wt. % and a bound maleic anhydride content of 0.5 to 4 wt. %, based on the total weight of the maleic anhydride grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0093]

[0023] Embodiment 7: The laminated foam article of Embodiment 6, wherein the foam composition comprises 45 to 55% by weight of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured by Ubbelohde viscometer in chloroform at 25°C, 25 to 35% by weight of rubber-modified polystyrene, 1 to 5% by weight of polystyrene-polybutadiene-polystyrene triblock copolymer, and 12 to 22% by weight of an organophosphate flame retardant.

[0094] Aspect 8: A method of making a laminated foam article, the method comprising thermally laminating first and second prepregs to opposite major surfaces of a foam core to form a laminated foam article comprising a foam core and first and second fiber reinforced skins respectively adhered to opposite major surfaces of the foam core, the foam core having a thickness of 2 to 40 mm and a density of 0.06 to 0.24 g / cm as measured by ASTM D1622-14. 3and the foam core comprises a foam composition comprising, based on the total weight of the foam composition, 40 to 79 wt. % poly(phenylene ether), 10 to 48 wt. % polystyrene, rubber-modified polystyrene, or a combination thereof, 1 to 10 wt. % block copolymer comprising a polystyrene block and a polybutadiene block, a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof, and 10 to 25 wt. % organophosphate flame retardant, wherein the poly(phenylene ether) the sum of the weight percent of the polystyrene or rubber-modified polystyrene or combination thereof, the block copolymer, and the organophosphate flame retardant is 95 to 100 weight percent, and the first and second prepregs independently have a thickness of 0.2 to 2 mm and independently comprise 35 to 65 weight percent of reinforcing fibers selected from the group consisting of glass fiber, carbon fiber, basalt fiber, poly(p-phenylene terephthalamide) fiber, and combinations thereof, and 35 to 65 weight percent of a thermoplastic skin composition, wherein the thermoplastic skin composition of the first and second prepregs is and, independently, 22 to 65 weight percent, based on the total weight of the thermoplastic skin composition, of a thermoplastic resin selected from the group consisting of poly(phenylene ether), poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof, wherein the thermoplastic resin has an intrinsic viscosity of 0.28 to 0.5 dL / g or 0.28 to 0.43 dL / g as measured by an Ubbelohde viscometer in chloroform at 25°C; 14 to 26 weight percent rubber-modified polystyrene; 14 to 40 weight percent organophosphate flame retardant; and 4 to 12 weight percent hydrogenated carbon. and 3 to 12 weight percent maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, wherein, independently, for each thermoplastic skin composition of the first and second prepregs, the sum of the weight percents of the thermoplastic resin, polystyrene or rubber-modified polystyrene or combinations thereof, hydrogenated hydrocarbon resin, organophosphate flame retardant, and maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer is 95 to 100 weight percent.

[0095] Embodiment 9: The manufacturing method of embodiment 8, wherein the step of thermally laminating the first and second prepregs to opposite major surfaces of the foam core includes the steps of contacting the first and second prepregs, respectively, to opposite major surfaces of the foam core to form a sandwich structure, and exposing the sandwich structure to a temperature of 250 to 290°C and a pressure of 0.8 to 3.2 MPa for 5 to 50 seconds to bond the first and second prepregs to the foam core, thereby forming a laminated foam article.

[0096]

[0023] Embodiment 10: The method of embodiment 8 or 9, wherein the foam composition comprises: 45 to 55% by weight of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured by Ubbelohde viscometer in chloroform at 25°C; 25 to 35% by weight of rubber-modified polystyrene; 1 to 5% by weight of a block copolymer comprising a polystyrene block and a polybutadiene block; and 12 to 22% by weight of an organophosphate flame retardant.

[0097] Aspect 11: The method of any of Aspects 8-10, wherein the thermoplastic resin is poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.45 dL / g as measured in chloroform at 25°C using an Ubbelohde viscometer.

[0098] Aspect 12. The process of any of Aspects 8-11, wherein the hydrogenated hydrocarbon resin is a hydrogenated poly(C6-C6) having a softening point of 105 to 145° C. as measured by ASTM E28-18. 20 olefins).

[0099] Aspect 13: The process of any of Aspects 8-12, wherein the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45 wt. % and a bound maleic anhydride content of 0.5 to 4 wt. %, based on the total weight of the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0100]

[0023] Aspect 14. The process of Aspect 8, wherein the reinforcing fibers are in the form of a woven glass fabric; and wherein the thermoplastic skin compositions of the first and second fiber reinforced skins independently comprise: 30 to 50 weight percent thermoplastic resin; 16 to 24 weight percent rubber-modified polystyrene; 20 to 35 weight percent organophosphate flame retardant; 5 to 12 weight percent hydrogenated hydrocarbon resin; and 3 to 11 weight percent maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer; The rubber-modified polystyrene comprises 80 to 95 wt. % polystyrene and 5 to 20 wt. % polybutadiene, based on the total weight of the rubber-modified polystyrene; and the hydrogenated hydrocarbon resin is a hydrogenated poly(C6-C8) having a number average molecular weight of 400 to 4,000 g / mol, as measured by gel permeation chromatography using polyethylene standards. 20 olefin), and the maleic anhydride grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45 wt. % and a bound maleic anhydride content of 0.5 to 4 wt. %, based on the total weight of the maleic anhydride grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0101] Aspect 15: A battery pack for an electric vehicle, comprising a battery and the laminated foamed product of any one of Aspects 1 to 7.

Claims

1. A laminated foam article, comprising: The laminated foamed product is A thickness of 2 to 40 millimeters (mm) and a density of 0.06 to 0.24 grams per centimeter as measured by ASTM D1622-14 ３ (g / cm ３ a foam core having a density of first and second fiber reinforced skins adhered to opposing major surfaces of the foam core; Including, the foam core comprises a foam composition; The foam composition comprises, relative to the total mass of the foam composition: 40 to 79 weight percent (wt%) poly(phenylene ether); 10 to 48 wt. % of polystyrene, rubber-modified polystyrene, or a combination thereof; 1 to 10% by weight of a block copolymer comprising a polystyrene block and a polybutadiene block, a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof; 10 to 25% by weight of an organophosphate flame retardant; Including, wherein the total mass % of the poly(phenylene ether), the polystyrene or rubber-modified polystyrene or a combination thereof, the block copolymer, and the organic phosphoric acid flame retardant is 95 to 100 mass %, the first and second fiber reinforced skins independently have a thickness of 0.2 to 2 mm, and independently, relative to the total mass of the fiber reinforced skins: 35 to 65 weight percent reinforcing fibers selected from the group consisting of glass fibers, carbon fibers, basalt fibers, poly(p-phenylene terephthalamide) fibers, and combinations thereof; 35 to 65 wt. % of a thermoplastic skin composition; Including, the thermoplastic skin compositions of the first and second fiber reinforced skins independently comprise, relative to the total weight of the thermoplastic skin composition: 22 to 65 weight percent of a thermoplastic resin selected from the group consisting of poly(phenylene ether), poly(phenylene ether)-polysiloxane block copolymers, and combinations thereof, wherein the thermoplastic resin has an intrinsic viscosity of 0.28 to 0.5 deciliters per gram (dL / g) as measured by an Ubbelohde viscometer in chloroform at 25°C; 14 to 26 wt. % of polystyrene, rubber-modified polystyrene, or a combination thereof; 14 to 40 wt. % of an organophosphate flame retardant; 4 to 12% by weight of a hydrogenated hydrocarbon resin; 3 to 12 wt. % of a maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer; Including, In this case, independently, for each of the thermoplastic skin compositions of the first and second fiber reinforced skins, the sum of the mass % values ​​of the thermoplastic resin, the polystyrene or rubber-modified polystyrene or a combination thereof, the organic phosphoric acid flame retardant, the hydrogenated hydrocarbon resin, and the maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer is 95 to 100 mass %. A laminated foamed product characterized by:

2. The laminated foamed article according to claim 1, The foaming composition comprises: 45 to 55 weight percent of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured in chloroform at 25°C by Ubbelohde viscometer; 25 to 35% by weight of rubber-modified polystyrene; 1 to 5% by weight of a polystyrene-polybutadiene-polystyrene triblock copolymer; 12 to 22 wt. % of an organophosphate flame retardant; A laminated foamed product comprising:

3. 3. The laminated foamed article according to claim 1, wherein the thermoplastic resin is poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.45 dL / g as measured in chloroform at 25°C with an Ubbelohde viscometer.

4. 4. The laminated foam article according to claim 1, wherein the hydrogenated hydrocarbon resin is hydrogenated poly(C) having a softening point of 105 to 145°C as measured by ASTM E28-18. ６ ~C ２０ A laminated foamed article comprising a polyolefin.

5. 5. The laminated foam article according to claim 1, wherein the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45 wt. % and a bound maleic anhydride content of 0.5 to 4 wt. %, based on the total weight of the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

6. The laminated foamed article according to claim 1, the reinforcing fibers are in the form of a glass fiber fabric; the thermoplastic skin compositions of the first and second fiber reinforced skins independently comprise: 30 to 50% by weight of a thermoplastic resin; 16 to 24% by weight of rubber-modified polystyrene; 20 to 35 wt. % of an organophosphate flame retardant; 5 to 12% by weight of a hydrogenated hydrocarbon resin; 3 to 11% by weight of a maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer; Including, the thermoplastic resin comprises poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.43 dL / g as measured by an Ubbelohde viscometer in chloroform at 25°C; the rubber-modified polystyrene comprises 80 to 95% by weight of polystyrene and 5 to 20% by weight of polybutadiene, based on the total weight of the rubber-modified polystyrene; The hydrogenated hydrocarbon resin is a hydrogenated poly(C) having a number average molecular weight of 400 to 4,000 grams per mole (g / mol) as determined by gel permeation chromatography using polyethylene standards. ６ ~C ２０ olefins), The maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45 wt. % and a bound maleic anhydride content of 0.5 to 4 wt. %, based on the total weight of the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

7. The laminated foamed article according to claim 6, The foaming composition comprises: 45 to 55 weight percent of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured in chloroform at 25°C by Ubbelohde viscometer; 25 to 35% by weight of rubber-modified polystyrene; 1 to 5% by weight of a polystyrene-polybutadiene-polystyrene triblock copolymer; 12 to 22 wt. % of an organophosphate flame retardant; A laminated foamed product comprising:

8. A method for producing a laminated foam article, comprising: the method includes thermally laminating first and second prepregs to opposite major surfaces of a foam core to form a laminated foam article comprising a foam core and first and second fiber-reinforced skins adhered to opposite major surfaces of the foam core, respectively; The foam core has a thickness of 2 to 40 mm and a density of 0.06 to 0.24 g / cm as measured by ASTM D1622-14. ３ has a density of the foam core comprises a foam composition; The foam composition comprises, relative to the total mass of the foam composition: 40 to 79 wt. % poly(phenylene ether); 10 to 48 wt. % of polystyrene, rubber-modified polystyrene, or a combination thereof; 1 to 10% by weight of a block copolymer comprising a polystyrene block and a polybutadiene block, a block copolymer comprising a polystyrene block and a hydrogenated polybutadiene block, or a combination thereof; 10 to 25% by weight of an organophosphate flame retardant; Including, wherein the total mass % of the poly(phenylene ether), the polystyrene or rubber-modified polystyrene or a combination thereof, the block copolymer, and the organic phosphoric acid flame retardant is 95 to 100 mass %, the first and second prepregs independently have a thickness of 0.2 to 2 mm and independently 35 to 65 weight percent reinforcing fibers selected from the group consisting of glass fibers, carbon fibers, basalt fibers, poly(p-phenylene terephthalamide) fibers, and combinations thereof; 35 to 65 wt. % of a thermoplastic skin composition; Including, The thermoplastic skin compositions of the first and second prepregs independently comprise, relative to the total mass of the thermoplastic skin compositions: 22 to 65 weight percent of a thermoplastic resin selected from the group consisting of poly(phenylene ether), poly(phenylene ether)-polysiloxane block copolymers, and combinations thereof, wherein the thermoplastic resin has an intrinsic viscosity of 0.28 to 0.5 dL / g as measured by an Ubbelohde viscometer in chloroform at 25°C; 14 to 26% by weight of polystyrene or rubber-modified polystyrene or a combination thereof; 14 to 40 wt. % of an organophosphate flame retardant; 4 to 12% by weight of a hydrogenated hydrocarbon resin; 3 to 12 wt. % of a maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer; Including, In this case, the total mass % of the thermoplastic resin, the polystyrene or rubber-modified polystyrene or a combination thereof, the hydrogenated hydrocarbon resin, the organic phosphoric acid flame retardant, and the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer in each of the thermoplastic skin compositions of the first and second prepregs is 95 to 100 mass %.

9. 9. The method of claim 8, wherein the step of thermally laminating first and second prepregs to opposite major surfaces of a foam core comprises: contacting the first and second prepregs, respectively, with opposite major surfaces of the foam core to form a sandwich structure; exposing the sandwich structure to a temperature of 250 to 290°C and a pressure of 0.8 to 3.2 megapascals for 5 to 50 seconds to bond the first and second prepregs to the foam core, thereby forming a laminated foam article; A manufacturing method comprising the steps of:

10. 10. The method according to claim 8 or 9, The foaming composition comprises: 45 to 55 weight percent of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.42 to 0.50 dL / g as measured in chloroform at 25°C by Ubbelohde viscometer; 25 to 35% by weight of rubber-modified polystyrene; 1 to 5% by weight of a block copolymer comprising a polystyrene block and a polybutadiene block; 12 to 22 wt. % of an organophosphate flame retardant; A manufacturing method comprising the steps of:

11. 11. The method according to claim 8, wherein the thermoplastic resin is poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.45 dL / g as measured in chloroform at 25°C using an Ubbelohde viscometer.

12. 12. The method according to claim 8, wherein the hydrogenated hydrocarbon resin is a hydrogenated poly(C) having a softening point of 105 to 145°C as measured by ASTM E28-18. ６ ~C ２０ olefin).

13. 13. The method of any one of claims 8 to 12, wherein the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45 wt. % and a bound maleic anhydride content of 0.5 to 4 wt. %, based on the total weight of the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

14. 9. The method of claim 8, the reinforcing fibers are in the form of a glass fiber fabric; the thermoplastic skin compositions of the first and second fiber reinforced skins independently comprise: 30 to 50% by weight of a thermoplastic resin; 16 to 24% by weight of rubber-modified polystyrene; 20 to 35 wt. % of an organophosphate flame retardant; 5 to 12% by weight of a hydrogenated hydrocarbon resin; 3 to 11% by weight of a maleic anhydride-grafted polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer; Including, the thermoplastic resin comprises poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.43 dL / g as measured by an Ubbelohde viscometer in chloroform at 25°C; the rubber-modified polystyrene comprises 80 to 95% by weight of polystyrene and 5 to 20% by weight of polybutadiene, based on the total weight of the rubber-modified polystyrene; The hydrogenated hydrocarbon resin is a hydrogenated poly(C) having a number average molecular weight of 400 to 4,000 g / mol as determined by gel permeation chromatography using polyethylene standards. ６ ~C ２０ olefins), The maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer has a polystyrene content of 15 to 45% by weight and a bound maleic anhydride content of 0.5 to 4% by weight, based on the total weight of the maleic anhydride-grafted-polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

15. A battery pack for an electric vehicle, comprising a battery and the laminated foamed product according to any one of claims 1 to 7.

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