WO2021009729A1

WO2021009729A1 - Metallized articles and methods for the manufacture thereof

Info

Publication number: WO2021009729A1
Application number: PCT/IB2020/056771
Authority: WO
Inventors: Chao Liu; Liang Shen; Lijuan Wang; Weiyun JI; Lili Xu; Cuihua OU
Original assignee: Shpp Global Technologies B.V.
Priority date: 2019-07-18
Filing date: 2020-07-17
Publication date: 2021-01-21

Abstract

An article includes a substrate and a surface metal layer on the substrate, wherein the surface metal layer is deposited by physical vapor deposition. The substrate includes a poly(etherimide), a poly(sulfone), or a combination thereof. Methods of making the article are also described herein.

Description

METALLIZED ARTICLES AND METHODS FOR THE MANUFACTURE THEREOF

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of European Patent Application No. 19186965.0 filed on July 18, 2019, which is incorporated by reference herein in its entirety.

BACKGROUND

[0001] Thermoplastic compositions find use in a wide variety of applications, including in consumer electronics. Currently, many consumer electronics applications rely on metal parts. However, there is an ongoing interest in replacing metal parts with parts molded from polymers, as molded polymer articles can offer the advantages such as lower cost, high production speed, wide design latitude, lighter weight, and desirable mechanical properties.

[0002] For many applications, a metallic coating on the polymeric article is desired to further impart hardness, wear resistance, and metallic appearance and feel to the articles.

Providing a metal layer on the surface of a plastic part can be challenging due to limited dimensional stability of the part under the high heat environment typically used to deposit a metal layer.

[0003] Accordingly, there remains a need in the art for improved polymer-containing articles having a metal coating layer, where the plastic parts can retain good dimensional stability during a coating process, and also maintain good mechanical properties for various end- use applications. It would be a further advantage to provide metallized articles which can offer metal coatings having improved durability and wear resistance.

SUMMARY

[0004] An article comprises a substrate comprising a poly(etherimide), a poly(sulfone), or a combination thereof; a surface metal layer disposed on the substrate, wherein the first metal layer is deposited by physical vapor deposition.

[0005] A method of making the article comprises depositing a surface metal layer on a substrate comprising a poly(etherimide), a poly(sulfone), or a combination thereof, wherein depositing the surface metal layer comprises physical vapor deposition.

[0006] The above described and other features are exemplified by the following detailed description.

DETAILED DESCRIPTION [0007] The present inventors have advantageously found that selection of a particular substrate material combined with a particular process for providing metal layers on the surface of the substrate can provide improved metallized articles. In particular, the present inventors have identified that using a substrate comprising a poly(etherimide), a poly(sulfone), or a combination there of can be especially advantageous. Such materials have the desired high heat resistance necessary to withstand a metal coating process. Other materials (e.g., polyamides, polyaryl ether ketones, liquid crystalline polymers, polycarbonates, and the like) having lower glass transition temperatures or lower heat deflection temperatures can suffer from deformation during metal coating (e.g., physical vapor deposition at 120 to 180°C). In a further

advantageous feature, the present inventors have also discovered that depositing metal layers on the surface of the substrate by a particular set of processes can be beneficial for improving adhesion of the metal layer to the polymer substrate, leading to improved performance of the final part (e.g., enhanced vibration wear resistance). In still a further advantageous feature, the present inventors have found that proper polishing of the surface of the metallized articles can provide a uniform surface quality and reduce surface defects, ultimately providing improved surface quality of the final articles.

[0008] Accordingly, an aspect of the present disclosure is an article comprising a substrate and a surface metal layer. The substrate comprises a poly(etherimide), a poly(sulfone), or a combination thereof. The poly(etherimide), poly(sulfone), or combination thereof has a glass transition temperature of greater than 180°C. Glass transition temperature can be determined by methods that are generally known, for example by differential scanning calorimetry (DSC). In an aspect, the substrate consists of the poly(etherimide), the

poly(sulfone), or a combination thereof. In an aspect, no polymer other than the

poly(etherimide) and the poly(sulfone) are present in the substrate. In an aspect, the substrate can exclude a poly(ester), a poly(amide), a poly(olefin) (e.g., polyethylene, polypropylene, and the like), a poly(aryl ether ketone), a liquid crystalline polymer, a poly(carbonate), a

poly(phenylene ether), or a poly(phenylene sulfide).

[0009] In an aspect, the substrate comprises the poly(etherimide). Poly(etherimide)s comprise more than 1, for example 2 to 1000, or 5 to 500, or 10 to 100 structural units of formula (1)

wherein each R is independently the same or different, and is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted C6-20 aromatic hydrocarbon group, a substituted or unsubstituted straight or branched chain C4-20 alkylene group, a substituted or unsubstituted C3-8 cycloalkylene group, in particular a halogenated derivative of any of the foregoing. In an aspect R is divalent group of one or more of the following formulas (2)

wherein Q¹ is -0-, -S-, -C(O)-, -SO2-, -SO-, -P(R^a)(=0)- wherein R^a is a Ci-s alkyl or C6-12 aryl, - C_yth_y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (which includes perfluoroalkylene groups), or -(CeH mj_z- wherein z is an integer from 1 to 4. In an aspect R is m- phenylene, p-phenylene, or a diarylene sulfone, in particular bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’-phenylene)sulfone, or a combination comprising at least one of the foregoing. In an aspect, at least 10 mole percent or at least 50 mole percent of the R groups contain sulfone groups, and in other aspects no R groups contain sulfone groups.

[0010] Further in formula (1), T is -O- or a group of the formula -O-Z-O- wherein the divalent bonds of the -O- or the -O-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions, and Z is an aromatic C6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 Ci-s alkyl groups, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing, provided that the valence of Z is not exceeded. Exemplary groups Z include groups of formula

(3)

wherein R^a and R^b are each independently the same or different, and are a halogen atom or a monovalent Ci-₆ alkyl group, for example; p and q are each independently integers of 0 to 4; c is 0 to 4; and X^a is a bridging group connecting the hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each Ce arylene group are disposed ortho, meta, or para (specifically para) to each other on the Ce arylene group. The bridging group X^a can be a single bond, -O-, -S-, -S(O)-, -S(0)₂-, -C(O)-, or a C_MS organic bridging group. The Ci-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The Ci-18 organic group can be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the Ci-is organic bridging group. A specific example of a group Z is a divalent group of formula (3a)

wherein Q is -0-, -S-, -C(O)-, -SO2-, -SO-, -P(R^a)(=0)- wherein R^a is a Ci-s alkyl or C6-12 aryl, or -C_yth_y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (including a perfluoroalkylene group). In an aspect Z is a derived from bisphenol A, such that Q in formula (3a) is 2,2-isopropylidene.

[0011] In an aspect in formula (1), R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing, and T is -O-Z-O- wherein Z is a divalent group of formula (3a). Alternatively, R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing, and T is -O-Z-O- wherein Z is a divalent group of formula (3a) and Q is 2,2-isopropylidene. Such materials are available under the trade name ULTEM from SABIC. Alternatively, the polyetherimide can be a copolymer comprising additional structural polyetherimide units of formula (1) wherein at least 50 mole percent (mol%) of the R groups are bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’-phenylene)sulfone, or a combination comprising at least one of the foregoing and the remaining R groups are p- phenylene, m-phenylene or a combination comprising at least one of the foregoing; and Z is 2,2-(4-phenylene)isopropylidene, i.e., a bisphenol A moiety, an example of which is

commercially available under the trade name EXTEM from SABIC.

[0012] In an aspect, the poly(etherimide) is a copolymer that optionally comprises additional structural imide units that are not poly(etherimide) units, for example imide units of formula (4) wherein R is as described in formula (1) and each V is the same or different, and is a substituted or unsubstituted C6-20 aromatic hydrocarbon group, for example a tetravalent linker of the formulas

wherein W is a single bond, -0-, -S-, -C(0)-, -SO2-, -SO-, a C1-18 hydrocarbylene group, - P(R^a)(=0)- wherein R^a is a Ci-s alkyl or C6-12 aryl, or -C_yth_y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (which includes perfluoroalkylene groups). These additional structural imide units preferably comprise less than 20 mol% of the total number of units, and more preferably can be present in amounts of 0 to 10 mol% of the total number of units, or 0 to 5 mol% of the total number of units, or 0 to 2 mol% of the total number of units. In an aspect, no additional imide units are present in the poly(etherimide).

[0013] The poly(etherimide) can be prepared by any of the methods known to those skilled in the art, including the reaction of an aromatic bis(ether anhydride) of formula (5) or a chemical equivalent thereof, with an organic diamine of formula (6)

wherein T and R are defined as described above. Copolymers of the poly(etherimide)s can be manufactured using a combination of an aromatic bis(ether anhydride) of formula (5) and an additional bis(anhydride) that is not a bis(ether anhydride), for example pyromellitic dianhydride or bis(3,4-dicarboxyphenyl) sulfone dianhydride.

[0014] Illustrative examples of aromatic bis(ether anhydride)s include 2,2-bis[4-(3,4- dicarboxyphenoxy)phenyl]propane dianhydride (also known as bisphenol A dianhydride or BPADA), 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4- dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(3,4- dicarboxyphenoxy)diphenyl sulfone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(2,3- dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2, 2-propane dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4-(2,3- dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4’- (hexafluoroisopropylidene)diphthalic anhydride; and 4-(2,3-dicarboxyphenoxy)-4'-(3,4- dicarboxyphenoxy)diphenyl sulfone dianhydride. A combination of different aromatic bis(ether anhydride)s can be used.

[0015] Examples of organic diamines include 1,4-butane diamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3- methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4- methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5- dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2, 2- dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3- methoxyhexamethylenediamine, l,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis-(4-aminocyclohexyl) methane, m-phenylenediamine, p- phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p- xylylenediamine, 2-methyl-4, 6-diethyl- 1 ,3-phenylene-diamine, 5-methyl-4, 6-diethyl- 1,3- phenylene-diamine, benzidine, 3,3’-dimethylbenzidine, 3,3’-dimethoxybenzidine, 1,5- diaminonaphthalene, bis(4-aminophenyl) methane, bis(2-chloro-4-amino-3,5-diethylphenyl) methane, bis(4-aminophenyl) propane, 2,4-bis(p-amino-t-butyl) toluene, bis(p-amino-t- butylphenyl) ether, bis(p-methyl-o-aminophenyl) benzene, bis(p-methyl-o-aminopentyl) benzene, 1, 3-diamino-4-isopropylbenzene, bis(4-aminophenyl) sulfide, bis-(4-aminophenyl) sulfone (also known as 4,4'-diaminodiphenyl sulfone (DDS)), and bis(4-aminophenyl) ether. Any regioisomer of the foregoing compounds can be used. C_M alkylated or poly(Ci-4)alkylated derivatives of any of the foregoing can be used, for example a polymethylated 1,6- hexanediamine. Combinations of these compounds can also be used. In an aspect the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 3,4'- diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, or a combination comprising at least one of the foregoing.

[0016] The poly(etherimide)s can have a melt index of 0.1 to 10 grams per minute (g/min), as measured by American Society for Testing Materials (ASTM) D1238 at 340 to 370°C, using a 6.7 kilogram (kg) weight. In an aspect, the poly(etherimide) has a weight average molecular weight (Mw) of 1,000 to 150,000 grams/mole (Dalton), as measured by gel permeation chromatography, using polystyrene standards. In an aspect the poly(etherimide) has a Mw of 10,000 to 80,000 Daltons. Such poly(etherimide)s typically have an intrinsic viscosity greater than 0.2 deciliters per gram (dl/g), or, more specifically, 0.35 to 0.7 dl/g as measured in m-cresol at 25 °C.

[0017] In an aspect, the substrate comprises the poly(sulfone). As used herein, the term “poly(sulfone)” can also refer to poly(aryl ether sulfones), poly(ether sulfones), and

poly(phenylene ether sulfones). Poly(aryl ether sulfone)s are linear thermoplastic polymers that possess, for example, high temperature resistance, good electrical properties, and good hydrolytic stability. A variety of poly(aryl ether sulfone)s are commercially available, including the polycondensation product of dihydroxy diphenyl sulfone with dichloro diphenyl sulfone and known as poly(ether sulfone) (PES), and the polymer of bisphenol-A and dichloro diphenyl sulfone known in the art as poly(sulfone) (PSU or PSF). Other poly(aryl ether sulfone)s are the poly(biphenyl ether sulfone)s, available from Solvay Inc. under the trademark of RADEL R resin. Poly(sulfone)s are also sold by Solvay Co. under the UDEL trade name.

Poly(ethersulfone)s are sold by Solvay under the RADEL A trade names and by BASF, as ULTRASON E. A variety of PES copolymers, for example comprising bisphenol A (BPA) moieties, other bisphenols and diphenyl sulfone moieties in molar ratios other than 1:1, can also be found. Methods for the preparation of poly(aryl ether sulfone)s are widely known. For example, two methods, the carbonate method, and the alkali metal hydroxide method, can be used. In the alkali metal hydroxide method, a double alkali metal salt of a dihydric phenol is contacted with a dihalobenzenoid compound in the presence of a dipolar, aprotic solvent under substantially anhydrous conditions. The carbonate method, in which at least one dihydric phenol and at least one dihalobenzenoid compound are heated, for example, with sodium carbonate or bicarbonate and a second alkali metal carbonate or bicarbonate is also disclosed in the art, for example in US Patent 4,176,222 . Alternatively, the poly(biphenyl ether sulfone), PSU and PES components can be prepared by any of the variety of methods known in the art for the preparation of poly (aryl ether).

[0018] The molecular weight of the poly (sulfone), as indicated by reduced viscosity data in an appropriate solvent such as methylene chloride, chloroform, N-methylpyrrolidone, or the like, can be at least 0.3 dl/g, preferably at least 0.4 dl/g and, typically, will not exceed about 1.5 dl/g. In some instances the poly(sulfone) weight average molecular weight can vary from 10,000 to 100,000 grams per mole as determined by gel permeation chromatography.

Poly (sulfone) s can have glass transition temperatures from 180 to 250°C in some instances.

[0019] The thermoplastic poly(sulfone)s, poly(ethersulfone)s and poly(phenylene ether sulfone)s can be prepared as described in US Patents 3,634,355, 4,008,203, 4,108,837 and 4,175,175, each of which is incorporated by reference herein in its entirety. [0020] The substrate can optionally further comprise one or more additives, with the proviso that any additives do not significantly adversely affect one or more desired properties of the substrate or the final article. The additive composition or individual additives can be mixed at a suitable time during the mixing of the components for forming the composition of the substrate. The additive composition can include an impact modifier, flow modifier, filler (e.g., a particulate polytetrafluoroethylene (PTFE), glass, carbon, mineral, or metal), reinforcing agent (e.g., glass fibers), antioxidant, heat stabilizer, light stabilizer, ultraviolet (UV) light stabilizer, UV absorbing additive, plasticizer, lubricant, release agent (such as a mold release agent), antistatic agent, anti-fog agent, antimicrobial agent, colorant (e.g., a dye or pigment), surface effect additive, radiation stabilizer, flame retardant, anti-drip agent (e.g., a PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), or a combination thereof. In general, the additives are used in the amounts generally known to be effective. For example, the total amount of the additive composition (other than any impact modifier, filler, or reinforcing agent) can be 0.001 to 10.0 wt%, or 0.01 to 5 wt%, each based on the total weight of the polymer in the composition. In an aspect, no additives are present.

[0021] The article further comprises a surface metal layer on the substrate. It will be understood that when an element is referred to as being“on” another element, it can be directly on the other element or intervening elements can be present therebetween. In contrast, when an element is referred to as being“directly on” another element, there are no intervening elements present. Thus, in an aspect, the article comprises a surface metal layer disposed directly on the surface of the substrate. In another aspect, the article can comprise a surface metal layer on the surface of the substrate, wherein one or more intervening layers are present, as will be discussed in further detail below.

[0022] The surface metal layer is deposited by physical vapor deposition (PVD). In an aspect, the surface metal layer is deposited by PVD at a temperature of 80 to 180°C, for example, 120 to 180°C. Metallization by PVD can be at reduced pressure. Physical vapor deposition methods that can be used to deposit the surface metal layer can include, but are not limited to, sputtering, laser ablation, cathodic arc deposition, and electron beam evaporation, preferably sputtering. In an aspect, the surface metal layer can comprise chromium (Cr), titanium (Ti), nickel (Ni), tungsten, an alloy thereof (e.g., TiCr, TiN, TiC, TiSi, TiO, CrC, CrN, CrO, and the like), or a combination thereof. The surface metal layer can have a thickness of 0.1 to 5 micrometers. The surface metal layer can comprise a single layer or more than one layer, wherein each layer is deposited by PVD, and the total thickness of the PVD layers is 0.1 to 5 micrometers. When more than one layer is present, each layer can comprise a metal that is the same or different from other PVD layers.

[0023] In an aspect, the article can further comprise a first intermediate metal layer. When present, the first intermediate metal layer can be positioned between the surface of the substrate and the surface metal layer. In an aspect, the first intermediate metal layer is disposed directly on the surface of the substrate, and the surface metal layer is disposed directly on the surface of the first intermediate layer (on a side opposite the substrate). In an aspect, the surface metal layer can be on the surface of the first intermediate layer, wherein one or more intervening layers are positioned therebetween, as will be discussed further below.

[0024] When present, the first intermediate metal layer can be deposited by electroless plating or electroplating, preferably electroless plating. The first intermediate metal layer can have a thickness of 0.1 to 5 micrometers. In an aspect, the first intermediate metal layer can comprise chromium (Cr), copper (Cu), nickel (Ni), or a combination thereof. In an aspect, the first intermediate metal layer can comprise a single layer or more than one layer, wherein each layer is deposited by electroless plating or electroplating, preferably electroless plating, and the total thickness of the layers is 0.1 to 5 micrometers. When more than one layer is present, each layer can comprise a metal that is the same or different from other layers.

[0025] In an aspect, the article can optionally further comprise a second intermediate metal layer. The second intermediate metal layer is positioned between the first intermediate metal layer and the surface metal layer. Thus in a specific aspect, the article can comprise a substrate, a first intermediate layer disposed directly on the substrate, a second intermediate metal layer disposed directly on the surface of the first intermediate metal layer (opposite the substrate), and a surface metal layer disposed directly on the surface of the second intermediate metal layer (opposite the first intermediate metal layer). Thus in an aspect, no intervening layers are positioned between any of the substrate, the first intermediate metal layer, the second intermediate metal layer, and the surface metal layer.

[0026] The second intermediate metal layer is deposited by electroplating. The second intermediate layer can have a thickness of 0.1 to 50 micrometers. In an aspect, the second intermediate metal layer can comprise a single layer or more than one layer, wherein each layer is deposited by electroplating, and the total thickness of the layers is 0.1 to 50 micrometers. When more than one layer is present, each layer can comprise a metal that is the same or different from other layers. The second intermediate metal layer can comprise chromium (Cr), copper (Cu), nickel (Ni), or a combination thereof. [0027] In an aspect, the article of the present disclosure can comprise a substrate comprising a poly(etherimide), a poly(sulfone), or a combination thereof; a first intermediate metal layer comprising copper or nickel, preferably copper, disposed directly on a surface of the substrate, wherein the first intermediate metal layer is deposited by electroless plating; a second intermediate metal layer comprising copper, chromium, nickel, or a combination thereof, preferably copper, chromium, or a combination thereof, disposed directly on a surface of the first intermediate metal layer opposite the substrate, wherein the second intermediate metal layer is deposited by electroplating; and a surface metal layer comprising chromium, titanium, nickel, tungsten, an alloy thereof (e.g., TiN, TiO, TiC, and the like), or a combination thereof disposed directly on a surface of the second intermediate metal layer opposite the first intermediate metal layer, wherein the surface metal layer is deposited by physical vapor deposition.

[0028] The article of the present disclosure can exhibit one or more advantageous physical properties. For example, the article can have a glass of greater than 60 when measured at 60°. The article can have a roughness of less than 0.2 micrometers as determined by optical profilometry. The article can have a vibration resistance of at least ten minutes. The article can have a cross-hatch adhesion test classification of at least 4B. The article can have a corrosion resistance of at least 48 hours as determined by a salt spray test according to ASTM B117.

[0029] The article of the present disclosure can generally be any article molded from the poly(etherimide), poly(sulfone), or combination thereof, and having a metal layer disposed thereon. In particular, the article can be a component of a consumer electronic device.

Preferably, the article can be a smartphone component, for example a middle frame, a press button, a card holder, a front cover, or a back cover.

[0030] The articles of the present disclosure can be prepared by providing the substrate comprising the poly(etherimide), the poly(sulfone), or the combination thereof, and depositing the surface metal layer on the substrate by physical vapor deposition. When the first or second intermediate metal layers are present as described above, the method further comprises (prior to depositing the surface metal layer) depositing the first intermediate metal layer on a surface of the substrate, wherein depositing the first intermediate metal layer comprises electroless plating; and optionally, depositing a second intermediate metal layer on a surface of the first

intermediate metal layer opposite the substrate, wherein depositing the second intermediate metal layer comprises electroplating. In an aspect, the process of preparing the articles of the present disclosure can further include polishing the surface metal layer. Polishing can include, for example, a physical polishing process for example using sand papers to reduce surface defects, such as welding lines, flow marks, and the like. Polishing can also include a subsequent step of fine polishing to obtain a high quality surface.

[0031] As discussed above and further in the working examples below, providing the metallized articles according to the method described herein, in particular where a specific combination of deposition techniques is used in a particular order can provide metallized articles with desired properties. The metallized articles can exhibit a unique combination of physical properties which make them particularly well-suited for applications in consumer electronics. Accordingly, a substantial improvement is provided by the present disclosure.

[0032] This disclosure is further illustrated by the following examples, which are non limiting.

EXAMPLES

[0033] Materials used for the following examples are described in Table 1.

Table 1

[0034] In each example, the molded parts were prepared by injection molding PEI (PEI- 1 or PEI-2) or PPSU. In examples 1-4, the molded part was first coated with a metal layer by electroless plating, then coated with a metal layer by electroplating, and finally coated with a metal layer deposited by physical vapor deposition (PVD). In example 5, the molded part with only coated with a metal layer deposited by PVD. In example 6, the molded part was only coated with a metal layer by electroless plating followed by a metal layer coated by

electroplating.

[0035] Each of the coated parts was examined in terms of its roughness, gloss, vibration resistance, and adhesion. Roughness was determined by optical profilometry. Gloss was determined at 60° according to ASTM D2457-13. The vibration wear test was conducted using a Germany Rosier vibration wear testing machine R180/530. Adhesion was determined by a cross-hatch adhesion test according to ASTM D3359. Adhesion classifications were assigned as follows: 5B (0% of area removed), 4B (less than 5% of area removed), 3B (5 to 15% of area removed), 2B (15 to 35% of area removed), IB (35 to 65% of area removed), and 0B (greater than 65% of area removed).

[0036] The structures of each example and the resulting properties are summarized in Table 2. Where more than one metal is listed for electroplating and PVD coating, the metals were deposited sequentially in the order listed. Table 2

Comparative example 2 (C2) in Table 2 shows that a metal layer coated on PEI using PVD easily wore off within ten minutes when the part was subjected to the vibration wear test. Comparative example 1 (Cl) in Table 2 shows that a PEI part having a copper layer and a chromium layer coated using electroless plating and electroplating has good wear resistance performance of 60 minutes when subjected to the vibration wear test.

[0037] This disclosure further encompasses the following aspects.

[0038] Aspect 1: An article comprising: a substrate comprising a poly(etherimide), a poly(sulfone), or a combination thereof; a surface metal layer disposed on the substrate, wherein the first metal layer is deposited by physical vapor deposition.

[0039] Aspect 2: The article of aspect 1, further comprising a first intermediate metal layer, wherein the first intermediate metal layer is disposed between a surface of the substrate and the surface metal layer, and wherein the first intermediate metal layer is deposited by electroless plating.

[0040] Aspect 3: The article of aspect 1 or 2, further comprising a second intermediate metal layer, wherein the second intermediate metal layer is disposed between the first intermediate metal layer and the surface metal layer, wherein the second intermediate metal layer is deposited by electroplating. [0041] Aspect 4: The article of claim 1, comprising the substrate; a first intermediate metal layer disposed on a surface of the substrate, wherein the first intermediate metal layer is deposited by electroless plating; a second intermediate metal layer disposed on a surface of the first intermediate metal layer opposite the substrate, wherein the second intermediate metal layer is deposited by electroplating; and a surface metal layer disposed on a surface of the second intermediate metal layer opposite the first intermediate metal layer, wherein the surface metal layer is deposited by physical vapor deposition.

[0042] Aspect 5: The article of any one of aspects 1 to 4, wherein the surface metal layer has a thickness of 0.1 to 5 micrometers.

[0043] Aspect 6: The articles of any one of aspects 2 to 5, wherein the first intermediate metal layer is deposited by electroless plating and has a thickness of 0.1 to 5 micrometers.

[0044] Aspect 7: The article of any one of aspects 3 to 6, wherein the second

intermediate metal layer has a thickness of 0.1 to 50 micrometers.

[0045] Aspect 8: The article of any one of aspects 2 to 7, wherein the first intermediate metal layer comprises Cr, Cu, Ni, or a combination thereof.

[0046] Aspect 9: The article of any one of aspects 1 to 8, wherein the article exhibits one or more of: a gloss of greater than 60 when measured at 60°; a roughness of less than 0.2 micrometers as determined by optical profilometry; a vibration resistance of at least ten minutes; a cross-hatch adhesion test classification of at least 4B; and a corrosion resistance of at least 48 hours as determined by a salt spray test according to ASTM B117.

[0047] Aspect 10: The article of any one of aspects 1 to 9, wherein the article is a consumer electronic component, preferably a smartphone component, more preferably a middle frame, a press button, card holder, camera holder, front cover, or back cover.

[0048] Aspect 11: The article of claim 1, comprising: a substrate comprising a poly(etherimide), a poly(sulfone), or a combination thereof; a first intermediate metal layer comprising copper or nickel disposed on a surface of the substrate, wherein the first intermediate metal layer is deposited by electroless plating; a second intermediate metal layer comprising copper, chromium, nickel or a combination thereof disposed on a surface of the first

intermediate metal layer opposite the substrate, wherein the second intermediate metal layer is deposited by electroplating; and a surface metal layer comprising chromium, titanium, nickel, tungsten, an alloy thereof, or a combination thereof disposed on a surface of the second intermediate metal layer opposite the first intermediate metal layer, wherein the surface metal layer is deposited by physical vapor deposition. [0049] Aspect 12: The article of any of aspects 1 to 11, wherein the substrate comprises a poly(etherimide).

[0050] Aspect 13: A method of making the article of any of aspects 1 to 12, the method comprising: depositing a surface metal layer on a substrate comprising a poly(etherimide), a poly(sulfone), or a combination thereof, wherein depositing the surface metal layer comprises physical vapor deposition.

[0051] Aspect 14: The method of aspect 13, further comprising, prior to depositing the surface metal layer, optionally, depositing a first intermediate metal layer on a surface of the substrate, wherein depositing the first intermediate metal layer comprises electroless plating; and optionally, depositing a second intermediate metal layer on a surface of the first intermediate metal layer opposite the substrate, wherein depositing the second intermediate metal layer comprises electroplating.

[0052] Aspect 15: The method of aspects 13 or 14, further comprising polishing the surface metal layer.

[0053] 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, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0054] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. “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 aspects”,“an aspect”, and so forth, means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. The term“combination thereof’ as used herein includes one or more of the listed elements, and is open, allowing the presence of one or more like elements not named. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects. [0055] 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.

[0056] 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 conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0057] 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 dash that 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.

[0058] 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. The 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. However, when the hydrocarbyl residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" means a branched or straight chain, saturated 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 carbon-carbon 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, -CiThn-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 carbon-carbon 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 Ci-₉ alkoxy, a C_1-9 haloalkoxy, a nitro (-NO₂), a cyano (-CN), a Ci-₆ alkyl sulfonyl (-S(=0)₂- alkyl), a Ce-n aryl sulfonyl (-S(=0)₂-aryl), a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a Ce-n aryl, a C7-13 arylalkylene, a C_4-12 heterocycloalkyl, and a C_3-12 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.

[0059] While particular aspects 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

CLAIMS What is claimed is:

1. An article comprising:

a substrate comprising a poly(etherimide), a poly(sulfone), or a combination thereof; a surface metal layer disposed on the substrate, wherein the first metal layer is deposited by physical vapor deposition.

2. The article of claim 1, further comprising a first intermediate metal layer, wherein the first intermediate metal layer is disposed between a surface of the substrate and the surface metal layer, and wherein the first intermediate metal layer is deposited by electroless plating.

3. The article of claim 1 or 2, further comprising a second intermediate metal layer, wherein the second intermediate metal layer is disposed between the first intermediate metal layer and the surface metal layer, wherein the second intermediate metal layer is deposited by

electroplating.

4. The article of claim 1, comprising

the substrate;

a first intermediate metal layer disposed on a surface of the substrate, wherein the first intermediate metal layer is deposited by electroless plating;

a second intermediate metal layer disposed on a surface of the first intermediate metal layer opposite the substrate, wherein the second intermediate metal layer is deposited by electroplating; and

a surface metal layer disposed on a surface of the second intermediate metal layer opposite the first intermediate metal layer, wherein the surface metal layer is deposited by physical vapor deposition.

5. The article of any one of claims 1 to 4, wherein the surface metal layer has a thickness of 0.1 to 5 micrometers.

6. The articles of any one of claims 2 to 5, wherein the first intermediate metal layer is deposited by electroless plating and has a thickness of 0.1 to 5 micrometers.

7. The article of any one of claims 3 to 6, wherein the second intermediate metal layer has a thickness of 0.1 to 50 micrometers.

8. The article of any one of claims 2 to 7, wherein the first intermediate metal layer comprises Cr, Cu, Ni, or a combination thereof.

9. The article of any one of claims 1 to 8, wherein the article exhibits one or more of:

a gloss of greater than 60 when measured at 60°;

a roughness of less than 0.2 micrometers as determined by optical profilometry;

a vibration resistance of at least ten minutes;

a cross-hatch adhesion test classification of at least 4B; and

a corrosion resistance of at least 48 hours as determined by a salt spray test according to ASTM B 117.

10. The article of any one of claims 1 to 9, wherein the article is a consumer electronic component, preferably a smartphone component, more preferably a middle frame, a press button, card holder, camera holder, front cover, or back cover.

11. The article of claim 1, comprising:

a substrate comprising a poly(etherimide), a poly(sulfone), or a combination thereof; a first intermediate metal layer comprising copper or nickel disposed on a surface of the substrate, wherein the first intermediate metal layer is deposited by electroless plating;

a second intermediate metal layer comprising copper, chromium, nickel or a combination thereof disposed on a surface of the first intermediate metal layer opposite the substrate, wherein the second intermediate metal layer is deposited by electroplating; and

a surface metal layer comprising chromium, titanium, nickel, tungsten, an alloy thereof, or a combination thereof disposed on a surface of the second intermediate metal layer opposite the first intermediate metal layer, wherein the surface metal layer is deposited by physical vapor deposition.

12. The article of any of claims 1 to 11, wherein the substrate comprises a poly(etherimide).

13. A method of making the article of any of claims 1 to 12, the method comprising: depositing a surface metal layer on a substrate comprising a poly(etherimide), a poly(sulfone), or a combination thereof, wherein depositing the surface metal layer comprises physical vapor deposition.

14. The method of claim 13, further comprising, prior to depositing the surface metal layer, optionally, depositing a first intermediate metal layer on a surface of the substrate, wherein depositing the first intermediate metal layer comprises electroless plating; and

optionally, depositing a second intermediate metal layer on a surface of the first intermediate metal layer opposite the substrate, wherein depositing the second intermediate metal layer comprises electroplating.

15. The method of claims 13 or 14, further comprising polishing the surface metal layer.