Metal plating of blends of acrylonitrile-butadiene-styrene and polar polymers without chromic acid etching

Abstract

A thermoplastic composition is described. A thermoplastic composition may include (a) a copolymer having units derived from a vinyl aromatic monomer and a vinyl nitrile monomer; (b) a rubber-modified thermoplastic polymer; (c) a polar polymer comprising a carboxylic acid, an alcohol, or a combination thereof; and (d) optionally, a processing additive. A metal-plated article comprising the thermoplastic polymer composition is also described. The thermoplastic composition may have an improved yellowness index (YI) compared to similar compositions that do not contain the polar polymer.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority from European patent application No. 22211169, filed on December 2, 2022, the entire contents of which are incorporated herein by reference in their entirety. Technical Field

[0002] The present invention relates to thermoplastic polymer compositions and methods for producing thermoplastic compositions.

[0003] Polymer plastic parts prepared from thermoplastic materials such as acrylonitrile-butadiene-styrene (ABS) polymers are often metallized when used in certain applications such as automotive applications. This thermoplastic material serves as a polymer substrate on which a metal coating can be deposited. For example, a polymer plastic part prepared from ABS polymer can be coated with a metal layer to impart a mirror-like gloss appearance to resemble a metal part while retaining the significant advantage of being lightweight. In addition, the metal coating can improve the mechanical strength, thermal stability, and chemical resistance of the polymer substrate below which the metal is coated. In this regard, ABS polymer is particularly suitable for automotive and other industrial applications due to its expected impact properties and other useful features.

[0004] The use of metal coatings on polymer plastic parts is problematic. A disadvantage of metal coatings is that they do not readily bond or adhere to most polymer-based substrates unless the surface of such polymer substrates is first chemically treated. Traditionally, the surface of a polymer substrate can be chemically etched using oxidizing agents such as hexavalent chromium trioxide or chromic acid / sulfuric acid mixtures or chromic acid / sulfuric acid / phosphoric acid mixtures. These strong oxidizing agents can micro-roughen and chemically alter the surface of the polymer substrate 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 can promote the adsorption of plating catalysts from aqueous solutions, which allows metal deposition to occur subsequently during the plating process. Following the etching process, the surface of the polymer substrate can be plated with metal. A suitable metric for measuring the success of the bond between the metal layer and the polymer substrate is peel strength, where greater peel strength is associated with better adhesion of the metal to the polymer substrate.

[0005] However, the use of hexavalent chromium compounds such as chromium trioxide presents certain risks and challenges, such as 1) health risks, as such compounds are extremely carcinogenic, 2) disposal of waste effluent from the etching process, which makes such etching processes not only environmentally harmful but also expensive, 3) purification of the etched plastic parts to remove any residual chromium trioxide that may be present as impurities, as such impurities adversely affect the metal plating process, and / or 4) the use of highly oxidizing acid solutions that can often damage the polymer substrate itself or render it structurally weaker than is desirable for metal plating.

[0006] In an effort to avoid these problems, many alternative processes to chromic acid etching have been investigated. For example, dry plasma etching has been proposed as an alternative to wet etching processes. However, the application of this method is limited to flat polymer parts. Alternatively, etching agents such as potassium permanganate have been used in attempts to replace chromic acid. Although the use of heated alkaline permanganate solutions has seen some limited commercial success, the applicability of permanganate solutions is largely limited due to their slower oxidation rate compared to chromic acid.

[0007] Another problem associated with ABS resins is that they can yellow during extrusion and / or molding. In particular, the yellowish appearance of molded parts limits their use in applications where visual appearance and surface aesthetics are important. The yellow coloration of ABS resins can be attributed to the presence of divinyl components, which oxidize when exposed to heat to produce a yellowish color. During melt processing, ABS color can yellow under influences such as heat, oxygen, stress, slight moisture, impurities, etc. How quickly ABS resins yellow is typically measured by their yellowness index (YI). A lower YI corresponds to a more stable color, while a higher YI corresponds to a less stable color. A lower YI is desirable. Although efforts to improve the YI of ABS resins have been ongoing, many of these efforts have also resulted in a reduction in the physical and / or mechanical properties of the resin. Summary of the Invention SUMMARY OF THE INVENTION

[0008] A solution to at least one of the problems associated with metal plating and / or yellowing of polymeric materials has been discovered. The solution may include a thermoplastic polymer composition comprising (a) a copolymer having units derived from a vinyl aromatic monomer and a vinyl nitrile monomer, (b) a rubber modified thermoplastic polymer, (c) a polar polymer comprising a carboxylic acid, an alcohol, or a combination thereof, and (d) a melt processing additive. In some embodiments of the present invention, such a polymer composition can be successfully metal plated. This success can be determined by peel strength testing. Advantageously, the thermoplastic composition can have suitable impact strength when presented in a molded form. This can allow such a polymer composition to be used to prepare metal-plated articles suitable for various industrial applications where the desired material has excellent impact strength. In addition, and in one aspect, the polymer composition of the present invention can be metal coated without having to use a chemical etching process that relies on an oxidizing agent such as hexavalent chromium trioxide or a chromic acid / sulfuric acid mixture or a chromic acid / sulfuric acid / phosphoric acid mixture.

[0009] In some embodiments, the polymer composition of the present invention may have a low YI compared to an ABS resin that does not contain a polar polymer. In particular, it has been found that the polar polymer portion of the polymer composition of the present invention can reduce the YI of the resin and increase whiteness (L value). This can be advantageous because it can allow the composition of the present invention to be metal-coated while having improved material whiteness. Without wishing to be bound by theory, it is believed that the reduced YI of the composition of the present invention can be attributed to the reaction of the polar groups of the polar polymer with colored impurities generated during ABS production and / or melt processing. The polar polymer (C) can migrate to at least a portion of the surface of the polymer composition. The migration of the polar polymer (C) can be initiated or accelerated, or both, while maintaining the polymer melt in the mold. In addition, the low molecular weight of the polar polymer (C) (e.g., a molecular weight of 5000 g / mol to 25000 g / mol) and / or the presence of polar components from the hydrolysis of the polar polymer (C) (e.g., acrylic acid or hydrolyzed polyvinyl acetate) can allow the polar polymer (C) to migrate to the surface of the polymer composition of the present invention. Additives that migrate to the surface help retain most of the bulk properties.

[0010] In one aspect of the present invention, a thermoplastic composition is described. A thermoplastic polymer composition may comprise, based on the total weight of the thermoplastic composition, (a) 30 to 79 wt%, preferably 60 to 75 wt%, more preferably 62 to 72 wt% of a copolymer comprising units derived from (i) a vinyl aromatic monomer and (ii) a vinyl nitrile monomer (A), (b) 20 to 50 wt%, preferably 20 to 30 wt%, more preferably 22 to 24 wt% of a rubber-modified thermoplastic polymer (B), (c) greater than 1 to 15 wt%, preferably 1 to 13 wt%, more preferably 3 to 10 wt% of a polar polymer comprising a carboxylic acid, an alcohol, an amide, or a combination thereof (C), and (d) greater than 0 to 5 wt%, preferably 1 to 2 wt%, more preferably 1.2 to 1.5 wt% of a processing additive (e.g., magnesium oxide (MgO), silicone fluid, ethylene bisstearamide (EBX) wax, magnesium stearate, or mixtures thereof). In some embodiments, lubricant processing additives can be removed from the thermoplastic compositions of the present invention. For example, ethylene-acrylic acid copolymer (polar polymer (C)) can act as a lubricant.

[0011] The vinyl aromatic monomer of copolymer (A) may include styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-hydroxystyrene, methoxystyrene or any combination thereof. The vinyl nitrile monomer of copolymer (A) may include acrylonitrile, α-chloroacrylonitrile, methacrylonitrile, ethacrylonitrile or any combination thereof. In a preferred aspect, the vinyl aromatic monomer may be styrene (S) and the vinyl nitrile monomer may be acrylonitrile (AN).

[0012] The rubber-modified polymer (B) may include a polymer rubber and a thermoplastic copolymer grafted onto the polymer rubber. The polymer rubber may include polymer units derived from a conjugated diene, wherein the conjugated diene may include 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, or any combination thereof. The grafted thermoplastic copolymer (D) may comprise polymer units derived from (i) a vinyl aromatic monomer which may comprise styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-5-hydroxystyrene, methoxystyrene, or any combination thereof, (ii) a vinyl nitrile monomer which may comprise acrylonitrile, methacrylonitrile, ethacrylonitrile, or any combination thereof, and (iii) optionally, a (meth)acrylic monomer which may comprise methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, or any combination thereof.

[0013] In a preferred aspect, the polymer rubber may comprise polymer units derived from 1,3-butadiene, and the grafted polymer rubber copolymer (D) may be derived from polymer units of styrene, acrylonitrile monomer, and optionally methyl methacrylate monomer. In a preferred aspect, the copolymer (A) may be a styrene-acrylonitrile copolymer (SAN), and the rubber-modified thermoplastic polymer (B) may be a polybutadiene rubber grafted with a styrene / methyl methacrylate / acrylonitrile copolymer. The combination of copolymer (A) and rubber-modified thermoplastic polymer (B) can produce acrylonitrile-butadiene-styrene (ABS).

[0014] The polar polymer (C) can have a molecular weight of 5,000 g / mol to 25,000 g / mol. In some aspects, the polar polymer (C) can be oligomeric or have a low molecular weight. In some aspects, the polar polymer (C) can include ethylene-acrylic acid copolymer, polyvinyl pyrrolidone polymer, polyvinyl alcohol polymer or a blend thereof. The ethylene-acrylic acid copolymer can include 1 wt % to 10 wt %, preferably 6.9 wt % acrylic acid, based on the gross weight of the polar polymer (C), and / or the polyvinyl alcohol polymer can include 70 wt % to 80 wt % of the hydrolyzed polyvinyl acetate, based on the gross weight of the polar polymer (C).

[0015] In some aspects, the thermoplastic compositions of the present invention can have a thermal conductivity of 3.0 kJ / m when measured according to ISO 180 / 1A. 2 Up to 30.0kJ / m 2 , preferably 4.0kJ / m 2 Up to 25.0kJ / m 2 , more preferably 5.0 kJ / m 2 Up to 20.0 kJ / m 2 The notched Izod impact strength of the thermoplastic composition may be 0.001 % or more. A portion or all of the thermoplastic composition may be molded. A portion or all of the surface of the molded thermoplastic composition may be surface treated. A metal coating may be bonded to at least a portion of the treated surface.

[0016] In some aspects, the thermoplastic polymer composition of the present invention may have a yellowness index (YI) that is less than that of a thermoplastic polymer composition that does not contain a polar polymer (C). The yellowness index of the thermoplastic polymer composition of the present invention may be less than 30, preferably less than 27, more preferably less than 22, or from 2 to 30, preferably from 20 to 27. The thermoplastic polymer composition may have increased white lightness (e.g., appear whiter) compared to a thermoplastic polymer composition that does not contain a polar polymer (C). Other aspects of the present invention describe methods for reducing the yellowness index of the thermoplastic polymer composition of the present invention. One method may include melt blending a thermoplastic composition comprising: (a) 30% to 79% by weight of a copolymer (A) comprising units derived from a vinyl aromatic monomer and a vinyl nitrile monomer; (b) 20% to 50% by weight of a rubber-modified thermoplastic polymer (B); (c) 1% to 15% by weight of a polar polymer (C) comprising a carboxylic acid, an alcohol, an amide, or a combination thereof; and (d) a melt processing additive.

[0017] The thermoplastic compositions of the present invention may be incorporated into articles of manufacture.

[0018] In some aspects, a metal-plated article comprising a thermoplastic composition of the present invention is described. The metal can be bonded to at least a portion of the surface of the thermoplastic composition. Non-limiting examples of metals include copper, chromium, nickel, or combinations thereof.

[0019] In other aspects of the present invention, a method for producing a thermoplastic composition of the present invention is described. A method may include melt blending 30% to 79% by weight of a copolymer (A), 20% to 50% by weight of a rubber-modified thermoplastic polymer (B), greater than 1% to 15% by weight of a polar polymer (C) and greater than 0% to 5% by weight of an optional processing additive. In some aspects, the thermoplastic composition may be molded into an article. In some cases, the article may be surface-treated by contacting the article with a chemical reagent under conditions suitable for surface-treating the article of the present invention. Non-limiting examples of the chemical reagent include a suspension of manganese oxide colloidal particles in a mineral acid mixture. The mineral acid mixture may include sulfuric acid and phosphoric acid. The surface-treated article of the present invention may be subjected to conditions suitable for bonding a metal layer to at least a portion of the treated surface to produce the metal-plated portion of the article.

[0020] Other embodiments of the present invention are discussed throughout this application.Any embodiment discussed for one aspect of the present invention is equally applicable to other aspects of the present invention, and vice versa.Every kind of embodiment described herein is understood to be an embodiment of the present invention applicable to other aspects of the present invention.It is conceivable that any embodiment or aspect discussed herein can be combined with other embodiments or aspects discussed herein and / or implemented for any method or composition of the present invention, and vice versa.In addition, composition of the present invention can be used for realizing method of the present invention.

[0021] The following include definitions of various terms and phrases used throughout this specification.

[0022] The term "treated surface" can refer to a portion of the surface of a thermoplastic composition of the present invention (including, for example, a molded thermoplastic composition) that has been exposed to, for example, a chemical agent.

[0023] The term "about" or "approximately" is defined as close as understood by one of ordinary skill in the art. In a non-limiting embodiment, these terms are defined as within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0024] The terms "wt %," "volume %," or "mole %" refer to the weight percent, volume percent, or mole percent of a component, respectively, based on the total weight, volume, or moles of the material in which the component is contained. In a non-limiting example, 10 grams of a component in 100 grams of a material refers to 10% by weight of the component.

[0025] The term "substantially" and variations thereof are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0026] When used in the claims and / or specification, the terms "inhibit" or "reduce" or "prevent" or "avoid" or any variation of these terms include any measurable decrease or complete inhibition to achieve the desired result.

[0027] When used in the claims and / or specification, the term "effective" means sufficient to achieve a desired, intended, or desired result.

[0028] When used in conjunction with any of the terms "comprising," "including," "containing," or "having" in the claims or the specification, the use of the word "a" or "an" may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one."

[0029] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”), or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or components or method steps.

[0030] The thermoplastic compositions of the present invention may "comprise or comprise," "consist essentially of," or "consist of" specific ingredients, components, compositions, etc. disclosed throughout this specification. With respect to the transition phrase "consisting essentially of," in one non-limiting aspect, a fundamental and novel property of the thermoplastic compositions of the present invention is their ability to enhance the adhesion of metal coatings to the surface of the thermoplastic composition.

[0031] Other objects, features and advantages of the present invention will become apparent from the following drawings, detailed description and examples. However, it should be understood that the drawings, detailed description and examples (although indicating specific embodiments of the present invention) are given only in an illustrative manner and are not intended to be limiting. Additionally, it is conceivable that changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from a specific embodiment may be combined with features from other embodiments. For example, features from an embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Advantages of the present invention will become apparent to those skilled in the art from the following detailed description taken with reference to the accompanying drawings.

[0033] Figure 1A and 1B are comparative thermoplastic compositions (respectively Figure 1A and 1B C10 and C11 in the present invention) and thermoplastic compositions of the present invention having different amounts of polar polymer (C) ( Figure 1A F10, F11, F13 and F14 in; and Figure 1B Graphical representation of notched Izod impact (NII) values for F15 and F16 in Figure 1.

[0034] Figure 2A and 2B are comparative thermoplastic compositions (respectively Figure 2A and 2B C10 and C11 in the present invention) and thermoplastic compositions of the present invention having different amounts of polar polymer (C) ( Figure 2A F10, F11, F13 and F14 in; and Figure 2B Graphical illustration of the Vicat softening temperature (VST) of F15 and F16).

[0035] Figure 3 is a graphical representation of (HDT) measurements for a comparative thermoplastic composition (C11) and thermoplastic compositions of the invention with different amounts of polar polymer (C) (F15 and F16).

[0036] Figure 4 is a graphic representation depicting the whiteness of ABS molded bars and molded bars of thermoplastic compositions of the present invention having different amounts of polar polymer (C).

[0037] Figure 5Scanning electron microscope (SEM) images of molded plaques of comparative thermoplastic compositions showing mineral acid pretreatment of manganese-containing colloidal particles. The manganese-containing colloid acid solution was prepared by mixing H3PO4 (219 mL / L), H2SO4 (573 mL / L or 605 mL / L), and MnO2 (60 g / L). All pretreatments were performed at 70°C. The top SEM image is an image obtained by pretreatment with 573 mL / L of H2SO4 for 10 minutes at 8000X and 2000X magnification. The second SEM image is an image obtained by pretreatment with 605 mL / L of H2SO4 for 10 minutes at 8000X and 2000X magnification. The third SEM image is an image obtained by pretreatment with 573 mL / L of H2SO4 for 20 minutes at 8000X and 2000X magnification. The bottom SEM images are images of the sample pretreated with 605 mL / L H2SO4 for 20 minutes at 8000 & 2000X magnification.

[0038] Figure 6 SEM images of molded plaques of thermoplastic compositions of the present invention with a polar polymer additive (3 wt% PE-AA) pretreated with manganese colloidal acid are shown. The manganese colloidal acid solution was prepared by mixing H3PO4 (219 mL / L), H2SO4 (573 mL / L or 605 mL / L), and MnO2 (60 g / L). All pretreatments were performed at 70°C. The top SEM image is an image obtained after pretreatment with 573 mL / L of H2SO4 for 10 minutes at 8000× and 500× magnification. The second SEM image is an image obtained after pretreatment with 605 mL / L of H2SO4 for 10 minutes at 8000× and 500× magnification. The third SEM image is an image obtained after pretreatment with 573 mL / L of H2SO4 for 20 minutes at 8000× and 500× magnification. The bottom SEM image is an image pretreated with 605 mL / L H2SO4 for 20 minutes at 8000 & 500X magnification.

[0039] Figure 7SEM images of molded test plaques of thermoplastic compositions of the present invention with polar polymer additives (10 wt% PE-AA) obtained by mixing thermoplastic compositions of the present invention with different polar polymer additives using acidic manganese colloid pretreatment. The acidic manganese colloid solution was prepared by mixing H3PO4 (219 mL / L), H2SO4 (573 mL / L or 605 mL / L), and MnO2 (60 g / L). All pretreatments were performed at 70°C. The top SEM is a 10-minute pretreatment with 573 mL / L of H2SO4. The second SEM is a 10-minute pretreatment with 605 mL / L of H2SO4. The third SEM is a 20-minute pretreatment with 573 mL / L of H2SO4. The bottom SEM is a 20-minute pretreatment with 605 mL / L of H2SO4.

[0040] Figure 8 Transmission electron microscopy (TEM) images of a comparative composition and a thermoplastic composition according to the invention with a polar polymer (C) (3 wt% PE-AA and 10 wt% PE-AA) before surface treatment are shown. The bottom TEM image shows the changes in the top surface area (skin layer) after surface treatment of the comparative composition and the composition according to the invention (with 3 wt% PE-AA). The changes are indicated by arrows.

[0041] Figure 9 is a graphical illustration of the peel strength measurements and repeatability of metallized test panels comprising a comparative sample (top panel) and thermoplastic compositions of the present invention (3 wt % (left panel) and 10 wt % PE-AA (right panel)) after hexavalent chromic acid etching.

[0042] Figure 10 is a graphical illustration of the peel strength measurements of metallized test panels comprising a comparative sample (top graph) and thermoplastic compositions of the present invention (3 wt% PE-AA (middle graph) and 10 wt% PE-AA (bottom graph)) after pretreatment with an acidic manganese colloidal solution for different times (10 and 20 minutes).

[0043] Figure 11 is a graphical illustration of the average peel force on metallized test panels comprising a comparative sample (C11) and thermoplastic compositions of the present invention (3 wt% PE-AA (F10) and 10 wt% PE-AA (F11)) after hexavalent chromic acid etching.

[0044] Figure 12 is a graphical illustration of the average peel force on metallized test panels comprising a comparative sample (C10) and inventive thermoplastic compositions (3 wt% PE-AA (F10) and 10 wt% PE-AA (F11)) after pretreatment with acidic manganese colloid at different concentrations and times.

[0045] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings.The drawings may not be drawn to scale. DETAILED DESCRIPTION Detailed description of the invention

[0046] A solution has been found for at least one of the problems associated with thermoplastic compositions to be metal plated and / or reducing the yellowness index of such compositions. In one aspect, the present invention may comprise a thermoplastic composition comprising from greater than 1% to 15% by weight of a polar polymer (C) comprising a carboxylic acid, an alcohol, an amide, or a combination thereof. Advantageously, the polar polymer (C), together with the aforementioned copolymer (A) and the aforementioned thermoplastic polymer (B), may allow the thermoplastic composition of the present invention to be surface treated for metal plating without the need for etching using hexavalent chromium compounds. Advantageously, the thermoplastic composition in molded form has suitable impact strength, thereby allowing such polymer articles to be used to prepare metal-plated articles suitable for industrial applications having excellent impact strength for a variety of desired materials. The thermoplastic compounds of the present invention also have improved yellowness index (YI) and / or whiteness compared to thermoplastic compounds that do not contain the polar polymer (C).

[0047] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections. A. Thermoplastic Compositions

[0048] The thermoplastic composition of the present invention may comprise (a) 30 to 79 wt% of the copolymer (A), (b) 20 to 50 wt% of the rubber modified thermoplastic polymer (B), (c) greater than 1 to 15 wt%, preferably 2 to 13 wt%, more preferably 3 to 10 wt% of the polar polymer (C), and (d) greater than 0 to 5 wt% of an optional processing additive. The thermoplastic composition may be molded or formed into a polymer article. The polymer article may have suitable impact properties necessary for certain applications, including door handles, brackets, lamp bodies, company logos and other decorative parts used in the automotive industry, household appliances, electronic devices, furniture, sanitary equipment and others. For example, the polymer article may have a ≥3.0 kJ / m 2 and ≤30.0kJ / m 2 or any range or value therebetween. For example, the notched Izod impact strength may be 3.0 kJ / m when measured according to ISO 180 / 1A. 2 4.0kJ / m 2 , 5kJ / m 2 、10kJ / m 2、15kJ / m 2 , 20kJ / m 2 , 25kJ / m 2 、30kJ / m 2 or ≥3.0 kJ / m 2 and ≤30.0kJ / m 2 , ≥4.0kJ / m 2 and ≤25.0kJ / m 2 , ≥5.0kJ / m 2 and ≤20.0kJ / m 2 . The thermoplastic composition of the present invention may have a yellowness index of 2 to 30, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 or any range or value therebetween. The yellowness index can be measured using known methods. A non-limiting example of a yellowness index method is ASTM E313-20. The thermoplastic polymer composition may have an increased white brightness (e.g., appear whiter) compared to a thermoplastic polymer composition that does not contain a polar polymer (C). The white brightness value may have a range of greater than 85, preferably 85 to 92, more preferably 86 to 90. White brightness can be measured using known methods. A non-limiting example of determining white brightness is CIELAB color space analysis. 1. Copolymer (A)

[0049] Copolymer (A) may comprise polymer units derived from (i) a vinyl aromatic monomer and (ii) a vinyl nitrile monomer. Copolymer (A) may be present in an amount greater than or equal to 30.0 wt % and less than or equal to 79.0 wt %, based on the total weight of the thermoplastic composition, or any range or value therebetween. For example, 30 wt %, 35 wt %, 40 wt %, 45 wt %, 50 wt %, 55 wt %, 60 wt %, 65 wt %, 70 wt %, 75 wt %, and 79 wt %, or ≥36.0 wt % and ≤78.0 wt %, ≥60.0 wt % and ≤75.0 wt %, and ≥62.0 wt % and ≤74.0 wt %, relative to the total weight of the thermoplastic polymer composition.

[0050] In some embodiments of the present invention, copolymer (A) has: ≥22.0 wt % and ≤38.0 wt % or any range or value therebetween of polymer units derived from vinyl nitrile monomers, relative to the total weight of copolymer (A). For example, 22 wt %, 23 wt %, 24 wt %, 25 wt %, 26 wt %, 27 wt %, 28 wt %, 29 wt %, 30 wt %, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35 wt %, 36 wt %, 37 wt %, 38 wt % or ≥25.0 wt % and ≤35.0 wt %, ≥30.0 wt % and ≤35.0 wt % of polymer units derived from vinyl nitrile monomers, relative to the total weight of copolymer (A). In a preferred aspect, copolymer (A) may have ≥30.0 wt % and ≤35.0 wt % of polymer units derived from vinyl nitrile monomers, relative to the total weight of copolymer (A).

[0051] The limiting examples of vinyl aromatic monomers can include styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-hydroxystyrene, methoxystyrene or any combination thereof. The limiting examples of vinyl nitrile monomers include acrylonitrile, α-chloroacrylonitrile, methacrylonitrile, ethacrylonitrile or any combination thereof. In a preferred aspect, the vinyl aromatic monomer is styrene and the vinyl nitrile monomer is acrylonitrile. Preferably, the multipolymer (A) is a styrene acrylonitrile (SAN) copolymer. In a preferred embodiment of the present invention, the multipolymer (A) is a styrene acrylonitrile copolymer with ≥30.0 wt % and ≤35.0 wt % of polymer units derived from acrylonitrile.

[0052] In some aspects of the present invention, multipolymer (A) can be, for example, a terpolymer comprising polymer units derived from (i) vinyl aromatic monomers, (ii) vinyl nitrile monomers and (iii) (meth) acrylic acid monomers. The vinyl aromatic monomers and vinyl nitrile monomers can be selected from monomers as defined above. Non-limiting examples of (meth) acrylic acid monomers can include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate and decyl methacrylate. Preferably, the (meth) acrylic acid monomer can be methyl methacrylate (MMA). Therefore, the multipolymer (A) can be a terpolymer comprising polymer units derived from styrene / acrylonitrile / methyl methacrylate or derived from α-methylstyrene / acrylonitrile / methyl methacrylate.

[0053] The copolymer (A) may have a suitable molecular weight and melt flow rate. The average molecular weight (Mw) of the copolymer (A) may be ≥50,000 g / mol and ≤100,000 g / mol or any range or value therebetween. For example, 50,000 g / mol, 55,000 g / mol, 60,000 g / mol, 65,000 g / mol, 70,000 g / mol, 75,000 g / mol, 80,000 g / mol, 85,000 g / mol, 90,000 g / mol, 95,000 g / mol, 100,000 g / mol, or ≥80,000 g / mol and ≤100,000 g / mol, ≥85,000 g / mol and ≤98,000 g / mol, ≥93,000 g / mol and ≤97,000 g / mol, as determined by gel permeation chromatography according to ASTM D5296-11 using a polystyrene-based calibration and tetrahydrofuran (THF) as solvent.

[0054] The melt flow rate of copolymer (A) can be ≥7.0 g / 10 min and ≤20.0 g / 10 min, or any value or range therebetween, as measured at 230° C. and a load of 1.2 kg according to ISO 1133 (2005). For example, 7.0 g / 10 min, 8.0 g / 10 min, 9 g / 10 min, 10 g / 10 min, 11 g / 10 min, 12 g / 10 min, 13 g / 10 min, 14 g / 10 min, 15 g / 10 min, 16 g / 10 min, 17 g / 10 min, 18 g / 10 min, 19 g / 10 min, 20 g / 10 min, or ≥8.0 g / 10 min and ≤15.0 g / 10 min, ≥9.0 g / 10 min and ≤11.0 g / 10 min. If the melt flow rate of copolymer (A) is higher than these rates, the overall impact properties of the thermoplastic polymer composition may be adversely affected, while if the melt flow rate of copolymer (A) is lower than these rates, the desired flow properties of the thermoplastic polymer cannot be achieved, affecting the melt processability of the thermoplastic polymer. 2. Rubber modified thermoplastic polymer (B)

[0055] In one aspect of the present invention, the thermoplastic polymer composition may include a suitable amount of a rubber component. The rubber-modified thermoplastic polymer (B) may be referred to as a high rubber graft or "HRG". The thermoplastic polymer composition may include at least 26.0 wt% of the rubber-modified thermoplastic polymer (B). In some aspects, the thermoplastic polymer composition may include a rubber-modified thermoplastic polymer (B) in an amount greater than or equal to 20.0 wt% and less than or equal to 50.0 wt% or any range or value therebetween. For example, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, or ≥30.0 wt% and ≤45.0 wt%, ≥20.0 wt% and ≤30.0 wt%, ≥22.0 wt% and ≤24.0 wt%, relative to the total weight of the thermoplastic polymer composition.

[0056] In some aspects, the thermoplastic polymer composition may include an amount of copolymer (A) of ≤79.0 wt %, while the amount of rubber-modified thermoplastic polymer (B) is ≥20.0 wt %, relative to the total weight of the thermoplastic polymer composition. The rubber-modified thermoplastic polymer (B) may include (i) a polymer rubber, (ii) a thermoplastic copolymer (D) grafted onto the polymer rubber. In some embodiments of the present invention, the polymer rubber may be a discontinuous elastomeric phase dispersed in a continuous rigid thermoplastic phase comprising the thermoplastic copolymer (D), wherein at least a portion of the rigid thermoplastic phase is grafted onto the discontinuous elastomeric phase. The polymer rubber may have a suitable particle-based morphology. For example, the polymer rubber may be in the form of rubber particles having a broad, unimodal particle size distribution. For example, the polymer rubber may have an average particle size of ≥50 nanometers (nm) and ≤1000 nanometers (nm), and any range or value therebetween. In a preferred aspect, the polymer rubber can have an average particle size of ≥200 nanometers (nm) and ≤500 nanometers (nm).

[0057] The rubber-modified thermoplastic polymer (B) may contain a suitable amount of the polymer rubber. The rubber-modified thermoplastic polymer (B) may contain a polymer rubber content of ≥55.0 wt % and ≤75.0 wt % or any value or range therebetween. For example, the polymer rubber content may be ≥55.0 wt % and ≤75.0 wt %, ≥57.0 wt % and ≤70.0 wt %, ≥60.0 wt % and ≤65.0 wt %, ≥60.0 wt % and ≤63.0 wt %, relative to the total weight of the rubber-modified thermoplastic polymer (B). The polymer rubber content can be determined, for example, using Fourier transform infrared microspectroscopy (FT-IR). Therefore, the rubber-modified thermoplastic polymer (B) may have a grafted thermoplastic copolymer (D) content of ≥25.0 wt % and ≤45.0 wt % or any range or value therebetween. For example, the content of the grafted thermoplastic copolymer (D) can be 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or ≥25.0 wt% and ≤45.0 wt%, ≥30.0 wt% and ≤43.0 wt%, ≥35.0 wt% and ≤40.0 wt%, ≥37.0 wt% and ≤40.0 wt%, relative to the total weight of the rubber-modified thermoplastic polymer (B). In some aspects of the present invention, the rubber-modified thermoplastic polymer (B) may have a polymer rubber content of ≥55.0 wt. % and ≤75.0 wt. %, ≥57.0 wt. % and ≤70.0 wt. %, ≥60.0 wt. % and ≤65.0 wt. %, ≥60.0 wt. % and ≤63.0 wt. %, and a grafted thermoplastic copolymer (D) content of ≥25.0 wt. % and ≤45.0 wt. %, ≥30.0 wt. % and ≤43.0 wt. %, ≥35.0 wt. % and ≤40.0 wt. %, ≥37.0 wt. % and ≤40.0 wt. %, relative to the total weight of the rubber-modified thermoplastic polymer (B). More preferably, the rubber-modified thermoplastic polymer (B) may have a polymer rubber content of ≥60.0 wt.-% and ≤65.0 wt.-%, more preferably ≥60.0 wt.-% and ≤63.0 wt.-%, and a grafted thermoplastic copolymer (D) content of ≥35.0 wt.-% and ≤40.0 wt.-%, preferably ≥37.0 wt.-% and ≤40.0 wt.-%, relative to the total weight of the rubber-modified thermoplastic polymer (B).

[0058] The polymer rubber may include polymer units derived from a conjugated diene. The non-limiting examples of the conjugated diene include 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 is 1,3-butadiene. In some aspects of the present invention, the conjugated diene may be 1,3-butadiene and the polymer rubber may be polybutadiene.

[0059] The rubber modified thermoplastic polymer (B) may include a grafted thermoplastic copolymer (D) grafted onto the polymer rubber. The grafted thermoplastic copolymer (D) may include polymer units derived from (i) a vinyl aromatic monomer, (ii) a vinyl nitrile monomer, and (iii) an optional (meth) acrylic monomer. Non-limiting examples of vinyl aromatic monomers include styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinyl xylene, butylstyrene, p-hydroxystyrene, methoxystyrene, and any combination thereof. Non-limiting examples of vinyl nitrile monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, and any combination thereof. Non-limiting examples of (meth) acrylic monomers include methyl methacrylate, ethyl methacrylate, and propyl methacrylate. In a preferred aspect, the vinyl aromatic monomer is styrene, the vinyl nitrile monomer is acrylonitrile, and the optional (meth) acrylic monomer is MMA.

[0060] In some embodiments, the grafted thermoplastic copolymer (D) may comprise polymer units derived from styrene, methyl methacrylate, and acrylonitrile, and the polymer rubber is a polybutadiene rubber comprising polymer units derived from 1,3-butadiene. In some aspects, the rubber-modified thermoplastic polymer (B) is a polybutadiene rubber grafted with a copolymer comprising polymer units derived from styrene, MMA, and acrylonitrile. 3. Polar polymer (C)

[0061] The polar polymer (C) may comprise carboxylic acid, alcohol and / or amide or any combination thereof and be present in the thermoplastic polymer composition in a suitable amount. For example, the thermoplastic composition may comprise ≥1.0 wt % and ≤15.0 wt % or any range or value therebetween. For example, 1 wt %, 5 wt %, 10 wt %, 15 wt % or ≥1.0 wt % and ≤13.0 wt %, ≥3.0 wt % and ≤10.0 wt %, relative to the gross weight of the thermoplastic polymer composition. Non-limiting examples of polar polymers (C) include ethylene-acrylic acid copolymers, polyvinyl pyrrolidone (PVP) polymers, polyvinyl alcohol (PVA) polymers or blends thereof. The representative structures of these compounds are shown in Scheme 1, where in EAA, x=1.6x10 2 Up to 8x10 2 and y = 4.8 to 35; in PVA, n = 1.1x10 2 to 5.5x10 2 In PVP, n = 45 to 2.2 x 10 2 . Plan I

[0062] The ethylene-acrylic acid copolymer can include 1% to 10% by weight or any range or numerical value therebetween of acrylic acid, based on the gross weight of the ethylene-acrylic acid copolymer. For example, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 1% to 10% by weight, 2% to 8% by weight, 3% to 7% by weight of acrylic acid, based on the gross weight of the ethylene-acrylic acid copolymer. The polyvinyl alcohol polymer can include 70% to 80% by weight or any range or numerical value therebetween of the hydrolyzed polyvinyl acetate, based on the gross weight of the polyvinyl alcohol. For example, 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight, 76% by weight, 77% by weight, 78% by weight, 79% by weight, 80% by weight or 70% to 80% by weight, or 73% to 78% by weight, based on the gross weight of the polyvinyl alcohol.

[0063] Polar polymer (C) can be oligomeric or have low molecular weight.The weight average molecular weight of polar polymer (C) can be 5,000g / mol to 25,000g / mol or any range therebetween.For example, 5,000g / mol, 10,000g / mol, 15,000g / mol, 20,000g / mol, 25,000g / mol, or ≥5,000g / mol and ≤18,000g / mol and ≥10,000g / mol, ≤18,000g / mol and ≥12,000g / mol and ≤18,000g / mol.For example, the determination of molecular weight is carried out according to ASTM D5296-11 using a polystyrene-based calibration and using gel permeation chromatography with tetrahydrofuran (THF) as solvent. 4. Melt processing additives

[0064] The thermoplastic polymer composition may contain optional processing additives in an amount greater than 0.0 wt % and less than 5.0 wt % or any range or value therebetween, based on the total weight of the thermoplastic composition, for example, 0.1 wt %, 1 wt %, 1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, 5 wt %, or greater than 1.0 wt % and less than 5.0 wt %, greater than 1.0 wt % and less than 2.0 wt %, preferably greater than 1.5 wt % and less than 2.5 wt %, based on the total weight of the thermoplastic polymer composition.

[0065] Non-limiting examples of processing additives may include magnesium oxide (MgO), silicone fluid, ethylene bis (stearamide) wax (EBS wax), magnesium stearate, or a mixture thereof. In a preferred aspect, a mixture of magnesium oxide (MgO), silicone oil, EBS wax, and magnesium stearate may be used. In some embodiments of the present invention, the MgO may be present in an amount of ≥0.01 wt % and ≤0.1 wt %, or ≥0.01 wt % and ≤0.05 wt %, relative to the gross weight of the thermoplastic polymer composition. In some embodiments of the present invention, the silicone oil may be present, for example, in an amount of ≥0.05 wt % and ≤0.5 wt %, or ≥0.1 wt % and ≤0.5 wt %, relative to the gross weight of the thermoplastic polymer composition. In some embodiments of the present invention, the EBS wax may be present in an amount of ≥0.5 wt % and ≤2.0 wt %, or ≥0.8 wt % and ≤1.5 wt %, relative to the gross weight of the thermoplastic polymer composition. In some embodiments of the present invention, the magnesium stearate may be present in an amount of ≥ 0.05 wt% and ≤ 0.5 wt%, or ≥ 0.1 wt% and ≤ 0.4 wt%, relative to the total weight of the thermoplastic polymer composition. 5. Other additives

[0066] Depending on the intended application, the thermoplastic composition may contain other additives. For example, the thermoplastic composition may contain additives in an amount of 0 to 20 wt %, preferably >0 and <20 wt % or 0.5 to <20 wt %, further preferably 0.5 to 15 wt %, further preferably 0.5 to 12 wt % or 0.5 to 8 wt %, based on the total weight of the layer, wherein the sum of the polymer and the additives may preferably be 100 wt %, based on the total weight of the layer.

[0067] Non-limiting examples of additives that may be used include anti-fog agents (e.g., glycerides), antioxidants, heat stabilizers, hindered amine light stabilizers, flow modifiers, UV absorbers, impact modifiers, coupling agents, colorants, and the like, or any combination thereof.

[0068] The coupling agent may comprise maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or a combination comprising at least one of the foregoing. Non-limiting examples of commercially available coupling agents include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or a combination comprising at least one of the foregoing. 3150 maleic anhydride grafted polypropylene, from DuPont (USA) P613 maleic anhydride grafted polypropylene, and from Addcomp (Germany) 20097Maleic anhydride grafted polypropylene homopolymer. The polymer matrix can comprise, based on the total weight of the polymer matrix, 0.1 to 5 weight percent of a coupling agent, or greater than or substantially equal to any one of the following, or between any two of the following: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and 5.0 weight percent.

[0069] Non-limiting examples of antioxidants include sterically hindered phenolic compounds, aromatic amines, phosphite compounds, carbon black, etc. Non-limiting examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol (CAS No. 128-37-0), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No. 6683-19-8), octadecyl 3-(3',5'-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No. 2082-79-3), 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (CAS No. 1709-70-2), 2,2'-thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No. No.41484-35-9), calcium bis(ethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate) (CAS No.65140-91-2), 1,3,5-tris(3',5'-di-tert-butyl-4-hydroxybenzyl) isocyanurate (CAS No.27676-62-6), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (CAS No.40601-76-1), ethylene bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate] (CAS No.32509-66-3), 4,4'-thiobis(2-tert-butyl-5-methylphenol) (CAS No.96-69-5), 2,2'-methylenebis-(6-(1-methyl-cyclohexyl)-p-cresol) (CAS No.77-62-3), 3,3'-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-N,N'-hexamethylenebispropionamide (CAS No.23128-74-7), 2,5,7,8-tetramethyl-2-(4',8',12'-trimethyltridecyl)-chroman-6-ol (CAS No.10191-41-0), 2,2-ethylenebis(4,6-di-tert-butylphenol) (CAS No.35958-30-6), 1,1,3-tris(2-methyl-4-hydroxy-5'-tert-butylphenyl)butane (CAS No.1843-03-4), 3,9-bis(1,1-dimethyl-2-(β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (CAS No.90498-90-1), 1,6-hexanediyl-bis(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)propionate) (CAS No.35074-77-2), 2,6-di-tert-butyl-4-nonylphenol (CAS No.4306-88-1), 4,4'-butylenebis(6-tert-butyl-3-methylphenol (CAS No.85-60-9); 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (CAS No.119-47-1); triethylene glycol bis-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS No.36443-68-2), 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionic acid C. 13 to C 15 Mixture of linear and branched alkyl esters (CAS No. 17090-93-0), 2,2'-thiobis(6-tert-butyl-p-cresol) (CAS No. 90-66-4), diethyl-(3,5-di-tert-butyl-4-hydroxybenzyl) phosphate (CAS No. 976-56-7), 4,6-bis(octylthiomethyl)-o-cresol (CAS No. 110553-27-0), phenylpropionic acid, octyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No. 125643-61-0), 1,1,3-tris[2-methyl-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-5-tert-butylphenyl]butane (CAS No. 180002-86-2), mixed styrenated phenols (CAS No. 61788-44-1), butylated and octylated phenol (CAS No. 68610-06-0), butylated reaction products of p-cresol and dicyclopentadiene (CAS No. 68610-51-5).

[0070] Non-limiting examples of phosphite antioxidants include one of the following: tris(2,4-di-tert-butylphenyl)phosphite (CAS No. 31570-04-4), tris(2,4-di-tert-butylphenyl)phosphate (CAS No. 95906-11-9), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (CAS No. 26741-53-7); and tetrakis(2,4-dibutylphenyl)-4,4'-biphenylene diphosphite (CAS No. 119345-01-6), and bis(2,4-dicumylphenyl)pentaerythritol diphosphite (CAS No. 154862-43-8).

[0071] Non-limiting examples of UV stabilizers include hindered amine light stabilizers, hydroxybenzophenones, hydroxyphenylbenzotriazoles, cyanoacrylates, oxanilides, hydroxyphenyltriazines, and combinations thereof. Non-limiting examples of hindered amine light stabilizers include polymers of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol (CAS No. 65447-77-0); poly[[6-((1,1,3,3-tetramethylbutyl)amino)-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[2,2,6,6-tetramethyl-4-piperidinyl)imino]] (CAS No. 70624-18-9); and 1,5,8,12-tetrakis[4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane (CAS No.106990-43-6).

[0072] Non-limiting examples of heat stabilizers include phenothiazine, p-methoxyphenol, cresol, benzhydrol, 2-methoxy-hydroquinone, 2,5-di-tert-butylquinone, diisopropylamine and distearyl thiodipropionate (CAS No. 693-36-7). Distearyl thiodipropionate is sold as PS 820 (BASF, Germany).

[0073] Non-limiting examples of antioxidants include mixtures of at least two of the following: 1,3,5-Trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene sold by BASF 1330 (Germany) and Tris[2,4-bis(2-methyl-2-propane)phenyl]phosphite sold by BASF 168 (Germany) and Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate sold under the trade name Chimassorb 1010 (BASF, Germany), and 1,5,8,12-tetrakis[4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane sold under the trade name Chimassorb 119 (BASF, Germany).

[0074] Other additives may include stabilizers, UV absorbers, impact modifiers, and crosslinking agents. Non-limiting examples of stabilizers may include commercially available BASF B225. In a further aspect, pure polypropylene can be introduced as an optional additive. Non-limiting examples of UV absorbers include 4-substituted-2-hydroxybenzophenones and their derivatives, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their derivatives, 2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives, or combinations thereof. Non-limiting examples of impact modifiers include elastomers / soft blocks dissolved in matrix-forming monomers, such as bulk HIPS, bulk ABS, reactor-modified PP, Lomod, Lexan EXL and / or the like; thermoplastic elastomers dispersed in a matrix material by compounding, such as diblock, triblock and multiblock copolymers, (functionalized) olefin (co)polymers and / or the like; predetermined core-shell (base-graft) particles distributed in a matrix material by compounding, such as MBS, ABS-HRG, AA, ASA-XTW, SWIM and / or the like; or combinations thereof. Non-limiting examples of cross-linking agents include divinylbenzene, benzoyl peroxide, alkylene glycol di(meth)acrylates such as ethylene glycol diacrylate and / or the like, alkylene triol tri(meth)acrylates, polyester di(meth)acrylates, bisacrylamide, triallyl cyanurate, triallyl isocyanurate, allyl (meth)acrylate, diallyl maleate, diallyl fumarate, diallyl adipate, triallyl citrate, triallyl phosphate, or combinations thereof. B. Method of making the thermoplastic composition

[0075] The method for producing the thermoplastic composition may involve melt blending the copolymer (A), modified rubber polymer (B), polar polymer (C) and optional processing additive (D) described in Section A to form an extruded composition. The extruded composition can be further processed to form a molded article. For example, a combination of extrusion and injection molding can be used to form the molded thermoplastic composition of the present invention. In one aspect, the copolymer (A), the rubber modified thermoplastic polymer (B), the polar polymer (C) and the optional additive mixture can be introduced into an extruder and extruded to form an extruded form. The form can be any form, such as pellets, spheres or the like. The extruded form can be subjected to conditions suitable for producing molded thermoplastic compositions. For example, the thermoplastic pellets of the present invention can be injection molded into strips, sheets or some form. The injection molding temperature can be ≥210.0°C and ≤250.0°C, or any range or value therebetween. For example, the injection molding temperature can be 210° C., 220° C., 230° C., 240° C., 250° C., or ≥215.0° C. and ≤240.0° C., and ≥220° C. and ≤230° C., or any range or value therebetween. An injection molding speed of ≥10.0 mm / sec and ≤40.0 mm / sec, or any range or value therebetween, can be utilized. For example, the injection molding speed can be 10 mm / sec, 15 mm / sec, 20 mm / sec, 25 mm / sec, 30 mm / sec, 35 mm / sec, 40 mm / sec, or ≥15 mm / sec and ≤35.0 mm / sec, ≥25.0 mm / sec and ≤30.0 mm / sec, or any value or range therebetween. In some embodiments of the present invention, 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 the injection molding speed is 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.

[0076] The method may include physically blending the ingredients before introducing them into the extruder hopper. For example, in some embodiments of the present invention, before loading into the hopper, pellets of the polar polymer (C) and the copolymer (A) may be premixed in a container to obtain a group of uniformly mixed pellets, which are then introduced into the hopper together with a pre-blend comprising the rubber-modified thermoplastic polymer (B) and the optional processing additive. In some embodiments, the physically mixed formulation may be melt blended once introduced into the extruder through the hopper. For example, melt blending is performed in a 10-barrel Coperion ZSK-26mm co-rotating twin-screw extruder with an L / D ratio of 40:1. The extrusion conditions may be performed under suitable torque, under specific mechanical energy, under a specific RPM, or a combination thereof. The extrusion torque may be ≥30.0% and ≤75.0%, preferably ≥40.0% and ≤70.0%, more preferably ≥50.0% and ≤65.0%. The specific mechanical energy may be ≥0.10 kWh / t and ≤0.25 kWh / t, preferably ≥0.12 kWh / t and ≤0.22 kWh / t; and the extrusion screw revolutions per minute (RPM) may be ≥170 and ≤260. In some aspects, the material throughput may be adjusted to be maintained at ≥8.0 Kg / h and ≤30.0 Kg / h, ≥10 Kg / h and ≤25.0 Kg / h, wherein the specific mechanical energy (SME) is 0.15 kWh / t to 0.22 kWh / t, and the screw RPM is 250. C. Surface treated polymer products

[0077] In some embodiments of the present invention, the thermoplastic composition of the present invention may be surface treated. The surface treatment may include contacting at least a portion of the thermoplastic composition of the present invention (e.g., a molded thermoplastic composition) with a chemical agent for a sufficient period of time (e.g., ≥5.0 minutes and ≤30.0 minutes, preferably ≥10.0 minutes and ≤20.0 minutes, preferably ≥15.0 minutes and ≤20.0 minutes) to form a surface-treated thermoplastic composition. The contact temperature range may be 60°C to 80°C or ≥60.0°C to ≤80.0°C, preferably ≥65.0°C to ≤75.0°C. In some embodiments, the thermoplastic composition of the present invention may be contacted with the chemical agent for any period of time between ≥15.0 minutes and ≤20.0 minutes, and at a temperature of ≥65.0°C and ≤75.0°C. The surface-treated polymer article may have suitable surface polarity while retaining desired impact strength. The properties of surface polarity and impact strength can be attributed to a purposeful combination of process parameters of suitable polymer article, suitable chemical agent selection, and suitable contact / exposure temperature and time period.

[0078] Advantageously, the surface-treated polymer article can be produced without the need for a hexavalent chromium compound, thereby avoiding the shortcomings associated with conventional etching processes using hexavalent chromium compounds. The polymer article can be contacted with a chemical reagent for a suitable period of time to ensure the introduction of desired surface roughness. For example, if the polymer article is in contact with the chemical reagent for an excessively long time (e.g., greater than 30 minutes), the surface of the polymer article may be damaged, and if the polymer article is in contact with the chemical reagent for an excessively short time (e.g., less than 5 minutes), the surface morphology of the polymer article is not sufficiently changed to allow the surface-treated polymer article to adhere to the metal layer. The chemical reagent can be a suspension of sulfuric acid solution (70.0 volume %) of manganese oxide colloidal particles suspended in a mineral acid mixture, potassium permanganate solution (6.5 volume %), or any combination thereof. In some aspects, the chemical reagent can be a colloidal suspension comprising manganese oxide colloidal particles suspended in a mineral acid mixture of sulfuric acid and phosphoric acid. For example, for 1 liter of solution, the manganese oxide colloidal particles may be present in an amount of ≥50.0 g / L and ≤70.0 g / L, preferably ≥55.0 g / L and ≤65.0 g / L, phosphoric acid may be 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 sulfuric acid may be present in an amount of ≥560.0 mL / L and ≤580.0 mL / L, preferably ≥570.0 mL / L and ≤575.0 mL / L. The chemical reagent may comprise sulfuric acid (H2SO4) having a molar concentration of ≥8.0 M and ≤14.0 M, preferably ≥9.0 M and ≤12.0 M, and / or phosphoric acid having a molar concentration of ≥2.0 M and ≤6.0 M, preferably ≥3.0 M and ≤5.0 M.

[0079] The surface-treated thermoplastic composition of the present invention can retain the impact properties of the polymer article even after surface treatment with a chemical agent. For example, the surface-treated polymer article can have a notched Izod impact strength of 3 kJ / m when measured according to ISO 180 / 1A. 2 Up to 30kJ / m 2 , or 3 kJ / m 2 , 5kJ / m 2 、10kJ / m 2 、15kJ / m 2 , 20kJ / m 2 , 25kJ / m 2 、30kJ / m 2 , or ≥4.0kJ / m 2 and ≤25.0kJ / m 2 , ≥5.0kJ / m 2 and ≤20.0kJ / m 2, or any range or value therebetween. In one aspect, a thermoplastic composition comprising 30 to 70 wt% of a copolymer SAN (copolymer (A)), 20 to 50 wt% of ABS (copolymer (B)), 1 to 5 wt% of an ethylene-acrylic acid copolymer (polar polymer (C)) has a thermal conductivity of 17 kJ / m 2 Up to 25kJ / m 2 Notched Izod impact strength. D. Metal-Coated Thermoplastic Compositions

[0080] In one aspect of the present invention, the thermoplastic composition of the present invention can be metal-plated. The metal-plated thermoplastic composition can have a metal layer attached to a portion of the surface-treated thermoplastic composition. The metal layer can have a peel strength of ≥0.14 N / mm to 0.35 N / mm, or 0.14 N / mm, 0.16 N / mm, 0.2 N / mm, 0.3 N / mm, 0.34 N / mm, or ≥0.14 N / mm and ≤2.0 N / mm, ≥0.16 N / mm and ≤2.0 N / mm, ≥0.2 N / mm and ≤1.5 N / mm, ≥0.3 N / mm and ≤1.5 N / mm, or any range or value therebetween, as determined according to ASTM B 533-85 (2004).

[0081] The metal-plated thermoplastic compositions of the present invention can be produced by known metal plating techniques. For example, a combination of electroless plating and electroplating can be used to metal plate the thermoplastic compositions of the present invention. In one aspect, the surface-treated thermoplastic composition can be subjected to a chemical treatment to produce a metal-plated precursor material. The metal-plated precursor article can be contacted with a metal electrolyte solution at any applied current (e.g., ≥1.0 amps and ≤4.0 amps, and for a period of ≥5 minutes and ≤30 minutes) to produce a metal-plated article.

[0082] Electroless plating may include the following steps: (i) sensitizing the surface-treated thermoplastic composition with a suitable sensitizing solution (e.g., SnCl2 / HCl solution), followed by activation with an activation solution (e.g., PdCl2 / HCl solution) to form an activated article, and (ii) thereafter treating the activated article with sodium dihydrogen phosphate (NaH2PO4) and an electroless plating solution to obtain a precursor article. A non-limiting example of an electroless plating solution may include CuSO4.5H2O (15 g / L), NaKC4H4O6.4H2O (30 g / L), HCHO (100 mL / L), and NaOH (4 g / L). Alternatively, the electroless plating solution may include NiSO4.6H2O (15 g / L), NaKC4H4O6.4H2O (30 g / L), HCHO (100 mL / L), and NaOH (4 g / L). The metal electrolyte can be nickel sulfate, copper sulfate, an aluminum salt (such as aluminum chloride or aluminum sulfate), a zinc-based salt (such as zinc sulfate or zinc chloride), a silver salt (such as silver sulfate or silver chloride), or a mixture of a zinc salt and a silver salt. The chemical plating process can result in the formation of a metal-plated thermoplastic composition. The metal-plated thermoplastic composition of the present invention can have the appropriate conductivity required for the electroplating process. The metal layer can be 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 metal alloy-based layer, preferably the metal layer is a copper-based layer. The metal alloy can be selected from brass. The metal-plated thermoplastic composition can be used for door handles, brackets, lamp bodies, company logos and many other decorative parts used in the automotive industry, household appliances, electronic devices, furniture, sanitary equipment, etc. E. Manufactured products

[0083] The thermoplastic composition of the present invention can be formed into an article (e.g., an extrusion molded article, an injection molded article, a compression molded article, a rotational molded article, a blow molded article, an injection blow molded article, a 3D printed article, a thermoformed article, a foamed article, or a cast film) that is not surface treated and / or does not have a metal coating, and is included in or is an article of manufacture. Non-limiting examples of articles of manufacture include vehicle exterior and / or interior parts, train exterior and / or interior parts, aircraft exterior and / or interior parts, building exterior and / or interior parts, electrical equipment parts, electronic equipment parts, industrial equipment parts, medical packaging films and / or components, medical trays, blister packs, medical component containers, food packaging films, or food containers. Example

[0084] The present invention will be described in detail by specific embodiment.The following examples are only for illustrative purposes and are not intended to limit the present invention in any way. Those skilled in the art will readily recognize various non-critical parameters, which can be changed or modified to produce substantially the same result. Example 1 (Preparation of Thermoplastic Compositions of the Present Invention and Comparative Thermoplastic Compositions)

[0085] All formulations were prepared on a 4 Kg scale. When the mixture of the pellets (copolymer (A)) and the polar polymer (C) is added through the main hopper / feeder, the butadiene rubber (CYCOLAC TM A pre-blend of INP 362 (a rubber-modified thermoplastic polymer (B)) along with EBX wax, magnesium stearate, magnesium oxide, and a processing additive of silicone fluid was fed via a side feeder (see Table 1). Each formulation contained a different type of polar polymer (C), such as ethylene-acrylic acid copolymer, polyvinyl pyrrolidone polymer, or polyvinyl alcohol polymer, at varying loadings. The details of the formulations are listed in Table 1. A comparative thermoplastic sample was prepared by mixing equal amounts of both SAN556 and SAN581 (copolymer (A)) without any polar polymer additives and melt-blending them with HRG (rubber-modified thermoplastic polymer (B)) and the processing additive. The inventive thermoplastic composition was prepared in the same manner as the comparative sample, but pellets of the polar polymer (C) were pre-mixed with the SAN mixture in a plastic container before loading into the main hopper to produce a uniformly mixed pellet. Similarly, the pre-blend was obtained in the form of a uniform powder by dry-blending the HRG and processing additive in a separate plastic container. In each formulation, equal amounts of two types of SAN (556, 581), polyethylene-acrylic acid copolymer (PE-AA) containing 6.9 wt% acrylic acid (Nucrel 30707), and polyvinyl alcohol (PVOH) polymer containing 80% hydrolyzed polyvinyl acetate were used. Table 1 *ETC-C10 and C-11 use equal amounts of SAN556 and SAN581; **ETC-F16 uses SAN581; ***ETC-P15 uses SAN556, while F10-F14 use equal amounts of both types of SAN (556 and 581).

[0086] The physically mixed formulations were melt blended in a 10-barrel Coperion ZSK-26 mm co-rotating twin-screw extruder with a 40:1 L / D ratio. The material throughput during extrusion was adjusted to maintain the specific mechanical energy (SME) between 0.172 and 0.185 while maintaining the screw RPM at 250. The temperature profile used during extrusion and the processing parameters used in this study are shown in Tables 2 and 3, respectively. Table 2 lists the temperature profile used during extrusion of the comparative thermoplastic composition (control) and the formulated thermoplastic composition of the present invention. Table 3 lists the extrusion details. Table 2 barrel <![CDATA[1 st ]]> <![CDATA[2 nd ]]> <![CDATA[3 rd ]]> <![CDATA[4 th ]]> <![CDATA[5 th ]]> <![CDATA[6 th ]]> <![CDATA[7 th ]]> <![CDATA[8 th ]]> <![CDATA[9 th ]]> <![CDATA[10 th ]]> Temperature 170 204 225 230 240 240 240 240 240 245 Table 3 coding Torque (%) RPM Throughput (Kg / h) SME (kWh / t) C10 48-51 250 14 0.172-0.178 F10 47-49 250 14 0.171-0.179 F11 40-43 250 13 0.172-0.177 F13 48-52 250 16 0.175-0.179 F14 57-60 250 18 0.174-0.183 C10 48-51 250 14 0.172-0.178 F15 47-49 250 14 0.217-0.223 F16 40-43 250 13 0.182-0.187

[0087] During extrusion, the thermoplastic composition containing 10 wt% PE-AA (F11) exhibited relatively lower torque values (40-43%) compared to the torque values observed for the control samples (C10, 48-51%), indicating a decrease in melt viscosity. This decrease in melt viscosity with the incorporation of 10 wt% PE-AA is attributed to the plasticizing effect of EAA due to its lower molecular weight. On the other hand, the thermoplastic composition incorporating 10 wt% PVOH (F14) exhibited slightly higher torque values (57-60%), possibly indicating an increase in melt viscosity.

[0088] Injection molding of test specimens (e.g., ISO tensile bars, ISO impact bars, and 3 mm test plaques) was performed on an L&T Detech 100-ton molding machine equipped with a 32 mm diameter screw. Injection molding was performed at a temperature of 240°C, and the injection speed was maintained at 20 mm / sec. The molded parts were conditioned at 23°C and 50% relative humidity for 72 hours. Example 2 (Test results of the thermoplastic composition of the present invention and the comparative thermoplastic composition)

[0089] Notched Izod impact (NII) performance is measured according to test ISO 180 / 1A and is shown in Figure 1A and Figure 1B The NII values of the thermoplastic compositions incorporating 3 wt% of the polar polymer (C) (F10) were similar to or slightly higher than the NII values of the comparative thermoplastic composition (C10). The NII values of the thermoplastic compositions incorporating 6-10 wt% of the polar polymer (C) (F15 and F16, respectively) were significantly higher than the NII values of the comparative thermoplastic composition (C11).

[0090] The Vicat softening temperature (VST) measurements of the comparative thermoplastic composition and the thermoplastic composition of the present invention were performed using a CEAST apparatus equipped with a VICAT-6 station according to ISO-B120 (50 N force). Figure 2A and 2B The VST values of 3 wt% (F10), 6 wt% (F16) and 10 wt% (F11 and F15) PE-AA (polar polymer (C)) are comparable to the VST values of the comparative thermoplastic compositions (C10 and C11) without polar polymer (C).

[0091] Heat distortion temperature (HDT) measurements of the comparative thermoplastic composition and the inventive thermoplastic composition were performed using a CEAST apparatus equipped with a HDT-6 station according to ISO 75 (1.8 MPa, 120°C / hr). Figure 3 Compared to the control ABS (C11), the HDT values decreased (F15 decreased from 80°C to 70°C; F16 decreased from 80°C to 70°C).

[0092] Thermoplastic compositions of some embodiments of the present invention and control ABS were injection molded into impact bars to determine color difference. Figure 4 As shown, the visual appearance of the thermoplastic compositions of the present disclosure appears greatly improved compared to the control ABS strips. Relatively speaking, the inventive thermoplastic compositions (F15, F16) appear whiter in color, while the control ABS composition (C11) without the polar polymer (C) appears darker.

[0093] Yellowness Index (YI) is measured according to ASTM E313-20, is based on spectrophotometric data and indicates how the color of a test sample changes from clear or white to yellow.

[0094] As shown in Table 4, the YI of the inventive thermoplastic composition (C16) is 7 units lower than the YI of the control ABS composition. A further decrease in YI (12 units) can be seen for the inventive thermoplastic composition (C15) containing 10 wt% polar polymer (C). Table 4 lists color measurements analyzed using the CIELAB color space. The letters L*, a*, and b* each represent one of the three values used in the CIELAB color space for measuring objective color and calculating color differences: L* represents lightness (on a scale of 0 to 100, from black to white), while a* and b* represent chroma (with no specific numerical limits). Negative a* corresponds to green, positive a* corresponds to red, negative b* corresponds to blue, and positive b* corresponds to yellow. An increase of 3 units in L* indicates an increase in the white lightness of the formulated sample relative to the control sample. Table 4 Sample code sample L* a* b* YI EtcP-C11 Comparison with ABS 83.87 0.54 17.58 33.54 EtcP-F16 ABS-PE-AA 6% 86.48 0.99 13.44 26.25 EtcP-F15 ABS-PE-AA 10% 86.51 1.31 10.59 21.56 Example 3 (Pretreatment of Molded Plaques of Comparative Thermoplastic Composition and Inventive Thermoplastic Composition)

[0095] Molded test panels of a comparative thermoplastic composition (C10) and the inventive thermoplastic compositions (F10-F14) were pretreated with an acidic manganese colloid solution at various times and concentrations. The existing pretreatment etching solution was prepared by mixing CrO3 and H2SO4. By using optimized acid pretreatment conditions, a preferred surface morphology was achieved, which enabled mechanical interlocking and chemical bonding, and provided strong metal-thermoplastic composition resin interfacial adhesion. Table 5 shows the chemicals and conditions used to pretreat molded test panels of the comparative thermoplastic composition and the formulated thermoplastic compositions of the present invention. In the case of the manganese colloid, pretreatment times were 10 and 20 minutes, as detailed in Table 5. Table 5 Example 4 (Pretreatment of Molded Plaques of Comparative Thermoplastic Compositions and Inventive Thermoplastic Compositions Using Acidic Colloidal Manganese)

[0096] For direct comparison, the surface morphology changes resulting from the acidic manganese colloid treatment were compared to samples of the same composition subjected to a conventional standard hexavalent chromium-based etching process. Molded test panels of a comparative thermoplastic composition (C10) and a thermoplastic composition of the present invention (F10) (with 3 wt% PE-AA) were pretreated with acidic manganese colloid at two different sulfuric acid levels. The acidic manganese colloid was prepared by mixing H3PO4 (219 mL / L), H2SO4 (573 mL / L and 605 mL / L), and MnO2 (60 g / L) at 70°C for 10 and 20 minutes. Example 5 (Analysis of Comparative Thermoplastic Compositions and Inventive Thermoplastic Compositions Using Acidic Colloidal Manganese Pretreatment)

[0097] Figure 5 and 6 Surface morphologies of treated samples of a comparative thermoplastic composition (C10) and a thermoplastic composition (F10) according to the invention incorporating 3 wt.% PE-acrylic acid (polymer (C)) as deduced by SEM microscopy analysis are shown in FIG. Figure 5As shown, when the surface morphology of the thermoplastic composition of the present invention was treated with an acidic manganese colloid with a relatively low sulfuric acid concentration (prepared by mixing H3PO4 (219 mL / L), H2SO4 (573 mL / L), and MnO2 (60 g / L) at 70°C for 10 and 20 minutes), there was little change in the surface morphology. When the sulfuric acid concentration was increased during the preparation of the acidic manganese colloid (prepared by mixing H3PO4 (219 mL / L), H2SO4 (605 mL / L), and MnO2 (60 g / L) at 70°C for 10 and 20 minutes), the surface morphology changed significantly, with the appearance of non-uniform cavities. It can be concluded that while pretreatment of the comparative thermoplastic composition with an acidic manganese colloid obtained at a relatively low sulfuric acid concentration did not result in a significant change in the surface morphology, similar pretreatment with an acidic manganese colloid obtained at a relatively high sulfuric acid concentration resulted in the development of roughness and cavities. It is clear that pretreatment with acidic manganese colloid obtained with higher sulfuric acid concentration for a longer duration (20 min) leads to an over-etched surface with an irregular peak-valley pattern.

[0098] like Figure 6 As shown in the SEM images in Figure 2, pretreatment of molded plaques of the inventive thermoplastic composition (EtcP-F10) containing 3 wt% polar polymer (C)PE-AA with acidic manganese colloid at various sulfuric acid concentrations and durations resulted in varying morphological characteristics. For example, while pretreatment with H3PO4 (219 mL / L), H2SO4 (573 mL / L), and MnO2 (60 g / L) at 70°C for 10 minutes did not result in significant morphological changes, a longer pretreatment time (20 minutes) resulted in the formation of microcavities on the surface. Furthermore, increasing the sulfuric acid concentration in the acidic manganese colloid from 573 mL / L to 605 mL / L resulted in a significant amount of porosity and a skeletal morphology with subsurface undercuts. These morphological characteristics are similar to those observed for the comparative thermoplastic sample (C10) etched with hexavalent chromium. The presence of subsurface undercuts allows for a strong mechanical interlock between the metal and the plastic. To investigate the effect of morphology on metal-plastic interfacial adhesion, all of these formulations were metallized and subsequently tested for peel adhesion.

[0099] Similar pretreatment experiments were also carried out on a thermoplastic composition according to the invention incorporating 10 wt.% PE-AA (F11). In this case, the morphological features were evident regardless of the concentration of sulfuric acid in the acidic manganese colloid, e.g. Figure 7 However, different surface morphologies were observed using a longer pretreatment time (20 min).

[0100] Comparative thermoplastic composition (C10) Figure 8The TEM analysis shown reveals the presence of a surface region with elongated / distorted butadiene rubber domains that extend 3-5 microns compared to the bulk region, which contains circular domains of varying sizes. In contrast, the surface region of the thermoplastic composition of the present invention appears to have a higher roughness (F10), or even becomes thicker and extends 8-10 microns (F11). However, the surface region changes significantly after etching, and the surface layer appears thinner, which is attributed to the acid treatment removing part of the top layer. Figure 8 Representative images of the etched surface areas of samples C10 and F10 are shown. Example 6 (Metal Plating of Molded Plaques of Comparative Thermoplastic Compositions and Inventive Thermoplastic Compositions) Chemical plating process:

[0101] General procedure. The surface of the substrate was electrolessly plated by placing the substrate in a plating bath, wherein the ions in the plating bath were reduced and bound to the polar groups of the polymer substrate to form a metal layer on the surface of the substrate. All pretreated samples were sensitized in a SnCl2 (10 g / L) / HCl (40 mL / L) solution and activated in a PdCl2 (0.25 g / L) / HCl (2.5 mL / L) solvent. The electroless plating bath contained CuSO4.5H2O (15 g / L), NaKC4H4O6.4H2O (30 g / L), HCHO (100 mL / L) and NaOH (4 g / L). All samples were electrolessly plated for 15 minutes. The coated samples were tested for sheet resistance and used for electroplating by the following process. Electroplating process:

[0102] General Procedure. This electrodeposition experiment involved a copper deposition step and was performed using a MiniContact RS electroplating system. The electrolyte solution consisted of 75 g / L copper sulfate and 200 mL / L sulfuric acid. The applied current was 1.5 amperes and the temperature was 29°C. The plating time for both the comparative thermoplastic composition and the inventive thermoplastic composition was 30 minutes.

[0103] The electroplating process conditions were optimized with respect to applied current and treatment time. Furthermore, a statistically significant trend in metal growth was confirmed on the test panels of the formulated thermoplastic composition of the present invention. Furthermore, the thickness of the metal layer grown on the test panel surface appeared to increase when the treatment time was varied from 5 minutes to 30 minutes.

[0104] Different parameters (current and time) need to be considered in order to have limited control over the metal thickness during electroplating. In order to compare the final peel strength of different samples, a constant metal thickness is required to ensure that the difference in peel strength is mainly due to the different bonding processes (i.e. chemical vs. mechanical). However, in these embodiments, the surface conductivity of each sample varies due to the electroless plating step. Therefore, all samples are cut into the same diameter to maintain the same surface area. Electroplating is carried out on the same day while keeping the pH value, electrolyte concentration, applied current, treatment time and temperature constant. Example 7 (Peel test of comparative thermoplastic composition and thermoplastic composition of the present invention)

[0105] Thermoplastic compositions of the invention (PE-AA (3 wt%, F10) and PE-AA (10 wt%, F11)) and a comparative sample (C10, ABS) were metallized and tested for peel adhesion. Figure 9 The average peel force of C10, F10 and F11 is shown, as well as the peel force observed after a conventional hexachromic acid etching process. Sample F10 exhibits peel strength values in the range of 0.16-0.27 N / mm, with the inventive thermoplastic composition F11 exhibiting significantly higher peel strength values.

[0106] After pretreatment with manganese colloidal acid prepared with varying concentrations of sulfuric acid (see Example 5), the copper films on the test formulations were metallized as described in Example 6 and tested for peel force measurements. Figure 10 The peel test results for the inventive test formulations F10 and F11, as well as a control (C10, ABS), are shown. Low loadings (3 wt%) of the PE-AA additive (inventive polar polymer (C)) in the thermoplastic composition exhibited metal-plastic adhesion forces ranging from 0.11 to 0.25 N / mm. High loadings (10 wt%) of the PE-AA additive in the inventive thermoplastic composition exhibited peel forces ranging from 0.01 to 0.22 N / mm. The inventive F10 thermoplastic composition (PE-AA (3 wt%)), prepared by etching for 10 minutes at a low (573 mL / L) sulfuric acid concentration in manganese colloid, exhibited better peel forces than the sample etched for 20 minutes.

[0107] When pretreated with conventional hexachromic acid, the average peel strength values estimated by taking the surface area into account are higher for the formulated thermoplastic compositions of the invention (e.g. F11) (0.29 N / mm) than the value observed for the comparative thermoplastic composition (C10) (0.22 N / mm), e.g. Figure 11 shown.

[0108] The peel test results of the thermoplastic composition of the present invention and the comparative thermoplastic composition pretreated with acidic manganese colloid are as follows: Figure 12 As shown. After pretreatment with (H3PO4 (219 mL / L), H2SO4 (605 mL / L), MnO2 (60 g / L)) at 70°C for 10 minutes, the comparative thermoplastic composition exhibited a maximum peel force of 0.27 N / mm. The inventive thermoplastic formulation F10 achieved an optimal peel force of 0.19 N / mm at all sulfuric acid concentrations with an etching time of 10 minutes. Increasing the etching time slightly reduced the metal-plastic peel force. In the case of another inventive thermoplastic composition, F11, after pretreatment with (H3PO4 (219 mL / L), H2SO4 (605 mL / L), MnO2 (60 g / L)) at 70°C for 20 minutes, a maximum peel force of 0.15 N / mm was achieved. Interestingly, ABS / PE-AA (3 wt%) exhibited better peel adhesion when treated with a lower acid concentration for a similar duration of 10 minutes. This may be interesting in terms of reducing processing costs and speeding up plating, which may result in significant savings in plating costs.

[0109] From the peel tests, it was determined that the use of conventional hexachromic acid with a high loading of polar polymer (C) (e.g., F11 10 wt% PE-AA) improved etching ability and metal-plastic adhesion compared to the comparative thermoplastic sample (C10). From the results, it was determined that the textures provided by the thermoplastic compositions of the present invention provided better metal-plastic interlocking and good peel force compared to the comparative thermoplastic compositions that did not include the polar polymer (C).

[0110] Although the embodiments of the present application and advantages thereof have been described in detail, it should be understood that various changes, substitutions and modifications may be made herein without departing from the spirit and scope of the embodiments defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the specific embodiments of the processes, machines, manufactures, material compositions, means, methods and steps described in the specification. Those skilled in the art will readily appreciate from the above disclosure that processes, machines, manufactures, material compositions, means, methods or steps that currently exist or are later developed and perform substantially the same functions or achieve substantially the same results as those described herein may be utilized. Therefore, the appended claims are intended to include these processes, machines, manufactures, material compositions, means, methods or steps within their scope.

Claims

1. A thermoplastic polymer composition comprising, based on the total weight of the thermoplastic polymer composition: (a) 30 to 79 weight percent of a copolymer (A) comprising units derived from (i) a vinyl aromatic monomer and (ii) a vinyl nitrile monomer; (b) 20 to 50 wt% of a rubber-modified thermoplastic polymer (B); (c) 1 to 15 wt% of a polar polymer (C) comprising a carboxylic acid, an alcohol, an amide, or a combination thereof, wherein the polar polymer (C) has a molecular weight of 5,000 to 25,000 g / mol; and (d) Melt processing additives.

2. The thermoplastic polymer composition of claim 1, comprising: (a) 60% to 75% by weight, preferably 62% to 74% by weight, of copolymer (A); (b) 20 to 30 wt. %, preferably 22 to 24 wt. % of a rubber-modified thermoplastic polymer (B); (c) 1 to 13 wt%, preferably 3 to 10 wt% of a polar polymer (C); and (d) 1 to 5 wt. %, preferably 1.2 to 1.5 wt. % of processing additives.

3. The polymer composition of any one of claims 1 to 2, wherein the vinyl aromatic monomer comprises styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-hydroxystyrene, methoxystyrene or any combination thereof, preferably, the vinyl aromatic monomer is styrene, and the vinyl nitrile monomer comprises acrylonitrile, α-chloroacrylonitrile, methacrylonitrile, ethacrylonitrile or any combination thereof, preferably acrylonitrile.

4. The polymer composition of any one of claims 1 to 3, wherein the rubber-modified polymer (B) comprises: a polymer rubber comprising polymer units derived from a conjugated diene, wherein the conjugated diene comprises 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, or any combination thereof, preferably 1,3-butadiene; and A grafted thermoplastic copolymer (D), wherein the grafted thermoplastic copolymer (D) is grafted onto the polymer rubber, and wherein the grafted thermoplastic copolymer (D) comprises polymer units derived from: (i) a vinyl aromatic monomer comprising styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-5-hydroxystyrene, methoxystyrene or any combination thereof, preferably styrene; (ii) a vinyl nitrile monomer comprising acrylonitrile, methacrylonitrile, ethacrylonitrile or any combination thereof, preferably acrylonitrile; and (iii) optionally, a (meth)acrylic monomer comprising methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, propyl methacrylate or any combination thereof, preferably methyl methacrylate (MMA).

5. The thermoplastic polymer composition according to any one of claims 1 to 4, wherein copolymer (A) is a styrene-acrylonitrile copolymer (SAN) and the rubber-modified thermoplastic polymer (B) is a polybutadiene rubber grafted with a styrene / methyl methacrylate / acrylonitrile copolymer.

6. The thermoplastic polymer composition of any one of claims 1 to 5, wherein the polar polymer (C) comprises an ethylene-acrylic acid copolymer, a polyvinyl pyrrolidone polymer, a polyvinyl alcohol polymer, or a blend thereof.

7. The thermoplastic polymer composition of claim 6, wherein the ethylene-acrylic acid copolymer comprises 1 to 10 weight percent, preferably 6.9 weight percent, of acrylic acid, based on the total weight of the ethylene-acrylic acid copolymer, and the polyvinyl alcohol polymer comprises 70 to 80 percent of hydrolyzed polyvinyl acetate, based on the total weight of the polyvinyl alcohol copolymer.

8. The thermoplastic polymer composition of any of claims 1-7, wherein the melt processing additive comprises magnesium oxide (MgO), silicone fluid, ethylene bisstearamide (EBX) wax, magnesium stearate, or mixtures thereof.

9. The thermoplastic polymer composition according to any one of claims 1 to 8, wherein the molded part of the thermoplastic polymer composition is surface treated.

10. The thermoplastic polymer composition of any one of claims 1 to 9, having a thermal conductivity of 3.0 kJ / m2 when measured according to ISO 180 / 1A. 2 Up to 30.0kJ / m 2 , preferably 4.0kJ / m 2 Up to 25.0kJ / m 2 , more preferably 5.0 kJ / m 2 Up to 20.0 kJ / m 2 Notched Izod impact strength.

11. The thermoplastic polymer composition of any of claims 1-10, further comprising a metal coating bonded to at least a portion of a surface of the thermoplastic polymer composition.

12. The thermoplastic polymer composition of any one of claims 1 to 11, wherein the thermoplastic polymer composition is comprised in an article of manufacture, preferably a molded article of manufacture.

13. The thermoplastic polymer composition of any of claims 1 to 12, wherein the thermoplastic polymer composition has a yellowness index (YI) that is less than a thermoplastic polymer composition that does not contain the polar polymer (C).

14. The thermoplastic polymer composition of any of claims 1-13, wherein the thermoplastic polymer composition has a yellowness index (YI) of less than 30, preferably less than 27, more preferably less than 22, or even more preferably from 2 to 30.

15. A metal-plated article of manufacture comprising the thermoplastic polymer composition of any of claims 1-14 and a metal bonded to at least a portion of a surface of the thermoplastic polymer composition, wherein the metal comprises copper, chromium, nickel, or a combination or alloy thereof.

16. A process for producing the thermoplastic polymer composition of any one of claims 1 to 14, the process comprising melt blending a thermoplastic composition comprising: (a) 30 to 79 wt% of a copolymer (A) comprising units derived from a vinyl aromatic monomer and a vinyl nitrile monomer; (b) 20 to 50 wt% of a rubber-modified thermoplastic polymer (B); (c) 1 to 15 wt% of a polar polymer (C) comprising a carboxylic acid, an alcohol, an amide, or a combination thereof; and (d) Melt processing additives.

17. The method of claim 16, further comprising: molding the thermoplastic composition into an article and contacting the surface of the article with a chemical agent under conditions suitable for surface treating the article, wherein the chemical agent preferably comprises a suspension of colloidal manganese oxide particles in a mineral acid mixture comprising sulfuric acid and phosphoric acid; as well as The surface-treated article is subjected to conditions suitable for bonding a metal layer to at least a portion of the treated surface to produce a metal-plated portion of the article.

18. A method of reducing the yellowness index (YI) of a thermoplastic polymer composition according to any one of claims 1 to 14, the method comprising melt blending a thermoplastic composition comprising: (a) 30 to 79 wt% of a copolymer (A) comprising units derived from a vinyl aromatic monomer and a vinyl nitrile monomer; (b) 20 to 50 wt% of a rubber-modified thermoplastic polymer (B); (c) 1 to 15 wt% of a polar polymer (C) comprising a carboxylic acid, an alcohol, an amide, or a combination thereof; and (d) Melt processing additives.

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