Chromic Acid Etch-Free Metal Plating of Acrylonitrile-Butadiene-Styrene and Polar Polymer Blends

Abstract

A thermoplastic composition is described. The 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 including a carboxylic acid, an alcohol, or a combination thereof; and (d) optional processing additives. A metal-plated article including the thermoplastic polymer composition is also described. The thermoplastic composition may have an improved yellowness index (YI) compared to a similar composition without the polar polymer.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to European Patent Application No. 22211169, filed December 2, 2022, the entire contents of which are incorporated herein by reference. [Technical Field]

[0002] The present invention relates to thermoplastic polymer compositions and methods for making thermoplastic compositions. [Background technology]

[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. The thermoplastic material serves as a polymer substrate onto which a metal coating can be deposited. For example, polymer plastic parts prepared from ABS polymers can be coated with a metal layer to impart a mirror-finish appearance similar to that of metal parts while retaining the distinct advantage of being lightweight. Furthermore, metal coatings can improve the mechanical strength, thermal stability, and chemical resistance of the polymer substrate onto which the metal is coated. In this regard, ABS polymers are particularly useful in automotive and other industrial applications due to their desirable impact properties and other useful characteristics. Summary of the Invention [Problem to be solved by the invention]

[0004] The use of metal coatings on polymer plastic parts presents challenges. Metal coatings have the disadvantage of not easily bonding or adhering to most polymer-based substrates unless the surface is first chemically treated. Traditionally, polymer substrate surfaces can be chemically etched with oxidizing agents such as chromium(VI) trioxide or mixtures of chromium / sulfuric acid or chromium / sulfuric acid / phosphoric acid. These strong oxidizing agents can micro-roughen and chemically alter the surface of polymer substrates 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 subsequent metal deposition during the plating process. After the etching process, the surface of the polymer substrate can be metal-plated. One suitable metric for measuring the success of the bond between the metal layer and the polymer substrate is peel strength; the higher the peel strength, the better the adhesion of the metal on the polymer substrate.

[0005] However, the use of hexavalent chromium compounds, such as chromium trioxide, poses certain risks and challenges, such as: 1) health risks due to the highly carcinogenic nature of such compounds; 2) disposal of waste liquids from the etching process, which makes the etching process not only environmentally hazardous but also expensive; 3) purification of the etched plastic parts to remove any residual chromium trioxide that may be present as an impurity that adversely affects the metal plating process; and / or 4) the use of highly oxidizing acid solutions, which can often damage the polymer substrate itself or make it structurally weak against metal plating.

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

[0007] Another problem associated with ABS resins is their potential for yellowing during the extrusion and / or molding process. 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 upon exposure to heat to produce a yellowish color. During melt processing, the color of ABS can yellow under the influence of heat, oxygen, stress, trace moisture, impurities, and other factors. How quickly an ABS resin yellows is often measured by its yellowness index (YI). A lower YI correlates with more stable color, while a higher YI correlates with less stable color. A lower YI is desirable. While efforts are underway to improve the YI of ABS resins, many of these efforts can also lead to a deterioration in the resin's physical and / or mechanical properties. [Means for solving the problem]

[0008] A solution to at least one of the problems associated with metal plating and / or yellowing of polymeric materials has been discovered. This solution can include a thermoplastic polymer composition comprising: (a) a copolymer having units derived from vinyl aromatic and vinyl nitrile monomers; (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 polymeric compositions can be successfully metal-plated. Success can be determined by peel strength testing. Advantageously, the thermoplastic composition can have suitable impact strength when provided in a molded form. This allows such polymeric compositions to be used to prepare metal-plated products suitable for various industrial applications where excellent impact strength is desired. Also, in one aspect, the polymeric compositions of the present invention can be coated with metal without the need for chemical etching processes that rely on oxidizing agents such as chromium (VI) trioxide or mixtures of chromium / sulfuric acid or chromium / sulfuric acid / phosphoric acid.

[0009] In some embodiments, the polymer composition of the present invention may have a lower YI compared to an ABS resin that does not contain a polar polymer. In particular, it has been discovered that the polar polymer portion of the polymer composition of the present invention can reduce the resin's YI and increase its whiteness (L value). This may be advantageous in that the composition of the present invention can be metal-coated while improving the material's whiteness. While not intending to be bound by theory, it is believed that the reduced YI of the composition of the present invention may be due to a reaction between the polar groups of the polar polymer and colored impurities generated during the manufacture and / or melt processing of ABS. The polar polymer (C) may migrate to at least a portion of the surface of the polymer composition. The migration of the polar polymer (C) may be initiated or promoted, or both, while the polymer melt is held in a mold. Furthermore, the low molecular weight of the polar polymer (C) (e.g., a molecular weight of 5,000 g / mol to 25,000 g / mol) and / or the presence of polar components due to hydrolysis of the polar polymer (C) (e.g., acrylic acid or hydrolyzed polyvinyl acetate) may allow the polar polymer (C) to migrate to the surface of the polymer composition of the present invention. The additives migrating to the surface help to retain most of the bulk properties.

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

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

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

[0013] In a preferred embodiment, the polymer rubber can include polymer units derived from 1,3-butadiene, a graft polymer rubber copolymer (D) derived from styrene polymer units, acrylonitrile monomer, and optionally methyl methacrylate monomer. In a preferred embodiment, the copolymer (A) can be a styrene-acrylonitrile copolymer (SAN), and the rubber-modified thermoplastic polymer (B) can be a polybutadiene rubber grafted with a styrene / methyl methacrylate / acrylonitrile copolymer. The combination of the copolymer (A) and the 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 / mole to 25,000 g / mole. In some embodiments, the polar polymer (C) can be an oligomer or have a low molecular weight. In some embodiments, the polar polymer (C) can comprise an ethylene-acrylic acid copolymer, a polyvinylpyrrolidone polymer, a polyvinyl alcohol polymer, or a blend thereof. The ethylene-acrylic acid copolymer can comprise 1% to 10% by weight, preferably 6.9% by weight, of acrylic acid based on the total weight of the polar polymer (C), and / or the polyvinyl alcohol polymer can comprise 70% to 80% by weight, of hydrolyzed polyvinyl acetate based on the total weight of the polar polymer (C).

[0015] In some embodiments, the thermoplastic compositions of the present invention have a modulus of elasticity of 3.0 kJ / m when measured according to ISO 180 / 1A. 2 ~30.0kJ / m 2 , preferably 4.0 kJ / m 2 ~25.0kJ / m 2 , more preferably 5.0 kJ / m 2 ~20.0kJ / m 2 The thermoplastic composition may have a notched Izod impact strength of 1000 MPa or less. Some or all of the thermoplastic composition may be molded. Some or all of the surfaces of the molded thermoplastic composition may be surface treated. A metal coating may be adhered to at least a portion of the treated surface.

[0016] In some embodiments, the thermoplastic polymer composition of the present invention may have a lower Yellowness Index (YI) than a thermoplastic polymer composition in which the polar polymer (C) is not present. 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 whiteness (e.g., appear whiter) compared to a thermoplastic polymer composition in which the polar polymer (C) is not present. Another embodiment of the present invention describes a method for reducing the Yellowness Index of the thermoplastic polymer composition of the present invention. The method may include melt-mixing 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 composition of the present invention may be included in an article to be manufactured.

[0018] In some embodiments, a metal-plated article is described that includes the thermoplastic composition of the present invention. The metal can be adhered 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 another aspect of the present invention, a method for producing the thermoplastic composition of the present invention is described. The method can include melt-mixing 30% to 79% by weight of copolymer (A), 20% to 50% by weight of rubber-modified thermoplastic polymer (B), greater than 1% to 15% by weight of polar polymer (C), and greater than 0% to 5% by weight of optional processing additives. In some embodiments, the thermoplastic composition can be molded into an article. In some examples, the article can be surface-treated by contacting the article with a chemical agent under conditions suitable for surface-treating the article of the present invention. Non-limiting examples of chemical agents include a suspension of manganese oxide colloidal particles in a mineral acid mixture. The mineral acid mixture can include sulfuric acid and phosphoric acid. The surface-treated article of the present invention can be subjected to conditions suitable for depositing a metal layer on at least a portion of the treated surface to produce a metal-plated portion of the article.

[0020] Other embodiments of the present invention are discussed throughout this application. Any embodiment discussed with respect to one aspect of the present invention also applies to other aspects of the present invention, and vice versa. Each embodiment described herein is understood to be an embodiment of the present invention that is applicable to other aspects of the present invention. It is contemplated that any embodiment or aspect discussed herein can be combined with other embodiments or aspects discussed herein and / or implemented with respect to any method or composition of the present invention, and vice versa. Furthermore, compositions of the present invention can be used to achieve methods of the present invention.

[0021] The following contains 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 reagent.

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

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

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

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

[0027] The term "effective," as used in the specification and / or claims, means adequate to accomplish a desired, expected, or intended result.

[0028] The use of the terms "a" or "an," when used in conjunction with any of the terms "comprising," "including," "containing," or "having" in the claims or specification, can mean "one," but is also consistent with the meanings of "one or more," "at least one," and "one or more."

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

[0030] The thermoplastic compositions of the present invention may "comprise," "consist essentially of," or "consist" of the specific components, elements, compositions, etc. disclosed throughout this specification. With respect to the transitional phrase "consisting essentially of," in one non-limiting aspect, a basic and novel feature 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. It should be understood, however, that the drawings, detailed description, and examples, while indicating specific embodiments of the present invention, are given by way of illustration only and are not intended to be limiting. It is further anticipated 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 specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any other embodiment. In further embodiments, additional features may be added to the specific embodiments described herein. [Brief explanation of the drawings]

[0032] Advantages of the present invention will become apparent to those skilled in the art with the benefit of the following detailed description and by reference to the accompanying drawings. [Figure 1A] 1A and 1B are graphical representations of notched Izod impact (NII) values ​​of comparative thermoplastic compositions (C10 and C11 in FIGS. 1A and 1B, respectively) and thermoplastic compositions of the present invention having different amounts of polar polymer (C) (F10, F11, F13, and F14 in FIG. 1A; and F15 and F16 in FIG. 1B). [Figure 1B] 1A and 1B are graphical representations of notched Izod impact (NII) values ​​of comparative thermoplastic compositions (C10 and C11 in FIGS. 1A and 1B, respectively) and thermoplastic compositions of the present invention having different amounts of polar polymer (C) (F10, F11, F13, and F14 in FIG. 1A; and F15 and F16 in FIG. 1B). [Figure 2A] 2A and 2B, respectively) and inventive thermoplastic compositions having different amounts of polar polymer (C) (F10, F11, F13, and F14 in FIG. 2A; and F15 and F16 in FIG. 2B). [Figure 2B] 2A and 2B, respectively) and inventive thermoplastic compositions having different amounts of polar polymer (C) (F10, F11, F13, and F14 in FIG. 2A; and F15 and F16 in FIG. 2B). [Figure 3] 1 is a graphical representation of (HDT) measurements for a comparative thermoplastic composition (C11) and thermoplastic compositions of the present invention having different amounts of polar polymer (C) (F15 and F16). [Figure 4] 1 is a diagram of molded bars of thermoplastic compositions of the present invention with different amounts of polar polymer (C) and molded bars of ABS showing whiteness. [Figure 5]Scanning electron microscope (SEM) images of manganese colloid particles containing mineral acid-pretreated molded plaques of a comparative thermoplastic composition are shown. The manganese colloid-containing 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 shows the pretreatment with 573 mL / L of H2SO4 for 10 minutes at 8000x and 2000x magnification. The second SEM image shows the pretreatment with 605 mL / L of H2SO4 for 10 minutes at 8000x and 2000x magnification. The third SEM image shows the pretreatment with 573 mL / L of H2SO4 for 20 minutes at 8000x and 2000x magnification. The bottom SEM is pretreated with 605 mL / L H2SO4 for 20 minutes at 8000x and 2000x magnification. [Figure 6] Figure 1 shows SEM images of manganese colloidal acid-pretreated molded plaques of a thermoplastic composition of the present invention with a polar polymer additive (3 wt% PE-AA). 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 shows the pretreatment with 573 mL / L of H2SO4 for 10 minutes at 8000x and 500x magnification. The second SEM image shows the pretreatment with 605 mL / L of H2SO4 for 10 minutes at 8000x and 500x magnification. The third SEM image shows the pretreatment with 573 mL / L of H2SO4 for 20 minutes at 8000x and 500x magnification. The bottom SEM is pretreated with 605 mL / L H2SO4 for 20 minutes at 8000x and 500x magnification. [Figure 7]Figure 1 shows SEM images of molded plaques of a thermoplastic composition of the present invention with a polar polymer additive (10 wt% PE-AA) that was pretreated with an acidic manganese colloid, obtained by blending the thermoplastic composition of the present invention with different polar polymer additives. The manganese colloid-containing acid solution was prepared by blending 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 shows a 10-minute pretreatment with 573 mL / L of H2SO4. The second SEM image shows a 10-minute pretreatment with 605 mL / L of H2SO4. The third SEM image shows a 20-minute pretreatment with 573 mL / L of H2SO4. The bottom SEM image shows a 20-minute pretreatment with 605 mL / L of H2SO4. [Figure 8] 1 shows transmission electron microscope (TEM) images of a comparative composition and a thermoplastic composition of the present invention having a polar polymer (C) (3% by weight PE-AA and 10% by weight PE-AA) before surface treatment. The bottom TEM shows the changes in the upper surface region (skin layer) after surface treatment of the comparative composition with 3% by weight PE-AA. The changes are indicated by arrows. [Figure 9] 1 is a graphical representation of peel strength measurements and reproducibility of metallized plaques comprising thermoplastic compositions of the present invention (3 wt. % PE-AA (left graph) and 10 wt. % PE-AA (right graph)) after hexavalent chromic acid etching. [Figure 10] 1 is a graphical representation of peel strength measurements of metallized plaques comprising 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) and a comparative sample (top graph). [Figure 11] 1 is a graphical representation of the average peel force for metallized plaques containing thermoplastic compositions of a comparative sample (C11) and the present invention (3 wt. % PE-AA (F10) and 10 wt. % PE-AA (F11)) after hexavalent chromic acid etching. [Figure 12]FIG. 1 is a graphical representation of the average peel force for metallized plaques containing a comparative sample (C10) and thermoplastic compositions of the present invention (3 wt. % PE-AA (F10) and 10 wt. % PE-AA (F11)) after pretreatment with acidic manganese colloid at different concentrations and times.

[0033] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings, which may not be to scale. DETAILED DESCRIPTION OF THE INVENTION

[0034] A discovery has been made that provides a solution to at least one of the problems associated with reducing the yellowness index of thermoplastic compositions and / or compositions to be metal plated. In one aspect, the present invention can include a thermoplastic composition comprising greater than 1% to 15% by weight of a polar polymer (C) containing a carboxylic acid, an alcohol, an amide, or a combination thereof. Advantageously, the polar polymer (C), along with the copolymer (A) and the thermoplastic polymer (B), enables the thermoplastic composition of the present invention to be surface treated for metal plating without the need for hexavalent chromium compounds for etching. Advantageously, the thermoplastic composition in molded form has adequate impact strength, thereby enabling such polymeric articles to be used to prepare metal-plated articles suitable for various industrial applications where excellent impact strength is desired. The thermoplastic composition of the present invention can also have an improved yellowness index (YI) and / or whiteness compared to a thermoplastic composition not containing the polar polymer (C).

[0035] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

[0036] A. Thermoplastic composition The thermoplastic composition of the present invention may comprise (a) 30% to 79% by weight of copolymer (A), (b) 20% to 50% by weight of rubber-modified thermoplastic polymer (B), (c) greater than 1% to 15%, preferably 2% to 13%, more preferably 3% to 10% by weight of polar polymer (C), and (d) greater than 0% to 5% by weight of optional processing additives. The thermoplastic composition may be molded or formed into a polymer article. The polymer article may have suitable impact properties required for specific applications, including door handles, holders, lamp bodies, corporate logos, and other decorative parts used in the automotive industry, household appliances, electronic devices, furniture, sanitaryware, etc. For example, the polymer article may have a thermal shock resistance of 3.0 kJ / m 2 or more and 30.0 kJ / m 2 It may have a notched Izod impact strength of 3.0 kJ / m or less, or any range or value therebetween, as measured in accordance with ISO 180 / 1A. 2 , 4.0 kJ / m 2 , 5kJ / m 2 , 10 kJ / m 2 , 15kJ / m 2 , 20kJ / m 2 , 25kJ / m 2 , 30kJ / m 2 , or 3.0 kJ / m 2 ≥ 30.0kJ / m 2 Below, 4.0kJ / m 2 or more and 25.0 kJ / m 2 Below, 5.0kJ / m 2 More than 20.0kJ / m 2The 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 methodologies. A non-limiting example of a yellowness index method is ASTM E313-20. The thermoplastic polymer composition may have increased white brightness (e.g., appear whiter) compared to a thermoplastic polymer composition in the absence of the polar polymer (C). The white brightness value may be greater than 85, preferably in the range of 85 to 92, and more preferably in the range of 86 to 90. The white brightness can be measured using known methodologies. A non-limiting example of a method for measuring white brightness is CIELAB color space analysis.

[0037] 1. Copolymer (A) Copolymer (A) may comprise polymer units derived from (i) vinyl aromatic monomers and (ii) vinyl nitrile monomers. Based on the total weight of the thermoplastic composition, copolymer (A) may be present in an amount of 30.0% by weight or more and 79.0% by weight or less, or any range or value therebetween. For example, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, and 79% by weight, or 36.0% by weight or more and 78.0% by weight or less, 60.0% by weight or more and 75.0% by weight or less, and 62.0% by weight or more and 74.0% by weight or less, based on the total weight of the thermoplastic polymer composition.

[0038] In some embodiments of the present invention, copolymer (A) has polymer units derived from vinyl nitrile monomers in an amount of 22.0% by weight or more and 38.0% by weight or less, or any range or value therebetween, based on the total weight of copolymer (A). For example, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38% by weight or more and 35.0% by weight or less, or 30.0% by weight or more and 35.0% by weight or less, based on the total weight of copolymer (A). In a preferred embodiment, copolymer (A) can have polymer units derived from vinyl nitrile monomers in an amount of 30.0% by weight or more and 35.0% by weight or less, based on the total weight of copolymer (A).

[0039] Non-limiting examples of vinyl aromatic monomers include styrene, α-methylstyrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-hydroxystyrene, methoxystyrene, or any combination thereof. Non-limiting examples of vinyl nitrile monomers include acrylonitrile, α-chloroacrylonitrile, methacrylonitrile, ethacrylonitrile, or any combination thereof. In a preferred embodiment, the vinyl aromatic monomer is styrene and the vinyl nitrile monomer is acrylonitrile. Preferably, copolymer (A) is a styrene-acrylonitrile (SAN) copolymer. In a preferred embodiment of the present invention, copolymer (A) is a styrene-acrylonitrile copolymer having 30.0% by weight or more and 35.0% by weight or less of polymer units derived from acrylonitrile.

[0040] In some embodiments of the present invention, the copolymer (A) may be, for example, a terpolymer containing polymer units derived from (i) a vinyl aromatic monomer, (ii) a vinyl nitrile monomer, and (iii) a (meth)acrylic monomer. The vinyl aromatic monomer and the vinyl nitrile monomer may be selected from the monomers defined above. Non-limiting examples of the (meth)acrylic monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, and decyl methacrylate. Preferably, the (meth)acrylic monomer is methyl methacrylate (MMA). Thus, the copolymer (A) may be a terpolymer containing polymer units derived from styrene / acrylonitrile / methyl methacrylate or alpha-methyl-styrene / acrylonitrile / methyl methacrylate.

[0041] The copolymer (A) can have a suitable molecular weight and melt flow rate. The average molecular weight (Mw) of the copolymer (A) can be 50,000 g / mol or more and 100,000 g / mol or less, 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 greater than or equal to 80,000 g / mol and less than or equal to 100,000 g / mol, greater than or equal to 85,000 g / mol and less than or equal to 98,000 g / mol, or greater than or equal to 93,000 g / mol and less than or equal to 97,000 g / mol, when measured according to gel permeation chromatography according to ASTM D5296-11 using a polystyrene-based calibration with tetrahydrofuran (THF) as the solvent.

[0042] The melt flow rate of copolymer (A), measured at 230°C under a 1.2 kg load according to ISO 1133 (2005), can be 7.0 g / 10 min or more and <20.0 g / 10 min or any value or range therebetween, such as 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 or more and 15.0 g / 10 min or less, or 9.0 g / 10 min or more and 11.0 g / 10 min or less. If the melt flow rate of the copolymer (A) is above the aforementioned rate, it may adversely affect the overall impact properties of the thermoplastic polymer composition, while if the melt flow rate of the copolymer (A) is below the aforementioned rate, the desired flow properties of the thermoplastic polymer may not be obtained, affecting the melt processability of the thermoplastic polymer.

[0043] 2. Rubber-modified thermoplastic polymer (B) In one embodiment of the present invention, the thermoplastic polymer composition can contain a suitable amount of rubber component. The rubber-modified thermoplastic polymer (B) can be referred to as high rubber graft or "HRG." The thermoplastic polymer composition can contain at least 26.0% by mass of the rubber-modified thermoplastic polymer (B). In some embodiments, the thermoplastic polymer composition can contain the rubber-modified thermoplastic polymer (B) in an amount of 20.0% by mass or more and 50.0% by mass or less, or any range or value therebetween. For example, the amount can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, or 30.0% by mass or more and 45.0% by mass or less, 20.0% by mass or more and 30.0% by mass or less, or 22.0% by mass or more and 24.0% by mass or less, based on the total weight of the thermoplastic polymer composition.

[0044] In some embodiments, the thermoplastic polymer composition may comprise copolymer (A) in an amount of 79.0% by weight or less and rubber-modified thermoplastic polymer (B) in an amount of 20.0% by weight or more, based on the total weight of the thermoplastic polymer composition. The rubber-modified thermoplastic polymer (B) may comprise (i) a polymer rubber and (ii) a thermoplastic copolymer (D) grafted to the polymer rubber. In some embodiments of the present invention, the polymer rubber may be a discontinuous elastomeric phase dispersed throughout a continuous rigid thermoplastic phase comprising the thermoplastic copolymer (D), with at least a portion of the rigid thermoplastic phase grafted to 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, monomodal particle size distribution. For example, the polymer rubber may have an average particle size of 50 nanometers (nm) or more and 1000 nanometers (nm) or less, and any range or value therebetween. In a preferred embodiment, the polymer rubber may have an average particle size of 200 nanometers (nm) or more and 500 nanometers (nm) or less.

[0045] The rubber-modified thermoplastic polymer (B) can contain a suitable amount of polymer rubber. The rubber-modified thermoplastic polymer (B) can contain a polymer rubber content of 55.0% by mass or more and 75.0% by mass or less, or any value or range therebetween. For example, the polymer rubber content can be 55.0% by mass or more and 75.0% by mass or less, 57.0% by mass or more and 70.0% by mass or less, 60.0% by mass or more and 65.0% by mass or less, or 60.0% by mass or more and 63.0% by mass or less, based on the total weight of the rubber-modified thermoplastic polymer (B). The polymer rubber content can be measured, for example, using Fourier transform infrared microspectroscopy (FT-IR). Thus, the rubber-modified thermoplastic polymer (B) can have a graft thermoplastic copolymer (D) content of 25.0% by mass or more and 45.0% by mass or less, or any range or value therebetween. For example, the content of the graft thermoplastic copolymer (D) may be 25 mass%, 30 mass%, 35 mass%, 40 mass%, 45 mass%, or 25.0 mass% or more and 45.0 mass% or less, 30.0 mass% or more and 43.0 mass% or less, 35.0 mass% or more and 40.0 mass% or less, or 37.0 mass% or more and 40.0 mass% or less, based on the total weight of the rubber-modified thermoplastic polymer (B). In some embodiments of the present invention, the rubber-modified thermoplastic polymer (B) may have a polymer rubber content of 55.0% to 75.0% by weight, 57.0% to 70.0% by weight, 60.0% to 65.0% by weight, or 60.0% to 63.0% by weight, based on the total weight of the rubber-modified thermoplastic polymer (B), and a graft thermoplastic copolymer (D) content of 25.0% to 45.0% by weight, 30.0% to 43.0% by weight, 35.0% to 40.0% by weight, or 37.0% to 40.0% by weight.More preferably, the rubber-modified thermoplastic polymer (B) may have a polymer rubber content of 60.0% by mass or more and 65.0% by mass or less, more preferably 60.0% by mass or more and 63.0% by mass or less, and a graft thermoplastic copolymer (D) content of 35.0% by mass or more and 40.0% by mass or less, preferably 37.0% by mass or more and 40.0% by mass or less, based on the total weight of the rubber-modified thermoplastic polymer (B).

[0046] The polymeric rubber may comprise polymeric units derived from conjugated dienes. Non-limiting examples of conjugated dienes 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, and preferably, the conjugated diene is 1,3-butadiene. In some embodiments of the present invention, the conjugated diene is 1,3-butadiene, and the polymeric rubber may be polybutadiene.

[0047] The rubber-modified thermoplastic polymer (B) may comprise a grafted thermoplastic copolymer (D) grafted onto the polymer rubber. The grafted thermoplastic copolymer (D) may comprise 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, vinyl toluene, vinyl xylene, butyl styrene, 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 embodiment, the vinyl aromatic monomer is styrene, the vinyl nitrile monomer is acrylonitrile, and the optional (meth)acrylic monomer is MMA.

[0048] In some embodiments, the grafted thermoplastic copolymer (D) can include polymeric units derived from styrene, methyl methacrylate, and acrylonitrile, and the polymeric rubber is a polybutadiene rubber that can include polymeric units derived from 1,3-butadiene. In some aspects, the rubber-modified thermoplastic polymer (B) is a polybutadiene rubber grafted with a copolymer including polymeric units derived from styrene, MMA, and acrylonitrile.

[0049] 3. Polar polymers (C) The polar polymer (C) can comprise a carboxylic acid, an alcohol, and / or an amide, or any combination thereof, and can be present in the thermoplastic polymer composition in any suitable amount. For example, the thermoplastic polymer composition can comprise 1.0% by weight or more and 15.0% by weight or less, or any range or value therebetween. For example, 1%, 5%, 10%, 15%, or 1.0% by weight or more and 13.0% by weight or less, or 3.0% by weight or more and 10.0% by weight or less, based on the total weight of the thermoplastic polymer composition. Non-limiting examples of polar polymer (C) include ethylene-acrylic acid copolymers, polyvinylpyrrolidone (PVP) polymers, polyvinyl alcohol (PVA) polymers, or blends thereof. Representative structures of these compounds are shown in Scheme I, where x = 1.6 × 10 in EAA. 2 ~8×l0 2 and y = 4.8 ~ 35, and n = 1.1 × l0 in PVA. 2 ~5.5×l0 2 and n = 45 to 2.2 × 10 in PVP. 2 is. [ka]

[0050] The ethylene-acrylic acid copolymer can contain 1% to 10% by weight of acrylic acid, or any range or value therebetween, based on the total weight of the ethylene-acrylic acid copolymer. For example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 1% to 10%, 2% to 8%, or 3% to 7% by weight of acrylic acid, based on the total weight of the ethylene-acrylic acid copolymer. The polyvinyl alcohol polymer can contain 70% to 80% by weight of hydrolyzed polyvinyl acetate, or any value or range therebetween, based on the total weight of the polyvinyl alcohol. For example, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, or 70% to 80% or 73% to 78% by weight of hydrolyzed polyvinyl acetate, based on the total weight of the polyvinyl alcohol.

[0051] The polar polymer (C) may be oligomeric or have a low molecular weight. The weight-average molecular weight of the polar polymer (C) may be 5,000 g / mol to 25,000 g / mol or any range therebetween. For example, 5,000 g / mol, 10,000 g / mol, 15,000 g / mol, 20,000 g / mol, 25,000 g / mol, or 5,000 g / mol to 18,000 g / mol, 10,000 g / mol to 18,000 g / mol, and 12,000 g / mol to 18,000 g / mol. For example, molecular weight measurements were performed using gel permeation chromatography according to ASTM D5296-11 using a polystyrene-based calibration with tetrahydrofuran (THF) as the solvent.

[0052] 4. Melt processing additives The thermoplastic polymer composition can include the optional processing additive in an amount of 0.0% to 5.0% by weight or less, or any range or value therebetween, based on the total weight of the thermoplastic polymer composition, for example, 0.1%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or 1.0% to 5.0% by weight or less, 1.0% to 2.0% by weight or less, preferably 1.5% to 2.5% by weight or less, based on the total weight of the thermoplastic polymer composition.

[0053] Non-limiting examples of processing additives include magnesium oxide (MgO), silicone oil, ethylene bis(stearamide) wax (EBS wax), magnesium stearate, or mixtures thereof. In a preferred embodiment, a mixture of magnesium oxide (MgO), silicone oil, EBS wax, and magnesium stearate can be used. In some embodiments of the present invention, MgO can be present in an amount of 0.01% to 0.1% by weight, or 0.01% to 0.05% by weight, based on the total weight of the thermoplastic polymer composition. In some embodiments of the present invention, silicone oil can be present in an amount of 0.05% to 0.5% by weight, or 0.1% to 0.5% by weight, based on the total weight of the thermoplastic polymer composition. In some embodiments of the present invention, EBS wax can be present in an amount of 0.5% to 2.0% by weight, or 0.8% to 1.5% by weight, based on the total weight of the thermoplastic polymer composition. In some embodiments of the present invention, magnesium stearate may be present in an amount of 0.05% to 0.5% by weight, or 0.1% to 0.4% by weight, based on the total weight of the thermoplastic polymer composition.

[0054] 5. Other additives The thermoplastic composition may contain other additives depending on the intended use. For example, the thermoplastic composition may contain additives in an amount of 0 to 20% by weight, preferably greater than 0 and less than 20% by weight or 0.5 to 20% by weight, more preferably 0.5 to 15% by weight, and even more preferably 0.5 to 12% by weight or 0.5 to 8% by weight, based on the total weight of the layer, and the sum of the polymer and additives may preferably be 100% by weight based on the total weight of the layer.

[0055] Non-limiting examples of additives that may be used include anti-fog agents (e.g., glycerol esters), antioxidants, heat stabilizers, hindered amine light stabilizers, flow modifiers, UV absorbers, impact modifiers, coupling agents, colorants, and the like, or any combination thereof.

[0056] 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 Polybond® 3150 maleic anhydride grafted polypropylene from Chemtura (USA), Fusabond® P613 maleic anhydride grafted polypropylene from DuPont (USA), and Priex® 20097 maleic anhydride grafted polypropylene homopolymer from Addcomp (Germany). The polymer matrix may comprise 0.1 to 5 weight percent coupling agent, or greater than or substantially equal to any one of, or between any two of, the following, based on the total weight of the polymer matrix: 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 coupling agent.

[0057] 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'-thiodiethylenebis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (CAS 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. 276 76-62-6), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (CAS number 40601-76-1), ethylene bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate] (CAS number 32509-66-3), 4,4'-thiobis(2-tert-butyl-5-methylphenol) (CAS number 96-69-5), 2,2'-methylene-bis-(6-(1-methyl (4,6-di-tert-butylphenol)-para-cresol (CAS No. 77-62-3), 3,3'-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-N,N'-hexamethylenedipropionamide (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-ethylidenebis(4,6-di-tert-butylphenol) (CAS No. 35958-30-6), 1,1,3-Tris(2-methyl-4-hydroxy-5'-tert-butylphenyl)butane (CAS number 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 number 90498-90-1), 1,6-hexanediyl-bis(3,5-bis(1,1-dimethylethyl)-4-hydroxybenzene)propanoate) (CAS number 35074-77-2), 2,6-di- tert-Butyl-4-nonylphenol (CAS No. 4306-88-1), 4,4'-butylidenebis(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 ~C 15 Mixture of linear and branched alkyl esters (CAS No. 17090-93-0), 2,2'-thiobis(6-tert-butyl-para-cresol) (CAS No. 90-66-4), diethyl-(3,5-di-tert-butyl-4-hydroxybenzyl)phosphate (CAS No. 976-56-7), 4,6-bis(octylthiomethyl)-ortho-cresol (CAS No. 110553-27-0), benzenepropanoic acid, octyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate Noate (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 phenol (CAS No. 61788-44-1), butylated, octylated phenol (CAS No. 68610-06-0), butylated reaction products of p-cresol and dicyclopentadiene (CAS No. 68610-51-5).

[0058] Non-limiting examples of phosphite antioxidants include one of 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-di-butylphenyl)-4,4′-biphenylene diphosphonite (CAS No. 119345-01-6), and bis(2,4-dicumylphenyl)pentaerythritol diphosphite (CAS No. 154862-43-8).

[0059] 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 dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (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-piperidyl)imino]hexamethyl methylene[2,2,6,6-tetramethyl-4-piperidyl)imino]] (CAS No. 70624-18-9)]; and 1,5,8,12-tetrakis[4,6-bis(N-butyl-Nl,2,2,6,6-pentamethyl-4-piperidylamino)-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane (CAS No. 106990-43-6).

[0060] Non-limiting examples of heat stabilizers include phenothiazine, p-methoxyphenol, cresol, benzhydrol, 2-methoxy-p-hydroquinone, 2,5-di-tert-butylquinone, diisopropylamine, and distearyl thiodipropionate (CAS number 693-36-7). In a preferred embodiment, distearyl thiodipropionate sold under the trade name Irganox® PS820 (BASF, Germany) is used.

[0061] Non-limiting examples of antioxidants include 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene sold under the trade name Irganox® 1330 (BASF, Germany), tris[2,4-bis(2-methyl-2-propanyl)phenyl]phosphite sold under the trade name Irgafos® 168 (BASF, Germany), and tris[2,4-bis(2-methyl-2-propanyl)phenyl]phosphite sold under the trade name Irganox® 1010 (BASF, Germany). and a mixture of at least two of these, such as pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate), sold under the trade name Chimassorb 119 (BASF, Germany), and 1,5,8,12-tetrakis[4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidylamino)-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane, sold under the trade name Chimassorb 119 (BASF, Germany).

[0062] Other additives may include stabilizers, UV absorbers, impact modifiers, and crosslinkers. A non-limiting example of a stabilizer may be Irganox® B225, available from BASF. In a further embodiment, neat polypropylene may be incorporated 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 elastomer / soft blocks dissolved in matrix-forming monomers, such as bulk HIPS, bulk ABS, reactively modified PP, Lomod, Lexan EXL, etc., thermoplastic elastomers dispersed in a matrix material by compounding di-, tri-, and multi-block copolymers, (functionalized) olefin (co)polymers, etc., such as MBS, ABS-HRG, AA, ASA-XTW, SWIM. or combinations thereof. Non-limiting examples of crosslinking agents include divinylbenzene, benzoyl peroxide, alkylene diol di(meth)acrylates such as glycol bisacrylates, alkylene triol tri(meth)acrylates, polyester di(meth)acrylates, bisacrylamides, triallyl cyanurate, triallyl isocyanurate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl adipate, triallyl ester of citric acid, triallyl ester of phosphoric acid, or combinations thereof.

[0063] B. Method for producing thermoplastic compositions A method for producing a thermoplastic composition may include melt-blending the copolymer (A) described in Section A, the modified rubber polymer (B), the polar polymer (C), and optional processing additives (D) to form an extruded composition. The extruded composition may be further processed to form a molded article. For example, a combination of extrusion and injection molding may be used to form the molded thermoplastic composition of the present invention. In one embodiment, the copolymer (A), the rubber-modified thermoplastic polymer (B), the polar polymer (C), and optional additive mixture may be introduced into an extruder and extruded to form an extrudate. The molded body may be in any form, such as pellets, spheres, etc. The extrudate may be subjected to conditions suitable to produce a molded thermoplastic composition. For example, the thermoplastic pellets of the present invention may be injection molded into a bar, sheet, or molded body. The injection molding temperature may be 210.0°C or higher and 250.0°C or lower, 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 from 215.0°C to 240.0°C, and from 220°C to 230°C, or any range or value therebetween. Injection speeds of from 10.0 mm / sec to 40.0 mm / sec, or any range or value therebetween, can be utilized. For example, the injection 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 from 15 mm / sec to 35.0 mm / sec, from 25.0 mm / sec to 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 or higher and 250.0°C or lower, preferably 215.0°C or higher and 240.0°C or lower, more preferably 220°C or higher and 230°C or lower, and at an injection speed maintained at 10.0 mm / sec or higher and 40.0 mm / sec or lower, preferably 15 mm / sec or higher and <35.0 mm / sec or lower, more preferably 25.0 mm / sec or higher and 30.0 mm / sec or lower.

[0064] The method may include physically blending the raw materials before introducing them into the hopper of the extruder. For example, in some embodiments of the present invention, pellets of the polar polymer (C) and copolymer (A) may be premixed in a container to obtain a homogeneously mixed set of pellets before being introduced into the hopper together with a preblend containing the rubber-modified thermoplastic polymer (B) and optional processing additives. In some embodiments, the physically mixed compound may be melt-blended upon being introduced into the extruder through the hopper. For example, melt-blending may be 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 an appropriate torque, a specific mechanical energy, a specific RPM, or a combination thereof. The extrusion torque may be 30.0% or more and 75.0% or less, preferably 40.0% or more and 70.0% or less, and more preferably 50.0% or more and 65.0% or less. The specific mechanical energy can be greater than or equal to 0.10 kWh / t and less than or equal to 0.25 kWh / t, preferably greater than or equal to 0.12 kWh / t and less than or equal to 0.22 kWh / t; and the extrusion screw revolutions per minute (RPM) can be greater than or equal to 170 and less than or equal to 260. In some embodiments, the material throughput can be adjusted to be maintained between greater than or equal to 8.0 Kg / h and less than or equal to 30.0 Kg / h, greater than or equal to 10 Kg / h and less than or equal to 25.0 Kg / h, with a specific mechanical energy (SME) between 0.15 kWh / t and 0.22 kWh / t and a screw RPM of 250.

[0065] C. Surface-treated polymeric articles In some embodiments of the present invention, the thermoplastic composition of the present invention can be surface-treated. Surface treatment can include contacting at least a portion of the thermoplastic composition of the present invention (e.g., a molded thermoplastic composition) with a chemical reagent for a sufficient time (e.g., 5.0 minutes or more and 30.0 minutes or less, preferably 10.0 minutes or more and 20.0 minutes or less, preferably 15.0 minutes or more and 20.0 minutes or less) to form a surface-treated thermoplastic composition. The contact temperature can range from 60°C to 80°C or from 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 can be contacted with the chemical reagent at a temperature of 65.0°C to 75.0°C for any period of time from 15.0 minutes to 20.0 minutes. The surface-treated polymeric article can have suitable surface polarity while retaining the desired impact strength. The surface polarity and impact strength attributes can be attributed to the deliberate combination of a suitable polymeric article, suitable selection of chemical reagent, and suitable process parameters of contact / exposure temperature and time.

[0066] Advantageously, the surface-treated polymeric article can be produced without the use of hexavalent chromium compounds, thereby avoiding the drawbacks associated with conventional etching processes that use hexavalent chromium compounds. The polymeric article can be contacted with the chemical reagent for a suitable time to ensure the desired surface roughness is incorporated. For example, if the polymeric article is contacted with the chemical reagent for too long (e.g., more than 30 minutes), the surface of the polymeric article may be damaged, while if the polymeric article is contacted with the chemical reagent for too short (e.g., less than 5 minutes), the surface morphology of the polymeric article may not change sufficiently to allow adhesion of the surface-treated polymeric article to the metal layer. The chemical reagent can be a suspension of manganese oxide colloidal particles in a sulfuric acid solution (70.0% by volume) suspended in a mineral acid mixture, a potassium permanganate solution (6.5% by volume), or any combination thereof. In some embodiments, 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 a 1 liter solution, the manganese oxide colloidal particles can be present in an amount of 50.0 g / L to 70.0 g / L, preferably 55.0 g / L to 65.0 g / L, the phosphoric acid can be present in an amount of 210.0 mL / L to 230.0 mL / L, preferably 215.0 mL / L to 225.0 mL / L, and the sulfuric acid can be present in an amount of 560.0 mL / L to 580.0 mL / L, preferably 570.0 mL / L to 575.0 mL / L. The chemical reagents can include sulfuric acid (H2SO4) having a molar strength of 8.0 M to 14.0 M, preferably 9.0 M to 12.0 M, and / or phosphoric acid having a molar strength of 2.0 M to 6.0 M, preferably 3.0 M to 5.0 M.

[0067] The surface-treated thermoplastic composition of the present invention can preserve the impact properties of polymeric articles even after surface treatment with chemical reagents. For example, the surface-treated polymeric article can have an impact strength of 3 kJ / m when measured according to ISO 180 / 1A. 2 ~30kJ / m 2 or 3 kJ / m2 , 5kJ / m 2 , 10 kJ / m 2 , 15kJ / m 2 , 20kJ / m 2 , 25kJ / m 2 , 30kJ / m 2 , or 4.0 kJ / m 2 or more and 25.0 kJ / m 2 Below, 5.0kJ / m 2 More than 20.0kJ / m 2 In one embodiment, a thermoplastic composition comprising 30% to 70% by weight of copolymer SAN (copolymer (A)), 20% to 50% by weight of ABS (copolymer (B)), and 1% to 5% by weight of an ethylene-acrylic acid copolymer (polar polymer (C)) can have a notched Izod impact strength of 17 kJ / m or less, or any range or value therebetween. 2 ~25kJ / m 2 It has a notched Izod impact strength of

[0068] D. Metal-Plated Thermoplastic Compositions In one embodiment 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 adhered to a portion of the surface-treated thermoplastic composition. The metal layer can have a peel strength, measured according to ASTM B533-85(2004), of 0.14 N / mm or more 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 or more to 2.0 N / mm or less, 0.16 N / mm or more to 2.0 N / mm or less, 0.2 N / mm or more to 1.5 N / mm or less, 0.3 N / mm or more to 1.5 N / mm or less, or any range or value therebetween.

[0069] The metal-plated thermoplastic compositions of the present invention can be produced by known metal plating techniques. For example, the thermoplastic compositions of the present invention can be metal-plated using a combination of chemical plating and electroplating. In one embodiment, 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 an applied current (e.g., 1.0 ampere or more and 4.0 amperes or less for a time period of 5 minutes or more and 30 minutes or less) to produce a metal-plated article.

[0070] Chemical plating can include the following steps: (i) sensitizing the surface-treated thermoplastic composition with a suitable sensitizing solution, such as a SnCl / HCl solution, followed by activation with an activating solution, such as a PdCl / HCl solution, to form an activated article; and (ii) subsequently treating the activated article with monosodium phosphate (NaHPO) and a chemical plating solution to obtain a precursor article. Non-limiting examples of chemical plating solutions include CuSO 5H O (15 g / L), NaKCHO 4H O (30 g / L), HCHO (100 ml / L), and NaOH (4 g / L). Alternatively, the chemical plating solution can include NiSO 6H O (15 g / L), NaKCHO 4H O (30 g / L), HCHO (100 ml / L), and NaOH (4 g / L). The metal electrolyte can be nickel sulfate, copper sulfate, aluminum salts (e.g., aluminum chloride or aluminum sulfate), zinc-based salts (e.g., zinc sulfate or zinc chloride), silver salts (e.g., silver sulfate or silver chloride), or a mixture of zinc and silver salts. A metal-plated thermoplastic composition can be formed by a chemical plating process. The metal-plated thermoplastic composition of the present invention can have the appropriate electrical conductivity required for performing an 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, a silver-based layer, or a metal alloy-based layer, and 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, holders, lamp bodies, corporate logos, and many other decorative parts used in the automotive industry, household appliances, electronics, furniture, sanitaryware, etc.

[0071] E. Manufactured articles The thermoplastic compositions of the present invention can be formed into articles (e.g., extrusion-molded articles, injection-molded articles, compression-molded articles, rotational molded articles, blow-molded articles, injection-blow-molded articles, 3D-printed articles, thermoformed articles, foamed articles, or cast films) that are not subjected to surface treatments and / or do not have a metallic coating, and are included in or are articles of manufacture. Non-limiting examples of articles of manufacture include exterior and / or interior vehicle parts, exterior and / or interior train parts, exterior and / or interior airplane parts, exterior and / or interior building parts, electrical equipment parts, electronic equipment parts, industrial equipment parts, medical packaging films and / or parts, medical trays, blister packs, medical ingredient containers, food packaging films, or food containers.

[0072] Example The present invention will be described in detail below with specific examples. The following examples are provided for illustrative purposes only and are not intended to limit the present invention in any way. Those skilled in the art will easily recognize various non-critical parameters that can be changed or modified to produce essentially the same results.

[0073] Example 1 (Preparation of Thermoplastic Compositions of the Invention and Comparative Thermoplastic Compositions) All formulations were prepared at a 4 kg scale. A mixture of SAN (SABIC® 556 or 581) pellets (copolymer (A)) and polar polymer (C) was added through the main hopper / feeder, while a preblend of butadiene rubber (CYCOLAC™ INP362, rubber-modified thermoplastic polymer (B)) was fed through a side feeder along with processing additives EBX wax, magnesium stearate, magnesium oxide, and silicone fluid (see Table 1). Each formulation contained different amounts of a different type of polar polymer (C), e.g., ethylene-acrylic acid copolymer, polyvinylpyrrolidone polymer, or polyvinyl alcohol polymer. Details of the formulations are shown in Table 1. A comparative thermoplastic sample was prepared by mixing equal amounts of both SAN556 and SAN581 (copolymer (A)) and melt-blending them with HRG (rubber-modified thermoplastic polymer (B)) and processing additives without any polar polymer additives. The thermoplastic compositions of the present invention were prepared in the same manner as the comparative samples, except that the polar polymer (C) pellets and the SAN mixture were premixed in a plastic container before being poured into the main hopper to produce homogeneously mixed pellets. Similarly, the HRG and processing additives were dry-blended in a separate plastic container to obtain a homogeneous powder preblend. In each formulation, two types of SAN (556, 581) were used in equal amounts, along with a polyethylene acrylic acid copolymer (PE-AA) (Nucrel 30707) containing 6.9% by weight of acrylic acid, and a polyvinyl alcohol (PVOH) polymer containing 80% hydrolyzed polyvinyl acetate. [Table 1]

[0074] The physically mixed formulations were melt mixed in a 10-barrel Coperion ZSK-26mm co-rotating twin-screw extruder with an L / D ratio of 40:1. Material throughput during extrusion was adjusted to maintain a specific mechanical energy (SME) of 0.172-0.185 while maintaining a screw RPM of 250. The temperature profile used during extrusion and the processing parameters used during this study are shown in Tables 2 and 3, respectively. Table 2 shows the temperature profile used during extrusion of the comparative thermoplastic composition (control) and the compounded thermoplastic composition of the present invention. Table 3 shows the extrusion details. [Table 2] [Table 3]

[0075] During the extrusion process, relatively lower torque values ​​(40-43%) were evident for the 10 wt% PE-AA-containing thermoplastic composition (F11) compared to those observed for the comparative sample (C10, 48-51%), indicating a decrease in melt viscosity. Such a decrease in melt viscosity with the incorporation of 10 wt% PE-AA was attributed to the plasticizing effect of EAA due to its lower molecular weight nature. On the other hand, slightly higher torque values ​​(57-60%) were evident for the thermoplastic composition incorporating 10 wt% PVOH (F14), possibly indicating an increase in melt viscosity.

[0076] Test specimens, including ISO tensile bars, ISO impact bars, and 3 mm color plaques, were injection molded 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 / s. The molded parts were kept conditioned at 23°C and 50% RH for 72 hours.

[0077] Example 2 (Test Results of Thermoplastic Compositions of the Present Invention and Comparative Thermoplastic Compositions) Notched Izod impact (NII) properties were measured according to ISO 180 / 1A and are shown in Figures 1A and 1B. The NII value of the thermoplastic composition (F10) incorporating 3% by weight of polar polymer (C) is similar to or slightly higher than that of the comparative thermoplastic composition (C10). The NII values ​​of the thermoplastic compositions (F15 and F16, respectively) incorporating 6 to 10% by weight of polar polymer (C) are significantly higher than that of the comparative thermoplastic composition (C11).

[0078] Vicat softening temperature (VST) measurements of the comparative thermoplastic compositions and the thermoplastic compositions of the present invention were performed in accordance with ISO-B120 using a CEAST apparatus equipped with a VICAT-6 station at a force of 50 N. The results are shown in Figures 2A and 2B. The VST values ​​of the PE-AA containing 3% by weight (F10), 6% by weight (F16), and 10% by weight (F11 and F15) polar polymer (C) compositions are comparable to the VST values ​​of the comparative thermoplastic compositions (C10 and C11) that do not contain polar polymer (C).

[0079] Heat deformation treatment (HDT) measurements of the comparative thermoplastic compositions and the thermoplastic compositions of the present invention were performed according to ISO 75 using a CEAST apparatus equipped with an HDT-6 station at 120°C / hr at 1.8 MPa. The results are shown in Figure 3. HDT decreased compared to the control ABS (C11) (from 80°C to 70°C for F15 and from 80°C to 70°C for F16).

[0080] Thermoplastic compositions of some embodiments of the present invention and a control ABS were injection molded into impact bars, and color differences were measured. As shown in Figure 4, the visual appearance of the thermoplastic compositions of the present disclosure appeared significantly improved compared to the control ABS bar. On a relative basis, the thermoplastic compositions of the present invention (F15, F16) exhibited a whiter color compared to the control ABS composition (C11), which did not contain the polar polymer (C) and exhibited a darker color.

[0081] Yellowness Index (YI) measurements were made according to ASTM E313-20 and were derived from spectrophotometric data and indicated the extent to which the color of the test sample changed from clear or white to yellow.

[0082] As shown in Table 4, the YI of the inventive thermoplastic composition (C16) was 7 units lower than the YI of the control ABS composition. A further decrease in YI (12 units) was evident for the inventive thermoplastic composition (C15) containing 10 wt. % polar polymer (C). Table 4 shows color measurements using CIELAB color space analysis. * , a * and b * represent each of the three values ​​used by the CIELAB color space to measure objective color and calculate color differences. * represents brightness from black to white on a scale of 0 to 100, and a * and b * represents chromaticity and has no specific numerical limit. * corresponds to green, and positive a * corresponds to red, and negative b * corresponds to blue, and positive b * corresponds to yellow. * A 3 unit increase in β-glucan increased the whiteness of the formulated samples compared to the control sample. [Table 4]

[0083] Example 3 (Pretreatment of Molded Plaques of Comparative and Inventive Thermoplastic Compositions) Molded plaques of the comparative thermoplastic composition (C10) and the inventive thermoplastic compositions (F10-F14) were pretreated with an acidic manganese colloid solution for various times and concentrations. The conventional pretreatment etching solution was prepared by mixing CrO3 and H2SO4. The optimal acid pretreatment conditions achieved favorable surface morphology, which enabled mechanical interlocking along with chemical adhesion, resulting in strong metal-thermoplastic resin interfacial adhesion. The chemicals and conditions used to pretreat the molded plaques of the comparative thermoplastic composition and the inventive compounded thermoplastic composition are listed in Table 5. For the manganese colloid, the pretreatment time was varied between 10 and 20 minutes, as detailed in Table 5. [Table 5]

[0084] Example 4 (Pretreatment of Molded Plaques of Comparative and Inventive Thermoplastic Compositions with Acidic Colloidal Manganese) For direct comparison, the changes in surface morphology due to acidic manganese colloid treatment were compared to samples of the same composition subjected to a conventional standard hexachrome-based etching process. Molded plaques of a comparative thermoplastic composition (C10) and an inventive thermoplastic composition (containing 3% PE-AA by weight) (F10) were pretreated with acidic manganese colloid in two different amounts of sulfuric acid. 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 10–20 minutes.

[0085] Example 5 (Analysis of Comparative Thermoplastic Compositions Pretreated with Acidic Colloidal Manganese and Thermoplastic Compositions of the Invention) The surface morphologies of treated samples for a comparative thermoplastic composition (C10) and a 3 wt. % PE-acrylic acid (polymer (C))-incorporated thermoplastic composition (F10) of the present invention, as inferred from SEM microscopy, are shown in Figures 5 and 6, respectively. As shown in Figure 5, there was only a slight change in the surface morphology of the thermoplastic composition of the present invention when treated with acidic manganese colloid (prepared by mixing H3PO4 (219 mL / L), H2SO4 (573 mL / L), and MnO2 (60 g / L) for 10 and 20 minutes at 70 °C) at a low amount of sulfuric acid. When the sulfuric acid concentration was increased in the preparation of acidic manganese colloid (prepared by mixing H3PO4 (219 mL / L), H2SO4 (605 mL / L), and MnO2 (60 g / L) for 10 and 20 minutes at 70 °C), a significant change in surface morphology was evident, accompanied by the appearance of non-uniform cavities. Therefore, it can be concluded that pretreatment of molded plaques of the comparative thermoplastic composition with an acidic manganese colloid obtained using a lower concentration of sulfuric acid did not result in significant changes to the surface morphology, whereas similar pretreatment using an acidic manganese colloid obtained using a higher concentration of sulfuric acid resulted in roughness and the creation of voids. Clearly, pretreatment using an acidic manganese colloid obtained using a higher concentration of sulfuric acid for a longer duration (20 minutes) resulted in an overly etched surface, with an irregular pattern of peaks and valleys.

[0086] As shown in the SEM images in Figure 6, pretreatment of molded plaques of a thermoplastic composition of the present invention containing 3 wt% polar polymer (C) PE-AA (EtcP-F10) with acidic manganese colloid at various sulfuric acid concentrations and durations resulted in various morphological characteristics. For example, pretreatment with H3PO4 (219 mL / L), H2SO4 (573 mL / L), and MnO2 (60 g / L) for 10 min at 70 °C did not result in significant morphological changes, while longer pretreatment times (20 min) resulted in the formation of small cavities on the surface. Furthermore, increasing the sulfuric acid concentration in the acidic manganese colloid from 573 mL / L to 605 mL / L produced a skeletal morphology with significant voids and subsurface undercuts. Such morphological characteristics are similar to those observed for the hexachrome-etched comparative thermoplastic sample (C10). The presence of subsurface undercuts may enable strong mechanical interlocking between the metal and plastic. To investigate the effect of morphology on metal-plastic interfacial adhesion, all of these formulations were metallized and then tested for peel adhesion.

[0087] Similar pretreatment experiments were performed using a thermoplastic composition (F11) incorporating 10 wt% PE-AA of the present invention. In this case, morphological features were evident regardless of the sulfuric acid concentration in the acidic manganese colloid, as shown in Figure 7. However, different surface morphologies were observed with longer pretreatment times (20 min).

[0088] As shown in Figure 8, TEM analysis of molded plaques of the comparative thermoplastic composition (C10) revealed the presence of skin regions with elongated / deformed butadiene rubber domains, which extended up to 3-5 microns compared to the bulk region, which contained rounded domains of various sizes. In comparison, the skin regions of the inventive thermoplastic compositions appeared to have higher roughness (F10) or were even thicker, extending up to 8-10 microns (F11). However, there was a significant change in the skin regions after the etching treatment; the skin regions appeared thinner due to the removal of part of the top layer by the acid treatment. Representative images of the etched skin regions for samples C10 and F10 are shown in Figure 8.

[0089] Example 6 (Metal Plating of Molded Plaques of Comparative and Inventive Thermoplastic Compositions) Chemical Plating Process: General Procedure: The surface of the substrate was electrochemically plated by placing the substrate in a plating bath. The metal ions in the plating bath were reduced and bonded to the polar groups of the polymer substrate, forming a metal layer on the substrate surface. 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) solution. The electrochemical 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 electrochemically plated for 15 minutes. The sheet resistance of the coated samples was tested and used for electroplating using the process described below.

[0090] Electroplating process: General Procedures. The electroplating experiments consisted of a copper deposition process and were 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 amps and the temperature was 29°C. The plating time was 30 minutes for both the comparative thermoplastic composition and the inventive thermoplastic composition.

[0091] The process conditions for electroplating were optimized with respect to applied current and treatment time. Furthermore, a statistically significant trend was identified for metal growth on plaques of the formulated thermoplastic composition of the present invention. Furthermore, the thickness of the metal layer grown on the surface of the plaque was observed to increase with treatment time from 5 to 30 minutes.

[0092] To achieve finite control of metal thickness during electroplating, different parameters (current and time) must be considered. To compare the final peel strength of different samples, a constant metal thickness is required to ensure that differences in peel strength are primarily due to different adhesion processes, i.e., chemical vs. mechanical. However, in these examples, the surface conductivity of each sample varied due to the chemical plating process. Therefore, all samples were cut to the same diameter to maintain the same surface area. Electroplating was performed on the same day, keeping the pH, electrolyte concentration, applied current, treatment time, and temperature unchanged.

[0093] Example 7 (Peel Testing of Comparative Thermoplastic Compositions and Thermoplastic Compositions of the Invention) Thermoplastic compositions of the present 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 shows the average peel forces of C10, F10, and F11, along with those observed after a conventional hexachromate etching process. Sample F10 exhibited peel strength values ​​in the range of 0.16 to 0.27 N / mm, while slightly higher peel strength values ​​are evident for thermoplastic composition F11 of the present invention.

[0094] Copper films on test formulations after pretreatment with manganese colloidal acid (see Example 5) made with various concentrations of sulfuric acid were metallized as described in Example 6 and tested for peel force measurements. Figure 10 shows peel test results for both inventive test formulations F10 and F11 and a control (C10, ABS). Low loadings (3 wt%) of PE-AA additive (inventive polar polymer (C)) in the thermoplastic compositions had metal-plastic adhesion strengths ranging from 0.11 to 0.25 N / mm. Higher loadings (10 wt%) of PE-AA additive in inventive thermoplastic compositions had peel forces ranging from 0.01 to 0.22 N / mm. The inventive F10 thermoplastic composition (PE-AA (3 wt%)) etched with a low (573 mL / L) concentration of sulfuric acid in manganese colloid for 10 minutes had better peel force than the sample etched for 20 minutes.

[0095] The average peel strength values ​​estimated by considering the surface area were higher (0.29 N / mm) for the compounded thermoplastic compositions of the present invention (e.g., F11) than the value (0.22 N / mm) observed for the comparative thermoplastic composition (C10) when pretreated with conventional hexachromate, as shown in Figure 11.

[0096] Peel test results for a comparative thermoplastic composition pretreated with acidic manganese colloid and a compounded thermoplastic composition of the present invention are shown in Figure 12. The comparative thermoplastic composition had a maximum peel force of 0.27 N / mm after pretreatment with H3PO4 (219 mL / L), H2SO4 (605 mL / L), and MnO2 (60 g / L) for 10 minutes at 70°C. The inventive thermoplastic compound F10 achieved a best peel force of 0.19 N / mm at any sulfuric acid concentration for a 10-minute etching time. However, increasing the etching time slightly decreased the metal-plastic peel force. Another inventive thermoplastic compound F11 achieved a maximum peel force of 0.15 N / mm after pretreatment with H3PO4 (219 mL / L), H2SO4 (605 mL / L), and MnO2 (60 g / L) for 20 minutes at 70°C. Interestingly, ABS / PE-AA (3 wt%) exhibits better peel adhesion under similar 10-minute treatments with lower acid concentrations, which is interesting in terms of lowering processing costs and speeding up plating, potentially resulting in significant savings in plating costs.

[0097] Peel testing determined that the use of conventional hexachromate 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). The results determined that the texture provided using the thermoplastic composition of the present invention provided better metal-plastic bonding and better peel strength compared to the comparative thermoplastic composition without the polar polymer (C).

[0098] Although the embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions, and alterations can be made herein without departing from the spirit and scope of the embodiments, as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the processes, machines, manufacture, compositions of matter, means, methods, and steps described herein. As will be readily apparent from the above disclosure, those skilled in the art can utilize existing or future-developed processes, machines, manufacture, compositions of matter, means, methods, or steps that perform substantially the same function or achieve substantially the same results as the corresponding embodiments described herein. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

1. A thermoplastic polymer composition comprising, based on a total weight of the thermoplastic polymer composition: (a) 30% to 79% by weight of a copolymer (A) comprising units derived from (i) a vinyl aromatic monomer and (ii) 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 having a molecular weight of 5,000 g / mole to 25,000 g / mole; and (d) Melt processing additives 1. A thermoplastic polymer composition comprising:

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

3. 3. The thermoplastic polymer composition according to claim 1 or 2, characterized in that 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 rubber-modified polymer (B) is A polymer rubber comprising polymer units derived from a conjugated diene, said conjugated diene comprising 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 graft thermoplastic copolymer (D), grafted to the polymer rubber, the graft thermoplastic copolymer (D) comprising polymer units derived from: (i) a vinyl aromatic monomer comprising styrene, α-methylstyrene, dibromostyrene, vinyl toluene, vinyl xylene, butyl styrene, 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). The thermoplastic polymer composition according to any one of claims 1 to 3, characterized in that it comprises

5. 5. The thermoplastic polymer composition according to claim 1, wherein the 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. 6. The thermoplastic polymer composition according to claim 1, wherein the polar polymer (C) comprises an ethylene-acrylic acid copolymer, a polyvinylpyrrolidone polymer, a polyvinyl alcohol polymer, or a blend thereof.

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

8. 8. The thermoplastic polymer composition of any one of claims 1 to 7, characterized in that the melt processing additive comprises magnesium oxide (MgO), silicone fluid, ethylene bisstearylamide (EBX) wax, magnesium stearate, or mixtures thereof.

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

10. 3.0 kJ / m when measured according to ISO 180 / 1A ２ ~30.0 kJ / m ２ , preferably 4.0 kJ / m ２ ~25.0 kJ / m ２ , more preferably 5.0 kJ / m ２ ~20.0 kJ / m ２ 10. The thermoplastic polymer composition according to any one of claims 1 to 9, characterized in that it has a notched Izod impact strength of

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

12. Thermoplastic polymer composition according to any one of claims 1 to 11, characterized in that it is comprised in an article of manufacture, preferably a moulded article of manufacture.

13. 13. The thermoplastic polymer composition according to any one of claims 1 to 12, characterized in that the thermoplastic polymer composition has a lower Yellowness Index (YI) than the thermoplastic polymer composition in the absence of the polar polymer (C).

14. 14. The thermoplastic polymer composition according to any one of claims 1 to 13, characterized in that 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. 15. A metal-plated article comprising the thermoplastic polymer composition of any one of claims 1 to 14 and a metal adhered 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. 15. A method for producing the thermoplastic polymer composition of any one of claims 1 to 14, comprising melt blending a thermoplastic composition, said 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) Melt processing additives A method comprising:

17. forming 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, the chemical agent preferably comprising a suspension of colloidal manganese oxide particles in a mineral acid mixture comprising sulfuric acid and phosphoric acid; and subjecting the surface-treated article to conditions suitable for adhering a metal layer to at least a portion of the treated surface to produce a metal-plated portion of the article.

17. The method of claim 16, further comprising:

18. 15. A method for reducing the yellowness index (YI) of the thermoplastic polymer composition of any one of claims 1 to 14, comprising melt blending the thermoplastic composition, wherein the thermoplastic composition comprises: (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) Melt processing additives A method comprising:

Images