Sustainable Solutions for Metal Plating on Plastic Articles

Abstract

The present disclosure relates to polymer articles comprising a thermoplastic polymer composition, the thermoplastic polymer composition comprising: (i) a copolymer (A) comprising polymerization units derived from vinyl aromatic monomers and vinyl nitrile monomers; (ii) a rubber-modified thermoplastic polymer (E); (iii) a functionalized polymer (FP), and optionally (iv) an additive mixture. The present disclosure further relates to surface-treated polymer articles comprising the polymer articles, and methods for preparing such surface-treated polymer articles. The present disclosure further relates to plated articles comprising a metal layer disposed on a polymer substrate layer comprising the surface-treated polymer articles. Further, the present disclosure relates to a process for manufacturing the plated articles.

Description

Detailed Description of the Invention

[0001] [Cross - Reference to Related Applications] None.

[0002] [Disclosed Field] The present disclosure relates to the field of plating metal layers on polymer substrates. In particular, the present disclosure relates to a metal - plated article having a metal layer coated on a polymer substrate including a surface - treated polymer article, and a manufacturing process of such a metal - plated article. The present disclosure further relates to a polymer article including a thermoplastic polymer composition suitable for metal plating, such as a composition based on acrylonitrile - butadiene - styrene (ABS) polymer. The present disclosure further relates to a surface - treated polymer article including the polymer article, and a method of preparing such a surface - treated polymer article.

[0003] [Background] Polymer plastic parts prepared from thermoplastic materials such as acrylonitrile - butadiene - styrene (ABS) resin are often metallized when used in certain applications such as automotive applications, and the thermoplastic material functions as a polymer substrate on which a metal coating is deposited. For example, a polymer plastic part prepared from ABS resin may be coated with a metal layer to impart a mirror - finished appearance similar to that of a metal part while retaining the distinct advantage of being lightweight unlike conventional metal parts. In addition, the metal coating can also improve the mechanical strength, thermal stability, and chemical resistance of the underlying polymer substrate coated with the metal. In this regard, ABS polymer is particularly useful for automotive and other industrial applications due to its desirable impact properties and other useful characteristics.

[0004] Unfortunately, according to many industry players, metal coatings do not readily adhere or bond to most polymer substrates unless the surface of the polymer substrate is chemically treated first. For example, a common treatment often used in conventional metal plating processes is to chemically etch the polymer substrate with an oxidizing reagent such as chromium trioxide, or a mixture of chromic acid / sulfuric acid or chromic acid / sulfuric acid / phosphoric acid. Typically, these strong oxidizing agents chemically modify and typically micro-roughen the polymer substrate surface by forming polar organic functional groups such as R-COOH, R-OH, R-SO3, and R-CH=O on the substrate surface. The presence of these polar groups promotes the adsorption of the plating catalyst from the aqueous solution, and subsequent metal deposition occurs readily during the plating process. Such a process results in a successful metal coating on the polymer substrate.

[0005] Conventional plating processes enabled a strong bond between the metal layer and the polymer substrate formed from ABS. One measurement criterion suitable for measuring the success of the adhesion between the metal layer and the polymer substrate is to measure the peel strength. The greater the peel strength, the better the adhesion of the metal to the polymer substrate. Thus, the conventional use of hexavalent chromium trioxide for etching results in a treated polymer substrate with excellent adhesion to the metal layer.

[0006] However, the use of hexavalent chromium compounds such as chromium trioxide poses certain risks and challenges, including: 1) health risks due to the extremely high carcinogenicity of chromium trioxide, 2) the effective disposal of the waste liquid generated from the etching process, such processes not only make the etching process environmentally harmful but also costly, 3) the purification of the etched plastic parts to remove chromium trioxide remaining as an impurity (such as impurities that adversely affect the metal plating process), and 4) the high oxidation of the acid solution often causes the polymer substrate itself to be damaged or structurally weakened for metal plating.

[0007] To avoid such problems, many processes alternative to chromic acid etching have been studied in the past. For example, the dry plasma etching process has been proposed as an alternative to the wet etching process. However, this method can only be applied to flat polymer parts. In the past, etching reagents such as potassium permanganate have also been used as alternatives to chromic acid. The use of a heated alkaline potassium permanganate solution had limited commercial success because the oxidation rate was slower than that of chromic acid, and the application range of the potassium permanganate solution was mostly limited.

[0008] As a further alternative approach to avoiding hexavalent chromium compounds during etching, it is described in patents / patent applications such as US4415406A and EP2009142B1. Although the technical solutions described in these disclosures seem promising, there is still room for further improvement in the metal plating process without using hexavalent chromium compounds for etching.

[0009] Accordingly, exemplary embodiments of the present disclosure are directed to polymer articles having excellent impact properties that can be plated with a metal layer without the need to use a hexavalent chromium compound as an etchant. Some embodiments of the present disclosure are directed to surface-treated polymer articles that can be used as substrates for depositing a metal layer while having excellent metal-plastic adhesion and excellent impact properties. Various embodiments of the present disclosure are directed to suitable methods for surface-treating polymer articles without the need to use a hexavalent chromium compound as an etchant. Some embodiments of the present disclosure are directed to metal-plated polymer articles having excellent bonding of a metal layer to a polymer substrate.

[0010] 〔Summary〕 Exemplary embodiments of the present disclosure are directed to polymer articles comprising a thermoplastic polymer composition, the thermoplastic polymer composition comprising, consisting of, or essentially consisting of the following: a. A copolymer (A) present in an amount of ≥ 35.0 wt% and ≤ 70.0 wt%, preferably ≥ 45.0 wt% and ≤ 56.0 wt%, based on the total weight of the thermoplastic polymer composition, the copolymer (A) comprising or consisting of polymerization units derived from (i) a vinyl aromatic monomer and (ii) a vinyl nitrile monomer; b. A rubber-modified thermoplastic polymer (E) present in an amount of ≥ 26.0 wt% and ≤ 50.0 wt%, preferably ≥ 30.0 wt% and ≤ 50.0 wt%, based on the total weight of the thermoplastic polymer composition; c. A functionalized polymer (FP) present in an amount of ≥ 1.0 wt% and ≤ 15.0 wt% based on the total weight of the thermoplastic polymer composition, the functionalized polymer (FP) being any one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably a styrene maleic anhydride (SMA) copolymer; and d. An additive mixture present in an amount of ≥ 0.0 wt% and ≤ 5.0 wt% based on the total weight of the thermoplastic polymer composition.

[0011] Preferably, the additive mixture comprises, consists of, or consists essentially of magnesium oxide (MgO), silicone oil, wax, and magnesium stearate. The sum of components (a), (b), (c), and (d) (when present) is 100.0 wt%.

[0012] Preferably, the polymer article comprises a thermoplastic polymer composition, the thermoplastic polymer composition comprising, consisting of, or consisting essentially of: a. A copolymer (A) present in an amount of ≥ 45.0 wt% and ≤ 56.0 wt% based on the total weight of the thermoplastic polymer composition, the copolymer (A) comprising or consisting of polymerization units derived from (i) a vinyl aromatic monomer and (ii) a vinyl nitrile monomer; b. A rubber-modified thermoplastic polymer (E) present in an amount of ≥ 30.0 wt% and ≤ 50.0 wt% based on the total weight of the thermoplastic polymer composition; c. A functionalized polymer (FP) present in an amount of ≥ 1.0 wt% and ≤ 15.0 wt% based on the total weight of the thermoplastic polymer composition, which is any one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably a styrene maleic anhydride (SMA) copolymer, the functionalized polymer (FP); and d. An additive mixture present in an amount of ≥ 0.0 wt% and ≤ 5.0 wt% based on the total weight of the thermoplastic polymer composition.

[0013] Preferably, the additive mixture comprises, consists of, or consists essentially of magnesium oxide (MgO), silicone oil, wax, and magnesium stearate. The sum of components (a), (b), (c), and (d) (when present) is 100.0 wt%.

[0014] In some embodiments of the present disclosure; a. The copolymer (A) is present in an amount of ≥ 40.0 wt% and ≤ 60.0 wt%, preferably ≥ 45.0 wt% and ≤ 56.0 wt% based on the total weight of the thermoplastic polymer composition, and the copolymer (A) comprises or consists of polymerization units derived from (i) vinyl aromatic monomers and (ii) vinyl nitrile monomers; b. The rubber-modified thermoplastic polymer (E) is present in an amount of ≥ 30.0 wt% and ≤ 45.0 wt%, preferably ≥ 35.0 wt% and ≤ 45.0 wt% based on the total weight of the thermoplastic polymer composition; c. The functionalized polymer (FP) is present in an amount of ≧3.0 wt% and ≦12.0 wt%, preferably ≧6.0 wt% and ≦12.0 wt%, based on the total weight of the thermoplastic polymer composition, and the functionalized polymer (FP) is any one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably, styrene maleic anhydride (SMA) copolymer; and d. The additive mixture is present in an amount of ≧1.0 wt% and ≦3.0 wt%, based on the total weight of the thermoplastic polymer composition.

[0015] Preferably, the additive mixture comprises, consists of, or consists essentially of magnesium oxide (MgO), silicone oil, wax, and magnesium stearate. The sum of components (a), (b), (c), and (d) is 100.0 wt%.

[0016] Preferably, the polymer article comprises a thermoplastic polymer composition, which comprises, consists essentially of, or consists of: a. A copolymer (A) present in an amount of ≧35.0 wt% and ≦70.0 wt%, preferably ≧40.0 wt% and ≦60.0 wt%, preferably ≧45.0 wt% and ≦56.0 wt%, based on the total weight of the thermoplastic polymer composition, the copolymer (A) comprising or consisting of polymerization units derived from (i) vinyl aromatic monomers, and (ii) vinyl nitrile monomers; b. A rubber-modified thermoplastic polymer (E) present in an amount of ≧26.0 wt% and ≦50.0 wt%, preferably ≧30.0 wt% and ≦50.0 wt%, preferably ≧30.0 wt% and ≦45.0 wt%, preferably ≧35.0 wt% and ≦45.0 wt%, based on the total weight of the thermoplastic polymer composition; c. A functional polymer (FP) present in an amount of ≥1.0 wt% and ≤15.0 wt%, preferably ≥3.0 wt% and ≤12.0 wt%, preferably ≥6.0 wt% and ≤12.0 wt%, based on the total weight of the thermoplastic polymer composition, which is any one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably a functional polymer (FP) that is a styrene maleic anhydride (SMA) copolymer; and d. An additive mixture present in an amount of ≥0.0 wt% and ≤5.0 wt%, preferably >0.0 wt% and ≤5.0 wt%, preferably ≥1.0 wt% and ≤5.0 wt%, preferably ≥1.0 wt% and ≤3.0 wt%, based on the total weight of the thermoplastic polymer composition.

[0017] Preferably, the additive mixture comprises, consists of, or consists essentially of magnesium oxide (MgO), silicone oil, wax, and magnesium stearate. The sum of components (a), (b), (c), and (d) is 100.0 wt%.

[0018] The sum of components (a), (b), (c), and (d) is 100.0 wt%.

[0019] It is particularly preferred that the polymer article comprises a thermoplastic polymer composition, which consists of or consists essentially of the following: a. A copolymer (A) present in an amount of ≥35.0 wt% and ≤70.0 wt%, preferably ≥40.0 wt% and ≤60.0 wt%, preferably ≥45.0 wt% and ≤56.0 wt%, based on the total weight of the thermoplastic polymer composition, which consists of polymerization units derived from (i) a vinyl aromatic monomer and (ii) a vinyl nitrile monomer, copolymer (A); b. A rubber-modified thermoplastic polymer (E) present in an amount of ≥26.0 wt% and ≤50.0 wt%, preferably ≥30.0 wt% and ≤50.0 wt%, based on the total weight of the thermoplastic polymer composition. c. A functional polymer (FP) present in an amount of ≥ 1.0 wt% and ≤ 15.0 wt%, preferably ≥ 3.0 wt% and ≤ 12.0 wt%, based on the total weight of the thermoplastic polymer composition, which is any one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably a styrene maleic anhydride (SMA) copolymer; and d. An additive mixture present in an amount of ≥ 0.0 wt% and ≤ 5.0 wt% based on the total weight of the thermoplastic polymer composition.

[0020] The sum of components (a), (b), (c) and (d) is 100.0 wt%.

[0021] Preferably, the vinyl aromatic monomer is styrene and the vinyl nitrile monomer is acrylonitrile. Preferably, the additive mixture comprises, consists of, or consists essentially of magnesium oxide (MgO), silicone oil, wax and magnesium stearate.

[0022] It is particularly preferred that the polymer article comprises a thermoplastic polymer composition, and the thermoplastic polymer composition consists of the following: a. A copolymer (A) present in an amount of ≥ 35.0 wt% and ≤ 70.0 wt% based on the total weight of the thermoplastic polymer composition, which consists of polymerization units derived from (i) a vinyl aromatic monomer and (ii) a vinyl nitrile monomer; b. A rubber-modified thermoplastic polymer (E) present in an amount of ≥ 26.0 wt% and ≤ 50.0 wt%, preferably ≥ 30.0 wt% and ≤ 50.0 wt% based on the total weight of the thermoplastic polymer composition; c. A functionalized polymer (FP) present in an amount of ≧1.0 wt% and ≦15.0 wt%, preferably ≧3.0 wt% and ≦12.0 wt%, based on the total weight of the thermoplastic polymer composition, which is any one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably a styrene maleic anhydride (SMA) copolymer; and d. An additive mixture present in an amount of ≧0.0 wt% and ≦5.0 wt% based on the total weight of the thermoplastic polymer composition.

[0023] The sum of components (a), (b), (c) and (d) is 100.0 wt%.

[0024] Preferably, the vinyl aromatic monomer is styrene and the vinyl nitrile monomer is acrylonitrile. Preferably, the additive mixture comprises, consists of, or consists essentially of magnesium oxide (MgO), silicone oil, wax, and magnesium stearate.

[0025] In some embodiments of the present disclosure, the functionalized polymer (FP) may have, for example: a. A maleic anhydride content of ≧10.0 wt% and ≦45.0 wt%, preferably ≧15.0 wt% and ≦40.0 wt%, preferably ≧25.0 wt% and ≦35.0 wt%, preferably ≧30.0 wt% and ≦35.0 wt%, based on the total weight of the functionalized polymer (FP); and b. A weight average molecular weight of ≧1,000 g / mol and ≦25,000 g / mol, preferably ≧2,000 g / mol and ≦20,000 g / mol, preferably ≧5,000 g / mol and ≦18,000 g / mol, preferably ≧10,000 g / mol and ≦18,000 g / mol, preferably ≧12,000 g / mol and ≦18,000 g / mol as determined according to ASTM D5296-11.

[0026] In some embodiments of the present disclosure, (i) the vinyl aromatic monomer may be selected from, for example, styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-hydroxystyrene, and methoxystyrene, and preferably, the vinyl aromatic monomer is styrene; and / or (ii) the vinyl nitrile monomer is selected from acrylonitrile, α-chloroacrylonitrile, methacrylonitrile, and ethacrylonitrile, and preferably, the vinyl nitrile monomer is acrylonitrile. Preferably, the vinyl aromatic monomer is styrene and the vinyl nitrile monomer is acrylonitrile.

[0027] In some embodiments of the present disclosure, the rubber-modified thermoplastic polymer (E) may include, or may be obtained from, for example, the following: a. A polymer rubber containing polymerization units derived from a conjugated diene, wherein the conjugated diene is selected from 1,3-butadiene, isoprene, 1,3-heptadiene, methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, and any combination thereof, and preferably the conjugated diene is 1,3-butadiene; and b. A graft thermoplastic copolymer (C) grafted onto the polymer rubber and containing polymerization units derived from the following: i. A vinyl aromatic monomer selected from styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-hydroxystyrene, methoxystyrene, and any combination thereof, and preferably styrene; ii. A vinyl nitrile monomer selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, and any combination thereof, and preferably acrylonitrile; and iii. Optionally, a (meth)acrylic monomer selected from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and propyl methacrylate, preferably methyl methacrylate (MMA); Preferably, the graft thermoplastic copolymer (C) includes polymerization units derived from (i) styrene, (ii) methyl methacrylate, and (iii) acrylonitrile, and the polymer rubber is a polybutadiene rubber including polymerization units derived from 1,3-butadiene.

[0028] Preferably, in some embodiments of the present disclosure, the thermoplastic polymer composition comprises, consists of, or consists essentially of the following: a. Copolymer (A) present in an amount of ≧35.0 wt% and ≦70.0 wt%, preferably ≧40.0 wt% and ≦60.0 wt%, preferably ≧45.0 wt% and ≦56.0 wt% based on the total weight of the thermoplastic polymer composition, which is a styrene-acrylonitrile copolymer (SAN), Copolymer (A); b. Rubber-modified thermoplastic polymer (E) present in an amount of ≧26.0 wt% and ≦50.0 wt%, preferably ≧30.0 wt% and ≦50.0 wt%, preferably ≧30.0 wt% and ≦45.0 wt%, preferably ≧35.0 wt% and ≦45.0 wt% based on the total weight of the thermoplastic polymer composition, which is a polybutadiene rubber grafted with a styrene / methyl methacrylate / acrylonitrile / copolymer, Rubber-modified thermoplastic polymer (E); c. Functionalized polymer (FP) present in an amount of ≧1.0 wt% and ≦15.0 wt%, preferably ≧3.0 wt% and ≦12.0 wt%, preferably ≧6.0 wt% and ≦12.0 wt% based on the total weight of the thermoplastic polymer composition, which is a styrene maleic anhydride (SMA) copolymer, and the styrene maleic anhydride (SMA) copolymer has the following functionalized polymer (FP): i. A maleic anhydride content of ≧10.0 wt% and ≦45.0 wt%, preferably ≧15.0 wt% and ≦40.0 wt%, preferably ≧25.0 wt% and ≦35.0 wt%, based on the total weight of the styrene maleic anhydride (SMA) copolymer; and ii. A weight average molecular weight of ≧1,000 g / mol and ≦25,000 g / mol, preferably ≧2,000 g / mol and ≦20,000 g / mol, preferably ≧5,000 g / mol and ≦18,000 g / mol, preferably ≧10,000 g / mol and ≦18,000 g / mol, preferably ≧12,000 g / mol and ≦18,000 g / mol, as determined according to ASTM D5296-11; and d. An additive mixture present in an amount of ≧0.0 wt% and ≦5.0 wt%, >0.0 wt% and ≦5.0 wt%, preferably ≧1.0 wt% and ≦5.0 wt%, preferably ≧1.0 wt% and ≦3.0 wt%, based on the total weight of the thermoplastic polymer composition.

[0029] Preferably, the additive mixture comprises, consists of, or consists essentially of magnesium oxide (MgO), silicone oil, wax, and magnesium stearate. The sum of components (a), (b), (c), and (d) is 100.0 wt%.

[0030] In some embodiments of the present disclosure, the polymeric article has the following: a. A notched Izod impact strength of ≧15.0 kJ / m 2 and ≦50.0 kJ / m 2 , preferably ≧20.0 kJ / m 2 and ≦40.0 kJ / m 2 , preferably ≧20.0 kJ / m 2 and ≦30.0 kJ / m 2 , as measured according to ISO 180 / 1A; and / or b. An average surface roughness of ≧47.0 nm and ≦200.0 nm, preferably ≧47.0 nm and ≦80.0 nm, preferably ≧47.0 nm and ≦70.0 nm, as measured according to ASTM D7127.

[0031] In some embodiments of the present disclosure, the method of manufacturing the polymer article includes the following steps: a. Introducing a raw material set including copolymer (A), rubber-modified thermoplastic polymer (E), functionalized polymer, and optionally an additive mixture into an extruder to obtain an extrudable composition; b. Extruding the extrudable composition under extrusion conditions to form a set of extruded pellets; and c. Subjecting the set of extruded pellets to injection molding under the following conditions to form a polymer article: i. An injection molding temperature of ≥210.0 °C and ≤250.0 °C, preferably ≥215.0 °C and ≤240.0 °C, more preferably ≥220 °C and ≤230 °C; and ii. An injection speed of ≥10.0 mm / sec and ≤40.0 mm / sec, preferably ≥15 mm / sec and ≤35.0 mm / sec, more preferably ≥25.0 mm / sec and ≤30.0 mm / sec.

[0032] Some embodiments of the present disclosure are directed to surface-treated polymer articles obtained by a method including the following steps: a. Providing a polymer article according to one or more embodiments of the present disclosure; and b. Contacting at least a part of the polymer article with a chemical reagent for any time of ≥5.0 minutes and ≤30.0 minutes, preferably ≥10.0 minutes and ≤20.0 minutes, more preferably ≥15.0 minutes and ≤20.0 minutes, and at a temperature of ≥60.0 °C and ≤80.0 °C, preferably ≥65.0 °C and ≤75.0 °C, to form a surface-treated polymer article.

[0033] The polymer article used to form the surface-treated polymer article includes a thermoplastic polymer composition, and the thermoplastic polymer composition preferably consists of, or consists essentially of, the following: a. A copolymer (A) present in an amount of ≧35.0 wt% and ≦70.0 wt% based on the total weight of the thermoplastic polymer composition, the copolymer (A) consisting of polymerization units derived from (i) a vinyl aromatic monomer and (ii) a vinyl nitrile monomer; b. A rubber-modified thermoplastic polymer (E) present in an amount of ≧26.0 wt% and ≦50.0 wt%, preferably ≧30.0 wt% and ≦50.0 wt% based on the total weight of the thermoplastic polymer composition; c. A functionalized polymer (FP) present in an amount of ≧1.0 wt% and ≦15.0 wt%, preferably ≧3.0 wt% and ≦12.0 wt% based on the total weight of the thermoplastic polymer composition, the functionalized polymer (FP) being any one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably the functionalized polymer (FP) being a styrene maleic anhydride (SMA) copolymer; and d. An additive mixture present in an amount of ≧0.0 wt% and ≦5.0 wt% based on the total weight of the thermoplastic polymer composition.

[0034] The sum of components (a), (b), (c) and (d) is 100.0 wt%.

[0035] Preferably, the additive mixture comprises, consists of, or consists essentially of magnesium oxide (MgO), silicone oil, wax and magnesium stearate. Preferably, the vinyl aromatic monomer is styrene and the vinyl nitrile monomer is acrylonitrile.

[0036] In some embodiments of the present disclosure, the chemical reagent is a colloidal solution containing manganese oxide colloidal particles suspended in a mineral acid mixture containing sulfuric acid and phosphoric acid.

[0037] In some embodiments of the present disclosure, the colloidal solution containing manganese oxide colloidal particles suspended in a mineral acid mixture comprises the following: a. Manganese oxide colloidal particles present in an amount of ≥50.0 g / L and ≤70.0 g / L, preferably ≥55.0 g / L and ≤65.0 g / L; b. Phosphoric acid present in an amount of ≥210.0 ml / L and ≤230.0 ml / L, preferably ≥215.0 ml / L and ≤225.0 ml / L; and c. Sulfuric acid present in an amount of ≥560.0 ml / L and ≤580.0 ml / L, preferably ≥570.0 ml / L and ≤575.0 ml / L; Here, the total volume of the colloidal solution is 1.0 liter (L).

[0038] In some embodiments of the present disclosure, the surface-treated polymer article has the following: a. Notched Izod impact strength of ≥15.0 kJ / m 2 and ≤50.0 kJ / m 2 , preferably ≥20.0 kJ / m 2 and ≤40.0 kJ / m 2 , preferably ≥20.0 kJ / m 2 and ≤30.0 kJ / m 2 when measured according to ISO 180 / 1A; and / or b. The surface-treated polymer article has a water contact angle determined according to ASTM D5946-17 of ≥60.0° and ≤85.0°, preferably ≥65.0° and ≤80.0°, preferably ≥65° and ≤75°.

[0039] Some embodiments of the present disclosure are directed to metal-plated articles comprising the following: a. A metal layer; and b. A polymer substrate layer comprising a surface-treated polymer article according to one or more embodiments of the present disclosure; Here, the metal layer is disposed on at least a part of the polymer substrate layer, and preferably, the metal layer is adhered to the treated surface of the polymer substrate layer.

[0040] In some embodiments of the present disclosure, the peel strength determined in accordance with ASTM B 533-85(2004) is ≧0.14 N / mm, preferably ≧0.16 N / mm, preferably ≧0.2 N / mm, preferably ≧0.3 N / mm, preferably ≧0.34 N / mm, and the metal layer is adhered to the treated surface of the polymer substrate layer.

[0041] Some embodiments of the present disclosure are directed to a process for manufacturing a metal-plated article, comprising the following steps: a. providing a surface-treated polymer article according to one or more embodiments of the present disclosure; b. subjecting the surface-treated polymer article to electroless plating to form a metal-plated precursor article; and c. contacting the metal-plated precursor article with a metal electrolyte solution at an applied current of ≧1.0 ampere and ≦4.0 amperes, preferably ≧1.0 ampere and ≦3.0 amperes, and for a time of ≧5 minutes and ≦35 minutes, preferably ≧25 minutes and ≦35 minutes, to form a metal-plated article.

[0042] Some embodiments of the present disclosure are directed to the use of a surface-treated polymer article according to one or more embodiments of the present disclosure to improve the adhesion of a metal layer to a polymer substrate in a metal-plated article. Some embodiments of the present disclosure are directed to the use of a surface-treated polymer article according to one or more embodiments of the present disclosure as a substrate suitable for receiving a metal layer.

[0043] Other objects, features, and advantages of the present invention will become apparent from the following detailed description and examples. However, it should be understood that the detailed description and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Further, it is contemplated that modifications and variations within the spirit and scope of the invention will be apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments can be combined with features from other embodiments. For example, features from one embodiment can be combined with features from any of the other embodiments. In further embodiments, additional features can be added to the specific embodiments described herein.

[0044] 〔Detailed Description〕 The following provides definitions of various terms, expressions, and phrases used throughout this specification.

[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Throughout this specification and the following claims, numerous terms defined herein are referenced. All publications mentioned herein are incorporated herein by reference for the purpose of disclosing and describing the methods and / or materials associated with the publications.

[0046] The use of the words "a" or "an" when used in conjunction with the terms "comprising", "including", "containing", or "having" in a claim or specification can mean "one", but is also consistent with the meanings of "one or more", "at least one", and "one or more than one". The term "comprising" (and any inflection of "comprising" such as "comprise" and "comprises"), "having" (and any inflection of "having" such as "have" and "has"), "including" (and any inflection of "including" such as "includes" and "include"), or "containing" (and any inflection of "containing" such as "contains" and "contain") is inclusive or open-ended and does not exclude additional, unrecited elements, or method steps. The methods described herein can "comprise", "consist essentially of", or "consist of" the specific components, elements, compositions, etc. disclosed throughout the specification.

[0047] The term "polymer article" means an article or polymer sample prepared by a process including a molding process or an extrusion process, preferably an injection molding process.

[0048] The expression "at least a portion" means at least 25.0%, preferably at least 50.0%, preferably at least 75.0%, preferably 100.0% of a parameter such as surface area.

[0049] Various embodiments of the present disclosure are based, in part, on the discovery that polymer articles comprising certain thermoplastic materials that include a functionalized polymer can be electrolessly metallized without the use of a hexavalent chromium compound as an etchant. For example, such polymer articles can include a thermoplastic polymer composition that comprises, consists of, or consists essentially of: a. Copolymer (A) present in an amount of ≧35.0 wt% and ≦70.0 wt%, preferably ≧40.0 wt% and ≦60.0 wt%, preferably ≧45.0 wt% and ≦56.0 wt% based on the total weight of the thermoplastic polymer composition, the copolymer (A) comprising or consisting of polymerization units derived from (i) a vinyl aromatic monomer and (ii) a vinyl nitrile monomer; b. A rubber-modified thermoplastic polymer (E) present in an amount of ≧26.0 wt% and ≦50.0 wt%, preferably ≧30.0 wt% and ≦50.0 wt%, preferably ≧30.0 wt% and ≦45.0 wt%, preferably ≧35.0 wt% and ≦45.0 wt% based on the total weight of the thermoplastic polymer composition; c. A functionalized polymer (FP) present in an amount of ≧1.0 wt% and ≦15.0 wt%, preferably ≧3.0 wt% and ≦12.0 wt%, preferably ≧6.0 wt% and ≦12.0 wt% based on the total weight of the thermoplastic polymer composition, the functionalized polymer (FP) being any one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably the functionalized polymer (FP) being a styrene maleic anhydride (SMA) copolymer; and d. An additive mixture present in an amount of ≧0.0 wt% and ≦5.0 wt%, preferably >0.0 wt% and ≦5.0 wt%, preferably ≧1.0 wt% and ≦5.0 wt%, preferably ≧1.0 wt% and ≦3.0 wt% based on the total weight of the thermoplastic polymer composition.

[0050] Advantageously, the thermoplastic polymer composition constituting the polymer article has a desired composition of copolymer (A), rubber-modified thermoplastic polymer (E), functionalized polymer (FP), and optionally an additive mixture, which together enable surface treatment of the polymer article for metal plating without the need to use a hexavalent chromium compound for etching. Advantageously, the polymer article has suitable impact strength, whereby such polymer articles can be used in the preparation of metal-plated articles suitable for various industrial applications that require materials with excellent impact strength.

[0051] In some embodiments of the present disclosure, the polymer article comprises the thermoplastic polymer composition present in an amount of ≧ 95.0 wt%, preferably ≧ 97.0 wt%, preferably ≧ 98.0 wt%, preferably ≧ 99.0 wt%, preferably 100.0 wt% based on the total weight of the polymer article.

[0052] Copolymer (A) Copolymer (A) may be present in a suitable amount in the thermoplastic polymer composition, for example. For example, copolymer (A) may be present in an amount of ≧ 35.0 wt% and ≦ 70.0 wt%, preferably ≧ 36.0 wt% and ≦ 65.0 wt%, preferably ≧ 40.0 wt% and ≦ 63.0 wt%, preferably ≧ 40.0 wt% and ≦ 60.0 wt%, preferably ≧ 45.0 wt% and ≦ 60.0 wt%, preferably ≧ 45.0 wt% and ≦ 56.0 wt% based on the total weight of the thermoplastic polymer composition. Here, copolymer (A) comprises, or consists of, polymerized units derived from (i) vinyl aromatic monomers and (ii) vinyl nitrile monomers. Preferably, copolymer (A) consists of polymerized units derived from (i) vinyl aromatic monomers and (ii) vinyl nitrile monomers. In other words, copolymer (A) is derived only from vinyl aromatic monomers and vinyl nitrile monomers and not from other monomers.

[0053] Most preferably, the copolymer (A) may be present in an amount of, for example, ≧45.0 wt% and ≦60.0 wt%, preferably ≧45.0 wt% and ≦56.0 wt%, based on the total weight of the thermoplastic polymer composition, and the copolymer (A) contains polymerized units derived from (i) vinyl aromatic monomers and (ii) vinyl nitrile monomers.

[0054] In some embodiments of the present disclosure, the copolymer (A) has polymerized units derived from vinyl nitrile monomers in an amount of ≧22.0 wt% and ≦38.0 wt%, preferably ≧25.0 wt% and ≦35.0 wt%, more preferably ≧30.0 wt% and ≦35.0 wt%, based on the total weight of the copolymer (A). Most preferably, the copolymer (A) has polymerized units derived from vinyl nitrile monomers in an amount of ≧30.0 wt% and ≦35.0 wt%, based on the total weight of the copolymer (A).

[0055] More preferably, the vinyl aromatic monomer is styrene and the vinyl nitrile monomer is acrylonitrile. Preferably, the copolymer (A) is a styrene-acrylonitrile copolymer. In a preferred embodiment of the present disclosure, the copolymer (A) is a styrene-acrylonitrile copolymer having polymerized units derived from acrylonitrile in an amount of ≧30.0 wt% and ≦35.0 wt%. It is particularly preferred that the copolymer (A) is not a mixture of two or more different styrene-acrylonitrile copolymers.

[0056] In some aspects of the present disclosure, copolymer (A) can be, for example, a terpolymer comprising, or consisting of, polymerization units derived from (i) vinyl aromatic monomers, (ii) vinyl nitrile monomers, and (iii) (meth)acrylic monomers. The vinyl aromatic monomers and vinyl nitrile monomers can be selected from monomers as defined herein. The (meth)acrylic monomer can be selected from, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, iso-propyl methacrylate, butyl methacrylate, hexyl methacrylate, and decyl methacrylate. Preferably, the (meth)acrylic monomer can be methyl methacrylate (MMA). Thus, copolymer (A) can be, for example, a terpolymer comprising polymerization units derived from styrene / acrylonitrile / methyl methacrylate, or polymerization units derived from α-methylstyrene / acrylonitrile / methyl methacrylate.

[0057] Copolymer (A) can have a suitable molecular weight. For example, copolymer (A) has an average molecular weight (Mw) determined according to gel permeation chromatography in accordance with ASTM D5296-11 of ≧50,000 g / mol and ≦100,000 g / mol, preferably ≧80,000 g / mol and ≦100,000 g / mol, preferably ≧85,000 g / mol and ≦98,000 g / mol, preferably ≧93,000 g / mol and ≦97,000 g / mol. For example, the determination of the molecular weight was carried out using gel permeation chromatography with polystyrene-based calibration using tetrahydrofuran (THF) as a solvent in accordance with ASTM D5296-11.

[0058] The copolymer (A) can be selected, for example, to have appropriate flow characteristics. For example, the copolymer (A) can have a melt flow rate determined at 230 °C under a load of 1.2 kg in accordance with ISO 1133 (2005) of ≥ 7.0 g / 10 min and ≤ 20.0 g / 10 min, preferably ≥ 8.0 g / 10 min and ≤ 15.0 g / 10 min, preferably ≥ 9.0 g / 10 min and ≤ 11.0 g / 10 min. The inventors have found that if the melt flow rate of the copolymer (A) is too high, it may have an adverse effect on the overall impact properties of the thermoplastic polymer composition, while if the melt flow rate of the copolymer (A) is too low, the desired flow characteristics of the thermoplastic polymer cannot be obtained, which affects the processability of the thermoplastic polymer.

[0059] Rubber-modified thermoplastic polymer (E): In one aspect of the present disclosure, the thermoplastic polymer composition contains an appropriate amount of a rubber component. The rubber-modified thermoplastic polymer (E) can be referred to as a high rubber graft or "HRG". Preferably, the thermoplastic polymer composition contains at least 26.0 wt% of the rubber-modified thermoplastic polymer (E). Preferably, the thermoplastic polymer composition can contain the rubber-modified thermoplastic polymer (E) in an amount of, for example, ≥ 26.0 wt% and ≤ 50.0 wt%, preferably ≥ 30.0 wt% and ≤ 50.0 wt%, preferably ≥ 30.0 wt% and ≤ 45.0 wt%, preferably ≥ 35.0 wt% and ≤ 45.0 wt%, preferably ≥ 36.0 wt% and ≤ 43.0 wt% based on the total weight of the thermoplastic polymer composition.

[0060] Most preferably, in the thermoplastic polymer composition, the copolymer (A) is present in an amount of ≤ 60.0 wt%, preferably ≤ 56.0 wt%, while the rubber-modified thermoplastic polymer (E) is present in an amount of ≥ 26.0 wt%, preferably ≥ 30.0 wt% based on the total weight of the thermoplastic polymer composition.

[0061] The rubber-modified thermoplastic polymer (E) comprises, or consists of, (i) a polymer rubber, (ii) a graft thermoplastic copolymer (C). Here, the graft thermoplastic copolymer (C) is grafted onto the polymer rubber. In some embodiments of the present disclosure, the polymer rubber may be a discontinuous elastomeric phase dispersed across a continuous hard thermoplastic phase comprising the graft thermoplastic copolymer (C), with at least a portion of the hard thermoplastic phase grafted onto the discontinuous elastomeric phase.

[0062] The polymer rubber may, for example, have a suitable particle-based form. For example, the polymer rubber may be in the form of rubber particles having a wide range of unimodal particle size distributions. The polymer rubber may have an average particle size of, for example, ≧50 nanometers (nm) and ≦1000 nanometers (nm), preferably ≧200 nanometers (nm) and ≦500 nanometers (nm).

[0063] The rubber-modified thermoplastic polymer (E) contains an appropriate amount of polymer rubber. The rubber-modified thermoplastic polymer (E) may have a polymer rubber content of, for example, ≧55.0 wt% and ≦75.0 wt%, preferably ≧57.0 wt% and ≦70.0 wt%, preferably ≧60.0 wt% and ≦65.0 wt%, preferably ≧60.0 wt% and ≦63.0 wt%, based on the total weight of the rubber-modified thermoplastic polymer (E). The polymer rubber content can be determined, for example, using Fourier transform infrared microspectroscopy (FT-IR).

[0064] Therefore, the rubber-modified thermoplastic polymer (E) has a content of the graft thermoplastic copolymer (C) of ≧ 25.0 wt% and ≦ 45.0 wt%, preferably ≧ 30.0 wt% and ≦ 43.0 wt%, preferably ≧ 35.0 wt% and ≦ 40.0 wt%, preferably ≧ 37.0 wt% and ≦ 40.0 wt% based on the total weight of the rubber-modified thermoplastic polymer (E). Preferably, the rubber-modified thermoplastic polymer (E) has a polymer rubber content of ≧ 55.0 wt% and ≦ 75.0 wt%, preferably ≧ 57.0 wt% and ≦ 70.0 wt%, preferably ≧ 60.0 wt% and ≦ 65.0 wt%, preferably ≧ 60.0 wt% and ≦ 63.0 wt% based on the total weight of the rubber-modified thermoplastic polymer (E), and a content of the graft thermoplastic copolymer (C) of ≧ 25.0 wt% and ≦ 45.0 wt%, preferably ≧ 30.0 wt% and ≦ 43.0 wt%, preferably ≧ 35.0 wt% and ≦ 40.0 wt%, preferably ≧ 37.0 wt% and ≦ 40.0 wt% based on the total weight of the rubber-modified thermoplastic polymer (E).

[0065] More preferably, the rubber-modified thermoplastic polymer (E) has a polymer rubber content of ≧ 60.0 wt% and ≦ 65.0 wt%, preferably ≧ 60.0 wt% and ≦ 63.0 wt% based on the total weight of the rubber-modified thermoplastic polymer (E), and a content of the graft thermoplastic copolymer (C) of ≧ 35.0 wt% and ≦ 40.0 wt%, preferably ≧ 37.0 wt% and ≦ 40.0 wt% based on the total weight of the rubber-modified thermoplastic polymer (E).

[0066] The polymer rubber contains polymer units derived from conjugated dienes, and the conjugated dienes are selected from 1,3-butadiene, isoprene, 1,3-heptadiene, methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, and any combination thereof, and preferably, the conjugated diene is 1,3-butadiene.

[0067] More preferably, for example, the polymer rubber may contain polymerization units derived from conjugated dienes, such as 1,3-butadiene that forms polybutadiene.

[0068] For example, the rubber-modified thermoplastic polymer (E) may contain a graft thermoplastic copolymer (C). The graft thermoplastic copolymer (C) is grafted onto the polymer rubber and contains polymerization units derived from the following: i. Vinyl aromatic monomers selected from styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-hydroxystyrene, methoxystyrene, and any combination thereof, preferably styrene; ii. Vinyl nitrile monomers selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, and any combination thereof, preferably acrylonitrile; and iii. (Meth)acrylic monomers selected from methyl methacrylate, ethyl methacrylate, and propyl methacrylate, preferably methyl methacrylate (MMA).

[0069] Preferably, the graft thermoplastic copolymer (C) contains polymerization units derived from styrene, methyl methacrylate, and acrylonitrile, and the polymer rubber is a polybutadiene rubber containing polymerization units derived from 1,3-butadiene.

[0070] Preferably, the rubber-modified thermoplastic polymer (E) is a polybutadiene rubber grafted with a copolymer containing polymerization units derived from styrene, methyl methacrylate, and acrylonitrile.

[0071] In some embodiments of the present disclosure, the rubber-modified thermoplastic polymer (E) may contain a portion of the graft thermoplastic copolymer (C) that is not chemically grafted to the polymer rubber. The portion of the graft thermoplastic copolymer (C) that is not chemically grafted to the polymer rubber may be referred to as the "free thermoplastic copolymer (C)". For example, the rubber-modified thermoplastic polymer (E) may contain the graft thermoplastic copolymer (C) "free thermoplastic copolymer (C)" that is not chemically grafted to the polymer rubber in an amount of ≤ 15.0 wt%, preferably ≤ 10.0 wt%, preferably ≤ 5.0 wt%, preferably ≤ 2.0 wt%.

[0072] Functionalized polymer (FP) The functionalized polymer (FP) is present in an appropriate amount in the thermoplastic polymer composition. The functionalized polymer (FP) may be present, for example, in an amount of ≥ 1.0 wt% and ≤ 15.0 wt%, preferably ≥ 3.0 wt% and ≤ 12.0 wt%, preferably ≥ 6.0 wt% and ≤ 12.0 wt% based on the total weight of the thermoplastic polymer composition. The functionalized polymer (FP) is any one polymer selected from a styrene maleic anhydride (SMA) copolymer or a maleic anhydride grafted polystyrene (MA-g-PS), and preferably, the functionalized polymer (FP) is a styrene maleic anhydride (SMA) copolymer.

[0073] Preferably, the functionalized polymer (FP) has a maleic anhydride content of ≧10.0 wt% and ≦45.0 wt%, preferably ≧15.0 wt% and ≦40.0 wt%, preferably ≧25.0 wt% and ≦35.0 wt%, preferably ≧30.0 wt% and ≦35.0 wt% based on the total weight of the functionalized polymer (FP). Preferably, the functionalized polymer (FP) has a weight average molecular weight of ≧1,000 g / mol and ≦25,000 g / mol, preferably ≧2,000 g / mol and ≦20,000 g / mol, preferably ≧5,000 g / mol and ≦18,000 g / mol, preferably ≧10,000 g / mol and ≦18,000 g / mol, preferably ≧12,000 g / mol and ≦18,000 g / mol. For example, the determination of the molecular weight was carried out using gel permeation chromatography with polystyrene-based calibration using tetrahydrofuran (THF) as a solvent according to ASTM D5296-11.

[0074] Additive mixture The additive mixture, if present, can be present in the thermoplastic polymer composition, for example, in a suitable proportion. The thermoplastic polymer composition can include an additive mixture present in an amount of, for example, ≧0.0 wt% and ≦5.0 wt%, preferably >0.0 wt% and ≦5.0 wt%, preferably ≧1.0 wt% and ≦5.0 wt%, preferably ≧1.0 wt% and ≦3.0 wt%, preferably ≧1.0 wt% and ≦3.0 wt% based on the total weight of the thermoplastic polymer composition. Preferably, the additive mixture comprises, or consists of, magnesium oxide (MgO), silicone oil, wax, and magnesium stearate.

[0075] In some embodiments of the present disclosure, magnesium oxide (MgO) can be present in an amount of, for example, ≧0.01 wt% and ≦0.1 wt%, preferably ≧0.01 wt% and ≦0.05 wt% based on the total weight of the thermoplastic polymer composition. In some embodiments of the present disclosure, silicone oil can be present in an amount of, for example, ≧0.05 wt% and ≦0.5 wt%, preferably ≧0.1 wt% and ≦0.5 wt% based on the total weight of the thermoplastic polymer composition.

[0076] In some embodiments of the present disclosure, the wax can be present in an amount of, for example, ≧0.5 wt% and ≦2.0 wt%, preferably ≧0.8 wt% and ≦1.5 wt%, based on the total weight of the thermoplastic polymer composition. In some embodiments of the present disclosure, magnesium stearate can be present in an amount of, for example, ≧0.05 wt% and ≦0.5 wt%, preferably ≧0.1 wt% and ≦0.4 wt%, based on the total weight of the thermoplastic polymer composition.

[0077] Polymer article Preferably, the polymer article comprises a thermoplastic polymer composition, which comprises, consists of, or consists essentially of the following: a. Copolymer (A) present in an amount of ≧35.0 wt% and ≦70.0 wt%, preferably ≧40.0 wt% and ≦60.0 wt%, preferably ≧45.0 wt% and ≦56.0 wt%, based on the total weight of the thermoplastic polymer composition, which is a styrene-acrylonitrile copolymer (SAN), copolymer (A); b. Rubber-modified thermoplastic polymer (E) present in an amount of ≧26.0 wt% and ≦50.0 wt%, preferably ≧30.0 wt% and ≦50.0 wt%, preferably ≧30.0 wt% and ≦45.0 wt%, preferably ≧35.0 wt% and ≦45.0 wt%, based on the total weight of the thermoplastic polymer composition, which is a polybutadiene rubber grafted with a styrene / methyl methacrylate / acrylonitrile / copolymer, rubber-modified thermoplastic polymer (E); c. Functionalized polymer (FP) present in an amount of ≧1.0 wt% and ≦15.0 wt%, preferably ≧3.0 wt% and ≦12.0 wt%, preferably ≧6.0 wt% and ≦12.0 wt%, based on the total weight of the thermoplastic polymer composition, which is a styrene maleic anhydride (SMA) copolymer, and the styrene maleic anhydride (SMA) copolymer has the following, functionalized polymer (FP): i. A maleic anhydride content of ≧10.0 wt% and ≦45.0 wt%, preferably ≧15.0 wt% and ≦40.0 wt%, preferably ≧25.0 wt% and ≦35.0 wt%, based on the total weight of the styrene maleic anhydride (SMA) copolymer; and ii. A weight average molecular weight of ≧1,000 g / mol and ≦25,000 g / mol, preferably ≧2,000 g / mol and ≦20,000 g / mol, preferably ≧5,000 g / mol and ≦18,000 g / mol, preferably ≧10,000 g / mol and ≦18,000 g / mol, preferably ≧12,000 g / mol and ≦18,000 g / mol, as determined according to ASTM D5296-11; and d. An additive mixture present in an amount of ≧0.0 wt% and ≦5.0 wt%, >0.0 wt% and ≦5.0 wt%, preferably ≧1.0 wt% and ≦5.0 wt%, preferably ≧1.0 wt% and ≦3.0 wt%, based on the total weight of the thermoplastic polymer composition, the additive mixture comprising, consisting of, or consisting essentially of magnesium oxide (MgO), silicone oil, wax, and magnesium stearate.

[0078] Preferably, the polymeric article has the appropriate impact properties required for specific applications, including automotive parts. For example, when measured according to ISO 180 / 1A, the polymeric article has a notched Izod impact strength of ≧15.0 kJ / m 2 and ≦50.0 kJ / m 2 , preferably ≧20.0 kJ / m 2 and ≦40.0 kJ / m 2 , preferably ≧20.0 kJ / m 2 and ≦30.0 kJ / m 2 .

[0079] Preferably, the polymeric article comprises a thermoplastic polymer composition comprising, consisting of, or consisting essentially of the following: a. Copolymer (A), which is a styrene-acrylonitrile copolymer (SAN), present in an amount of ≥ 35.0 wt% and ≤ 70.0 wt% based on the total weight of the thermoplastic polymer composition; b. A rubber-modified thermoplastic polymer (E), present in an amount of ≥ 26.0 wt% and ≤ 50.0 wt%, which is a polybutadiene rubber grafted with a styrene / methyl methacrylate / acrylonitrile copolymer; c. A functionalized polymer (FP), present in an amount of ≥ 1.0 wt% and ≤ 15.0 wt% based on the total weight of the thermoplastic polymer composition, which is a styrene maleic anhydride (SMA) copolymer; and d. An additive mixture, present in an amount of ≥ 0.0 wt% and ≤ 5.0 wt% based on the total weight of the thermoplastic polymer composition.

[0080] Preferably, the additive mixture comprises, consists of, or consists essentially of magnesium oxide (MgO), silicone oil, wax, and magnesium stearate.

[0081] Preferably, the polymeric article comprises a thermoplastic polymer composition comprising, consisting of, or consisting essentially of: a. Copolymer (A), which is a styrene-acrylonitrile copolymer (SAN), present in an amount of ≥ 45.0 wt% and ≤ 56.0 wt% based on the total weight of the thermoplastic polymer composition; b. A rubber-modified thermoplastic polymer (E), present in an amount of ≥ 35.0 wt% and ≤ 45.0 wt%, which is a polybutadiene rubber grafted with a styrene / methyl methacrylate / acrylonitrile copolymer; c. A functionalized polymer (FP), present in an amount of ≥ 6.0 wt% and ≤ 12.0 wt% based on the total weight of the thermoplastic polymer composition, which is a styrene maleic anhydride (SMA) copolymer; and d. An additive mixture present in an amount of ≧ 1.0 wt% and ≦ 3.0 wt% based on the total weight of the thermoplastic polymer composition.

[0082] Method for manufacturing a polymer article Exemplary embodiments of the present disclosure are directed to a method for manufacturing a polymer article according to one or more embodiments of the present disclosure. The method for manufacturing a polymer article may include, for example, a combination of steps including extrusion molding and injection molding. Preferably, the method for manufacturing a polymer article includes the following steps: a. Introducing a raw material set including copolymer (A), rubber-modified thermoplastic polymer (E), functionalized polymer (FP), and optionally an additive mixture into an extruder to obtain an extrudable composition; b. Extruding the extrudable composition under extrusion conditions to form a set of extruded pellets; and c. Subjecting the set of extruded pellets to injection molding under the following conditions to form a polymer article: i. An injection molding temperature of ≧ 210.0 °C and ≦ 250.0 °C, preferably ≧ 215.0 °C and ≦ 240.0 °C, more preferably ≧ 220 °C and ≦ 230 °C; and ii. An injection speed of ≧ 10.0 mm / sec and ≦ 40.0 mm / sec, preferably ≧ 15 mm / sec and ≦ 35.0 mm / sec, more preferably ≧ 25.0 mm / sec and ≦ 30.0 mm / sec.

[0083] In some embodiments of the present disclosure, the extrusion molding process may include physically mixing the raw materials before introducing the raw materials into the hopper of the extruder. For example, in some embodiments of the present disclosure, before loading into the hopper, the pellets of the functionalized polymer (FP) and copolymer A may be premixed in a container to obtain a set of homogeneously mixed pellets, and then introduced into the hopper together with a pre-blend containing the rubber-modified thermoplastic polymer (E) and the additive mixture.

[0084] In some embodiments of the present disclosure, the physically mixed formulation introduced into the extruder via a hopper can be melt-kneaded in, for example, a 10-barrel Coperion ZSK-26mm co-rotating twin-screw extruder with an L / D ratio of 40:1. The extrusion conditions can include, for example, extruding at an appropriate torque, at a specific mechanical energy, and at a specific RPM. For example, the extrusion can be carried out under the following conditions: (a) A torque of ≧30.0% and ≦75.0%, preferably ≧40.0% and ≦72.0%, more preferably ≧50.0% and ≦70.0%; (b) A specific mechanical energy of ≧0.10 KWh / Kg and ≦0.25 KWh / Kg, preferably ≧0.12 KWh / Kg and ≦0.22 KWh / Kg; and (c) A rotational speed (RPM) of the extrusion screw of approximately ≧240 and ≦260 per minute.

[0085] In a preferred embodiment of the present disclosure, the material throughput is adjusted to be maintained between ≧8.0 Kg / h and ≦30.0 Kg / h, preferably between ≧8.0 Kg / h and ≦25.0 Kg / h, and preferably, while maintaining the screw rotational speed at 250 RPM, the specific mechanical energy (SME) is between 0.15 kWh / t and 0.22 kWh / t.

[0086] In some embodiments of the present disclosure, injection molding can be carried out at an injection molding temperature of ≧210.0 °C and ≦250.0 °C, preferably ≧215.0 °C and ≦240.0 °C, more preferably ≧220 °C and ≦230 °C, and at an injection speed maintained at ≧10.0 mm / sec and ≦40.0 mm / sec, preferably ≧15 mm / sec and ≦35.0 mm / sec, more preferably ≧25.0 mm / sec and ≦30.0 mm / sec.

[0087] Surface-treated polymer articles Exemplary embodiments of the present disclosure are directed to surface-treated polymer articles obtained by a method comprising the following steps: a. Providing a polymer article according to one or more embodiments of the present disclosure; and b. Contacting at least a portion of the polymer article with a chemical reagent at any time of ≧ 5.0 minutes and ≦ 30.0 minutes, preferably ≧ 10.0 minutes and ≦ 20.0 minutes, more preferably ≧ 15.0 minutes and ≦ 20.0 minutes, and at a temperature of ≧ 60.0 ° C and ≦ 80.0 ° C, preferably ≧ 65.0 ° C and ≦ 75.0 ° C, to form a surface-treated polymer article.

[0088] The polymer article used to form the surface-treated polymer article includes a thermoplastic polymer composition, and the thermoplastic polymer composition preferably consists of or consists essentially of the following: a. Copolymer (A) present in an amount of ≧ 35.0 wt% and ≦ 70.0 wt% based on the total weight of the thermoplastic polymer composition, the copolymer (A) consisting of polymerization units derived from (i) a vinyl aromatic monomer and (ii) a vinyl nitrile monomer; b. A rubber-modified thermoplastic polymer (E) present in an amount of ≧ 26.0 wt% and ≦ 50.0 wt%, preferably ≧ 30.0 wt% and ≦ 50.0 wt% based on the total weight of the thermoplastic polymer composition; c. A functionalized polymer (FP), which is a functionalized polymer (FP) present in an amount of ≧ 1.0 wt% and ≦ 15.0 wt%, preferably ≧ 3.0 wt% and ≦ 12.0 wt% based on the total weight of the thermoplastic polymer composition, and is any one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably a styrene maleic anhydride (SMA) copolymer; and d. An additive mixture present in an amount of ≧ 0.0 wt% and ≦ 5.0 wt% based on the total weight of the thermoplastic polymer composition.

[0089] The surface-treated polymer article may include a thermoplastic polymer composition in an amount of > 95.0 wt%, preferably > 96.0 wt%, preferably > 99.0 wt%, preferably 100 wt% based on the total weight of the surface-treated polymer article.

[0090] More preferably, the polymeric article is contacted with a chemical reagent at any time between ≧ 15.0 minutes and ≦ 20.0 minutes and at a temperature between ≧ 65.0 °C and ≦ 75.0 °C. The surface-treated polymeric article has an appropriate surface polarity while maintaining the desired impact strength. The attributes of surface polarity and impact strength can be attributed to, for example, a suitable combination of a suitable polymeric article, a suitable choice of chemical reagent, and appropriate process parameters of temperature and time of contact / exposure for the purpose.

[0091] Exemplary embodiments of the present disclosure include polymeric articles according to one or more embodiments of the present disclosure, and are directed to surface-treated polymeric articles having a water contact angle determined according to ASTM D5946-17 of ≧ 60.0° and ≦ 85.0°, preferably ≧ 65.0° and ≦ 80.0°, preferably ≧ 65° and ≦ 75°.

[0092] Advantageously, the surface-treated polymeric article has a sufficiently low water contact angle that exhibits the appropriate surface polarity functionality required for the polymeric article to adhere to the metal layer.

[0093] Preferably, the surface-treated polymeric article can retain the impact properties of the polymeric article even after surface treatment with a chemical reagent. For example, the surface-treated polymeric article has a notched Izod impact strength of ≧ 15.0 kJ / m 2 and ≦ 50.0 kJ / m 2 , preferably ≧ 20.0 kJ / m 2 and ≦ 40.0 kJ / m 2 , preferably ≧ 20.0 kJ / m 2 and ≦ 30.0 kJ / m 2 when measured according to ISO 180 / 1A.

[0094] Thus, in some embodiments of the present disclosure, the surface-treated polymeric article has: a. When measured according to ISO 180 / 1A, ≧ 15.0 kJ / m 2 and ≦ 50.0 kJ / m 2, preferably ≥ 20.0 kJ / m 2 and ≤ 40.0 kJ / m 2 , preferably ≥ 20.0 kJ / m 2 and ≤ 30.0 kJ / m 2 of the notched Izod impact strength; and b. The surface-treated polymer article has a water contact angle determined according to ASTM D5946-17 of ≥ 60.0° and ≤ 85.0°, preferably ≥ 65.0° and ≤ 80.0°, preferably ≥ 65° and ≤ 75°.

[0095] Exemplary embodiments of the present disclosure are directed to surface-treated polymer articles comprising a thermoplastic polymer composition, the thermoplastic polymer composition comprising, consisting of, or consisting essentially of the following: a. Copolymer (A) present in an amount of ≥ 35.0 wt% and ≤ 70.0 wt%, preferably ≥ 40.0 wt% and ≤ 60.0 wt%, preferably ≥ 45.0 wt% and ≤ 56.0 wt% based on the total weight of the thermoplastic polymer composition, which is a styrene-acrylonitrile copolymer (SAN), copolymer (A); b. Rubber-modified thermoplastic polymer (E) present in an amount of ≥ 26.0 wt% and ≤ 50.0 wt%, preferably ≥ 30.0 wt% and ≤ 50.0 wt%, preferably ≥ 30.0 wt% and ≤ 45.0 wt%, preferably ≥ 35.0 wt% and ≤ 45.0 wt% based on the total weight of the thermoplastic polymer composition, which is a polybutadiene rubber grafted with a styrene, methyl methacrylate, acrylonitrile copolymer, rubber-modified thermoplastic polymer (E); c. Functionalized polymer (FP) present in an amount of ≥ 1.0 wt% and ≤ 15.0 wt%, preferably ≥ 3.0 wt% and ≤ 12.0 wt%, preferably ≥ 6.0 wt% and ≤ 12.0 wt% based on the total weight of the thermoplastic polymer composition, which is a styrene maleic anhydride (SMA) copolymer, functionalized polymer (FP); and d. An additive mixture present in an amount of ≧0.0 wt% and ≦5.0 wt%, preferably ≧1.0 wt% and ≦5.0 wt%, preferably ≧1.0 wt% and ≦3.0 wt%, based on the total weight of the thermoplastic polymer composition;, wherein the surface-treated polymer article has the following: i. When measured according to ISO 180 / 1A, ≧15.0 kJ / m 2 and ≦50.0 kJ / m 2 , preferably ≧20.0 kJ / m 2 and ≦40.0 kJ / m 2 , preferably ≧20.0 kJ / m 2 and ≦30.0 kJ / m 2 of the notched Izod impact strength; and / or ii. A water contact angle of ≧60.0° and ≦85.0°, preferably ≧65.0° and ≦80.0°, preferably ≧65° and ≦75°, determined according to ASTM D5946-17. Further here, the additive mixture comprises, or consists of, magnesium oxide (MgO), silicone oil, wax, and magnesium stearate.

[0096] The inventors have found that the water contact angle of the surface-treated polymer article is lower than that of the polymer article itself, which indicates that the wettability of the surface is improved, thereby increasing the tendency to adhere to the metal layer.

[0097] Exemplary embodiments of the present disclosure are directed to a method for manufacturing a surface-treated polymer article according to one or more embodiments of the present disclosure, the method comprising the following steps: a. Providing a polymer article of the claims according to one or more embodiments of the present disclosure; and b. Contacting the polymer article according to one or more embodiments of the present disclosure with a chemical reagent for any time between ≧5.0 minutes and ≦30.0 minutes, preferably between ≧10.0 minutes and ≦20.0 minutes, preferably between ≧15.0 minutes and ≦20.0 minutes, and at a temperature condition between ≧60.0°C and ≦80.0°C, preferably between ≧65.0°C and ≦75.0°C, to form a surface-treated polymer article.

[0098] Advantageously, the surface-treated polymer article is manufactured without using a hexavalent chromium compound, thereby avoiding all the drawbacks associated with conventional etching processes that use such hexavalent chromium compounds.

[0099] The polymer article can be contacted with a chemical reagent for an appropriate time, for example, to ensure that the desired surface roughness is incorporated. For example, if the polymer article is contacted with a chemical reagent for too long (long exposure time), the surface of the polymer article may be damaged, while if the polymer article is contacted with a chemical reagent for too short a time, the surface morphology of the polymer article does not change sufficiently to enable adhesion to the metal layer of the surface-treated polymer article.

[0100] The chemical reagent can be selected, for example, from a sulfuric acid solution at a concentration of 70.0% by volume, a colloidal solution containing manganese oxide colloidal particles suspended in a mineral acid mixture, a potassium permanganate solution at a concentration of 6.5% by volume, and any combination thereof. More preferably, the chemical reagent is a colloidal solution containing manganese oxide colloidal particles suspended in a mineral acid mixture containing sulfuric acid and phosphoric acid.

[0101] Preferably, the colloidal solution containing manganese oxide colloidal particles suspended in a mineral acid mixture comprises: a. Manganese oxide colloidal particles present in an amount of ≧50.0 g / L and ≦70.0 g / L, preferably ≧55.0 g / L and ≦65.0 g / L; b. Phosphoric acid present in an amount of ≧210.0 ml / L and ≦230.0 ml / L, preferably ≧215.0 ml / L and ≦225.0 ml / L; and c. Sulfuric acid present in an amount of ≧560.0 ml / L and ≦580.0 ml / L, preferably ≧570.0 ml / L and ≦575.0 ml / L; where the total volume of the colloidal solution is 1.0 liter (L).

[0102] The chemical reagent can include, for example, sulfuric acid (H2SO4) having a molar strength of ≥ 8.0 M and ≤ 14.0 M, preferably ≥ 9.0 M and ≤ 12.0 M. The chemical reagent can include, for example, phosphoric acid having a molar strength of ≥ 2.0 M and ≤ 6.0 M, preferably ≥ 3.0 M and ≤ 5.0 M.

[0103] The inventors have surprisingly found that when the polymer article of the present disclosure is treated with an appropriate chemical reagent at a specific temperature for a specific time, the resulting surface-treated polymer article has a desired surface roughness and polar functionality comparable to that of a polymer surface etched with a hexavalent chromium compound.

[0104] In other words, the surface-treated polymer article according to one or more embodiments of the present disclosure has surface properties suitable for metal plating without using a hexavalent chromium compound. For example, when contacted with a chemical reagent for an exposure time of less than 5 minutes, the desired surface roughness and polar functionality required for metal adhesion may not be obtained, while when the article is exposed to the chemical reagent for an exposure time of more than 30 minutes, the surface of the plastic article may be damaged.

[0105] Metal-plated products One aspect of the present disclosure is directed to metal-plated articles including: a. A metal layer; and b. A polymer substrate layer including a surface-treated polymer article according to one or more embodiments of the present disclosure; wherein the metal layer is disposed on the polymer substrate layer, and preferably, the metal layer is adhered to the treated surface of the polymer substrate layer. As used herein, the expression "treated surface" means a portion of the polymer substrate layer or the surface-treated polymer article that has been exposed to a chemical reagent for surface treatment.

[0106] The peel strength determined according to ASTM B 533-85 (2004) is ≥ 0.14 N / mm, preferably ≥ 0.16 N / mm, preferably ≥ 0.2 N / mm, preferably ≥ 0.3 N / mm, preferably ≥ 0.34 N / mm, and the metal layer is adhered to the treated surface of the polymer substrate layer.

[0107] Preferably, the peel strength determined according to ASTM B 533-85(2004) is ≧0.14 N / mm and ≦2.0 N / mm, preferably ≧0.16 N / mm and ≦2.0 N / mm, preferably ≧0.2 N / mm and ≦1.5 N / mm, preferably ≧0.3 N / mm and ≦1.5 N / mm, and the metal layer is adhered to the treated surface of the polymer substrate layer.

[0108] The peel strength is a suitable index for the adhesion of the polymer substrate to the metal layer. The inventors believe that the surface-treated molded article has an appropriate surface roughness and polarity, thereby providing desired anchor points on the surface of the article and being suitable for use as a polymer substrate for metal plating.

[0109] The surface roughness can be determined, for example, using a contact surface roughness meter DektakXT that measures the surface roughness of thin and thick films using a mechanical stylus. The roughness of the surface-treated polymer article can be determined, for example, using a mechanical stylus with a tip radius of 12.5 μm that can be lowered to contact the article surface under a load adjustable from 1 mg to 15 mg. The article can be displaced towards the operator in the horizontal plane over a distance of, for example, up to 55 mm. Software such as the Vision64 application can be used to determine the roughness of a given article by calculating and displaying the results of hills and valleys for the surface properties.

[0110] The metal-plated article can be manufactured, for example, by a combination of chemical plating and electroplating. For example, the process for manufacturing a metal-plated article includes the following steps: a. providing a surface-treated polymer article according to one or more embodiments of the present disclosure; b. subjecting the surface-treated polymer article to chemical plating to form a metal-plating precursor article; and c. Contacting the metal plating precursor article with a metal electrolyte solution for an applied current of any value greater than or equal to 1.0 ampere and less than or equal to 4.0 amperes and for a time greater than or equal to 5 minutes and less than or equal to 30 minutes to form a metal plated article.

[0111] Chemical plating may include, for example, (i) a step of sensitizing a surface-treated polymer article with a suitable sensitizing solution such as, for example, a SnCl2 / HCl solution, and then activating it with an activating solution such as, for example, a PdCl2 / HCl solution to form an activated article, and (ii) thereafter, treating the activated article with sodium dihydrogen phosphate (NaH2PO4) and a chemical plating solution to obtain a metal plating precursor article.

[0112] The chemical plating solution may include, for example, CuSO4·5H2O (15 g / L), NaKC4H4O6·4H2O (30 g / L), HCHO (100 ml / L), and NaOH (4 g / L). Alternatively, the chemical plating solution may include, for example, NiSO4·6H2O (15 g / L), NaKC4H4O6·4H2O (30 g / L), HCHO (100 ml / L), and NaOH (4 g / L). The metal electrolyte may be selected from, for example, nickel sulfate, copper sulfate, aluminum salts such as aluminum chloride or aluminum sulfate, zinc salts such as zinc sulfate or zinc chloride, silver salts such as silver sulfate or silver chloride, and mixtures of metal salts.

[0113] A metal plating precursor article is formed by a chemical plating process. The metal plating precursor article has suitable conductivity required for performing an electroplating process. The metal layer may be, for example, a copper-based layer, an aluminum-based layer, a nickel-based layer, a zinc-based layer, a gold-based layer, or a silver-based layer, or a layer based on a metal alloy. Preferably, the metal layer is a copper-based layer. The metal alloy may be selected from, for example, brass.

[0114] The metal plated article may be selected from, for example, automotive parts and housing structures of electrical appliances.

[0115] The following shows specific examples that illustrate some embodiments of the present disclosure. The examples are for illustrative purposes only and are not intended to limit the present invention. It should be understood that the embodiments and aspects disclosed in this specification are not mutually exclusive, and such aspects and embodiments can be combined in any way. Those skilled in the art will readily recognize parameters that can be changed or modified to obtain substantially the same results.

[0116] Example Example 1 Objective: To demonstrate the features of the present disclosure, the following samples were prepared and the peel strength of the metal layer with respect to the polymer substrate was evaluated. Polymer samples with sample codes D13, D21, and D22 are those of the present invention having a thermoplastic polymer composition according to one or more embodiments of the present disclosure, and the chemical reagents used to prepare the surface-modified polymer articles are manganese oxide colloidal particles suspended in a mineral acid mixture containing sulfuric acid and phosphoric acid. Samples D20, D14, and EC2 are comparative samples. Sample EC2 does not contain a functionalized polymer. All samples were surface-treated with the chemical reagent H3PO4(4.2M)-H2SO4(9.4M)-MnO2(60g / L) colloid.

[0117] Sample Materials: The various materials used are as follows:

[0118] [Table 1]

[0119] Details of the sample compositions are as follows. All samples were prepared at a total weight of 4.0 kg.

[0120] [Table 2]

[0121] The additive mixture contains 0.04 wt% magnesium oxide, 0.2 wt% silicone oil, 1.0 wt% EBX wax, and 0.3 wt% magnesium stearate, based on the total weight of the sample.

[0122] Details of the acrylonitrile content and maleic anhydride content are as follows in the table:

[0123]

Table 3

[0124] Process for preparing the polymer article (sample plaque): For the preparation of the sample, a process combining extrusion molding and injection molding was used.

[0125] Extrusion process: All formulations were prepared on a 4.0 Kg scale. A mixture of styrene-acrylonitrile (SAN) pellets and a functionalized polymer, styrene-maleic anhydride (SMA) copolymer, was added through a hopper / feeder while a pre-blend of 1) a rubber-modified thermoplastic polymer (E) (polybutadiene rubber particles grafted with a styrene / methyl methacrylate / acrylonitrile copolymer, also referred to as HRG), and 2) an additive mixture containing EBX wax, magnesium stearate, magnesium oxide, and silicone fluid was fed through a side feeder connected to barrel 2 of the extruder.

[0126] The control sample (EC2) was prepared by mixing equal amounts of two different grades of copolymer (A), styrene acrylonitrile SAN556 (acrylonitrile content 34.0 wt%) and SAN581 (acrylonitrile content 25.0 wt%), which contain no functional additives at all. Before loading into the hopper, the pellets of SMA and SAN were pre-mixed (physically mixed) in a plastic container to obtain a homogeneous pellet mixture. Similarly, a homogeneous powder pre-blend was obtained by dry blending (physically mixing) the rubber-modified thermoplastic polymer (E) and the additive mixture in a separate container.

[0127] Once the physical blend formulation containing copolymer (A), rubber-modified thermoplastic polymer (E), and functionalized polymer, which had been introduced into the extruder, was melt-kneaded using a 10-barrel Coperion ZSK-26mm co-rotating twin-screw extruder with an L / D ratio of 40:1. During the extrusion process, the screw RPM was maintained at 250 while adjusting the material throughput so that the specific mechanical energy (SME) was maintained between 0.15 KWh / Kg and 0.22 KWh / Kg.

[0128] The parameters of the extrusion process are as follows:

[0129]

Table 4

[0130] In the case of a severe screw design, the screw has an extra neutral kneading block and small back-conveying elements, while in the case of a mild screw design, the back-conveying kneading block becomes smaller. The temperature profile of the extrusion barrel is as follows:

[0131]

Table 5

[0132] Injection molding process: The injection molding process was carried out using a 100-ton molding machine manufactured by L&T Detech equipped with a screw with a diameter of 32 mm. The molded products were conditioned at 23 °C and a relative humidity (R H ) of 50% for 72 hours. After conditioning, an impact strength test was conducted on all the molding formulations.

[0133]

Table 6

[0134] The polymer articles obtained in the forming process were tested for notched Izod impact strength according to ISO 180 / 1A. The results are as follows:

[0135]

Table 7

[0136] From the above table, it is clear that the polymer articles or sample plaques of the present invention prepared from the thermoplastic polymer composition according to one or more embodiments of the present disclosure have the desired impact properties.

[0137] Process for preparing a surface-treated polymer article (referred to as a pretreatment step): The polymer article or sample plaque obtained in the above process was contacted with a chemical reagent containing H3PO4 (4.2M) - H2SO4 (9.4M) - MnO2 (60 g / L). The treatment time was maintained at 20 minutes and the temperature condition was maintained at 70 °C to obtain a surface-treated polymer article.

[0138] The water contact angle of the surface-treated polymer article was measured according to ASTM D5946, and the notched Izod impact strength was measured according to ISO 180 / 1A. The results are as follows:

[0139]

Table 8

[0140] From Table 8, it can be seen that the surface-treated polymer article has the required water contact angle and can retain the desired impact properties. Furthermore, it was observed that the surface-treated molded article has a lower water contact angle than the starting polymer article before the pretreatment step, exhibits improved surface wettability, and is thus more suitable for adhesion to a metal layer. For example, the surface-treated article derived from the polymer article / sample plaque of D22 has a water contact angle approximately 43% lower than that of the polymer article D22 before surface treatment, while the surface-treated molded article D13 has a water contact angle approximately 13% lower after surface treatment.

[0141] Furthermore, no significant change in the surface morphology was observed within 5 minutes after contact with the chemical reagent. However, when the exposure time was further prolonged, a significant change in the surface morphology was observed.

[0142] For example, when the molded plaques of D13 or D22 were pretreated with H3PO4(4.2M)-H2SO4(9.4M)-MnO2(60g / L) for 20 minutes, the number of cavities on the surface increased, and the shape thus formed was similar to that of a typical hexavalent chromium etching sample.

[0143] These findings indicate that many cavities are formed by treating the substrate with manganese oxide colloid using high-concentration sulfuric acid / phosphoric acid for 20 minutes. However, it was observed that the surface of the polymer article was significantly damaged at exposure times exceeding 30 minutes or higher exposure times exceeding 20 minutes.

[0144] Manufacturing process of the metal-plated article: Once the surface-treated polymer article was obtained, it was plated with a metal layer. In this example, the metal layer was a copper layer. The process of depositing a metal layer on the surface-treated polymer article included a combination of processes, namely 1) a chemical plating step followed by 2) an electroplating step, to obtain a metal-plated article as the final product.

[0145] Chemical plating process: The chemical plating process included the step of introducing the surface-treated polymer article into the plating bath, reducing metal ions in the plating bath and bonding them to the polar groups on the article surface to form a metal layer. During the chemical plating process, all samples were sensitized with a SnCl2(10g / L) / HCl(40ml / L) solution (sensitizing solution), and then activated using a PdCl2(0.25g / L) / HCl(2.5ml / L) solution (activating solution). After activation, the samples were treated with the solution in the chemical plating bath containing CuSO4.5H2O(15g / L), NaKC4H4O6.4H2O(30g / L), HCHO(100ml / L) and NaOH(4g / L) for 15 minutes to obtain a metal-plated precursor article, and then the metal-plated precursor article was electroplated.

[0146] Electroplating process: In the electroplating process, an electrodeposition process step of depositing copper layers one by one on a metal plating precursor article was performed using a MiniContact RS electroplating system. During the process, a copper metal-based electrolyte containing 75 g / l of copper sulfate and 200 ml / l of sulfuric acid was used. The applied current was maintained at 1.5 amperes and the temperature was 29 °C. The electroplating time was maintained for 30 minutes to obtain a metal-plated article.

[0147] Results: For the obtained metal-plated articles, the degree of adhesion of the metal layer (copper layer) to the polymer substrate including the surface-treated polymer article was evaluated for each sample. The peel strength was determined according to ASTM B 533-85 (2004). The results of the peel strength are as follows:

[0148]

Table 9

[0149] From the above results, it is clear that the metal-plated article having a polymer substrate derived from sample D22 shows the highest peel strength and high adhesion between the metal layer (copper) and the polymer substrate. Advantageously, the polymer substrate also has excellent impact properties, thereby imparting the desired impact properties to the metal-plated article.

[0150] The metal-plated article derived from sample D13 has a peel strength that is more than 90% higher than that of the metal-plated article derived from sample D20 and nearly 127% higher than that of sample EC2 (sample EC2 contains no functionalized polymer).

[0151] Example 2 (Comparative Example) Objective: As an alternative approach, a portion of the sample was surface-treated with a certain alternative chemical reagent different from that used in Example 1. The surface-treated polymer article thus obtained was plated by the same process as described in Example 1. Thereafter, the peel strength was evaluated for each of the metal-plated articles thus obtained. The thermoplastic polymer composition constituting each sample was the same as that used in Example 1.

[0152]

Table 10

[0153] From the above table, it is clear that when treated with reagents such as 70% H2SO4, 6.5% KMnO4, or 5% KMnO4, none of the samples became the desired surface-treated polymer articles with the required adhesion characteristics.

[0154] From the results obtained in Example 1 and Example 2, it is clear that only when a polymer article containing an appropriate thermoplastic polymer composition is surface-treated under appropriate conditions using an appropriate chemical reagent, such treatment can obtain a surface-treated article having the desired surface roughness and morphology necessary for metal-plastic adhesion.

Claims

1. A polymer article comprising a thermoplastic polymer composition, wherein the thermoplastic polymer composition comprises the following: a. Copolymer (A) present in an amount of ≥35.0 wt% and ≤70.0 wt%, preferably ≥45.0 wt% and ≤56.0 wt%, relative to the total weight of the thermoplastic polymer composition, wherein copolymer (A) comprises polymerization units derived from (i) vinyl aromatic monomers and (ii) vinyl nitrile monomers; b. A rubber-modified thermoplastic polymer (E) present in an amount of ≥26.0 wt% and ≤50.0 wt%, preferably ≥30.0 ​​wt% and ≤50.0 wt%, relative to the total weight of the thermoplastic polymer composition; c. A functionalized polymer (FP) present in an amount of ≥1.0 wt% and ≤15.0 wt% with respect to the total weight of the thermoplastic polymer composition, which is one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably styrene maleic anhydride (SMA) copolymer; and d. Additive mixture present in an amount of ≥0.0 wt% and ≤5.0 wt% relative to the total weight of the thermoplastic polymer composition.

2. a. The copolymer (A) is present in an amount of ≥40.0 wt% and ≤60.0 wt%, preferably ≥45.0 wt% and ≤56.0 wt%, relative to the total weight of the thermoplastic polymer composition, and the copolymer (A) comprises polymerization units derived from (i) vinyl aromatic monomers and (ii) vinyl nitrile monomers; b. The rubber-modified thermoplastic polymer (E) is present in an amount of ≥30.0 ​​wt% and ≤45.0 wt%, preferably ≥35.0 wt% and ≤45.0 wt%, relative to the total weight of the thermoplastic polymer composition; c. The functionalized polymer (FP) is present in an amount of ≥3.0 wt% and ≤12.0 wt%, preferably ≥6.0 wt% and ≤12.0 wt%, relative to the total weight of the thermoplastic polymer composition, and the functionalized polymer (FP) is one polymer selected from styrene maleic anhydride (SMA) copolymer or maleic anhydride grafted polystyrene (MA-g-PS), preferably styrene maleic anhydride (SMA) copolymer; and d. The polymer article according to claim 1, wherein the additive mixture is present in an amount of ≥1.0 wt% and ≤5.0 wt%, preferably ≥1.0 wt% and ≤3.0 wt%, based on the total weight of the thermoplastic polymer composition.

3. The functionalized polymer (FP) is the polymer article according to claim 1 or 2, having the following: a. A maleic anhydride content of ≥10.0 wt% and ≤45.0 wt%, preferably ≥15.0 wt% and ≤40.0 wt%, preferably ≥25.0 wt% and ≤35.0 wt%, preferably ≥30.0 ​​wt% and ≤35.0 wt%, relative to the total weight of the functionalized polymer (FP); and b. Weight-average molecular weight of ≥1,000 g / mol and ≤25,000 g / mol, preferably ≥2,000 g / mol and ≤20,000 g / mol, preferably ≥5,000 g / mol and ≤18,000 g / mol, preferably ≥10,000 g / mol and ≤18,000 g / mol, preferably ≥12,000 g / mol and ≤18,000 g / mol, as determined according to ASTM D5296-11.

4. a. The vinyl aromatic monomer is selected from styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, and p-hydroxystyrene, methoxystyrene, preferably the vinyl aromatic monomer is styrene; and / or b. The vinyl nitrile monomer is selected from acrylonitrile, α-chloroacrylonitrile, methacrylonitrile, and ethacrylonitrile, and preferably the vinyl nitrile monomer is acrylonitrile. Preferably, the polymer article according to claim 1 or 2, wherein the vinyl aromatic monomer is styrene and the vinyl nitrile monomer is acrylonitrile.

5. The rubber-modified thermoplastic polymer (E) is the polymer article according to claim 1 or 2, having the following: a. Polymer rubber comprising polymerization units derived from a conjugated diene, wherein the conjugated diene is selected from 1,3-butadiene, isoprene, 1,3-heptadiene, methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, and any combination thereof, preferably the conjugated diene being 1,3-butadiene; b. A grafted thermoplastic copolymer (C) grafted onto the polymer rubber and containing polymerization units derived from the following: i. Vinyl aromatic monomers selected from styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-hydroxystyrene, methoxystyrene, and any combination thereof, preferably styrene; ii. A vinyl nitrile monomer selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, and any combination thereof, preferably acrylonitrile; and iii. (Meth)acrylic monomers, optionally selected from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and propyl methacrylate, preferably methyl methacrylate (MMA); Preferably, the graft thermoplastic copolymer (C) comprises polymerization units derived from (i) styrene, (ii) methyl methacrylate, and (iii) acrylonitrile, and the polymer rubber is a polybutadiene rubber comprising polymerization units derived from 1,3-butadiene.

6. The polymer article according to claim 1 or 2 comprises the following thermoplastic polymer composition: a. Copolymer (A) present in an amount of ≥35.0 wt% and ≤70.0 wt%, preferably ≥40.0 wt% and ≤60.0 wt%, preferably ≥45.0 wt% and ≤56.0 wt%, relative to the total weight of the thermoplastic polymer composition, wherein copolymer (A) is a styrene-acrylonitrile copolymer (SAN); b. A rubber-modified thermoplastic polymer (E) present in an amount of ≥26.0 wt% and ≤50.0 wt%, preferably ≥30.0 ​​wt% and ≤45.0 wt%, preferably ≥35.0 wt% and ≤45.0 wt%, relative to the total weight of the thermoplastic polymer composition, wherein the rubber-modified thermoplastic polymer (E) is polybutadiene rubber grafted with styrene / methyl methacrylate / acrylonitrile / copolymer; and c. A functionalized polymer (FP) present in an amount of ≥1.0 wt% and ≤15.0 wt%, preferably ≥3.0 wt% and ≤12.0 wt%, preferably ≥6.0 wt% and ≤12.0 wt%, relative to the total weight of the thermoplastic polymer composition, wherein the functionalized polymer (FP) is a styrene-maleic anhydride (SMA) copolymer, and the styrene-maleic anhydride (SMA) copolymer has the following: i. A maleic anhydride content of ≥10.0 wt% and ≤45.0 wt%, preferably ≥15.0 wt% and ≤40.0 wt%, preferably ≥25.0 wt% and ≤35.0 wt%, relative to the total weight of the styrene-maleic anhydride (SMA) copolymer; and ii. Weight-average molecular weights of ≥1,000 g / mol and ≤25,000 g / mol, preferably ≥2,000 g / mol and ≤20,000 g / mol, preferably ≥5,000 g / mol and ≤18,000 g / mol, preferably ≥10,000 g / mol and ≤18,000 g / mol, preferably ≥12,000 g / mol and ≤18,000 g / mol, as determined according to ASTM D5296-11; and d. An additive mixture present in an amount of ≥0.0 wt% and ≤5.0 wt%, preferably ≥1.0 wt% and ≤5.0 wt%, and preferably ≥1.0 wt% and ≤3.0 wt%, relative to the total weight of the thermoplastic polymer composition.

7. A method for producing a polymer article according to claim 1 or 2, comprising the following steps: a. A step of introducing a raw material set containing a copolymer (A), a rubber-modified thermoplastic polymer (E), a functionalized polymer (FP), and optionally an additive mixture into an extruder to obtain an extrudeable composition; b. A step of extruding the extrudeable composition under extrusion conditions to form a set of extruded pellets; and c. The process of subjecting the set of extruded pellets to injection molding under the following conditions to form a polymer article: i. Injection molding temperature ≥210.0°C and ≤250.0°C, preferably ≥215.0°C and ≤240.0°C, more preferably ≥220°C and ≤230°C; and ii. An injection speed of ≥10.0 mm / sec and ≤40.0 mm / sec, preferably ≥15 mm / sec and ≤35.0 mm / sec, more preferably ≥25.0 mm / sec and ≤30.0 mm / sec.

8. Surface-treated polymer articles obtained by a method comprising the following steps: c. A step of providing a polymer article according to claim 1 or 2; and d. A step of contacting at least a portion of the polymer article with a chemical reagent for any time of ≥ 5.0 minutes and ≤ 30.0 minutes, preferably ≥ 10.0 minutes and ≤ 20.0 minutes, more preferably ≥ 15.0 minutes and ≤ 20.0 minutes, and at a temperature of ≥ 60.0°C and ≤ 80.0°C, preferably ≥ 65.0°C and ≤ 75.0°C, to form a surface-treated polymer article.

9. The surface-treated polymer article according to claim 8, wherein the chemical reagent is a colloidal solution comprising manganese oxide colloid particles suspended in a mineral acid mixture containing sulfuric acid and phosphoric acid.

10. A colloidal solution comprising manganese oxide colloid particles suspended in a mineral acid mixture comprises the following, for the surface-treated polymer article according to claim 8: a. Manganese oxide colloid particles present in amounts of ≥ 50.0 g / L and ≤ 70.0 g / L, preferably ≥ 55.0 g / L and ≤ 65.0 g / L; b. Phosphoric acid present in an amount of ≥210.0 ml / L and ≤230.0 ml / L, preferably ≥215.0 ml / L and ≤225.0 ml / L; and c. Sulfuric acid present in an amount of ≥ 560.0 ml / L and ≤ 580.0 ml / L, preferably ≥ 570.0 ml / L and ≤ 575.0 ml / L. Here, the total volume of the colloidal solution is 1.0 liter (L).

11. The surface-treated polymer article according to claim 8, having the following: a. When measured according to ISO 180 / 1A, ≥ 15.0 kJ / m ２ Furthermore, ≤ 50.0 kJ / m ２ Preferably ≥ 20.0 kJ / m ２ Furthermore, ≤ 40.0 kJ / m ２ Preferably ≥ 20.0 kJ / m ２ Furthermore, ≤ 30.0 kJ / m ２ Izod impact strength with notches; and / or b. The surface-treated polymer article has a water contact angle determined according to ASTM D5946-17 of ≥60.0° and ≤85.0°, preferably ≥65.0° and ≤80.0°, preferably ≥65° and ≤75°.

12. Includes the following: a. Metal layer; and b. A polymer substrate layer comprising the surface-treated polymer article described in claim 8; A metal-plated article wherein the metal layer is disposed on at least a portion of the polymer substrate layer, and preferably the metal layer is bonded to the treated surface of the polymer substrate layer.

13. The metal-plated article according to claim 12, wherein the metal layer is adhered to the treated surface of the polymer substrate layer with a peel strength of ≥0.14 N / mm, preferably ≥0.16 N / mm, preferably ≥0.2 N / mm, preferably ≥0.3 N / mm, preferably ≥0.34 N / mm, as determined in accordance with ASTM B 533-85 (2004).

14. The process for manufacturing metal-plated articles includes the following steps: a. A step of providing a surface-treated polymer article according to claim 8; b. A step of subjecting the surface-treated polymer article to chemical plating to form a metal-plated precursor article; and c. A step of forming a metal-plated article by contacting the metal-plated precursor article with a metal electrolyte solution for a period of time of ≥1.0 ampere and ≤4.0 ampere, preferably ≥1.0 ampere and ≤3.0 ampere, and ≥5 minutes and ≤35 minutes, preferably ≥25 minutes and ≤35 minutes.

15. Use of the surface-treated polymer article according to claim 8 for improving the adhesion of a metal layer to a polymer substrate in a metal-plated article.