Laser directly structured compositions comprising crystalline polyesters

Abstract

A thermoplastic composition comprising: (a) from about 1% to about 99% by weight of at least one crystalline polyester; (b) from about 1% to about 99% by weight of a polycarbonate copolymer; (c) from about 10% to about 50% by weight of a reinforcing filler; and (d) from about 1% to about 10% by weight of a laser direct structuring (LDS) additive. In particular aspects, the at least one crystalline polyester comprises polybutylene terephthalate (PBT), and the polycarbonate copolymer comprises a polycarbonate-siloxane (PC-Si) copolymer. In further aspects, the at least one reinforcing filler comprises glass fibers, and in particular aspects comprises flat glass fibers. 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 laser direct structuring (LDS) compositions based on crystalline polyesters, and in particular to compositions comprising a crystalline polyester and a polycarbonate copolymer. Background Art

[0002] Laser Direct Structuring (LDS), which consists of laser activation and subsequent chemical plating procedures, is widely used to produce circuit components in the consumer electronics industry, such as mobile phone technology. In particular, the LDS process can be used to produce antennas for mobile devices. LDS materials based on polycarbonate (PC) are favored by antenna manufacturers because they offer a good balance of flow, mechanical and dimensional stability properties. However, PC has low chemical resistance, which can lead to corrosion problems in alkaline plating and, therefore, to low surface gloss. For glass-filled PC, this problem becomes even more severe. Corroded PC results in glass with a "floating" appearance, which is undesirable for consumers. For at least these reasons, glass-filled PC LDS materials are unpopular.

[0003] To meet the high modulus requirements of mobile antenna applications, glass-filled polyamide (PA) LDS materials are used, which offer good chemical resistance and a high-gloss surface after alkaline plating. However, the anisotropic properties of PA lead to warping, a common problem with crystalline polymers. In addition, PA's moisturizing issues further lead to poor dielectric stability, which is sensitive to antenna performance and is unsuitable for 5G mobile applications.

[0004] Aspects of the present disclosure address these and other shortcomings. Summary of the Invention

[0005] Aspects of the disclosure relate to thermoplastic compositions comprising: (a) from about 1% to about 99% by weight of at least one crystalline polyester; (b) from about 1% to about 99% by weight of a polycarbonate copolymer; (c) from about 10% to about 50% by weight of a reinforcing filler; and (d) from about 1% to about 10% by weight of a laser direct structuring (LDS) additive. In particular aspects, the at least one crystalline polyester comprises polybutylene terephthalate (PBT), and the polycarbonate copolymer comprises a polycarbonate-siloxane (PC-Si) copolymer. In further aspects, the at least one reinforcing filler comprises glass fiber, and in particular aspects comprises flat glass fiber. The composition has improved adhesion, surface appearance, and / or warpage properties compared to a comparative composition not comprising the polycarbonate copolymer. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0007] Figure 1 are photographs comparing plating performance of comparative compositions and example compositions according to aspects of the disclosure.

[0008] Figure 2 are photographs comparing the warpage performance of comparative compositions and example compositions according to aspects of the disclosure.

[0009] Figure 3 are photographs comparing the warpage performance of comparative compositions and example compositions according to aspects of the disclosure. DETAILED DESCRIPTION

[0010] The present 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 the present disclosure offer good and balanced performance in flow, mechanical, dimensional stability, and chemical resistance properties. The combination of crystalline polyesters (e.g., polybutylene terephthalate (PBT)) and PC copolymers provides a composition suitable for high modulus applications such as mobile phone antennas, which is beneficial for both current and next-generation telecommunications applications.

[0011] The present disclosure may be understood more readily by reference to the following detailed description of the disclosure and the examples included therein. In various aspects, the present disclosure relates to thermoplastic compositions comprising: (a) from about 1% to about 99% by weight of at least one crystalline polyester; (b) from about 1% to about 99% by weight of a polycarbonate copolymer; (c) from about 10% to about 50% by weight of a reinforcing filler; and (d) from about 1% to about 10% by weight of a laser direct structuring (LDS) additive.

[0012] Before disclosing and describing the compounds, compositions, articles, systems, devices and / or methods of the present invention, it should be understood that they are not limited to specific synthetic methods unless otherwise specified, or to specific reagents unless otherwise specified, as these may of course vary. It should also be understood that the terminology used herein is for the purpose of describing specific aspects only and is not intended to be limiting.

[0013] The present disclosure covers various combinations of elements of the present disclosure, for example, combinations of elements from dependent claims that depend upon the same independent claim.

[0014] Furthermore, it should be understood that, unless expressly stated otherwise, it is not intended that any method described herein be construed as requiring that its steps be performed in a specific order. Therefore, in the absence of a method claim stating that its steps are to be followed or otherwise specifically stating in the claims or specification that the steps are limited to a specific order, no order is to be inferred in any respect. This applies to any possible non-express basis for interpretation, including: logical issues regarding the arrangement of steps or operational flows; ordinary meaning derived from grammatical organization or punctuation; and the number or type of aspects described in the specification.

[0015] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials in connection with which the publications are cited.

[0016] definition

[0017] It will also be understood that the terms used herein are for the purpose of describing specific aspects only and are not intended to be limiting. As used in the specification and in the claims, the term "comprising" may include the aspects "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 a number of terms that will be defined herein.

[0018] As used in the specification and 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.

[0019] As used herein, the term "combination" is inclusive of blends, mixtures, alloys, reaction products, and the like.

[0020] Ranges can be expressed herein as from a value (a first value) to another value (a second value). When such a range is expressed, the range includes one or both of the first and second values ​​in some aspects. Similarly, when a value is expressed as an approximation by using the antecedent "about," it will be understood that the specific value forms another aspect. It will be further understood that the endpoints of each range are significant relative to and independent of the other endpoints. It is also understood that many values ​​are disclosed herein, and in addition to the value itself, each value is also disclosed herein as "about" the specific value. For example, if the value "10" is disclosed, "about 10" is also disclosed. It is also understood that each unit between two specific units is also disclosed. For example, if 10 and 15 are disclosed, 11, 12, 13, and 14 are also disclosed.

[0021] As used herein, the terms "about" and "at or about" mean that the amount or value in question can be the specified value, approximately the specified value, or about the same as the specified value. As used herein, it is generally understood that, unless otherwise indicated or inferred, nominal values ​​represent ±10% variations. The term is intended to convey that similar values ​​promote equivalent results or effects listed in the claims. That is, it is understood that amounts, dimensions, formulations, parameters and other quantities and features are not and do not need to be exact, but may be approximate and / or larger or smaller as needed, reflecting tolerances, conversion factors, rounding, measurement errors, etc., as well as other factors known to those skilled in the art. Typically, amounts, dimensions, formulations, parameters or other quantities or features are "about" or "approximate", whether or not explicitly stated as such. It is understood that when "about" is used before a quantitative value, unless otherwise specifically stated, the parameter also includes the specific quantitative value itself.

[0022] Disclosed are components to be used to prepare the compositions of the present disclosure, as well as the compositions themselves to be used in the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed, even if specific reference to each different individual and collective combination and permutation of these compounds is not explicitly disclosed, each combination and permutation is specifically contemplated and described herein. For example, if a specific compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules comprising the compound are discussed, then each combination and permutation of the compound, as well as possible modifications, is specifically contemplated unless explicitly stated to the contrary. Thus, if a class of molecules A, B, and C and a class of molecules D, E, and F are disclosed, and an example of a combination of molecules AD is disclosed, then even if each is not individually listed, each is considered individually and collectively, meaning that the combinations AE, AF, BD, BE, BF, CD, CE, and CF are considered disclosed. Similarly, any subset or combination of these is also disclosed. Thus, for example, a subset of AE, BF, and CE would be considered disclosed. This concept applies to all aspects of this application, including but not limited to steps in methods of preparing and using the compositions of the present disclosure. Thus, if there are a variety of 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 methods of the present disclosure.

[0023] References in the specification and subsequent claims to parts by weight of a particular element or component of a composition or article represent the weight relationship of that element or component to any other elements or components in the composition or article 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, and this ratio remains regardless of whether the compound contains additional components X and Y.

[0024] Unless expressly stated to the contrary, weight percentages of components are based on the total weight of the formulation or composition in which the component is included.

[0025] As used herein, the term "number average molecular weight" or "M n ” are used interchangeably and refer to the statistical average molecular weight of all polymer chains in a sample and are defined by the formula:

[0026]

[0027] Among them, M i is the molecular weight of the chain, and N iThe M of a polymer (e.g., a polycarbonate polymer) can be determined by methods well known to those skilled in the art using molecular weight standards (e.g., polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards). n .

[0028] As used herein, the term "weight average molecular weight" or "M w ” are used interchangeably and are defined by the following formula:

[0029]

[0030] Among them, M i is the molecular weight of the chain, and N i is the number of chains of this molecular weight. n In comparison, M w The molecular weight of a given chain is taken into account in determining the contribution to the molecular weight average. Thus, the greater the molecular weight of a given chain, the greater the contribution of that chain to the M w The M of a polymer (e.g., a polycarbonate polymer) can be determined by methods well known to those skilled in the art using molecular weight standards (e.g., polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards). w .

[0031] As used herein, the terms "polydispersity index" or "PDI" are used interchangeably and are defined by the following formula:

[0032]

[0033] The PDI has a value equal to or greater than 1, but approaches unity as the polymer chains approach uniform chain length.

[0034] As used herein, the terms "BisA," "BPA," or "bisphenol A," which may be used interchangeably, refer to a compound having a structure represented by the following formula:

[0035]

[0036] BisA may also be referred to as 4,4'-(propane-2,2-diyl)diphenol; p,p'-isopropylenebisphenol; or 2,2-bis(4-hydroxyphenyl)propane. BisA has CAS# 80-05-7.

[0037] As used herein, "polycarbonate" refers to an oligomer or polymer comprising the residues of one or more dihydroxy compounds (eg, dihydroxy aromatic compounds) connected by carbonate linkages; it also encompasses homopolycarbonates, copolycarbonates, and (co)polyester carbonates.

[0038] The terms "residue" and "structural unit" used with reference to components of a polymer are synonymous throughout this specification.

[0039] As used herein, the terms "weight percent," "weight % (wt%)," and "weight percent (wt.%)," which are used interchangeably, refer to the weight percentage of a given component based on the total weight of the composition, unless otherwise indicated. That is, all wt. % values ​​are based on the total weight of the composition, unless otherwise indicated. It should be understood that the sum of the wt. % values ​​of all components in a disclosed composition or formulation equals 100.

[0040] Unless otherwise indicated herein to the contrary, all test standards are the most current standards in effect at the time this application is filed.

[0041] Each of the materials disclosed herein is commercially available and / or methods for preparing the same are known to those skilled in the art.

[0042] It is understood that the compositions disclosed herein have certain functions. Certain structural requirements are disclosed herein for performing the disclosed functions, and it is understood that there are multiple structures that can perform the same functions related to the disclosed structures, and these structures will generally achieve the same results.

[0043] Thermoplastic composition

[0044] Aspects of the present disclosure relate to thermoplastic compositions comprising: (a) from about 1% to about 99% by weight of at least one crystalline polyester; (b) from about 1% to about 99% by weight of a polycarbonate copolymer; (c) from about 10% to about 50% by weight of a reinforcing filler; and (d) from about 1% to about 10% by weight of a laser direct structuring (LDS) additive. The combined weight percentage values ​​of all components do not exceed 100% by weight, and all weight percentage values ​​are based on the total weight of the composite.

[0045] In some aspects, 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 terephthalate acid (PCTA), copolymers thereof, or combinations thereof. In specific aspects, the at least one crystalline polyester comprises polybutylene terephthalate (PBT).

[0046] In some aspects, the composition comprises from about 1% to about 99% by weight of at least one crystalline polyester. In other aspects, the composition comprises from about 30% to about 99% by weight of at least one crystalline polyester. In further aspects, the composition comprises at least one crystalline polyester as a major component; that is, the at least one crystalline polyester is present in a greater amount than any other component of the composition, such as the polycarbonate copolymer or the reinforcing filler. In yet further aspects, the at least one crystalline polyester is present in the composition in a greater amount than the polycarbonate copolymer.

[0047] Suitable polycarbonate copolymers include, but are not limited to, polycarbonate-siloxane (PC-Si) copolymers, polycarbonate-isophthalate terephthalate resorcinol (PC-ITR) copolymers, or combinations thereof.

[0048] In some aspects, the composition comprises from about 1% to about 99% by weight of the polycarbonate copolymer. In certain aspects, the composition comprises from about 1% to about 30% by weight of the polycarbonate copolymer. In specific aspects, the composition comprises a lower content of the polycarbonate copolymer than the at least one crystalline polyester.

[0049] In certain aspects, the polycarbonate copolymer comprises a polycarbonate-siloxane (PC-Si) copolymer having a siloxane content of about 10 wt % to about 30 wt %. In specific aspects, 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 %.

[0050] Reinforcing fillers may include, but are not limited to, silica, talc, mica, carbon black, carbon fiber, aramid fiber, glass fiber, glass flakes, hollow glass beads, ground glass fiber, and combinations thereof. In certain aspects, the reinforcing filler comprises glass fiber. Any suitable glass fiber may be used.

[0051] In specific aspects, the glass fiber is a flat glass fiber. Fiber flatness is a function of the ratio of the width to the height of the fiber's rectangular cross-section. In some aspects, the flat glass fiber has a flatness of at least 2. In other aspects, the glass fiber has a flatness of about 2 to about 10, or about 2 to 5, or about 4.

[0052] LDS additives may include, but are not limited to, heavy metal mixture oxide spinels, such as copper chromium oxide spinels; copper salts, such as copper hydroxide phosphates, copper phosphates, copper sulfate, cuprous thiocyanate, spinel-based metal oxides (e.g., copper chromium oxide), organometallic complexes (e.g., palladium / palladium-containing heavy metal complexes), metal oxides, metal oxide-coated fillers, antimony-doped tin oxides coated on mica substrates, 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, etc., or a combination comprising at least one of the foregoing LDS additives.

[0053] In certain aspects, the LDS additive comprises a heavy metal mixture oxide spinel, a copper salt, an organometallic complex, a metal oxide, a metal oxide coated filler, 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 specific aspects, the LDS additive comprises copper chrome black spinel.

[0054] In some aspects, the composition further comprises about 1 wt % to about 10 wt % of a mineral filler other than a 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 a combination thereof. In some aspects, the mineral filler comprises talc.

[0055] In some aspects, the composition further comprises at least one impact modifier. In certain aspects, the at least one impact modifier comprises polyethylene-glycidyl methacrylate (PE-GMA), styrene-ethylene / 1-butylene-styrene (SEBS), or a combination thereof.

[0056] The thermoplastic composition has improved properties compared to conventional LDS compositions, and in particular, compared to conventional PBT and polycarbonate-based compositions. In one aspect, the composition has improved adhesion as measured according to ASTM D3359 compared to a comparative composition not including the polycarbonate copolymer. As used herein, improved adhesion means an increase in average adhesion of at least 1B grade when measured by a cross-hatch tape test at a laser power level of 7 watts (W) or higher and a frequency of 1 Hertz (Hz).

[0057] In other aspects, the composition has an improved surface appearance compared to a comparative composition that does not include the polycarbonate copolymer. In a further aspect, the composition has an improved surface appearance compared to a comparative composition that does not include PBT. The improved surface appearance can be visually observed by less reinforcing filler (e.g., glass filler) floating in a molded sample of the composition. The improved surface appearance can also be evaluated based on improved gloss when measured using the L*a*b* color method (i.e., the IELAB color space defined by the International Commission on Illumination (CIE)).

[0058] In certain aspects, the composition has reduced warpage when compared to a comparative composition that does not include the polycarbonate copolymer. Warpage or bending can be visually assessed in a molded sample of the composition. In specific aspects, warpage can be assessed by molding a sample of the composition that is at least 100 millimeters (mm) x 100 mm, such as, but not limited to, 150 mm x 150 mm, and observing the flatness of the sample. In other aspects, warpage can be assessed using a quantitative 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.

[0059] In some aspects, the composition has improved gloss as tested according to ASTM D523 compared to a comparative composition including a polycarbonate in place of the at least one crystalline polyester.

[0060] In a specific aspect, the composition is a laser direct structuring (LDS) composition suitable for use in LDS applications.

[0061] Manufacturing method

[0062] One or any of the aforementioned components described herein can first be dry-mixed with each other, or dry-mixed with any combination of the aforementioned components, and then fed into an extruder from one or more feeders, or fed into an extruder separately from one or more feeders. The filler used in this disclosure can also first be processed into a masterbatch and then fed into an extruder. The components can be fed into an extruder from a throat hopper or any side feeder.

[0063] The extruders used in the present disclosure can 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, rollers, rams, helical rotors, co-kneaders, disc-pack processors, various other types of extrusion equipment, or a combination comprising at least one of the foregoing.

[0064] The components can also be mixed together and then melt blended to form the thermoplastic composition. Melt blending of the components involves the use of shear forces, extensional forces, compressive forces, ultrasonic energy, electromagnetic energy, thermal energy, or a combination comprising at least one of the foregoing forces or energy forms.

[0065] The barrel temperature on the extruder during compounding can be set at a temperature at which at least a portion of the polymer has reached a temperature greater than or equal to about the melting temperature if the resin is a semicrystalline organic polymer, or at the flow point (e.g., glass transition temperature) if the resin is an amorphous resin.

[0066] If desired, the mixture comprising the aforementioned components may be subjected to multiple blending and forming steps. For example, the thermoplastic composition may first be extruded and formed into pellets. The pellets may then be fed into a molding machine where they may be formed into any desired shape or product. Alternatively, the thermoplastic composition may be formed into sheets or strands from a single melt blender and subjected to a post-extrusion process such as annealing, uniaxial or biaxial orientation.

[0067] In some aspects, the temperature of the melt in the present method can be kept as low as possible to avoid excessive thermal degradation of the components. In some aspects, 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 remains relatively short. In some aspects, the melt-processed composition exits the processing equipment, such as an extruder, through a small exit hole in the die. The resulting strands of molten resin can be cooled by passing the strands through a water bath. The cooled strands can be cut into pellets for packaging and further processing.

[0068] Manufacturing of products

[0069] In certain aspects, the present disclosure relates to shaped, formed, or molded articles comprising the thermoplastic compositions. The thermoplastic compositions can be molded into useful shaped articles by various means, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming, to form articles and structural components, such as 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 further aspects, the articles are extrusion molded. In yet further aspects, the articles are injection molded.

[0070] The present disclosure covers various combinations of elements of the present disclosure, such as combinations of elements from dependent claims that depend upon the same independent claim.

[0071] Aspects of public content

[0072] In various aspects, the present disclosure relates to and includes at least the following aspects.

[0073] Aspect 1. A thermoplastic composition comprising, consisting of, or consisting essentially of:

[0074] (a) from about 1% to about 99% by weight of at least one crystalline polyester;

[0075] (b) from about 1 weight percent to about 99 weight percent of a polycarbonate copolymer;

[0076] (c) from about 10% to about 50% by weight of a reinforcing filler; and

[0077] (d) from about 1 wt. % to about 10 wt. % of a laser direct structuring (LDS) additive,

[0078] The combined weight percentage values ​​of all components do not exceed 100 weight percent, and all weight percentage values ​​are based on the total weight of the composite.

[0079] Aspect 2. The thermoplastic composition according to aspect 1, wherein the at least one crystalline polyester comprises polybutylene terephthalate (PBT), polycyclohexanedimethylene terephthalate (PCT), polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polycyclohexanedimethylene terephthalate glycol (PCTG), polycyclohexanedimethylene terephthalate acid (PCTA), copolymers thereof, or combinations thereof.

[0080] Aspect 3. The thermoplastic composition according to aspect 1, wherein the at least one crystalline polyester comprises polybutylene terephthalate (PBT).

[0081] Aspect 4. The thermoplastic composition according to any of aspects 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.

[0082] Aspect 5. The thermoplastic composition of any of aspects 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%.

[0083] Aspect 6. The thermoplastic composition according to any of aspects 1 to 5, wherein the reinforcing filler comprises silica, talc, mica, carbon black, carbon fiber, aramid fiber, glass fiber, glass flakes, hollow glass beads, milled glass fiber, and combinations thereof.

[0084] Aspect 7. The thermoplastic composition of any of aspects 1 to 5, wherein the reinforcing filler comprises flat glass fibers.

[0085] Aspect 8. The thermoplastic composition of any of Aspects 1 to 7, wherein the LDS additive comprises a heavy metal mixture oxide spinel, a copper salt, an organometallic complex, a metal oxide, a metal oxide-coated filler, 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.

[0086] Aspect 9. The thermoplastic composition of any of aspects 1 to 7, wherein the LDS additive comprises copper chromium black spinel.

[0087] Aspect 10. The thermoplastic composition of any of aspects 1 to 9, wherein the composition further comprises from about 1 wt% to about 10 wt% of a mineral filler other than the reinforcing filler, and

[0088] The mineral filler comprises mica, talc, calcium carbonate, dolomite, wollastonite, barium sulfate, silica, kaolin, feldspar, barite, or a combination thereof.

[0089] Aspect 11. The thermoplastic composition of any of aspects 1 to 10, wherein the mineral filler comprises talc.

[0090] Aspect 12. The thermoplastic composition of any of aspects 1 to 11, wherein the composition further comprises at least one impact modifier.

[0091] 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.

[0092] Aspect 14. The thermoplastic composition of any of aspects 1 to 13, wherein the composition has improved adhesion as measured according to ASTM D3359 compared to a comparative composition not including the polycarbonate copolymer.

[0093] Aspect 15. The thermoplastic composition of any of aspects 1 to 14, wherein the composition has an improved surface appearance compared to a comparative composition not including the polycarbonate copolymer.

[0094] Aspect 16. The thermoplastic composition of any of aspects 1 to 15, wherein the composition has reduced warpage compared to a comparative composition not including the polycarbonate copolymer.

[0095] Aspect 17. The thermoplastic composition of any of aspects 1 to 16, wherein the composition has improved gloss as tested according to ASTM D523 compared to a comparative composition comprising a polycarbonate in place of the at least one crystalline polyester.

[0096] Aspect 18. The thermoplastic composition of any of aspects 1 to 17, wherein the composition is a laser direct structuring (LDS) composition suitable for use in LDS applications.

[0097] Aspect 19. The thermoplastic composition of any of aspects 1 to 18, wherein the composition comprises from about 1 wt% to about 30 wt% of the at least one crystalline polyester and from about 30 wt% to about 99 wt% of the polycarbonate copolymer.

[0098] Example

[0099] The following examples are given to provide one of ordinary skill in the art with a complete disclosure and description of how to prepare and evaluate the compounds, compositions, articles, devices and / or methods claimed herein, and are intended to be purely exemplary and not intended to limit the present disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), but some errors and deviations should be taken into account. Unless otherwise indicated, parts are parts by weight, temperatures are in ° C. or are ambient temperature, and pressures are at or near atmospheric pressure. Unless otherwise indicated, percentages relating to compositions are expressed in % by weight.

[0100] There are many variations and combinations of reaction conditions such as component concentrations, desired solvents, solvent mixtures, temperature, pressure and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained by the described methods. Only reasonable and routine experimentation will be required to optimize such process conditions.

[0101] The materials used in the comparative and example compositions described herein are listed in Table 1:

[0102] Table 1 – Materials

[0103]

[0104] The pellets were compounded from the composition according to conventional methods. The resin and additives were premixed and fed through the main throat; the glass fiber was fed downstream of the extruder. The PC-based (comparative) composition was compounded using an output of 40 kilograms per hour (kg / hr), a screw speed of 300 revolutions per minute (RPM), a vacuum of 0.6 bar, a torque of 55%, a barrel temperature of 255-265°C, and a die temperature of 265°C. The PBT (comparative and example) composition was compounded using an output of 50 kg / hr, a screw speed of 200 RPM, a vacuum of 0 bar, a torque of 80%, a barrel temperature of 240-250°C, and a die temperature of 250°C.

[0105] The pellets were injection molded according to the conditions given in Table 2:

[0106] Table 2-Injection molding parameters

[0107]

[0108]

[0109] Table 3 lists the resulting compositions:

[0110] Table 3 - Comparative and Example Compositions

[0111]

[0112] The properties of the compositions of Table 3 (C1, C2 and Ex1-Ex3) are listed in Table 4:

[0113] Table 4 - Properties of the compositions of Table 3

[0114]

[0115]

[0116] Specific adhesion properties of C2, Ex1, and Ex2, tested according to ASTM D3359 at 40 kilohertz (KHz) and 100 KHz at different powers, are provided in Table 5:

[0117] Table 5 - Adhesion Properties

[0118] Power (W) Frequency (KHz) C2 C3 Ex1 Ex2 3 40 5B 5B 5B 5B 3 100 5B 5B 5B 5B 5 40 4B 5B 5B 5B 5 100 4B 4B 4B 5B 7 40 4B 5B 5B 5B 7 100 1B 2B 4B 4B 8 40 4B 5B 5B 4B 8 100 1B 2B 4B 4B 10 40 4B 5B 5B 5B 10 100 1B 0B 3B 4B 11 40 4B 5B 5B 5B 11 100 1B 0B 3B 4B

[0119] Comparative composition C1 is a control formulation based on conventional 30 wt% glass-filled PC for LDS applications, while comparative composition C2 is a control formulation based on conventional 30 wt% glass-filled PBT for LDS applications. Ex1 and Ex2 combine PBT and PC copolymers with the same glass fiber type and loading. Ex3 is a PBT blend that includes a PC-ITR copolymer as the primary component (same glass fiber type and loading, but no impact modifier). As a more ideal control, comparative composition C0 should be close to Ex1 and Ex2, but its performance was not tested.

[0120] As shown in Table 4, Example compositions Ex1 and Ex2 have comparable mechanical properties and better thermal properties. For electroless plating after laser activation, the plating index is 0.9, which means sufficient metal deposition. Conventionally, glass fiber-filled PC LDS compounds exhibit poor appearance due to their poor chemical resistance when plated. However, in contrast, Example compositions Ex1 and Ex2 (which include PBT and PC copolymers (silicone or ITR)) are observed to have a more glossy appearance after plating. This is mainly attributed to the stronger chemical resistance of crystalline PBT. Further, the 85° geometry gloss data in Table 4 also demonstrates that the appearance of the crystalline polyester (PBT) / PC copolymer composition (Ex1, 86.1% gloss, and Ex2, 80.6% gloss) is better than that of the comparative composition including PC (C1, 73.5% gloss).

[0121] Plated chips of the compositions of C2, Ex1 and Ex2 are shown in FIG. Figure 1Adhesion data for these and other compositions are provided in Table 5. Compared to conventional PBT composition C2, Example compositions Ex1 and Ex2 exhibited better plating efficiency at higher laser powers (7-11 watts (W)) and frequencies (100 Hertz (Hz) and higher). This is attributed to the PC copolymer's better ability to form char upon laser ablation, whereas ablated PBT releases more fuel (CH2 units), resulting in a damaged / broken surface and poorer deposition of the metal layer.

[0122] Comparison of comparative composition C3 (which does not include a polycarbonate copolymer comprising a polycarbonate-siloxane (PC-Si) copolymer or a polycarbonate-isophthalate terephthalate resorcinol (PC-ITR) copolymer) with Ex1 and Ex2 shows similar performance. Example compositions Ex1 and Ex2 both maintain good plating properties above 7 W at a frequency of 100 KHz, while comparative composition C3 does not.

[0123] Warping is a common problem for crystalline polymers such as PBT or polyamide. PBT blends including PC copolymers provide better dimensional stability even for large molded parts. Figure 2 As shown in FIG, the comparative PBT board (C2, top) has significant bow when molded. The middle board (SLX, Ex1) comprising 10 wt% PC-ITR copolymer has better flatness, while the bottom board (SLX, Ex3) comprising 48.5 wt% PC-ITR copolymer is completely flat. Figure 3 As further shown in FIG, the bottom sheet (PC-ITR copolymer, Ex1) is much flatter than the top sheet (C3) comprising conventional polycarbonate.

[0124] The above description is intended to be illustrative and not restrictive. For example, the embodiments described above (or one or more aspects thereof) can be used in combination with each other. For example, those of ordinary skill in the art may use other aspects after reading the above description. An abstract is provided to comply with 37 CFR § 1.72 (b) to allow readers to quickly determine the nature of the technical disclosure. This abstract is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the above-mentioned specific embodiments, various features can be grouped together to streamline the present disclosure. This should not be interpreted as intending that the disclosed features that are not claimed for protection are essential to any claim. On the contrary, the subject matter of the present invention may be less than all the features of the specific disclosed aspects. Therefore, the appended claims are thus incorporated into the specific embodiments as examples or aspects, wherein each claim is independently a separate aspect, and it is expected that such aspects can be combined with each other in various combinations or permutations. The scope of the present disclosure should be determined with reference to the appended claims and the full scope of equivalents given by these claims.

Claims

1. A thermoplastic composition comprising: (a) 30 to 99 weight percent of at least one crystalline polyester comprising polybutylene terephthalate (PBT), polycyclohexanedimethylene terephthalate (PCT), polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polycyclohexanedimethylene terephthalate glycol (PCTG), polycyclohexanedimethylene terephthalate acid (PCTA), copolymers thereof, or combinations thereof; (b) 1 to 30 weight percent of a polycarbonate copolymer comprising a polycarbonate-siloxane (PC-Si) copolymer, a polycarbonate-isophthalate terephthalate resorcinol (PC-ITR) copolymer, or a combination thereof; (c) 10% to 50% by weight of reinforcing filler; and (d) 1 to 10 wt. % of a laser direct structuring (LDS) additive, wherein the polycarbonate copolymer comprises a polycarbonate-siloxane (PC-Si) copolymer having a siloxane content of 10 wt % to 30 wt %, wherein the at least one crystalline polyester is present in the composition in a greater amount than the polycarbonate copolymer, wherein the composition has Improved adhesion as measured according to ASTM D3359; Improved surface appearance; or Reduced warping; compared to a comparative composition not including the polycarbonate copolymer, and The combined weight percentage values ​​of all components do not exceed 100 weight percent, and all weight percentage values ​​are based on the total weight of the composition.

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

3. The thermoplastic composition of claim 1, wherein the reinforcing filler comprises silica, talc, mica, carbon black, carbon fiber, aramid fiber, glass fiber, glass flakes, hollow glass beads, or a combination thereof.

4. The thermoplastic composition of claim 3, wherein the glass fibers are milled glass fibers.

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

6. The thermoplastic composition of claim 1, wherein the LDS additive comprises a copper salt, an organometallic complex, a metal oxide, a metal oxide-coated filler, or a combination thereof.

7. The thermoplastic composition of claim 6, wherein the metal oxide is a heavy metal mixture oxide spinel, 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, or a silver-containing metal oxide.

8. The thermoplastic composition according to claim 1, wherein the composition further comprises 1 to 10 wt. % of a mineral filler other than the reinforcing filler, and The mineral filler comprises talc, calcium carbonate, dolomite, wollastonite, barium sulfate, kaolin, feldspar, barite, or a combination thereof.

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

10. The thermoplastic composition of claim 1, wherein the composition further comprises at least one impact modifier.

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. The thermoplastic composition of any one of claims 1 to 11, wherein the composition has improved gloss as tested according to ASTM D523 compared to a comparative composition comprising polycarbonate in place of the at least one crystalline polyester.

13. The thermoplastic composition according to any one of claims 1 to 11, wherein the composition is a laser direct structuring (LDS) composition suitable for use in LDS applications.

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