Laser direct structuring compositions containing crystalline polyesters

Abstract

A thermoplastic composition comprising: (a) about 1 wt% to about 99 wt% of at least one crystalline polyester; (b) about 1 wt% to about 99 wt% of a polycarbonate copolymer; (c) about 10 wt% to about 50 wt% of a reinforcing filler; and (d) about 1 wt% to about 10 wt% of a laser direct structuring (LDS) additive. In a detailed embodiment, the at least one crystalline polyester comprises polybutylene terephthalate (PBT), and the polycarbonate copolymer comprises a polycarbonate-siloxane (PC-Si) copolymer. In a further embodiment, the at least one reinforcing filler comprises glass fiber, and in a specific embodiment, flat glass fiber. The composition has improved adhesion, surface appearance, and / or warpage properties compared to a comparative composition not comprising the polycarbonate copolymer.

Description

[Technical Field]

[0001] The present disclosure relates to crystalline polyester-based laser direct structuring (LDS) compositions, and in particular to compositions comprising crystalline polyester and polycarbonate copolymer. [Background technology]

[0002] Laser direct structuring (LDS), which involves laser activation and a subsequent chemical plating procedure, is widely used to create circuit components in the consumer electronics industry, such as in mobile phone technology. Specifically, the LDS process can be used to fabricate antennas for mobile devices. Polycarbonate (PC)-based LDS materials are favored by antenna manufacturers because they offer a good balance of flow, mechanical properties, and dimensional stability. However, PC has poor chemical resistance, which can result in problems with alkaline plating erosion and therefore low surface gloss. This problem is exacerbated with glass-filled PC. Erosion of the PC can result in a "floating" glass appearance, which is undesirable for customers. For at least these reasons, glass-filled PC LDS materials are not favored.

[0003] To meet the high modulus requirements for mobile antenna applications, glass-filled polyamide (PA) LDS materials have been used, which offer good chemical resistance and a high-gloss surface after alkali plating. However, the anisotropic characteristics of PA result in warping, a common problem with crystalline polymers. The moisture retention issue of PA also leads to poor dielectric stability, which affects antenna performance and makes it unsuitable for 5G mobile applications.

[0004] These and other shortcomings are addressed by aspects of the present disclosure. Summary of the Invention [Means for solving the problem]

[0005] An embodiment of the present disclosure relates to a thermoplastic composition comprising: (a) about 1 wt% to about 99 wt% of at least one crystalline polyester; (b) about 1 wt% to about 99 wt% of a polycarbonate copolymer; (c) about 10 wt% to about 50 wt% of a reinforcing filler; and (d) about 1 wt% to about 10 wt% of a laser direct structuring (LDS) additive. In a detailed embodiment, the at least one crystalline polyester comprises polybutylene terephthalate (PBT), and the polycarbonate copolymer comprises a polycarbonate-siloxane (PC-Si) copolymer. In a further embodiment, the at least one reinforcing filler comprises glass fiber, and in a specific embodiment, flat glass fiber. The composition has improved adhesion, surface appearance, and / or warpage properties compared to a comparative composition that does not comprise the polycarbonate copolymer.

[0006] In the drawings, which are not necessarily drawn to scale, like numerals may describe like components in different views. Like numerals with different letter suffixes may represent different instances of like components. The drawings generally illustrate various aspects discussed herein by way of example, but not by way of limitation. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a photograph comparing the plating performance of comparative and example compositions according to embodiments of the present disclosure. [Figure 2] FIG. 2 is a photograph comparing the warpage performance of comparative and example compositions according to embodiments of the present disclosure. [Figure 3] FIG. 3 is a photograph comparing the warpage performance of comparative and example compositions according to embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0008] This disclosure relates to polyester / PC copolymer blends that address the chemical resistance issues of PC and the warpage issues of crystalline polymers. The compositions according to this disclosure offer a good balance of flow, mechanical, dimensional stability, and chemical resistance properties. The combination of a crystalline polyester (e.g., polybutylene terephthalate (PBT)) with a PC copolymer provides a composition suitable for high-modulus applications such as mobile phone antennas, which are beneficial for both current and next-generation communication applications.

[0009] The present disclosure may be more readily understood by reference to the following detailed description of the disclosure and the examples included therein. In various aspects, the present disclosure relates to a thermoplastic composition comprising: (a) from about 1 wt % to about 99 wt % of at least one crystalline polyester; (b) from about 1 wt % to about 99 wt % of a polycarbonate copolymer; (c) from about 10 wt % to about 50 wt % of a reinforcing filler; and (d) from about 1 wt % to about 10 wt % of a laser direct structuring (LDS) additive.

[0010] Before the present compounds, compositions, articles, systems, devices, and / or methods are disclosed and described, it is to be understood that they are not limited to particular synthetic methods, unless otherwise specified, or to particular reagents, unless otherwise specified, and as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0011] Various combinations of elements of the present disclosure are encompassed by the present disclosure, for example combinations of elements from dependent claims that are dependent on the same independent claim.

[0012] Furthermore, unless expressly stated otherwise, it is understood that it is in no way intended that any method described herein be construed as requiring that its steps be performed in a specific order. Thus, where a method claim does not actually recite the order in which its steps are to be followed, or where the claim or the specification does not otherwise specifically indicate that the steps are limited to a specific order, no order is intended to be inferred in any respect. This applies to matters of logic regarding the arrangement of steps or operational flow; the plain meaning derived from grammatical construction or punctuation; and any possible implicit basis for interpretation, including the number or type of aspects described in the specification.

[0013] All publications mentioned herein are incorporated by reference to disclose and describe the methodologies and / or materials in connection with which the publications are cited. definition

[0014] It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein and in the claims, the term "comprising" can include embodiments such as "consisting of" and "consisting essentially of." Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In this specification and in the appended claims, reference will be made to several terms that are intended to be defined herein.

[0015] As used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a polycarbonate copolymer" includes a mixture of two or more polycarbonate copolymers.

[0016] As used herein, the term "combination" is inclusive of blends, mixtures, alloys, reaction products, and the like.

[0017] Ranges can be expressed herein as from one value (first value) to another value (second value). When such a range is expressed, the range, in some embodiments, includes one or both of the first and second values. Similarly, when values ​​are expressed as approximations, it is understood that the use of the antecedent "about" introduces another embodiment of the particular value. It is further understood that the endpoints of each range are valid values ​​both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are multiple values ​​disclosed herein, and that each value is also herein disclosed as "about" that value in addition to the particular value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It is also understood that each unit between two specified units is also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0018] As used herein, the terms "about" and "at or near" mean that the quantity or value in question can be the specified value, approximately the specified value, or nearly the same as the specified value. As used herein, unless otherwise indicated or inferred, it is generally understood to be a variation of ±10% of the indicated nominal value. This term is intended to convey that an equivalent result or effect as recited in the claims is facilitated by a similar value. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and / or larger or smaller as desired, reflecting tolerances, conversion factors, rounding, measurement errors, and the like, as well as other factors known to those skilled in the art. In general, amounts, sizes, formulations, parameters, or other quantities or characteristics are "about" or "approximate," regardless of whether they are expressly stated as such. When "about" is used before a quantitative value, the parameter is also understood to include the specific quantitative value itself, unless specifically stated otherwise.

[0019] Disclosed are the components used to prepare the disclosed compositions, as well as the compositions themselves used within the methods disclosed herein. Because these and other materials are disclosed herein, when combinations, subsets, interactions, groups, etc. of these materials are disclosed, it is understood that each is specifically contemplated and described herein, even if specific reference to each of the various individual and collective combinations and permutations of these compounds may not be explicitly disclosed. For example, when particular compounds are disclosed and discussed, and multiple modifications that can be made to molecules comprising those compounds are discussed, what is specifically contemplated are each and every combination and permutation of those compounds, as well as modifications thereof that are possible unless specifically indicated to the contrary. Thus, when a class of molecules A, B, and C is disclosed, as well as a class of molecules D, E, and F, and an example of a combined molecule, AD, is disclosed, each is individually and collectively contemplated, even if not individually mentioned, meaning that the combinations AE, AF, BD, BE, BF, CD, CE, and CF are considered to be disclosed. Similarly, any subsets or combinations of these are also disclosed. Thus, for example, the subgroups AE, BF, and CE could be considered disclosed. This concept applies to all aspects of this application, including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, where there are various additional steps that can be performed, it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the disclosed methods.

[0020] Throughout this specification and the concluding claims, reference to parts by weight of a particular component or ingredient in a composition or article indicates the weight relationship between that component or ingredient and the other components or ingredients in the composition or article that are also expressed in parts by weight. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2:5, regardless of whether additional components are included in the compound.

[0021] Weight percent of a component is based on the total weight of the formulation or composition in which the component is included, unless specifically stated to the contrary.

[0022] As used herein, the term "number average molecular weight" or "M n " can be used interchangeably and refers to the statistical average molecular weight of all polymer chains in a sample and is expressed by the formula:

[0023]

number

[0024] As used herein, the term "weight average molecular weight" or "M w " can be used interchangeably, and the formula:

[0025]

number

[0026] As used herein, the terms "molecular weight dispersity index" or "PDI" may be used interchangeably and are defined by the formula:

[0027]

number

[0028] As used herein, the terms "BisA," "BPA," or "bisphenol A" may be used interchangeably and have the formula:

[0029] [ka] BisA refers to a compound having the structure: BisA can also refer to 4,4'-(propane-2,2-diyl)diphenol; p,p'-isopropylidenebisphenol; or 2,2-bis(4-hydroxyphenyl)propane. BisA has the CAS number 80-05-7.

[0030] As used herein, "polycarbonate" refers to an oligomer or polymer containing residues of one or more dihydroxy compounds, e.g., dihydroxy aromatic compounds, joined by carbonate linkages, and includes homopolycarbonates, copolycarbonates, and (co)polyestercarbonates.

[0031] The terms "residue" and "structural unit" used in reference to components of a polymer are synonymous throughout this specification.

[0032] As used herein, the terms "weight percent," "wt%," and "wt.%" can be used interchangeably and refer to the weight percent of a given component based on the total weight of the composition, unless otherwise specified. That is, all wt% values ​​are based on the total weight of the composition, unless otherwise specified. It is understood that the sum of the wt% values ​​of all components in a disclosed composition or formulation equals 100.

[0033] Unless otherwise stated herein to the contrary, all test standards are the latest standards in effect at the time of filing this application.

[0034] Each of the materials disclosed herein is commercially available and / or methods for its preparation are known to those skilled in the art.

[0035] It is understood that the compositions disclosed herein have specific functions, and while disclosed herein are specific structural requirements for performing the disclosed functions, it is understood that there are a variety of structures that can perform the same functions related to the disclosed structures, and that these structures will typically achieve the same results. thermoplastic composition

[0036] An embodiment of the present disclosure relates to a thermoplastic composition comprising: (a) about 1 wt % to about 99 wt % of at least one crystalline polyester; (b) about 1 wt % to about 99 wt % of a polycarbonate copolymer; (c) about 10 wt % to about 50 wt % of a reinforcing filler; and (d) about 1 wt % to about 10 wt % of a laser direct structuring (LDS) additive, wherein the combined weight percentage of all components does not exceed 100 wt %, and all weight percentages are based on the total weight of the composite.

[0037] In some embodiments, the at least one crystalline polyester comprises polybutylene terephthalate (PBT), polycyclohexylene dimethylene terephthalate (PCT), polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polycyclohexylene dimethylene terephthalate glycol (PCTG), polycyclohexylene dimethylene terephthalic acid (PCTA), copolymers thereof, or combinations thereof. In detailed embodiments, the at least one crystalline polyester comprises polybutylene terephthalate (PBT).

[0038] In some embodiments, the composition comprises from about 1 wt% to about 99 wt% of at least one crystalline polyester. In other embodiments, the composition comprises from about 30 wt% to about 99 wt% of at least one crystalline polyester. In further embodiments, the composition comprises at least one crystalline polyester as a major component; i.e., the at least one crystalline polyester is present in a greater amount than any other component in the composition, such as the polycarbonate copolymer or the reinforcing filler. In further embodiments, the at least one crystalline polyester is present in the composition in a greater amount than the polycarbonate copolymer.

[0039] Suitable polycarbonate copolymers include, but are not limited to, polycarbonate-siloxane (PC-Si) copolymer, polycarbonate-isophthalate terephthalate resorcinol (PC-ITR) copolymer, or combinations thereof.

[0040] In some embodiments, the composition comprises about 1 wt% to about 99 wt% of the polycarbonate copolymer. In particular embodiments, the composition comprises about 1 wt% to about 30 wt% of the polycarbonate copolymer. In detailed embodiments, the composition comprises a lower content of the polycarbonate copolymer compared to the at least one crystalline polyester.

[0041] In certain embodiments, the polycarbonate copolymer comprises a polycarbonate-siloxane (PC-Si) copolymer having a siloxane content of about 10 wt% to about 30 wt%. In specific embodiments, the PC-Si copolymer has a siloxane content of about 15 wt% to about 25 wt%, or about 18 wt% to about 22 wt%, or about 20 wt%.

[0042] Reinforcing fillers may include, but are not limited to, silica, talc, mica, carbon black, carbon fiber, aramid fiber, glass fiber, glass flake, hollow glass beads, crushed glass fiber, and combinations thereof. In certain embodiments, the reinforcing filler comprises glass fiber. Any suitable glass fiber may be used.

[0043] In detailed embodiments, the glass fibers are flattened glass fibers. The flatness of a fiber is a function of the ratio between the width and height of the rectangular cross section of the fiber. In some embodiments, the flattened glass fibers have a flatness of at least 2. In other embodiments, the glass fibers have a flatness of about 2 to about 10, or about 2 to about 5, or about 4.

[0044] LDS additives may include, but are not limited to, heavy metal mixed oxide spinels, such as copper chromium oxide spinels; copper salts, such as copper hydroxide phosphate, copper sulfate, copper thiocyanate, spinel-based metal oxides (such as copper chromium oxide), organometallic complexes (such as palladium / palladium-containing heavy metal complexes), metal oxides, metal oxide-coated fillers, antimony-doped tin oxide coated on a mica substrate, copper-containing metal oxides, zinc-containing metal oxides, tin-containing metal oxides, magnesium-containing metal oxides, aluminum-containing metal oxides, gold-containing metal oxides, silver-containing metal oxides, or the like, or combinations comprising at least one of the foregoing LDS additives.

[0045] In particular embodiments, the LDS additive comprises a heavy metal mixed oxide spinel, a copper salt, an organometallic complex, a metal oxide, a filler coated with a metal oxide, an antimony-doped tin oxide coated on a mica substrate, a copper-containing metal oxide, a zinc-containing metal oxide, a tin-containing metal oxide, a magnesium-containing metal oxide, an aluminum-containing metal oxide, a gold-containing metal oxide, a silver-containing metal oxide, or a combination thereof. In a detailed embodiment, the LDS additive comprises a copper chromite black spinel.

[0046] In some embodiments, the composition further comprises about 1 wt % to about 10 wt % of a mineral filler different from the reinforcing filler. The mineral filler may include, but is not limited to, mica, talc, calcium carbonate, dolomite, wollastonite, barium sulfate, silica, kaolin, feldspar, barite, or combinations thereof. In certain embodiments, the mineral filler comprises talc.

[0047] The composition, in some embodiments, further comprises at least one impact modifier. In certain embodiments, the at least one impact modifier comprises polyethylene-glycidyl methacrylate (PE-GMA), styrene-ethylene / 1-butene-styrene (SEBS), or a combination thereof.

[0048] The thermoplastic composition has improved properties compared to conventional LDS compositions, particularly compared to conventional PBT and polycarbonate-based compositions. In one embodiment, the composition has improved adhesion compared to a comparative composition that does not contain a polycarbonate copolymer, as determined in accordance with ASTM D3359. As used herein, improved adhesion means an increase in average adhesion by at least a 1B grade when measured by a cross-hatch tape test at a laser power level of 7 watts (W) or greater and a frequency of 1 hertz (Hz).

[0049] In other embodiments, the composition has an improved surface appearance compared to a comparative composition that does not contain the polycarbonate copolymer. In a further embodiment, the composition has an improved surface appearance compared to a comparative composition that does not contain PBT. The improved surface appearance can be visually observed by less free-floating reinforcing filler (e.g., glass fiber) in a molded sample of the composition. The improved surface appearance can also be evaluated based on improved gloss measured using the L*a*b* color system (i.e., the IELAB color space defined by the International Commission on Illumination (CIE)).

[0050] In certain embodiments, the composition has reduced warpage compared to a comparative composition that does not contain a polycarbonate copolymer. Warpage, or bending, can be visually observed in a molded sample of the composition. In a detailed embodiment, warpage can be assessed by molding a sample of the composition that is at least 100 millimeters (mm) x 100 mm, for example, but not limited to, 150 mm x 150 mm, and observing the flatness of the sample. In other embodiments, warpage can be assessed using a quantification method that involves molding a disk having a diameter of about 135 mm and a thickness of about 0.9 mm to about 1.2 mm.

[0051] In some embodiments, the composition has improved gloss as compared to a comparative composition comprising a polycarbonate in place of at least one crystalline polyester, tested according to ASTM D523.

[0052] In a detailed embodiment, the composition is a laser direct structuring (LDS) composition suitable for use in LDS applications. Manufacturing method

[0053] One or any of the aforementioned components described herein may first be dry-blended with each other or with any combination of the aforementioned components, and then fed into the extruder from a single or multiple feeder, or fed separately from a single or multiple feeder. The fillers used in the present disclosure may also be first processed into a masterbatch and then fed into the extruder. The components may be fed into the extruder from a throat hopper or any side feeder.

[0054] Extruders used in the present disclosure may have a single screw, multiple screws, intermeshing co-rotating or counter-rotating screws, non-intermeshing co-rotating or counter-rotating screws, reciprocating screws, pinned screws, screened screws, pinned barrels, rolls, rams, helical rotors, co-kneaders, disc-pack processors, various other types of extrusion equipment, or combinations comprising at least one of the foregoing.

[0055] The components may also be mixed together and then melt-blended to form the thermoplastic composition. Melt-blending the components may involve the use of shear force, extensional force, compression force, ultrasonic energy, electromagnetic energy, thermal energy, or a combination comprising at least one of the foregoing forms of force or energy.

[0056] The barrel temperature of the extruder during compounding can be set to a temperature at which at least a portion of the polymer reaches a temperature about equal to or higher than the melting temperature if the resin is a semi-crystalline organic polymer, or to the pour point (e.g., glass transition temperature) if the resin is an amorphous resin.

[0057] The mixture containing the aforementioned components may be subjected to multiple blending and forming steps, if desired. For example, the thermoplastic composition may first be extruded and formed into pellets. The pellets may then be fed to a molding machine where they may be formed into any desired shape or product. Alternatively, the thermoplastic composition exiting a single melt blender may be formed into sheets or strands and subjected to post-extrusion processes such as annealing, uniaxial or biaxial stretching, etc.

[0058] The temperature of the melt in this process may be kept as low as possible in some embodiments to avoid excessive thermal degradation of the components. In certain embodiments, the melt temperature is maintained between about 230°C and about 350°C, although higher temperatures can be used provided that the residence time of the resin in the processing equipment is kept relatively short. In some embodiments, the melt-processed composition exits the processing equipment, such as an extruder, through small exit holes in a die. The resulting strands of molten resin may be cooled by passing them through a water bath. The cooled strands can be cut into pellets for packaging and further handling. Articles of Manufacture

[0059] In certain aspects, the present disclosure relates to formed, formed, or molded articles comprising the thermoplastic compositions. The thermoplastic compositions can be molded into useful shapes by a variety of means, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming, to form articles and structural components for personal or commercial electronic devices, including, but not limited to, cell phones, tablet computers, personal computers, notebook and portable computers, and other such devices, medical applications, RFID applications, automotive applications, and the like. In a further aspect, the article is extruded. In yet another aspect, the article is injection molded.

[0060] Various combinations of elements of the present disclosure are encompassed by the present disclosure, for example combinations of elements from dependent claims that are dependent on the same independent claim. Aspects of the Disclosure

[0061] In various aspects, the present disclosure relates to and includes at least the following aspects:

[0062] Embodiment 1. (a) about 1 wt % to about 99 wt % of at least one crystalline polyester; (b) about 1 wt % to about 99 wt % of a polycarbonate copolymer; (c) about 10 wt% to about 50 wt% of a reinforcing filler; (d) about 1 wt % to about 10 wt % of a laser direct structuring (LDS) additive; 1. A thermoplastic composition comprising, consisting of, or consisting essentially of, wherein the combined weight percentage of all components does not exceed 100 wt%, all weight percentages being based on the total weight of said composite material.

[0063] Aspect 2. The thermoplastic composition of Aspect 1, wherein the at least one crystalline polyester comprises polybutylene terephthalate (PBT), polycyclohexylene dimethylene terephthalate (PCT), polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polycyclohexylene dimethylene terephthalate glycol (PCTG), polycyclohexylene dimethylene terephthalic acid (PCTA), copolymers thereof, or combinations thereof.

[0064] Embodiment 3. The thermoplastic composition of embodiment 1, wherein the at least one crystalline polyester comprises polybutylene terephthalate (PBT).

[0065] Embodiment 4. The thermoplastic composition of any one of embodiments 1 to 3, wherein the polycarbonate copolymer comprises a polycarbonate-siloxane (PC-Si) copolymer, a polycarbonate-isophthalate terephthalate resorcinol (PC-ITR) copolymer, or a combination thereof.

[0066] Embodiment 5. The thermoplastic composition of any one of embodiments 1 to 3, wherein the polycarbonate copolymer comprises a polycarbonate-siloxane (PC-Si) copolymer having a siloxane content of about 10 wt% to about 30 wt%.

[0067] Embodiment 6. The thermoplastic composition of any one of embodiments 1 to 5, wherein the reinforcing filler comprises silica, talc, mica, carbon black, carbon fiber, aramid fiber, glass fiber, glass flake, hollow glass beads, crushed glass fiber, and combinations thereof.

[0068] Embodiment 7. The thermoplastic composition of any one of embodiments 1 to 5, wherein the reinforcing filler comprises flat glass fibers.

[0069] Embodiment 8. The thermoplastic composition of any one of embodiments 1 to 7, wherein the LDS additive comprises a heavy metal mixed oxide spinel, a copper salt, an organometallic complex, a metal oxide, a filler coated with a metal oxide, an antimony-doped tin oxide coated on a mica substrate, a copper-containing metal oxide, a zinc-containing metal oxide, a tin-containing metal oxide, a magnesium-containing metal oxide, an aluminum-containing metal oxide, a gold-containing metal oxide, a silver-containing metal oxide, or a combination thereof.

[0070] Embodiment 9. The thermoplastic composition of any one of embodiments 1 to 7, wherein the LDS additive comprises a copper chromite black spinel.

[0071] Embodiment 10. The composition further comprising about 1 wt. % to about 10 wt. % of a mineral filler different from the reinforcing filler; 10. The thermoplastic composition of any one of the preceding embodiments, wherein the mineral filler comprises mica, talc, calcium carbonate, dolomite, wollastonite, barium sulfate, silica, kaolin, feldspar, barite, or a combination thereof.

[0072] Embodiment 11. The thermoplastic composition of any one of embodiments 1 to 10, wherein the mineral filler comprises talc.

[0073] Embodiment 12. The thermoplastic composition of any one of Embodiments 1 to 11, further comprising at least one impact modifier.

[0074] Aspect 13. The thermoplastic composition of Aspect 12, wherein the at least one impact modifier comprises polyethylene-glycidyl methacrylate (PE-GMA), styrene-ethylene / 1-butene-styrene (SEBS), or a combination thereof.

[0075] Embodiment 14. The thermoplastic composition of any one of embodiments 1 to 13, having improved adhesion, as determined according to ASTM D3359, relative to a comparative composition not comprising the polycarbonate copolymer.

[0076] Embodiment 15. The thermoplastic composition of any one of embodiments 1 to 14, having an improved surface appearance compared to a comparative composition not including the polycarbonate copolymer.

[0077] Embodiment 16. The thermoplastic composition of any one of embodiments 1 to 15, having reduced warpage compared to a comparative composition not including the polycarbonate copolymer.

[0078] Aspect 17. The thermoplastic composition of any one of Aspects 1 to 16, having improved gloss, as tested in accordance with ASTM D523, compared to a comparative composition comprising a polycarbonate in place of the at least one crystalline polyester.

[0079] Embodiment 18. The thermoplastic composition of any one of embodiments 1 to 17, which is a laser direct structuring (LDS) composition suitable for use in LDS applications.

[0080] Embodiment 19. The thermoplastic composition of any one of embodiments 1 to 18, comprising about 1 wt % to about 30 wt % of at least one crystalline polyester, and about 30 wt % to about 99 wt % of a polycarbonate copolymer. [Example]

[0081] The following examples are presented to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and / or methods claimed herein are made and evaluated, and are intended to be purely illustrative and not intended to limit the disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but it is desirable to account for some errors and deviations. Unless otherwise indicated, parts are parts by weight, temperature is °C or is ambient temperature, and pressure is at or near atmospheric. Percentages referring to compositions are wt% unless otherwise indicated.

[0082] There are numerous variations and combinations of reaction conditions, e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction ranges and conditions, that can be used to optimize the purity and yield of the products obtained from the described processes. Optimizing such process conditions will require only reasonable and routine experimentation.

[0083] The materials used in the comparative and example compositions described herein are shown in Table 1. Table 1 - Materials

[0084] [Table 1]

[0085] Pellets were compounded from these compositions using conventional processes. The resin and additives were premixed and fed through the main throat, and the glass fiber was fed downstream of the extruder. The PC-based (comparative) compositions were compounded using a 40 kilograms per hour (kg / h) output, a 300 revolutions per minute (RPM) screw speed, a 0.6 bar vacuum, 55% torque, a barrel temperature of 255-265°C, and a die temperature of 265°C. The PBT (comparative and exemplary) compositions were compounded using a 50 kg / h output, a 200 RPM screw speed, a 0 bar vacuum, 80% torque, a barrel temperature of 240-250°C, and a die temperature of 250°C.

[0086] The pellets were injection molded according to the conditions listed in Table 2. Table 2 - Injection molding parameters

[0087] [Table 2]

[0088] The compositions formed are illustrated in Table 3. Table 3 - Comparative and Example Compositions

[0089] [Table 3]

[0090] The properties of the compositions (C1, C2, Ex1 to Ex3) in Table 3 are listed in Table 4. Table 4 - Properties of the compositions in Table 3

[0091] [Table 4]

[0092] Specific adhesive properties of C2, Ex1, and Ex2 tested at various power outputs according to ASTM D3359 at 40 kilohertz (KHz) and 100 KHz are given in Table 5. Table 5 - Adhesive properties

[0093] [Table 5]

[0094] Comparative composition C1 uses 30 wt% glass-filled PC for conventional LDS applications, and comparative composition C2 is a control formulation using 30 wt% glass-filled PBT for conventional LDS applications. Ex1 and Ex2 combine PBT and PC copolymers with the same glass fiber type and loading. Ex3 is a PBT blend containing PC-ITR copolymer as the primary component (same glass fiber type and loading, but no impact modifier). Comparative composition C0 should be closer to Ex1 and Ex2 as a more ideal control, but its performance was not tested.

[0095] As shown in Table 4, Example Compositions Ex1 and Ex2 have comparable mechanical properties and better thermal properties. Furthermore, chemical plating after laser activation yielded a plating index of 0.9, indicating sufficient metal deposition. Traditionally, glass-fiber-filled PC LDS compounds have exhibited poor appearance due to glass fiber lifting during plating due to poor chemical resistance. In contrast, Example Compositions Ex1 and Ex2 containing PBT and PC copolymer (siloxane or ITR) were observed to have significantly higher gloss after plating. This is primarily due to the stronger chemical resistance provided by the crystalline PBT. Furthermore, the gloss data for the 85° geometry in Table 4 also demonstrates that the appearance of the crystalline polyester (PBT) / PC copolymer compositions (Ex1, 86.1% gloss and Ex2, 80.6% gloss) is better than the comparative composition containing PC (C1, 73.5% gloss).

[0096] Plated chips for compositions C2, Ex1, and Ex2 are illustrated in Figure 1. Adhesion data for these and other compositions are provided in Table 5. Compared to conventional PBT composition C2, example compositions Ex1 and Ex2 show better plating efficiency at higher laser powers (7-11 watts (W)) and frequencies (above 100 hertz (Hz)). This is due to the PC copolymer's better char formation ability during laser combustion, while the burned PBT releases more fuel (CH2 units), which can lead to damaged / destroyed surfaces and worse metal layer deposition.

[0097] Comparison of comparative composition C3 (which does not contain a polycarbonate copolymer, including polycarbonate-siloxane (PC-Si) copolymer or polycarbonate-isophthalate terephthalate resorcinol (PC-ITR) copolymer) with Ex1 and Ex2 shows similar performance. Both example compositions Ex1 and Ex2 maintain good plating properties at frequencies of 100 KHz and above 7 W, while comparative composition C3 does not.

[0098] Warpage is a common problem with crystalline polymers such as PBT and polyamide. PBT blends containing PC copolymers provide better dimensional stability, even for large molded parts. As demonstrated in Figure 2, the comparative PBT plaque (C2, top) had significant bending during molding. The middle plaque (SLX, Ex1) containing 10 wt% PC-ITR copolymer had significantly better flatness, while the bottom plaque (SLX, Ex3) containing 48.5 wt% PC-ITR copolymer was completely flat. As further demonstrated in Figure 3, the bottom plaque (PC-ITR copolymer, Ex1) was significantly flatter than the top plaque (C3) containing conventional polycarbonate.

[0099] The foregoing is intended to be illustrative, not limiting. For example, the above-described examples (or one or more aspects thereof) may be used in combination with each other. Other aspects may be used, for example, upon review by one of ordinary skill in the art. The Abstract is provided to enable the reader to quickly ascertain the nature of the technical disclosure in accordance with 37 CFR §1.72(b). It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. Also, in the above Detailed Description, various features may be grouped together to streamline the disclosure. However, no unclaimed disclosed feature should be construed as intended as essential to any claim. Rather, inventive subject matter may lie in fewer than all features of a particular disclosed embodiment. Thus, the appended claims are incorporated into the Detailed Description as examples or aspects, with each claim standing on its own as a separate embodiment, and it is contemplated that such embodiments can be combined with each other in various combinations or permutations. The scope of the present disclosure should preferably be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

1. (a) 1 wt % to 99 wt % of at least one crystalline polyester; (b) 1 wt % to 99 wt % of a polycarbonate copolymer, comprising a polycarbonate-siloxane (PC-Si) copolymer, a polycarbonate-isophthalate isophthalate terephthalate resorcinol (PC-ITR) copolymer, or a combination thereof; (c) 10 wt % to 50 wt % of a reinforcing filler; (d) 1 wt % to 10 wt % of a laser direct structuring (LDS) additive; A thermoplastic composition comprising: compared to a comparative composition that does not contain the polycarbonate copolymer, Low warpage as assessed by visually inspecting the flatness of a molded disc having a diameter of 135 mm and a thickness of 0.9 mm to 1.2 mm; A thermoplastic composition wherein the combined weight percentage of all components does not exceed 100 wt%, all weight percentages being based on the total weight of said thermoplastic composition.

2. 10. The thermoplastic composition of claim 1, wherein the at least one crystalline polyester comprises polybutylene terephthalate (PBT), polycyclohexylene dimethylene terephthalate (PCT), polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polycyclohexylene dimethylene terephthalate glycol (PCTG), polycyclohexylene dimethylene terephthalic acid (PCTA), copolymers thereof, or combinations thereof.

3. 10. The thermoplastic composition of claim 1, wherein the at least one crystalline polyester comprises polybutylene terephthalate (PBT).

4. 4. The thermoplastic composition of any of claims 1 to 3, wherein the polycarbonate copolymer comprises a polycarbonate-siloxane (PC-Si) copolymer having a siloxane content of 10 wt% to 30 wt%.

5. 5. The thermoplastic composition of any of claims 1 to 4, wherein the reinforcing filler comprises carbon black, carbon fiber, aramid fiber, glass fiber, glass flake, hollow glass beads, or combinations thereof.

6. 5. The thermoplastic composition of claim 1, wherein the reinforcing filler comprises flat glass fibers.

7. 7. The thermoplastic composition of any one of claims 1 to 6, wherein the LDS additive comprises a heavy metal mixed oxide spinel, a copper salt, an organometallic complex, a metal oxide coated filler, an antimony doped tin oxide, a copper-containing metal oxide, a zinc-containing metal oxide, a tin-containing metal oxide, a magnesium-containing metal oxide, an aluminum-containing metal oxide, a gold-containing metal oxide, a silver-containing metal oxide, or a combination thereof.

8. further comprising 1 wt. % to 10 wt. % of an additional mineral filler different from said reinforcing filler; 8. The thermoplastic composition of any one of claims 1 to 7, wherein the additional mineral filler comprises silica, talc, mica, calcium carbonate, dolomite, wollastonite, barium sulfate, silica, kaolin, feldspar, barite, or combinations thereof.

9. 9. The thermoplastic composition of claim 8, wherein the additional mineral filler comprises talc.

10. 10. The thermoplastic composition of any one of claims 1 to 9, further comprising at least one impact modifier.

11. 11. The thermoplastic composition of claim 10, wherein the at least one impact modifier comprises polyethylene-glycidyl methacrylate (PE-GMA), styrene-ethylene / 1-butene-styrene (SEBS), or a combination thereof.

12. 12. The thermoplastic composition of any one of claims 1 to 11, having improved adhesion as determined in accordance with ASTM D3359 compared to a comparative composition not containing the polycarbonate copolymer.

13. 13. The thermoplastic composition of any one of claims 1 to 12, having improved gloss, tested in accordance with ASTM D523, compared to a comparative composition comprising a polycarbonate in place of the at least one crystalline polyester.

14. 14. The thermoplastic composition of any one of claims 1 to 13, which is a laser direct structuring (LDS) composition suitable for use in LDS applications.

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