US20140296411A1

US20140296411A1 - High modulus laser direct structuring composites

Info

Publication number: US20140296411A1
Application number: US14/227,302
Authority: US
Inventors: Yunan Cheng; Tong Wu; Yangang Yan; Yuxian An
Original assignee: SABIC Innovative Plastics IP BV
Current assignee: SABIC Global Technologies BV
Priority date: 2013-04-01
Filing date: 2014-03-27
Publication date: 2014-10-02
Also published as: US9944768B2; KR20150138337A; EP2981578A1; CN105073893A; KR102203702B1; CN105073893B; WO2014162255A1; US20140296410A1

Abstract

The present disclosure relates to polymer compositions. The disclosed compositions comprise a thermoplastic polymer, a laser direct structuring additive, and a reinforcing filler. Also disclosed are methods for making the disclosed polymer composition and articles of manufacture comprising the disclosed polymer composition.

Description

CROSS REFERENCE TO RELATED PATENT APPLICATION

This application claims priority to U.S. Patent Application No. 61/807,239 filed Apr. 1, 2013, which is hereby incorporated herein by reference in its entirety.

BACKGROUND

Electrical components can be provided as molded injection devices (MID) with desired printed conductors. In contrast to conventional circuit boards made of fiberglass-reinforced plastic or the like, MID components manufactured in this way are three-dimensional (3D) molded parts having an integrated printed conductor layout and possibly further electronic or electromechanical components. The use of MID components of this type, even if the components have only printed conductors and are used to replace conventional wiring inside an electrical or electronic device, saves space, allowing the relevant device to be made smaller. It also lowers the manufacturing costs by reducing the number of assembly and contacting steps. These MID devices have great utility in cell phones, PDAs and notebook applications.
Stamp metal, flexible printed circuit board (FPCB) mounted and two-shot molding methods are three existing technologies to make an MID. However, stamping and FPCB mounted process have limitations in the pattern geometry, and the tooling is expensive. Also, altering of a RF pattern causes high-priced and time-consuming modifications in tooling. 2-shot-molding (two-component injection molding) processes have also been used to produce 3D-MIDs with real three-dimensional structures. For example, an antenna can be formed by subsequent chemical corrosion, chemical surface activation and selective metal coating. This method involves relatively high initial costs and is only economically viable for large production numbers. 2-shot-molding is also not regarded as an environmentally friendly process. All of these three methods are tool-based technologies, which have limited flexibility, long development cycles, difficult prototype, expensive design changes, and limited ability to produce miniaturization. Accordingly, it is increasingly popular to form MIDs using a laser direct structuring (LDS) process. In an LDS process a computer-controlled laser beam travels over the MID to activate the plastic surface at locations where the conductive path is to be situated.
Laser-supported or directed structuring process (LDS) for 3D MIDs simplifies the manufacturing process. For example, the LDS process allows for antenna structures to be directly and cost effectively integrated into a cell phone housing. Further, the LDS process allows for sophisticated mechatronic systems that integrate mechanical and electrical properties for automotive and medical applications. With a laser direct structuring process, it is also possible to obtain small conductive path widths (such as 150 microns or less). In addition, the spacing between the conductive paths can also be small. As a result, MIDs formed from this process can save space and weight in end-use applications. Another advantage of laser direct structuring is its flexibility. If the design of the circuit is to be changed, it is simply a matter of reprogramming the computer that controls the laser.
Accordingly, LDS technology is useful in mobile phones and notebooks where thinner, stronger and multiple antenna functions are especially needed. As a consequence of these demands, polymer composites are required which have high flow and strength and can be used in LDS processes.
Accordingly, what is needed are polymer compositions which have good plating performance, high tensile strength and can be readily used in LDS processes. Such polymer compositions will be particularly useful, for example, in industries (e.g., cell phones and notebooks) which require multiple antenna functions.

SUMMARY

In accordance with the purpose of the invention, as embodied and broadly described herein, the invention satisfies these and other needs. In one aspect, a polymer composition can comprise a thermoplastic polymer, a laser direct structuring additive, and a glass reinforcement component. As an example, the polymer composition is capable of being plated after being activated using a laser.
In another aspect, another polymer composition can comprise a thermoplastic polymer, a laser direct structuring additive, and a reinforcing filler. As an example, the polymer composition is capable of being plated after being activated using a laser. AS a further example, the flexural modulus is greater than about 3 GPa and the tensile modulus is greater than about 3 GPa.
Also disclosed is a method for making a polymer composition comprising forming a blend composition comprising a thermoplastic polymer, a laser direct structuring additive, and a reinforcing filler, wherein the polymer composition is capable of being plated after being activated using a laser, and wherein the flexural modulus is greater than about 3 GPa and the tensile modulus is greater than about 3 GPa.
Also disclosed is an article of manufacture comprising the disclosed polymer composition.
While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.
Other advantages will be set forth in part in the description which follows or may be learned by practice. The advantages will be realized and attained by means of the elements and combinations particularly pointed in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive, as claimed.

DETAILED DESCRIPTION

The present invention can be understood more readily by reference to the following detailed description, examples, drawings, and claims, and their previous and following description. However, before the present compositions, articles, devices, systems, and/or methods are disclosed and described, it is to be understood that this invention is not limited to the specific compositions, articles, devices, systems, and/or methods disclosed unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.
The following description of the invention is also provided as an enabling teaching of the invention in its best, currently known aspect. To this end, those of ordinary skill in the relevant art will recognize and appreciate that changes and modifications can be made to the various aspects of the invention described herein, while still obtaining the beneficial results of the present invention. It will also be apparent that some of the desired benefits of the present invention can be obtained by selecting some of the features of the present invention without utilizing other features. Accordingly, those of ordinary skill in the relevant art will recognize that many modifications and adaptations to the present invention are possible and can even be desirable in certain circumstances and are thus also a part of the present invention. Thus, the following description is provided as illustrative of the principles of the present invention and not in limitation thereof.
Various combinations of elements of this disclosure are encompassed by this invention, e.g., combinations of elements from dependent claims that depend upon the same independent claim.
Moreover, it is to be understood that unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of aspects described in the specification.
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.
It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is 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 defined otherwise, 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 invention belongs. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.
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” includes mixtures of two or more such polycarbonates. Furthermore, for example, reference to a filler includes mixtures of two or more such fillers.
Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the 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 particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
As used herein, the terms “optional” or “optionally” mean that the subsequently described event, condition, component, or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
As used herein, the term or phrase “effective,” “effective amount,” or “conditions effective to” refers to such amount or condition that is capable of performing the function or property for which an effective amount is expressed. As will be pointed out below, the exact amount or particular condition required will vary from one aspect to another, depending on recognized variables such as the materials employed and the processing conditions observed. Thus, it is not always possible to specify an exact “effective amount” or “condition effective to.” However, it should be understood that an appropriate effective amount will be readily determined by one of ordinary skill in the art using only routine experimentation.
Disclosed are component materials to be used to prepare disclosed compositions of the invention as well as the compositions themselves to be used within 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 that while specific reference of each various individual and collective combinations and permutation of these compounds can not be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would 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 compositions of the invention. 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 invention.
References in the specification and concluding claims to parts by weight, of a particular element or component in a composition or article denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a composition containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
A weight percent (wt %) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included. For example if a particular element or component in a composition or article is said to have 8% weight, it is understood that this percentage is relation to a total compositional percentage of 100%.
Compounds disclosed herein are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash (“-”) that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, —CHO is attached through carbon of the carbonyl group. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this invention belongs.
The term “alkyl group” as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. A “lower alkyl” group is an alkyl group containing from one to six carbon atoms.
The term “alkoxy” as used herein is an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group can be defined as —OR where R is alkyl as defined above. A “lower alkoxy” group is an alkoxy group containing from one to six carbon atoms.
The term “alkenyl group” as used herein is a hydrocarbon group of from 2 to 24 carbon atoms and structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (AB)C═C(CD) are intended to include both the E and Z isomers. This can be presumed in structural formulae herein wherein an asymmetric alkene is present, or it can be explicitly indicated by the bond symbol C.
The term “alkynyl group” as used herein is a hydrocarbon group of 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond.
The term “aryl group” as used herein is any carbon-based aromatic group including, but not limited to, benzene, naphthalene, etc. The term “aromatic” also includes “heteroaryl group,” which is defined as an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy.
The term “cycloalkyl group” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term “heterocycloalkyl group” is a cycloalkyl group as defined above where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulphur, or phosphorus.
The term “aralkyl” as used herein is an aryl group having an alkyl, alkynyl, or alkenyl group as defined above attached to the aromatic group. An example of an aralkyl group is a benzyl group.
The term “ester” as used herein is represented by the formula —C(O)OA, where A can be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
The term “carbonate group” as used herein is represented by the formula —OC(O)OR, where R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
The term “carboxylic acid” as used herein is represented by the formula —C(O)OH.
The term “aldehyde” as used herein is represented by the formula —C(O)H.
The term “keto group” as used herein is represented by the formula —C(O)R, where R is an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
The term “carbonyl group” as used herein is represented by the formula C═O.
The term “ether” as used herein is represented by the formula AOA¹, where A and A¹can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
As used herein, the terms “number average molecular weight” or “Mn” can be used interchangeably, and refer to the statistical average molecular weight of all the polymer chains in the sample and is defined by the formula:
$Mn = \frac{\sum N_{i} M_{i}}{\sum N_{i}}$
where M_iis the molecular weight of a chain and N_iis the number of chains of that molecular weight. Mn can be determined for polymers, such as polycarbonate polymers or polycarbonate-PMMA copolymers, by methods well known to a person having ordinary skill in the art. It is to be understood that as used herein, Mn is measured gel permeation chromatography and as calibrated with polycarbonate standards. For example, gel permeation chromatography can be carried out using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter with appropriate mobile phase solvents.
As used herein, the terms “weight average molecular weight” or “Mw” can be used interchangeably, and are defined by the formula:
$M_{w} = \frac{\sum N_{i} M_{i}^{2}}{\sum N_{i} M_{i}},$
where M_iis the molecular weight of a chain and N_iis the number of chains of that molecular weight. Compared to Mn, Mw takes into account the molecular weight of a given chain in determining contributions to the molecular weight average. Thus, the greater the molecular weight of a given chain, the more the chain contributes to the Mw. It is to be understood that as used herein, Mw is measured gel permeation chromatography. In some cases, Mw is measured gel permeation chromatography and calibrated with polycarbonate standards. Gel permeation chromatography can be carried out using a crosslinked styrene-divinyl benzene column, at a sample concentration of about 1 milligram per milliliter with appropriate mobile phase solvents.
As used herein, the terms “polydispersity index” or “PDI” can be used interchangeably, and are defined by the formula:
$PDI = \frac{Mw}{Mn}$
The PDI has a value equal to or greater than 1, but as the polymer chains approach uniform chain length, the PDI approaches unity.
The terms “polycarbonate” or “polycarbonates” as used herein includes copolycarbonates, homopolycarbonates and (co)polyester carbonates.
The terms “residues” and “structural units”, used in reference to the constituents of the polymers, are synonymous throughout the specification.
Each of the component materials disclosed herein are either commercially available and/or the methods for the production thereof are known to those of ordinary skill in the art.
It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.

I. Polymer Compositions

As summarized above, the disclosure provides high modulus polymer compositions that are particularly useful in connection with laser direct structuring (LDS) technology. For example, as described in greater detail below, aspects of the disclosure provide high modulus polymer compositions with enhanced plating performance that are capable of being used in a laser direct structuring (LDS) process. To that end, the disclosed polymer compositions generally comprise a blend comprising a thermoplastic polymer, a laser direct structuring additive, and a reinforcing filler.
The disclosed polymer compositions disclosed herein provide robust plating performance while maintaining superior tensile and flexural modulus properties. Robustness of plating performance can be measured via a performance ranking, or plating ranking, ranging from top performance (e.g., “best”) to bottom performance. The ranking can be partitioned in various levels. In one aspect, a plating ranking can have a level of “10” for top performance and a level of “0” for bottom performance.
The disclosed polymer compositions can exhibit, for example, improved mechanical, thermal, and/or morphological properties. Even further for example, the polymer compositions may show improved ductility and improved impact strength without adversely affecting other mechanical and thermal properties.
According to aspects of the disclosure, a molded article formed from the disclosed polymer compositions can exhibit a notched Izod impact energy at 23° C. at 2 lbf/ft. In further aspects, a molded article formed from a disclosed polymer composition can exhibit a notched Izod impact energy at 23° C. in the range of from 50 J/m to 250 J/m, including exemplary values of 60 J/m, 70 J/m, 80 J/m, 90 J/m, 100 J/m, 110 J/m, 120 J/m, 130 J/m, 140 J/m, 150 J/m, 160 J/m, 170 J/m, 180 J/m, 190 J/m, 200 J/m, 210 J/m, 220 J/m, 230 J/m, and 240 J/m. In still further aspects, a molded article formed from a disclosed polymer composition can exhibit a notched Izod impact energy at 23° C. in any range derived from any two values set forth above. For example, a molded article formed from a polymer composition can exhibit a notched Izod impact energy at 23° C. in the range of from 140 J/m to 160 J/m.
According to aspects of the disclosure, a molded article formed from the disclosed polymer compositions can exhibit an unnotched Izod impact energy at 23° C. at 5 lbf/ft. In further aspects, a molded article formed from a disclosed polymer composition can exhibit a an unnotched Izod impact energy at 23° C. in the range of from 550 J/m to 850 J/m, including exemplary impact energy values of 560 J/m, 570 J/m, 580 J/m, 590 J/m, 600 J/m, 610 J/m, 620 J/m, 630 J/m, 640 J/m, 650 J/m, 660 J/m, 670 J/m, 680 J/m, 690 J/m, 700 J/m, 710 J/m, 720 J/m, 730 J/m, 740 J/m, 750 J/m, 760 J/m, 770 J/m, 780 J/m, 790 J/m, 800 J/m, 810 J/m, 820 J/m, 830 J/m, and 840 J/m. In still further aspects, a molded article formed from a disclosed polymer composition can exhibit an unnotched Izod impact energy at 23° C. in any range derived from any two values set forth above. For example, a molded article formed from a polymer composition can exhibit an unnotched Izod impact energy at 23° C. in the range of from 650 J/m to 750 J/m.
In still further aspects, molded articles formed from the disclosed polymer compositions exhibit improved ductility. For example, a molded article formed from a disclosed polymer composition can exhibit a % ductility of 100% as measured according to ASTM D256-2010. In further aspects, a molded article formed from a disclosed polymer composition can exhibit a % ductility of at least 90% as measured according to ASTM D256-2010. In still a further aspect, a molded article formed from a disclosed polymer composition can exhibit a % ductility of at least 80% as measured according to ASTM D256-2010.
According to aspects of the disclosure, molded articles formed from the disclosed polymer compositions can exhibit improved tensile modulus. For example, the tensile modulus can be in the range of greater than 3.0 GPa. In yet another aspect, a molded article formed from the disclosed polymer composition exhibits tensile modulus least about 3 GPa to about 10 GPa, including exemplary values of about 3.1 GPa, 3.2 GPa, 3.3 GPa, 3.4 GPa, 3.5 GPa, 3.6 GPa, 3.7 GPa, 3.8 Gpa, 3.9 GPa, 4.0 GPa, 4.1 GPa, 4.2 GPa, 4.3 GPa, 4.4 GPa, 4.5 GPa, 4.6 GPa, 4.7 GPa, 4.8 GPa, 4.9 GPa, 5.0 GPa, 5.1 GPa, 5.2 GPa, 5.3 GPa, 5.4 GPa, 5.5 GPa, 5.6 GPa, 5.7 GPa, 5.8 GPa, 5.9 GPa, 6.0 GPa, 6.1 GPa, 6.2 GPa, 6.3 GPa, 6.4 GPa, 6.5 GPa, 6.6 GPa, 6.7 GPa, 6.8 GPa, 6.9 GPa, 7.0 GPa, 7.1 GPa, 7.2 GPa, 7.3 GPa, 7.4 GPa, 7.5 GPa, 7.6 GPa, 7.7 GPa, 7.8 GPa, 7.9 GPa, 8.0 GPa, 8.1 GPa, 8.2 GPa, 8.3 GPa, 8.4 GPa, 8.5 GPa, 8.6 GPa, 8.7 GPa, 8.8 GPa, 8.9 GPa, 9.0 GPa, 9.1 GPa, 9.2 GPa, 9.3 GPa, 9.4 GPa, 9.5 GPa, 9.6 GPa, 9.7 GPa, 9.8 GPa, and 9.9 GPa. In another aspect, the tensile modulus can be in any range derived from any two of the above tensile modulus values. For example, the tensile modulus can be in the range of from about 7.0 GPa to about 9.0 GPa. In a still further aspect, the tensile modulus can be in the range of from about 7.1 GPa to about 8.9 GPa.
In yet another aspect, a molded article formed from the disclosed polymer composition exhibits tensile strength ranging from 50 MPa to 250 MPa, including exemplary values of about 60 MPa, 70 MPa, 80 MPa, 90 MPa, 100 MPa, 110 MPa, 120 MPa, 130 MPa, 140 MPa, 150 MPa, 160 MPa, 170 MPa, 180 MPa, 190 MPa, 200 MPa, 210 MPa, 220 MPa, 230 MPa, and 240 MPa. In another aspect, the tensile strength can be in any range derived from any two of the above tensile strength values. For example, the tensile strength can be in the range of from about 50 MPa to 150 MPa. In a still further aspect, the tensile strength can be in the range of from about 60 MPa to 110 MPa.
In yet another aspect, a molded article formed from the disclosed polymer composition exhibits flexural strength ranging from 50 MPa to 250 MPa, including exemplary values of about 60 MPa, 70 MPa, 80 MPa, 90 MPa, 100 MPa, 110 MPa, 120 MPa, 130 MPa, 140 MPa, 150 MPa, 160 MPa, 170 MPa, 180 MPa, 190 MPa, 200 MPa, 210 MPa, 220 MPa, 230 MPa, and 240 MPa. In another aspect, the flexural strength can be in any range derived from any two of the above flexural strength values. For example, the flexural strength can be in the range of from about 100 MPa to 200 MPa. In a still further aspect, the flexural strength can be in the range of from about 120 MPa to 160 MPa.
In still further aspects, molded articles formed from the disclosed polymer composition can exhibit desirable values of percent elongation at break. For example, according to aspects, a molded article formed from the disclosed polymer compositions can exhibit an elongation at break in the range of from 0.1% to 30%, including exemplary values of 0.3%, 0.5%, 0.7% 1.0%, 1.5%, 2.0%, 2.3%, 2.5%, 2.7%, 3.0%, 3.3%, 3.5%, 3.7%, 4.0%, 4.5%, 5.0%, 5.5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21% 22%, 23%, 24%, 25%, 26%, 27%, 28%, and 29%. In still further aspects, the elongation at break percentage can be in a range derived from any two of the above listed exemplary elongation at break percentages. For example, the elongation at break can be in the range of from 10% to 30%. In a further aspect, the elongation at break can be in the range of from 10% to 20%.
According to aspects of the disclosure, molded articles formed from the disclosed polymer compositions can exhibit improved flexural modulus. For example, the flexural modulus can be in the range of greater than 3.0 GPa. In yet another aspect, a molded article formed from the disclosed polymer composition exhibits a flexural modulus of at least about 3 GPa to about 10 GPa, including exemplary values of about 3.1 GPa, 3.2 GPa, 3.3 GPa, 3.4 GPa, 3.5 GPa, 3.6 GPa, 3.7 GPa, 3.8 Gpa, 3.9 GPa, 4.0 GPa, 4.1 GPa, 4.2 GPa, 4.3 GPa, 4.4 GPa, 4.5 GPa, 4.6 GPa, 4.7 GPa, 4.8 GPa, 4.9 GPa, 5.0 GPa, 5.1 GPa, 5.2 GPa, 5.3 GPa, 5.4 GPa, 5.5 GPa, 5.6 GPa, 5.7 GPa, 5.8 GPa, 5.9 GPa, 6.0 GPa, 6.1 GPa, 6.2 GPa, 6.3 GPa, 6.4 GPa, 6.5 GPa, 6.6 GPa, 6.7 GPa, 6.8 GPa, 6.9 GPa, 7.0 GPa, 7.1 GPa, 7.2 GPa, 7.3 GPa, 7.4 GPa, 7.5 GPa, 7.6 GPa, 7.7 GPa, 7.8 GPa, 7.9 GPa, 8.0 GPa, 8.1 GPa, 8.2 GPa, 8.3 GPa, 8.4 GPa, 8.5 GPa, 8.6 GPa, 8.7 GPa, 8.8 GPa, 8.9 GPa, 9.0 GPa, 9.1 GPa, 9.2 GPa, 9.3 GPa, 9.4 GPa, 9.5 GPa, 9.6 GPa, 9.7 GPa, 9.8 GPa, and 9.9 GPa. In another aspect, the flexural modulus can be in any range derived from any two of the above flexural modulus values. For example, the flexural modulus can be in the range of from about 7.0 GPa to about 9.0 GPa. In a still further aspect, the flexural modulus can be in the range of from about 7.1 GPa to about 8.9 GPa.
According to aspects of the disclosure, molded articles formed from the disclosed polymer compositions can exhibit improved plating index. For example, the plating index can be in a range of from 0.1 to 2.0, including exemplary values of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. In the plating index can be in a range derived from any two of the above plating index values. For example, the plating index can be in a range of from 0.9 to 1.1. Further for example, the plating index can be in a range of from 0.5 to 1.5.
In still further aspects, molded articles formed from the disclosed polymer compositions can exhibit desirable heat deflection temperatures (HDT). For example, a molded article formed from a disclosed polymer composition can exhibit a heat deflection temperature in the range of from 90° C. to 150° C. In another aspect, a molded article formed from a disclosed polymer composition can exhibit a heat deflection temperature in the range of from 100° C. to 130° C. In another aspect, a molded article formed from a disclosed polymer composition can exhibit a heat deflection temperature in the range of from 110° C. to 130° C. In still further exemplary aspects, a molded article formed from a disclosed polymer composition can exhibit a heat deflection temperature of 126° C.
A. Thermoplastic Polymer
In one aspect, the thermoplastic polymer comprises polycarbonate, polycarbonate-polysiloxane, polyamide, ethylene vinyl acetate, ethylene vinyl alcohol, polyoxymethylene, polyacrylate, polyacrylonitrile, polyamide-imide, polyetherketone, polycaprolactone, polyhydroxyalkanoate, polyester, polyimide, polyketone, polylactic acid, polyurethane, or polyvinyl acetate, or a combination thereof. Many other thermoplastic polymers are known to skilled artisan and are within the scope of the present disclosure. Many of the above thermoplastic polymers are either commercially available or may be readily synthesized by well-known synthetic methods.
In still further aspects, the thermoplastic polymer is present in an amount ranging from 10 wt % to 90 wt %, based on the total weight of the composition, including exemplary values of 15 wt %, 20 wt %, 25 wt %, 30 wt %, 35 wt %, 40 wt %, 45 wt %, 50 wt %, 55 wt %, 60 wt %, 70 wt %, 75 wt %, 80 wt %, and 85 wt %. In another aspect, the weight percentage can be in any range derived from any two of the above weight percentage values. For example, the thermoplastic polymer can be present in an amount ranging from 15 wt % to 60 wt %. Further for example, the thermoplastic polymer can be present in an amount ranging from 15 wt % to 55 wt %.
B. Polycarbonate Polymer
The term polycarbonate as used herein is not intended to refer to only a specific polycarbonate or group of polycarbonates, but rather refers to the any one of the class of compounds containing a repeating chain of carbonate groups. In one aspect, a polycarbonate material can include any one or more of those polycarbonate materials disclosed and described in U.S. Pat. No. 7,786,246, which is hereby incorporated by reference in its entirety for the specific purpose of disclosing various polycarbonate compositions and methods for manufacture of same.
In one aspect, a polycarbonate polymer component as disclosed herein can be an aliphatic-diol based polycarbonate. In another aspect, the polycarbonate polymer component can comprise a carbonate unit derived from a dihydroxy compound, such as, for example, a bisphenol that differs from the aliphatic diol. In still further aspects, an exemplary polycarbonate polymer component includes aromatic polycarbonates conventionally manufactured through a transesterification reaction of an one or more aromatic dihydroxy compound(s) and a carbonic acid diester in the presence of one or more catalyst(s).
In one aspect, non-limiting examples of suitable bisphenol compounds include the following: 4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane 1,1-bis(4-hydroxyphenyl)isobutene, 1,1-bis(4-hydroxyphenyl)cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4-hydroxyphenyl)adamantine, (alpha, alpha′-bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene, 4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorene, 2,7-dihydroxypyrene, 6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindane bisphenol”), 3,3-bis(4-hydroxyphenyl)phthalide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, and the like, as well as combinations comprising at least one of the foregoing dihydroxy aromatic compounds.
In another aspect, exemplary bisphenol compounds can comprise 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (hereinafter “bisphenol A” or “BPA”), 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxy-1-methylphenyl)propane, 1,1-bis(4-hydroxy-t-butylphenyl)propane, 3,3-bis(4-hydroxyphenyl)phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (“PPPBP”), and 9,9-bis(4-hydroxyphenyl)fluorene. Combinations comprising at least one dihydroxy aromatic compound can also be used. In another aspect, other types of diols can be present in the polycarbonate.
In a yet another aspect, polycarbonates with branching groups can be useful, provided that such branching does not significantly adversely affect desired properties of the polycarbonate. Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization. These branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups. Specific examples include trimellitic acid, trimellitic anhydride, trimellitictrichloride, tris-p-hydroxy phenyl ethane, isatin-bis-phenol, tris-phenol TC (1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethylbenzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenonetetracarboxylic acid. In one aspect, a branching agent can be added at a level of about 0.05 to about 2.0 wt %. In a still another aspect, mixtures comprising linear polycarbonates and branched polycarbonates can be used.
The polycarbonate polymer component can comprise copolymers comprising carbonate units and other types of polymer units, including ester units, and combinations comprising at least one of homopolycarbonates and copolycarbonates. An exemplary polycarbonate copolymer of this type is a polyester carbonate, also known as a polyester-polycarbonate. Such copolymers further contain carbonate units derived from oligomeric ester-containing dihydroxy compounds (also referred to herein as hydroxy end-capped oligomeric acrylate esters). In another aspect, the first polycarbonate component does not comprise a separate polymer such as a polyester. In one aspect, an aliphatic-based polycarbonate comprises aliphatic units that are either aliphatic carbonate units derived from aliphatic diols, or a combination of aliphatic ester units derived from aliphatic diacids having greater than 13 carbons.
In one aspect, the molecular weight of any particular polycarbonate can be determined by, for example, gel permeation chromatography using universal calibration methods based on polystyrene (PS) standards. Generally polycarbonates can have a weight average molecular weight (Mw), of greater than about 5,000 g/mol based on PS standards. In one aspect, the polycarbonates can have an Mw of greater than or equal to about 20,000 g/mol, based on PS standards. In another aspect, the polycarbonates have an Mw based on PS standards of about 20,000 to 100,000 g/mol, including for example 30,000 g/mol, 40,000 g/mol, 50,000 g/mol, 60,000 g/mol, 70,000 g/mol, 80,000 g/mol, or 90,000 g/mol. In still further aspects, the polycarbonates have an Mw based on PS standards of about 22,000 to about 50,000 g/mol. In still further aspects, the polycarbonates have an Mw based on PS standards of about 25,000 to 40,000 g/mol.
Molecular weight (Mw and Mn) as described herein, and polydispersity as calculated therefrom, can be determined using gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column, and either PS or PC standards as specified. GPC samples can be prepared in a solvent such as methylene chloride or chloroform at a concentration of about 1 mg/ml, and can be eluted at a flow rate of about 0.2 to 1.0 ml/min. In one aspect, the glass transition temperature (Tg) of a polycarbonate can be less than or equal to about 160° C., less than or equal to about 150° C., less than or equal to about 145° C., less than or equal to about 140° C., or less than or equal to about 135° C. In a further aspect, the glass transition temperature of a polycarbonate can be from about 85° C. to about 160° C., from about 90° C. to about 160° C., from about 90° C. to about 150° C., or from about 90° C. to about 145° C. In a still further aspect, the glass transition temperature of a polycarbonate can be from about 85° C. to about 130° C., from about 90° C. to about 130° C., from about 90° C. to about 125° C., or from about 90° C. to about 120° C.
In one aspect, disclosed polycarbonate polymer components can be manufactured using an interfacial phase transfer process or melt polymerization. Although the reaction conditions for interfacial polymerization can vary, an exemplary process generally involves dissolving or dispersing a dihydric phenol reactant in aqueous caustic soda or potash, adding the resulting mixture to a water-immiscible solvent medium such as for example methylene chloride, and contacting the reactants with a carbonate precursor (such as phosgene) in the presence of a catalyst such as, for example, triethylamine or a phase transfer catalyst salt, under controlled pH conditions of, for example, about 8 to about 10.
The polycarbonate can, in various aspects, be prepared by a melt polymerization process. Generally, in the melt polymerization process, polycarbonates are prepared by co-reacting, in a molten state, the dihydroxy reactant(s) and a diaryl carbonate ester, such as diphenyl carbonate, or more specifically in an aspect, an activated carbonate such as bis(methyl salicyl)carbonate, in the presence of a transesterification catalyst. The reaction can be carried out in typical polymerization equipment, such as one or more continuously stirred reactors (CSTRs), plug flow reactors, wire wetting fall polymerizers, free fall polymerizers, wiped film polymerizers, BANBURY® mixers, single or twin screw extruders, or combinations of the foregoing. In one aspect, volatile monohydric phenol can be removed from the molten reactants by distillation and the polymer is isolated as a molten residue. In another aspect, a useful melt process for making polycarbonates utilizes a diaryl carbonate ester having electron-withdrawing substituents on the aryls. Examples of specifically useful diaryl carbonate esters with electron withdrawing substituents include bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(methyl salicyl)carbonate, bis(4-methylcarboxylphenyl)carbonate, bis(2-acetylphenyl)carboxylate, bis(4-acetylphenyl)carboxylate, or a combination comprising at least one of the foregoing.
The melt polymerization can include a transesterification catalyst comprising a first catalyst, also referred to herein as an alpha catalyst, comprising a metal cation and an anion. In one aspect, the cation is an alkali or alkaline earth metal comprising Li, Na, K, Cs, Rb, Mg, Ca, Ba, Sr, or a combination comprising at least one of the foregoing. The anion is hydroxide (OH⁻), superoxide (O₂ ⁻), thiolate (HS⁻), sulfide (S₂ ⁻), a C_1-20alkoxide, a C_6-20aryloxide, a C_1-20carboxylate, a phosphate including biphosphate, a C_1-20phosphonate, a sulfate including bisulfate, sulfites including bisulfites and metabisulfites, a C_1-20sulfonate, a carbonate including bicarbonate, or a combination comprising at least one of the foregoing. In another aspect, salts of an organic acid comprising both alkaline earth metal ions and alkali metal ions can also be used. Salts of organic acids useful as catalysts are illustrated by alkali metal and alkaline earth metal salts of formic acid, acetic acid, stearic acid and ethyelenediaminetetraacetic acid. The catalyst can also comprise the salt of a non-volatile inorganic acid. By “nonvolatile”, it is meant that the referenced compounds have no appreciable vapor pressure at ambient temperature and pressure. In particular, these compounds are not volatile at temperatures at which melt polymerizations of polycarbonate are typically conducted. The salts of nonvolatile acids are alkali metal salts of phosphites; alkaline earth metal salts of phosphites; alkali metal salts of phosphates; and alkaline earth metal salts of phosphates. Exemplary transesterification catalysts include, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium formate, sodium formate, potassium formate, cesium formate, lithium acetate, sodium acetate, potassium acetate, lithium carbonate, sodium carbonate, potassium carbonate, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium phenoxide, sodium phenoxide, potassium phenoxide, sodium sulfate, potassium sulfate, NaH₂PO₃, NaH₂PO₄, Na₂H₂PO₃, KH₂PO₄, CsH₂PO₄, Cs₂H₂PO₄, Na₂SO₃, Na₂S₂O₅, sodium mesylate, potassium mesylate, sodium tosylate, potassium tosylate, magnesium disodium ethylenediaminetetraacetate (EDTA magnesium disodium salt), or a combination comprising at least one of the foregoing. It will be understood that the foregoing list is exemplary and should not be considered as limited thereto. In one aspect, the transesterification catalyst is an alpha catalyst comprising an alkali or alkaline earth salt. In an exemplary aspect, the transesterification catalyst comprising sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, NaH₂PO₄, or a combination comprising at least one of the foregoing.
The amount of alpha catalyst can vary widely according to the conditions of the melt polymerization, and can be about 0.001 to about 500 μmol. In an aspect, the amount of alpha catalyst can be about 0.01 to about 20 μmol, specifically about 0.1 to about 10 μmol, more specifically about 0.5 to about 9 μmol, and still more specifically about 1 to about 7 μmol, per mole of aliphatic diol and any other dihydroxy compound present in the melt polymerization. In another aspect, a second transesterification catalyst, also referred to herein as a beta catalyst, can optionally be included in the melt polymerization process, provided that the inclusion of such a second transesterification catalyst does not significantly adversely affect the desirable properties of the polycarbonate. Exemplary transesterification catalysts can further include a combination of a phase transfer catalyst of formula (R3)4Q+X above, wherein each R3 is the same or different, and is a C1-10 alkyl group; Q is a nitrogen or phosphorus atom; and X is a halogen atom or a C1-8 alkoxy group or C6-18 aryloxy group. Exemplary phase transfer catalyst salts include, for example, [CH₃(CH₂)₃]₄N_X, [CH₃(CH₂)₃]₄P_X, [CH₃(CH₂)₅]₄N_X, [CH₃(CH₂)₆]₄N_X, [CH₃(CH₂)₄]₄N_X, CH₃[CH₃(CH₂)₃]₃N_X, and CH₃[CH₃(CH₂)₂]₃N_X, wherein X is Cl—, Br—, a C1-8 alkoxy group or a C6-18 aryloxy group. Examples of such transesterification catalysts include tetrabutylammonium hydroxide, methyltributylammonium hydroxide, tetrabutylammonium acetate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphoniumphenolate, or a combination comprising at least one of the foregoing. Other melt transesterification catalysts include alkaline earth metal salts or alkali metal salts. In various aspects, where a beta catalyst is desired, the beta catalyst can be present in a molar ratio, relative to the alpha catalyst, of less than or equal to 10, specifically less than or equal to 5, more specifically less than or equal to 1, and still more specifically less than or equal to 0.5. In other aspects, the melt polymerization reaction disclosed herein uses only an alpha catalyst as described hereinabove, and is substantially free of any beta catalyst. As defined herein, “substantially free of” can mean where the beta catalyst has been excluded from the melt polymerization reaction. In one aspect, the beta catalyst is present in an amount of less than about 10 ppm, specifically less than 1 ppm, more specifically less than about 0.1 ppm, more specifically less than or equal to about 0.01 ppm, and more specifically less than or equal to about 0.001 ppm, based on the total weight of all components used in the melt polymerization reaction.
In one aspect, a melt process employing an activated carbonate is utilized. As used herein, the term “activated carbonate”, is defined as a diarylcarbonate that is more reactive than diphenylcarbonate in transesterification reactions. Specific non-limiting examples of activated carbonates include bis(o-methoxycarbonylphenyl)carbonate, bis(o-chlorophenyl)carbonate, bis(o-nitrophenyl)carbonate, bis(o-acetylphenyl)carbonate, bis(o-phenylketonephenyl)carbonate, bis(o-formylphenyl)carbonate. Examples of specific ester-substituted diarylcarbonates include, but are not limited to, bis(methylsalicyl)carbonate (CAS Registry No. 82091-12-1) (also known as BMSC or bis(o-methoxycarbonylphenyl)carbonate), bis(ethylsalicyl)carbonate, bis(propylsalicyl)carbonate, bis(butylsalicyl)carbonate, bis(benzylsalicyl)carbonate, bis(methyl-4-chlorosalicyl)carbonate and the like. In one aspect, bis(methylsalicyl)carbonate is used as the activated carbonate in melt polycarbonate synthesis due to its lower molecular weight and higher vapor pressure. Some non-limiting examples of non-activating groups which, when present in an ortho position, would not be expected to result in activated carbonates are alkyl, cycloalkyl or cyano groups. Some specific and non-limiting examples of non-activated carbonates are bis(o-methylphenyl)carbonate, bis(p-cumylphenyl)carbonate, bis(p-(1,1,3,3-tetramethyl)butylphenyl)carbonate and bis(o-cyanophenyl)carbonate. Unsymmetrical combinations of these structures can also be used as non-activated carbonates.
In one aspect, an end-capping agent (also referred to as a chain-stopper) can optionally be used to limit molecular weight growth rate, and so control molecular weight in the polycarbonate. Exemplary chain-stoppers include certain monophenolic compounds (i.e., phenyl compounds having a single free hydroxy group), monocarboxylic acid chlorides, and/or monochloroformates. Phenolic chain-stoppers are exemplified by phenol and C1-C22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p- and tertiary-butyl phenol, cresol, and monoethers of diphenols, such as p-methoxyphenol. Alkyl-substituted phenols with branched chain alkyl substituents having 8 to 9 carbon atoms can be specifically mentioned. Certain monophenolic UV absorbers can also be used as a capping agent, for example 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, and the like.
In another aspect, endgroups can be derived from the carbonyl source (i.e., the diaryl carbonate), from selection of monomer ratios, incomplete polymerization, chain scission, and the like, as well as any added end-capping groups, and can include derivatizable functional groups such as hydroxy groups, carboxylic acid groups, or the like. In one aspect, the endgroup of a polycarbonate can comprise a structural unit derived from a diaryl carbonate, where the structural unit can be an endgroup. In a further aspect, the endgroup is derived from an activated carbonate. Such endgroups can be derived from the transesterification reaction of the alkyl ester of an appropriately substituted activated carbonate, with a hydroxy group at the end of a polycarbonate polymer chain, under conditions in which the hydroxy group reacts with the ester carbonyl from the activated carbonate, instead of with the carbonate carbonyl of the activated carbonate. In this way, structural units derived from ester containing compounds or substructures derived from the activated carbonate and present in the melt polymerization reaction can form ester endgroups. In another aspect, the ester endgroup derived from a salicylic ester can be a residue of BMSC or other substituted or unsubstituted bis(alkyl salicyl)carbonate such as bis(ethyl salicyl)carbonate, bis(propyl salicyl)carbonate, bis(phenyl salicyl)carbonate, bis(benzyl salicyl)carbonate, or the like. In one aspect, where a combination of alpha and beta catalysts are used in the melt polymerization, a polycarbonate polymer prepared from an activated carbonate can comprise endgroups in an amount of less than 2,000 ppm, less than 1,500 ppm, or less than 1,000 ppm, based on the weight of the polycarbonate. In another aspect, where only an alpha catalyst is used in the melt polymerization, a polycarbonate polymer prepared from an activated carbonate can comprise endgroups in an amount of less than or equal to 500 ppm, less than or equal to 400 ppm, less than or equal to 300 ppm, or less than or equal to 200 ppm, based on the weight of the polycarbonate.
In one aspect, the reactants for the polymerization reaction using an activated aromatic carbonate can be charged into a reactor either in the solid form or in the molten form. Initial charging of reactants into a reactor and subsequent mixing of these materials under reactive conditions for polymerization can be conducted in an inert gas atmosphere such as a nitrogen atmosphere. The charging of one or more reactants can also be done at a later stage of the polymerization reaction. Mixing of the reaction mixture is accomplished by any methods known in the art, such as by stirring. Reactive conditions include time, temperature, pressure and other factors that affect polymerization of the reactants. Typically the activated aromatic carbonate is added at a mole ratio of 0.8 to 1.3, and more preferably 0.9 to 1.3, and all subranges there between, relative to the total moles of monomer unit compounds (i.e., aromatic dihydroxy compound, and aliphatic diacid or diol). In a specific aspect, the molar ratio of activated aromatic carbonate to monomer unit compounds is 1.013 to 1.29, specifically 1.015 to 1.028. In another specific aspect, the activated aromatic carbonate is BMSC.
In one aspect, the melt polymerization reaction can be conducted by subjecting the reaction mixture to a series of temperature-pressure-time protocols. In some aspects, this involves gradually raising the reaction temperature in stages while gradually lowering the pressure in stages. In one aspect, the pressure is reduced from about atmospheric pressure at the start of the reaction to about 1 millibar (100 Pa) or lower, or in another aspect to 0.1 millibar (10 Pa) or lower in several steps as the reaction approaches completion. The temperature can be varied in a stepwise fashion beginning at a temperature of about the melting temperature of the reaction mixture and subsequently increased to final temperature. In one aspect, the reaction mixture is heated from room temperature to about 150° C. In such an aspect, the polymerization reaction starts at a temperature of about 150° C. to about 220° C. In another aspect, the polymerization temperature can be up to about 220° C. In other aspects, the polymerization reaction can then be increased to about 250° C. and then optionally further increased to a temperature of about 320° C., and all subranges there between. In one aspect, the total reaction time can be from about 30 minutes to about 200 minutes and all subranges there between. This procedure will generally ensure that the reactants react to give polycarbonates with the desired molecular weight, glass transition temperature and physical properties. The reaction proceeds to build the polycarbonate chain with production of ester-substituted alcohol by-product such as methyl salicylate. In one aspect, efficient removal of the by-product can be achieved by different techniques such as reducing the pressure. Generally the pressure starts relatively high in the beginning of the reaction and is lowered progressively throughout the reaction and temperature is raised throughout the reaction.
In one aspect, the progress of the reaction can be monitored by measuring the melt viscosity or the weight average molecular weight of the reaction mixture using techniques known in the art such as gel permeation chromatography. These properties can be measured by taking discrete samples or can be measured on-line. After the desired melt viscosity and/or molecular weight is reached, the final polycarbonate product can be isolated from the reactor in a solid or molten form. It will be appreciated by a person skilled in the art, that the method of making aliphatic homopolycarbonate and aliphatic-aromatic copolycarbonates as described in the preceding sections can be made in a batch or a continuous process and the process disclosed herein is preferably carried out in a solvent free mode. Reactors chosen should ideally be self-cleaning and should minimize any “hot spots.” However, vented extruders similar to those that are commercially available can be used.
In one aspect, the aliphatic homopolycarbonate and aliphatic-aromatic copolycarbonate can be prepared in an extruder in presence of one or more catalysts, wherein the carbonating agent is an activated aromatic carbonate. In one aspect, the reactants for the polymerization reaction can be fed to the extruder in powder or molten form. In another aspect, the reactants are dry blended prior to addition to the extruder. The extruder can be equipped with pressure reducing devices (e.g., vents), which serve to remove the activated phenol by-product and thus drive the polymerization reaction toward completion. The molecular weight of the polycarbonate product can, in various aspects, be manipulated by controlling, among other factors, the feed rate of the reactants, the type of extruder, the extruder screw design and configuration, the residence time in the extruder, the reaction temperature and the pressure reducing techniques present on the extruder. The molecular weight of the polycarbonate product can also depend upon the structures of the reactants, such as, activated aromatic carbonate, aliphatic diol, dihydroxy aromatic compound, and the catalyst employed. Many different screw designs and extruder configurations are commercially available that use single screws, double screws, vents, back flight and forward flight zones, seals, and sidestreams. One skilled in the art can find the best designs using generally known principals of commercial extruder design. Controlling the ratio diarylcarbonate/diol, specifically BMSC/diol can impact the Mw when using an activated carbonate. A lower ratio can generally give a higher molecular weight.
In an exemplary aspect, the polycarbonate polymer component comprises a bisphenol Apolycarbonate polymer. In another exemplary aspect, the polycarbonate component comprises a blend of at least two different grade bisphenol A polycarbonates. To that end, a polycarbonate grade can, for example, be characterized by the melt volume rate (MVR) of the polycarbonate. For example, a disclosed polycarbonate, such as a bisphenol A polycarbonate, can be characterized by exhibiting a Melt Flow Rate (MFR) in the range of from 4 g/10 min to 30 g/10 min at 300° C./1.2 kg. For example, the MFR can range from 10 g/10 min to 30 g/10 min, including for example a MFR in the range of from 15 g/10 min to 30 g/10 min. Further, for example, the MFR can be in the range of from 5 g/10 min to 30 g/10 min.
The polycarbonate component can be present in the polymer composition in any desired amount. For example, according to aspects of the disclosure, the polycarbonate polymer component can be present in an amount in the range of from about 10 weight % up to about 90 weight % relative to the total weight of the polymer composition, including further exemplary amounts of about 10 weight %, 15 weight %, 20 weight %, 25 weight %, 30 weight %, 35 weight %, 40 weight %, 45 weight %, 50 weight %, 55 weight %, 60 weight %, 65 weight %, 70 weight %, 75 weight %, 80 weight %, and 90 weight %. In still further aspects, the polycarbonate component can be present within any range of amount derived from any two of the above states values. For example, the polycarbonate polymer component can be present in an amount in the range of from about 10 weight % to about 15 weight %, or in an amount in the range of from about 5 weight % to about 20 weight %, or in an amount in the range of from about 50 weight % to about 80 weight %.
In aspects where the polycarbonate component comprises a blend of two or more polycarbonate polymers, it should be understood that each respect polycarbonate polymer present within the polycarbonate component can be present in any desired amount relative to the total weight percentage of the polycarbonate polymer component. For example, in an aspect wherein the polycarbonate polymer component comprises at least a first and a second polycarbonate polymer, the first polycarbonate polymer can be present in an amount in the range of from greater than 0 weight % to less than 100 weight % relative to the total weight of the polycarbonate polymer component. Similarly, the second polycarbonate polymer can also be present in an amount in the range of from greater than 0 weight % to less than 100 weight % relative to the total weight of the polycarbonate polymer component.
For example, in an exemplary aspect, a polycarbonate polymer component comprising two different grade bisphenol A polycarbonates can be present in the polymer composition in an amount in the range of from about 14 to 16 weight percent. According to this aspect, a first bisphenol A polycarbonate can be present in an amount in the range of from about 5 weight percent to about 6 weight percent relative to the total weight of polymer composition or, expressed in an alternative manner, in an amount in the range of from 35 weight percent to about 45 weight percent relative to the total weight percent of the polycarbonate component. Likewise, the second bisphenol A polycarbonate can be present in an amount in the range of from about 9 to about 10 weight percent relative to the total weight of polymer composition or, expressed in an alternative manner, in an amount in the range of from 55 weight percent to about 65 weight percent relative to the total weight percent of the polycarbonate component. In at least one aspect, the at least one polycarbonate comprises at least 5 weight percentage relative to the polymer composition's total weight percentage. For example, the total polycarbonate amount ranges from 5 wt % to 14 wt %, relative to the polymer composition's total weight percentage.
In another exemplary aspect, a polycarbonate polymer component comprising two different grade bisphenol A polycarbonates can be present in the polymer composition in an amount in the range of from about 70 to 72 weight percent. According to this aspect, a first bisphenol A polycarbonate can be present in an amount in the range of from about 53 to about 54 weight percent relative to the total weight of polymer composition or, expressed in an alternative manner, in an amount in the range of from 73 weight percent to about 78 weight percent relative to the total weight percent of the polycarbonate component. Likewise, the second bisphenol A polycarbonate can be present in an amount in the range of from about 17 to about 18 weight percent relative to the total weight of polymer composition or, expressed in an alternative manner, in an amount in the range of from 22 weight percent to about 27 weight percent relative to the total weight percent of the polycarbonate component.
C. Polycarbonate-Polysiloxane Copolymer
The disclosed polymer compositions further comprise a polycarbonate-polysiloxane block copolymer component. As used herein, the term polycarbonate-polysiloxane copolymer is equivalent to polysiloxane-polycarbonate copolymer, polycarbonate-polysiloxane polymer, or polysiloxane-polycarbonate polymer. The polysiloxane-polycarbonate copolymer comprises polydiorganosiloxane blocks comprising structural units of the general formula (I) below:
wherein the polydiorganosiloxane block length (E) is from about 20 to about 60; wherein each R group can be the same or different, and is selected from a C_1-13monovalent organic group; wherein each M can be the same or different, and is selected from a halogen, cyano, nitro, C₁-C₈alkylthio, C₁-C₈alkyl, C₁-C₈alkoxy, C₂-C₈alkenyl, C₂-C₈alkenyloxy group, C₃-C₈cycloalkyl, C₃-C₈cycloalkoxy, C₆-C₁₀aryl, C₆-C₁₀aryloxy, C₇-C₁₂aralkyl, C₇-C₁₂aralkoxy, C₇-C₁₂alkylaryl, or C₇-C₁₂alkylaryloxy, and where each n is independently 0, 1, 2, 3, or 4. The polysiloxane-polycarbonate copolymer also comprises polycarbonate blocks comprising structural units of the general formula (II) below:
wherein at least 60 percent of the total number of R¹groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties
According to exemplary non-limiting aspects of the disclosure, the polycarbonate-polysiloxane block copolymer comprises diorganopolysiloxane blocks of the general formula (III) below:
wherein x represents an integer from about 20 to about 60. The polycarbonate blocks according to these aspects can be derived from bisphenol-A monomers.
Diorganopolysiloxane blocks of formula (III) above can be derived from the corresponding dihydroxy compound of formula (IV):
wherein x is as described above. Compounds of this type and others are further described in U.S. Pat. No. 4,746,701 to Kress, et al and U.S. Pat. No. 8,017,0697 to Carrillo. Compounds of this formula can be obtained by the reaction of the appropriate dihydroxyarylene compound with, for example, an alpha, omega-bisacetoxypolydiorangonosiloxane under phase transfer conditions.
Such dihydroxypolysiloxanes can be made by effecting a platinum catalyzed addition between a siloxane hydride of the formula (V):
wherein x is a previously defined, and an aliphatically unsaturated monohydric phenol such as eugenol to yield a compound of formula (IV).
The polycarbonate-polysiloxane copolymer may be manufactured by reaction of a diphenolic polysiloxane, such as that depicted by formula (IV), with a carbonate source and a dihydroxy aromatic compound such as bisphenol-A, optionally in the presence of a phase transfer catalyst as described above. Suitable conditions are similar to those useful in forming polycarbonates. For example, the copolymers can be prepared by phosgenation at temperatures from below 0° C. to about 100° C., including for example, at temperatures from about 25° C. to about 50° C. Since the reaction is exothermic, the rate of phosgene addition can be used to control the reaction temperature. The amount of phosgene required will generally depend upon the amount of the dihydric reactants. Alternatively, the polycarbonate-polysiloxane copolymers can be prepared by co-reacting, in a molten state, the dihydroxy monomers and a diaryl carbonate ester, such as diphenyl carbonate, in the presence of a transesterification catalyst as described above.
In the production of the polycarbonate-polysiloxane copolymer, the amount of dihydroxydiorganopolysiloxane can be selected so as to provide the desired amount of diorganopolysiloxane units in the copolymer. The particular amounts used will therefore be determined depending on desired physical properties of the composition, the value of x (for example, within the range of about 20 to about 60), and the type and relative amount of each component in the composition, including the type and amount of polycarbonate, type and amount of polycarbonate-polysiloxane copolymer, and type and amount of any other additives. Suitable amounts of dihydroxydiorganopolysiloxane can be determined by one of ordinary skill in the art without undue experimentation using the guidelines taught herein.
For example, according to aspects of the disclosure, the polysiloxane-polycarbonate block copolymer can be provided having any desired level of siloxane content. For example, the siloxane content can be in the range of from 4 mole % to 30 mole %. In additional aspects, the siloxane content of the polysiloxane-polycarbonate block copolymer can be in the range of from 4 mole % to 20 mole %. In still further aspects, the siloxane content of the polysiloxane-polycarbonate block copolymer can be in the range of from 4 mole % to 8 mole %. In a further aspect, the polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content in the range of from 5 to 7 mole wt %. In an even further exemplary aspect, the siloxane content of the polysiloxane-polycarbonate block copolymer can be about 6 mole %. Still further, the diorganopolysiloxane blocks can be randomly distributed in the polysiloxane-polycarbonate block copolymer.
The disclosed polysiloxane-polycarbonate block copolymers can also be end-capped as similarly described in connection with the manufacture of polycarbonates set forth herein. For example, according to aspects of the disclosure, a polysiloxane-polycarbonate block copolymer can be end capped with p-cumyl-phenol.
A non-limiting example of a polycarbonate-siloxane copolymer includes transparent EXL, available from SABIC Innovative Plastics. The transparent EXL from SABIC is a polycarbonate-polysiloxane (9030T) copolymer, having been tested commercially and found to have about 6 mole % siloxane, a Mw of about 44,600, and a Mn of about 17800 in a polystyrene standard using chloroform solvent.
The polysiloxane polycarbonate copolymer component can be present in the polymer composition in any desired amount. For example, in aspects of the disclosure, the polysiloxane polycarbonate copolymer is present in an amount of at least 10 weight percent relative to the total weight of the polymer composition. For example, the polycarbonate-polysiloxane copolymer can be present in an amount in the range of from 10 weight % to 90 weight % relative to the total weight of the polymer composition, including exemplary amounts of 15 weight %, 20 weight %, 25 weight %, 30 weight %, 35 weight %, 40 weight %, 45 weight %, 50 weight %, 55 weight %, 60 weight %, 65 weight %, 70 weight %, 75 weight %, 80 weight %, 85 weight %, and 90 weight %. In still further aspects, the polysiloxane polycarbonate copolymer can be present within any range of amounts derived from any two of the above stated values. For example, the polysiloxane polycarbonate copolymer can be present in an amount in the range of from about 10 weight % to about 20 weight %, or in an amount in the range of from about 60 weight % to about 90 weight %.
D. Laser Direct Structuring Additive
The disclosed polymer compositions further comprise a conventional laser direct structuring additive (LDS) additive. As used herein, a laser direct structuring additive refers to metal containing additives suitable for use in a laser direct structuring process. To that end, as discussed more fully herein, an LDS additive is selected such that, after activating with a laser, a conductive path can be formed by a subsequent standard metallization or plating process. As such, when the LDS additive is exposed to a laser, elemental metal is released or activated. The laser thus draws the circuit pattern onto the thermoplastic part and leaves behind a roughened surface containing embedded metal particles. These particles act as nuclei for the crystal growth during a subsequent metallization or plating process, such as a copper plating process or other plating processes, including gold plating, nickel plating, silver plating, zinc plating, tin plating or the like.
According to aspects of the disclosure, the laser direct structuring additive can comprise one or more metal oxides, including for example, oxides of chromium, copper, or combinations thereof. These laser direct structuring additives can also be provided having spinel type crystal structures. In one aspect, the laser direct structuring additive comprises a metal oxide, a copper salt, a metal oxide spinel, or a mixture of metal oxide spinels, or a combination thereof.
An exemplary and non-limiting example of a commercially available laser direct structuring additive includes PK3095 black pigment, commercially available from Ferro Corp., USA. The PK3095, for example, comprises chromium oxides (Cr₂O₃, Cr₂O₄ ²⁻, Cr₂O₇ ²⁻) and oxides of copper (CuO), as determined using XPS. The PK3095 black pigment also has a spinel type crystal structure. Another exemplary commercially available laser direct structuring additive is the Black 1G pigment black 28 commercially available from The Shepherd Color company. The Black 1G pigment black 28 comprises copper chromate and has a pH of about 7.3. The Black 1G pigment also has a spinel type crystal structure.
In one aspect, the laser direct structuring additive can be present in the polymer composition in an amount in the range of from about 1 weight % to about 10 weight % relative to the total weight of the polymer composition, including for example, amounts of about 1 weight %, about 2 weight %, about 3 weight %, about 4 weight %, about 5 weight %, about 6 weight %, about 7 weight %, about 8 weight %, about 9 weight % and about 10 weight %. In still further aspects, the laser direct structure (LDS) additive can be present in the polymer composition in an amount within any range of amounts derived from any two of the above stated values. For example, the laser direct structuring additive can be present in an amount of from 7 weight % to 10 weight % relative to the total weight of the polymer composition. Alternatively, the laser direct structuring additive can be present in the polymer composition in an amount in the range of from 9 weight % to 10 weight % relative to the total weight of the polymer composition. In an even further aspect, the laser direct structuring additive can be present in the polymer composition in an amount of about 10 weight % relative to the total weight of the polymer composition.
E. Reinforcing Fillers
The disclosed polymer compositions further comprise a reinforcing filler, such as, for example, an inorganic filler or reinforcing agent. The specific composition of a filler, can vary, provided that the filler is chemically compatible with the remaining components of the polymer composition. In one aspect, the polymer composition comprises a reinforcing filler comprising a glass reinforcement component, a carbon fiber, a mineral filler, or talc, or a combination thereof
In one aspect, the glass reinforcement component comprises a glass fiber, flat glass, long glass, short glass, large diameter glass, small diameter glass, or nano glass, or a combination thereof. In another aspect, the glass reinforcement component comprises E-glass, A-glass, C-glass, D-glass, R-glass, or S-glass, or a combination thereof. In a further aspect, the E-glass comprises E-glass derivatives that are fluorine free and/or boron-free.
In one aspect, the glass reinforcement component diameter ranges from 4 μm to 35 μm, including exemplary values of 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 26 μm, 28 μm, 30 μm, 32 μm, and 34 μm. In still further aspects, the diameter can in a range derived from any two of the above stated values. For example, the diameter can range from 5 μm to 34 μm.
In another aspect, an exemplary filler can comprise silicates and silica powders, such as aluminum silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, crystalline silica graphite, natural silica sand, or the like; boron powders, such as boron-nitride powder, boron-silicate powders, or the like; oxides, such as TiO₂, aluminum oxide, magnesium oxide, or the like; calcium sulfate (as its anhydride, dihydrate or trihydrate), or the like; talc, including fibrous, modular, needle shaped, lamellar talc, or the like; wollastonite; surface-treated wollastonite; glass spheres such as hollow and solid glass spheres, silicate spheres, aluminosilicate, or the like; kaolin, including hard kaolin, soft kaolin, calcined kaolin, kaolin comprising various coatings known in the art to facilitate compatibility with the polymeric matrix resin, or the like; single crystal fibers or “whiskers” such as silicon carbide, alumina, boron carbide, iron, nickel, copper, or the like; fibers (including continuous and chopped fibers), sulfides such as molybdenum sulfide, zinc sulfide or the like; barium compounds such as barium titanate, barium ferrite, barium sulfate, heavy spar, or the like; metals and metal oxides such as particulate or fibrous aluminum, bronze, zinc, copper and nickel or the like; flaked fillers such as glass flakes, flaked silicon carbide, aluminum diboride, aluminum flakes, steel flakes or the like; fibrous fillers, for example short inorganic fibers such as those derived from blends comprising at least one of aluminum silicates, aluminum oxides, magnesium oxides, and calcium sulfate hemihydrate or the like; natural fillers and reinforcements, such as wood flour obtained by pulverizing wood, fibrous products such as cellulose, cotton, or the like; organic fillers such as polytetrafluoroethylene; reinforcing organic fibrous fillers formed from organic polymers capable of forming fibers such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), aromatic polyamides, aromatic polyimides, polyetherimides, polytetrafluoroethylene, or the like; as well as additional fillers and reinforcing agents such as mica, clay, feldspar, flue dust, fillite, quartz, quartzite, perlite, tripoli, diatomaceous earth, carbon black, or the like, or combinations comprising at least one of the foregoing fillers or reinforcing agents.
The reinforcing filler can be present in the polymer composition in an amount in the range of from greater than 0 weight % to about 60 weight % relative to the total weight of the polymer composition, including for example, amounts of about 5 weight %, about 10 weight %, about 15 weight %, about 20 weight %, about 25 weight %, about 30 weight %, about 35 weight %, about 40 weight %, about 45 weight %, about 50 weight %, about 55 weight %, and about 60 weight %. In still further aspects, the reinforcing filler can be present in the polymer composition in an amount within any range of amounts derived from any two of the above stated values. For example, the reinforcing filler can be present in an amount of from 5 weight % to 30 weight % relative to the total weight of the polymer composition. Alternatively, the reinforcing filler can be present in the polymer composition in an amount in the range of from 35 weight % to 50 weight % relative to the total weight of the polymer composition. In an even further aspect, the reinforcing filler can be present in the polymer composition in an amount of about 30 weight % relative to the total weight of the polymer composition.
F. Optional Polymer Composition Additives
The disclosed polymer compositions can optionally comprise one or more additives conventionally used in the manufacture of molded thermoplastic parts with the proviso that the optional additives do not adversely affect the desired properties of the resulting composition. Mixtures of optional additives can also be used. Such additives may be mixed at a suitable time during the mixing of the components for forming the composite mixture. For example, the disclosed polymer composition can further comprise at least one additive comprising a plasticizer, a stabilizer, an anti-static agent, a flame-retardant, an impact modifier, a colorant, an antioxidant, or a mold release agent, or a combination thereof. In one aspect, the composition further comprises one or more optional additives selected from an antioxidant, flame retardant, and stabilizer.
Exemplary heat stabilizers include, for example, organophosphites such as triphenylphosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono- and di-nonylphenyl)phosphite or the like; phosphonates such as dimethylbenzenephosphonate or the like, phosphates such as trimethyl phosphate, or the like, or combinations including at least one of the foregoing heat stabilizers. Heat stabilizers are generally used in amounts of from 0.01 to 0.5 parts by weight based on 100 parts by weight of the total composition, excluding any filler.
Exemplary antioxidants include, for example, organophosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritoldiphosphite, distearylpentaerythritoldiphosphite or the like; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes, such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, or the like; butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylatedthiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds; esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or the like; amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the like, or combinations including at least one of the foregoing antioxidants. Antioxidants are generally used in amounts of from 0.01 to 0.5 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.
Exemplary light stabilizers include, for example, benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxy benzophenone or the like or combinations including at least one of the foregoing light stabilizers. Light stabilizers are generally used in amounts of from 0.1 to 1.0 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.
Exemplary plasticizers include, for example, phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate, tris-(octoxycarbonylethyl) isocyanurate, tristearin, epoxidized soybean oil or the like, or combinations including at least one of the foregoing plasticizers. Plasticizers are generally used in amounts of from 0.5 to 3.0 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.
Exemplary antistatic agents include, for example, glycerol monostearate, sodium stearylsulfonate, sodium dodecylbenzenesulfonate or the like, or combinations of the foregoing antistatic agents. In one aspect, carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or any combination of the foregoing may be used in a polymeric resin containing chemical antistatic agents to render the composition electrostatically dissipative.
Exemplary mold releasing agents include for example, metal stearate, stearyl stearate, pentaerythritoltetrastearate, beeswax, montan wax, paraffin wax, or the like, or combinations including at least one of the foregoing mold release agents. Mold releasing agents are generally used in amounts of from 0.1 to 1.0 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.
Exemplary UV absorbers include for example, hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates; oxanilides; benzoxazinones; 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (CYASORB™ 5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB™ 531); 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol (CYASORB™ 1164); 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) (CYASORB™ UV-3638); 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane (UVINUL™ 3030); 2,2′-(1,4-phenylene) bis(4H-3,1-benzoxazin-4-one); 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane; nano-size inorganic materials such as titanium oxide, cerium oxide, and zinc oxide, all with particle size less than 100 nanometers; or the like, or combinations including at least one of the foregoing UV absorbers. UV absorbers are generally used in amounts of from 0.01 to 3.0 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.
Exemplary lubricants include for example, fatty acid esters such as alkyl stearyl esters, e.g., methyl stearate or the like; mixtures of methyl stearate and hydrophilic and hydrophobic surfactants including polyethylene glycol polymers, polypropylene glycol polymers, and copolymers thereof e.g., methyl stearate and polyethylene-polypropylene glycol copolymers in a suitable solvent; or combinations including at least one of the foregoing lubricants. Lubricants are generally used in amounts of from 0.1 to 5 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.
Exemplary blowing agents include for example, low boiling halohydrocarbons and those that generate carbon dioxide; blowing agents that are solid at room temperature and when heated to temperatures higher than their decomposition temperature, generate gases such as nitrogen, carbon dioxide, ammonia gas, such as azodicarbonamide, metal salts of azodicarbonamide, 4,4′ oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammonium carbonate, or the like, or combinations including at least one of the foregoing blowing agents. Blowing agents are generally used in amounts of from 1 to 20 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.
As noted above, the disclosed polymer compositions can optionally further comprises a flame retardant additive. In various aspects, the flame retardant additive can comprise any flame retardant material or mixture of flame retardant materials suitable for use in the inventive polymer compositions. In another aspect, the flame retardant additive comprises a phosphate containing material. In another aspect, the flame retardant additive comprises a halogen containing material. In other aspects, the flame retardant additive is free of or substantially free of one or more of phosphate and/or a halogen. In still another aspect, the flame retardant additive comprises an oligomer organophosphorous flame retardant, including for example, bisphenol A diphenyl phosphate (BPADP). In a further aspect, the flame retardant is selected from oligomeric phosphate, polymeric phosphate, oligomeric phosphonate, or mixed phosphate/phosphonate ester flame retardant compositions. In a still further aspect, the flame retardant is selected from triphenyl phosphate; cresyldiphenylphosphate; tri(isopropylphenyl)phosphate; resorcinol bis(diphenylphosphate); and bisphenol-A bis(diphenyl phosphate). In a yet further aspect, the flame retardant is bisphenol-A bis(diphenyl phosphate).
The concentration of a flame retardant additive can vary, and the present invention is not intended to be limited to any particular flame retardant concentration. In one aspect, the disclosed composition can comprises from greater than 0 wt % to about 20 wt % of flame retardant additive, including for example, about 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt %, or 19 wt %. In still further aspects, the flame retardant additive can be present in any range of amounts derived from the above values. For example, the flame retardant additive can be present in the polycarbonate composition in an amount in the range of from about 5 wt % to about 15 wt %, or event from about 10 wt % to about 20 wt %. Flame retardant additives are commercially available, and one of skill in the art could readily select an appropriate flame retardant additive.
Additionally, materials to improve flow and other properties may be added to the composition, such as low molecular weight hydrocarbon resins. Particularly useful classes of low molecular weight hydrocarbon resins are those derived from petroleum C₅to C₉feedstock that are derived from unsaturated C₅to C₉monomers obtained from petroleum cracking. Non-limiting examples include olefins, e.g., pentenes, hexenes, heptenes and the like; diolefins, e.g., pentadienes, hexadienes and the like; cyclic olefins and diolefins, e.g., cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, methyl cyclopentadiene and the like; cyclic diolefindienes, e.g., dicyclopentadiene, methylcyclopentadiene dimer and the like; and aromatic hydrocarbons, e.g., vinyltoluenes, indenes, methylindenes and the like. The resins can additionally be partially or fully hydrogenated.

Methods of Manufacture

In a further aspect, the invention relates to a method for making a polymer composition, the method comprising forming a blended composition comprising a thermoplastic polymer, a laser direct structuring additive and a reinforcing filler.
In one aspect, the laser direct structuring process involves three steps: 1) injection molding, 2) laser structuring, and 3) metallizing.
In a further aspect, during the injection molding step, the laser direct structuring additive and reinforcing filler may be mixed with the thermoplastic polymer. In another aspect, the blend composition further comprises one or more optional additives selected from an antioxidant, flame retardant, inorganic filler, and stabilizer. In a still further aspect, single shot injection molding can be used to produce the parts or articles to be laser structured. In at least one aspect, the polymer composition may be mixed at this step and used in the LDS process. In another aspect, additional ingredients may be added to the polymer composition after this step.
As described herein, the present invention relates to blended polymer compositions. The blended polymer compositions of the present disclosure may be formed using any known method of combining multiple components to form a polymer resin. In one aspect, the components are first blended in a high-speed mixer. Other low shear processes including but not limited to hand mixing may also accomplish this blending. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, one or more of the components may be incorporated into the composition by feeding directly into the extruder at the throat and/or downstream through a sidestuffer. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate is immediately quenched in a water batch and pelletized. The pellets so prepared when cutting the extrudate may be one-fourth inch long or less as desired. Such pellets may be used for subsequent molding, shaping, or forming. In one aspect, the blend composition is formed by twin screw extrusion.
In a further aspect, during the laser structuring step, a laser is used to form a conductive path during the laser structuring step. In a still further aspect, the laser used to form a conductive path is laser direct structuring. In a yet further aspect, laser direct structuring comprises laser etching. In an even further aspect, laser etching is carried out to provide an activated surface.
In a further aspect, at least one laser beam draws at least one pattern on the surface of the polymer composition during the laser structuring step. In a still further aspect, the employed filler composition may release at least one metallic nucleus. In a yet further aspect, the at least one metallic nucleus that has been released may act as a catalyst for reductive copper plating process.
In a further aspect, laser etching is carried out at about 1 w to about 10 w power with a frequency from about 30 kHz to about 110 kHz and a speed of about 1 m/s to about 5 m/s. In a still further aspect, laser etching is carried out at about 1 w to about 10 w power with a frequency from about 40 kHz to about 100 kHz and a speed of about 2 m/s to about 4 m/s. In a yet further aspect, laser etching is carried out at about 3.5 w power with a frequency of about 40 kHz and a speed of about 2 m/s.
In a further aspect, a rough surface may form in the LDS process. In a still further aspect, the rough surface may entangle the copper plate with the polymer matrix in the polymer composition, which may provide adhesion between the copper plate and the polymer composition.
The metalizing step can, in various aspects, be performed using conventional techniques. For example, in one aspect, an electroless copper plating bath is used during the metallization step in the LDS process. Thus, in various aspects, plating a metal layer onto a conductive path is metallization. In a still further aspect, metallization can comprise the steps: a) cleaning the etched surface; b) additive build-up of tracks; and c) plating.

Articles of Manufacture

Shaped, formed, or molded articles including the polymer compositions are also provided. The polymer compositions can be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding and thermoforming to form articles such as, for example, personal computers, notebook and portable computers, cell phone antennas and other such communications equipment, medical applications, RFID applications, automotive applications, and the like.
The blended polymer compositions, or compounds, disclosed herein provide robust plating performance while maintaining good mechanical properties. Evaluation of the mechanical properties can be performed through various tests, such as Izod test, Charpy test, Gardner test, etc., according to several standards (e.g., ASTM D256). Robustness of plating performance can be measured via a performance ranking, or plating ranking, ranging from top performance (e.g., “best”) to bottom performance. The ranking can be partitioned in various levels. In one aspect, a plating ranking can have a level of “10” for top performance and a level of “0” for bottom performance.
In a further aspect, the method comprises forming a molded part from the formed blend composition. In another aspect, the method further comprises subjecting the molded part to a laser direct structuring process.
In one aspect, the molded article formed from the composition exhibits ductile failure mode according to ASTM D256-2010.
In one aspect, the article comprises the product of extrusion molding or injection molding a composition comprising a thermoplastic polymer, a laser directing structuring additive, and a reinforcing filler.
In a further aspect, the molded article further comprises a conductive path formed by activation with a laser. In a yet further aspect, the article further comprises a metal layer plated onto the conductive path. In an even further aspect, the metal layer is a copper layer. In a still further aspect, the metal layer has a thickness of about 0.8 micrometers or higher as measured according to ASTM B568.
In various aspects, the polymer composition may be used in the field of electronics. In a further aspect, non-limiting examples of fields which may use 3D MIDs, LDS process, or polymer composition include electrical, electro-mechanical, Radio Frequency (RF) technology, telecommunication, automotive, aviation, medical, sensor, military, and security. In a still further aspect, the use of 3D MIDs, LDS processes, or polymer compositions may also be present in overlapping fields, for example in mechatronic systems that integrate mechanical and electrical properties which may, for example, be used in automotive or medical engineering.
In one aspect, molded articles according to the present invention can be used to produce a device in one or more of the foregoing fields. In a still further aspect, non-limiting examples of such devices in these fields which may use 3D MIDs, LDS processes, or polymer compositions according to the present invention include a computer device, a household appliance, a decoration device, an electromagnetic interference device, a printed circuit, a Wi-Fi device, a Bluetooth device, a GPS device, a cellular antenna device, a smart phone device, an automotive device, a military device, an aerospace device, a medical device, a hearing aid, a sensor device, a security device, a shielding device, a RF antenna device, or a RFID device.
In a still further aspect, the molded articles can be used to manufacture devices in the automotive field. In a further aspect, non-limiting examples of such devices in the automotive field which may use 3D MIDs, LDS processes, or the disclosed polymer compositions in the vehicle's interior include adaptive cruise control, headlight sensors, windshield wiper sensors, and door/window switches. In a further aspect, non-limiting examples of devices in the automotive field which may use 3D MIDs, LDS process, or the disclosed polymer compositions in the vehicle's exterior include pressure and flow sensors for engine management, air conditioning, crash detection, and exterior lighting fixtures.
Plastic plating was developed for industrial application because of the low cost, the ability to mold large and complex parts, and the reduction of weight. Plastic plating also allows the rapid development of new designs and reduced space requirements in both production and the devices themselves. As gasoline prices rise, consumers have become more interested in automotive weight reduction. Non-limiting examples of plastic materials which may be plated include acrylonitrile butadiene styrene (ABS), polypropylene, polysulfone, polyethersulfone, polyetherimide, Teflon, polyarylether, polycarbonate, polyphenylene oxide, polyacetal. The LDS process may be used for plastic plating and the plastic material may be included in the polymer composition or in the polymer matrix of the polymer composition.
In one aspect, the molded articles may have a thickness ranging from 1.2 mm to 2.0 mm. For example, the molded article may have a thickness of 1.6 mm. In further aspect, the molded article may have a thickness ranging from 2.8 to 3.5 mm. For example, the molded article may have a thickness of 3.2 mm.
In a further aspect, the resulting disclosed compositions can be used to provide any desired shaped, formed, or molded articles. For example, the disclosed compositions may be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding and thermoforming. As noted above, the disclosed compositions are particularly well suited for use in the manufacture of electronic components and devices. As such, according to some aspects, the disclosed compositions can be used to form articles such as printed circuit board carriers, burn in test sockets, flex brackets for hard disk drives, and the like.
The disclosed methods include at least the following aspects.
Aspect 1: A polymer composition comprising:

- a. a thermoplastic polymer;
- b. a laser direct structuring additive; and
- c. a glass reinforcement component;
  - wherein the polymer composition is capable of being plated after being activated using a laser.

Aspect 2: The polymer composition of aspect 1, wherein the thermoplastic polymer comprises polycarbonate, polycarbonate-polysiloxane copolymer, polyamide, ethylene vinyl acetate, ethylene vinyl alcohol, polyoxymethylene, polyacrylate, polyacrylonitrile, polyamide-imide, polyetherketone, polycaprolactone, polyhydroxyalkanoate, polyester, polyimide, polyketone, polylactic acid, polyurethane, or polyvinyl acetate or a combination thereof.
Aspect 3: The polymer composition of aspects 1-2, wherein the laser direct structuring additive comprises a metal oxide, a copper salt, a metal oxide spinel, or a mixture of metal oxide spinels, or a combination thereof.
Aspect 4: The polymer composition of aspects 1-3, wherein the thermoplastic polymer is present in an amount ranging from about 10 wt % to about 90 wt % based on the total weight of the composition.
Aspect 5: The polymer composition of aspects 1-4, wherein the glass reinforcement component is present an amount ranging from greater than 0 wt % to about 60 wt % based on the total weight of the composition.
Aspect 6: The polymer composition of aspects 1-5, wherein the laser direct structuring additive is present in an amount ranging from about 1 wt % to about 10 wt % based on the total weight of the composition.
Aspect 7: The polymer composition of aspects 1-6, wherein the thermoplastic polymer is present in an amount ranging from about 10 wt % to about 90 wt % based on the total weight of the composition, the glass reinforcement component is present in an amount ranging from greater than 0 wt % to about 60 wt % based on the total weight of the composition, and the laser direct structuring additive is present in an amount ranging from about 1 wt % to about 10 wt % based on the total weight of the composition.
Aspect 8: The polymer composition of aspects 1-7, wherein the flexural modulus is greater than about 3 GPa.
Aspect 9: The polymer composition of aspects 1-8, wherein the tensile modulus is greater than about 3 GPa.
Aspect 10: The polymer composition of aspects 1-9, wherein the flexural modulus is greater than about 3 GPa and the tensile modulus is greater than about 3 GPa.
Aspect 11: The polymer composition of aspects 1-10, wherein the thermoplastic polymer comprises polycarbonate.
Aspect 12: The polymer composition of any one of aspects 1-11, wherein the tensile modulus, flexural modulus, and/or plating index increase with an increasing concentration of glass reinforcement component.
Aspect 13: The polymer composition of aspects 1-12, wherein the thermoplastic polymer comprises polyamide.
Aspect 14: The polymer composition of aspects 1-13 further comprising at least one additive comprising plasticizer, stabilizer, anti-static agent, flame-retardant, impact modifier, colorant, antioxidant, or mold release agent, or a combination thereof.
Aspect 15: A polymer composition of aspects 1-14, wherein the glass reinforcement component comprises a glass fiber, flat glass, long glass, short glass, large diameter glass, small diameter glass, or nano glass, or a combination thereof.
Aspect 16: A polymer composition comprising:

- a. a thermoplastic polymer;
- b. a laser direct structuring additive; and
- c. a reinforcing filler
  - wherein the polymer composition is capable of being plated after being activated using a laser;
  - wherein the flexural modulus is greater than about 3 GPa and the tensile modulus is greater than about 3 GPa.

Aspect 17: The polymer composition of aspect 16, wherein the reinforcing filler comprises a glass reinforcement component, a carbon fiber, a mineral filler, or talc, or a combination thereof.
Aspect 18: The polymer composition of any one of aspects 16-17, further comprising at least one additive comprising a plasticizer, stabilizer, anti-static agent, flame-retardant, impact modifier, colorant, antioxidant, or mold release agent, or a combination thereof.
Aspect 19: A method for making a polymer composition comprising forming a blend composition comprising:

- a. a thermoplastic polymer;
- b. a laser direct structuring additive; and
- c. a reinforcing filler;
- wherein the polymer composition is capable of being plated after being activated using a laser;
- wherein the flexural modulus is greater than about 3 GPa and the tensile modulus is greater than about 3 GPa.

Aspect 20: The method of aspect 19, wherein the blend composition further comprises a plasticizer, stabilizer, anti-static agent, flame-retardant, impact modifier, colorant, antioxidant, or mold release agent or a combination thereof.
Aspect 21: The method of aspects 19 or 20, wherein the blend composition is formed by twin screw extrusion.
Aspect 22: An article of manufacture comprising the polymer composition of aspects 1-21.
Aspect 23: The article manufacture of aspect 22, wherein the article comprises a computer device, a household appliance, a decoration device, an electromagnetic interference device, a printed circuit, a Wi-Fi device, a Bluetooth device, a GPS device, a cellular antenna device, a smart phone device, an automotive device, a military device, an aerospace device, a medical device, a hearing aid, a sensor device, a security device, a shielding device, a RF antenna device, or a RFID device.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other aspects of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Examples

The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the methods, devices, and systems disclosed and claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in degrees Celsius (° C.) or is at ambient temperature, and pressure is at or near atmospheric.

Compounding Profile

Table 1 illustrates the compounding profile and equipment set up for glass filled PC LDS.

TABLE 1

Parameters	Unit	Glass filled, LDS capable polycarbonate

Compounder Type	NONE	TEM-37BS
Barrel Size	mm	1500
Die	mm	3
Feed (Zone 0) Temp	NONE	50
Zone 1 Temp	° C.	100
Zone 2 Temp	° C.	150
Zone 3 Temp	° C.	200
Zone 4 Temp	° C.	255
Zone 5 Temp	° C.	255
Zone 6 Temp	° C.	255
Zone 7 Temp	° C.	255
Zone 8 Temp	° C.	255
Zone 9 Temp	° C.	260
Zone 10 Temp	° C.	260
Zone 11 Temp	° C.	260
Die Temp	° C.	265
Screw speed	rpm	300
Throughput	kg/hr	40
Torque	NONE	70
Vacuum 1	MPa	−0.08
Side Feeder 1 speed	rpm	>200
Melt temperature	NONE	275

Table 2 illustrates the molding profile and equipment set up for glass filled PC LDS.

TABLE 2

Parameters	Unit	Glass filled, LDS capable polycarbonate

Cnd: Pre-drying time	Hour	3
Cnd: Pre-drying temp	° C.	110
Molding Machine	NONE	FANUC
Mold Type (insert)	NONE	ASTM tensile, flexual, Izod, colorchip
Hopper temp	° C.	50
Zone 1 temp	° C.	270
Zone 2 temp	° C.	275
Zone 3 temp	° C.	280
Nozzle temp	° C.	275
Mold temp	° C.	100
Screw speed	rpm	100
Back pressure	kgf/cm²	30
Cooling time	s	15
Injection speed	mm/s	50
Holding pressure	kgf/cm²	800
Max. Injection pres-	kgf/cm²	1000
sure

Formulation and Performance Comparison of Glass Filled, LDS Additive Contained, Polycarbonate Composites

Table 3 illustrates the formulation and performance comparison of the polymer composition comprising a polycarbonate, a LDS additive, and a 0-50 wt % glass reinforcement filler. It is shown that as the glass fiber added, the flexural modulus increases from 2110 MPa to 3340 MPa, the tensile modulus increases from 2134 MPa to 3956 MPa, and the average plating index (PI) increases from 0.30 to 0.91. Furthermore as the glass loading increases, the flexural modulus increases from 3340 MPa to 13100 MPa, the tensile modulus increases from 3956 MPa to 15310 MPa, and the average plating index increases from 0.91 to 1.10. Table 4 shows the LDS plating performance comparison of the polymer composition comprising a polycarbonate, a LDS additive, and a 0-50 wt % glass reinforcement filler. The plating effect of the glass reinforcement filled material is significantly better than unfilled material across a wide range of laser parameters, and the plating effect shows a general increase as glass loading increases across varieties of laser parameters.

TABLE 3

Item Code	Item Description	Unit	0GF	10GF	20GF	30GF	40GF	50GF

C914089/C914090	PC	%	91	81	71	61	51	41
F593895	LDS additive	%	3	3	3	3	3	3
F232	Acrylic polymer impact mod	%	5	5	5	5	5	5
G512972	Flat glass fiber	%		10	20	30	40	50
F542, F538, F527, F722236, F8260,	Additives	%	1	1	1	1	1	1
F4520

Typical Property	Test Method	Test Description	Unit	0GF	10GF	20GF	30GF	40GF	50GF

ASH	ASTM D 5630	2.0 g, 900° C., >20 minutes.	%	3.1	13.1	22.9	32.6	42.6	52.4
HDT	ASTM D 648	0.45 MPa/3.2 mm	° C.	117	126	126	126	124	125
Flexual Modulus	ASTM D 790	3.2 mm, 1.27 mm/min	MPa	2110	3340	5710	7200	9440	13100
Flexual Strength	ASTM D 790	yield, 3.2 mm, 1.27 mm/min	MPa	82	116	149	167	183	201
Tensile Modulus	ASTM D 638	5 mm/min	MPa	2134	3956	6261	8789	11052	15310
Tensile Strength	ASTM D 638	break, 5 mm/min	MPa	41	67	94	109	124	145
Tensile Elongation	ASTM D 638	break, 5 mm/min	%	45.6	3.6	2.6	2.3	2.2	1.9
Notched IZOD	ASTM D256	23° C., 2 lbf/ft	J/m	621	142	163	156	146	120
Unnotched IZOD	ASTM D256	23° C., 5 lbf/ft	J/m	2140	738	735	671	561	466
PI	Average			0.30	0.91	0.94	1.06	1.14	1.10

TABLE 4

Power, w	Frequency, kHz	Speed, m/s	0GF	10GF	20GF	30GF	40GF	50GF

10	100	2	0.63	1.24	1.27	1.34	1.48	1.49
10	70	2	1.07	1.27	1.30	1.40	1.53	1.62
10	40	2	1.34	1.28	1.41	1.49	1.65	1.77
2	100	2	0.00	0.01	0.02	0.03	0.03	0.02
2	70	2	0.00	0.12	0.19	0.37	0.32	0.27
2	40	2	0.01	0.86	0.92	1.03	1.10	1.00
7	80	4	0.02	1.08	1.13	1.24	1.35	1.23
5	80	4	0.01	0.56	0.47	0.93	0.81	0.72
3	80	4	0.00	0.03	0.09	0.18	0.15	0.12
3	100	2	0.00	0.18	0.24	0.47	0.41	0.34
3	70	2	0.01	0.70	0.78	0.93	0.97	0.87
3	40	2	0.06	1.08	1.14	1.25	1.36	1.25
5	100	4	0.00	0.45	0.51	0.63	0.65	0.58
3	100	4	0.00	0.01	0.01	0.01	0.01	0.01
9	80	4	0.17	1.24	1.32	1.47	1.59	1.48
5	100	2	0.02	1.25	1.29	1.37	1.51	1.39
5	70	2	0.14	1.33	1.36	1.44	1.60	1.49
5	40	2	0.73	1.44	1.46	1.48	1.67	1.69
11	100	4	0.31	1.36	1.38	1.41	1.58	1.52
9	100	4	0.05	1.24	1.29	1.40	1.53	1.41
7	100	4	0.01	1.06	1.11	1.23	1.33	1.22
8	100	2	0.67	1.28	1.31	1.36	1.52	1.53
8	70	2	0.92	1.32	1.30	1.40	1.53	1.60
8	40	2	1.05	1.36	1.27	1.49	1.58	1.67
Average PI			0.30	0.91	0.94	1.06	1.14	1.10

Example of Glass Filled Polyamide

Table 5 illustrates the compounding profile and equipment set up for glass filled PA LDS.

TABLE 5

Parameters	Unit	Glass filled, LDS capable polyamide

Compounder Type	NONE	TEM-37BS
Barrel Size	mm	1500
Die	mm	3
Feed (Zone 0) Temp	NONE	50
Zone 1 Temp	° C.	100
Zone 2 Temp	° C.	150
Zone 3 Temp	° C.	200
Zone 4 Temp	° C.	255
Zone 5 Temp	° C.	255
Zone 6 Temp	° C.	255
Zone 7 Temp	° C.	255
Zone 8 Temp	° C.	255
Zone 9 Temp	° C.	255
Zone 10 Temp	° C.	255
Zone 11 Temp	° C.	255
Die Temp	° C.	260
Screw speed	rpm	350
Throughput	kg/hr	50
Torque	NONE	65
Vacuum 1	MPa	−0.08
Side Feeder 1 speed	rpm	300
Melt temperature	NONE	260

Table 6 illustrates the molding profile and equipment set up for glass filled PA LDS.

TABLE 6

Parameters	Unit	Glass filled, LDS capable polyamide

Cnd: Pre-drying time	Hour	4
Cnd: Pre-drying temp	° C.	120
Molding Machine	NONE	FANUC
Mold Type (insert)	NONE	ASTM tensile, flexual, Izod, colorchip
Hopper temp	° C.	50
Zone 1 temp	° C.	270-280
Zone 2 temp	° C.	275-285
Zone 3 temp	° C.	280-300
Nozzle temp	° C.	280-300
Mold temp	° C.	80-120
Screw speed	rpm	100
Back pressure	kgf/cm²	30-50
Cooling time	s	15
Injection speed	mm/s	50-150
Holding pressure	kgf/cm²	600-800
Max. Injection pres-	kgf/cm²	1000
sure

Table 7 illustrates the formulation and performance comparison of the polymer composition comprising a polyamide, a LDS additive, and a 0-50 wt % glass reinforcement filler. It is shown that as the glass fiber added, the flexural modulus increases from 2510 MPa to 4170 MPa, the tensile modulus increases from 3116 MPa to 5181 MPa, and the average plating index has a significant increase from 0.35 to 0.64. Furthermore as the glass fiber loading increases from 10 wt % to 50 wt %, the flexural modulus increases from 4170 MPa to 13900 MPa, the tensile modulus increases form 5181 MPa to 16635 MPa, and the average plating index increases from 0.64 to 0.81.

TABLE 7

Item Code	Item Description	Unit	0GF	10GF	30GF	40GF	50GF

83404	PA66	%	96	86	66	56	46
F593895	LDS additive	%	3	3	3	3	3
G512950	Flat glass fiber	%		10	30	40	50
F542, 25808, F0013187	Additives		1	1	1	1	1

Typical Property	Test Method	Test Description	Unit	0GF	10GF	30GF	40GF	50GF

ASH	ASTM D 5630	2.0 g, 900° C., >20 minutes.	%	2.1	12.0	29.9	37.0	43.6
HDT 0.45 MPa	ASTM D 648	0.45 MPa/3.2 mm	° C.	236	255	259	260	260
HDT 1.82 MPa	ASTM D 648	1.82 MPa/3.2 mm	° C.	78	243	250	252	254
Flexual Modulus	ASTM D 790	3.2 mm, 1.27 mm/min	MPa	2510	4170	8340	10600	13900
Flexual Strength	ASTM D 790	yield, 3.2 mm, 1.27 mm/min	MPa	104	134	230	275	317
Tensile Modulus	ASTM D 638	5 mm/min	MPa	3116	5181	9868	13224	16635
Tensile Strength	ASTM D 638	break, 5 mm/min	MPa	76	94	160	194	215
Tensile Elongation	ASTM D 638	break, 5 mm/min	%	3.9	2.3	2.8	2.7	2.7
Notched IZOD	ASTM D256	23° C., 2 lbf/ft	J/m	55	33	94	125	138
Unnotched IZOD	ASTM D256	23° C., 5 lbf/ft	J/m	1020	370	697	974	1100
Dk	1.1 GHz			3.073	3.233	3.580	3.853	4.113
Df	1.1 GHz			0.013	0.012	0.012	0.011	0.011
PI	Average			0.35	0.64	0.80	0.83	0.81

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other aspects of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims

What is claimed is:

1. A polymer composition comprising:

a. a thermoplastic polymer;

b. a laser direct structuring additive; and

c. a glass reinforcement component;

wherein the polymer composition is capable of being plated after being activated using a laser.

2. The polymer composition of claim 1, wherein the thermoplastic polymer comprises polycarbonate, polycarbonate-polysiloxane copolymer, polyamide, ethylene vinyl acetate, ethylene vinyl alcohol, polyoxymethylene, polyacrylate, polyacrylonitrile, polyamide-imide, polyetherketone, polycaprolactone, polyhydroxyalkanoate, polyester, polyimide, polyketone, polylactic acid, polyurethane, or polyvinyl acetate or a combination thereof.

3. The polymer composition of claim 1, wherein the thermoplastic polymer is present in an amount ranging from about 10% by weight to about 90% by weight based on the total weight of the composition.

4. The polymer composition of claim 1, wherein the thermoplastic polymer is present in an amount ranging from about 10% by weight to about 90% by weight based on the total weight of the composition, the glass reinforcement component is present in an amount ranging from greater than 0% by weight to about 60% by weight based on the total weight of the composition, and the laser direct structuring additive is present in an amount ranging from about 1% by weight to about 10% by weight based on the total weight of the composition.

5. The polymer composition of claim 1, wherein the thermoplastic polymer comprises a polycarbonate.

6. The polymer composition of claim 1, wherein the thermoplastic polymer comprises a polyamide.

7. The polymer composition of claim 1, wherein the laser direct structuring additive comprises a metal oxide, a copper salt, a metal oxide spinel, or a mixture of metal oxide spinels, or a combination thereof.

8. The polymer composition of claim 1, wherein the laser direct structuring additive is present in an amount from about 1% by weight to about 10% by weight based on the total weight of the composition.

9. The polymer composition of claim 1, wherein the glass reinforcement component is present an amount from greater than 0% by weight to about 60% by weight based on the total weight of the composition.

10. The polymer composition of claim 1, wherein the glass reinforcement component comprises a glass fiber, a flat glass, a long glass, a short glass, a large diameter glass, a small diameter glass, or a nano glass, or a combination thereof.

11. The polymer composition of claim 1, wherein the polymer composition has a flexural modulus of greater than about 3 GPa.

12. The polymer composition of claim 1, wherein the polymer composition has a tensile modulus of greater than about 3 GPa.

13. The polymer composition of claim 1, wherein the polymer composition has a flexural modulus of greater than about 3 GPa and a tensile modulus of greater than about 3 GPa.

14. The polymer composition of claim 1, wherein the polymer composition has one or more of a tensile modulus, a flexural modulus, and a plating index that increase with an increasing concentration of the glass component.

15. The polymer composition of claim 1, further comprising at least one additive comprising a plasticizer, a stabilizer, an anti-static agent, a flame-retardant, an impact modifier, a colorant, an antioxidant, or a mold release agent, or a combination thereof.

16. A polymer composition comprising:

a. a thermoplastic polymer;

b. a laser direct structuring additive; and

c. a reinforcing filler;

wherein the polymer composition is capable of being plated after being activated using a laser; and

wherein the polymer composition has a flexural modulus of greater than about 3 GPa and a tensile modulus of greater than about 3 GPa.

17. The polymer composition of claim 16, wherein the reinforcing filler comprises a glass reinforcement component, a carbon fiber, a mineral filler, or a talc, or a combination thereof.

18. The polymer composition of claim 16, further comprising at least one additive comprising a plasticizer, a stabilizer, an anti-static agent, a flame-retardant, an impact modifier, a colorant, an antioxidant, or a mold release agent, or a combination thereof.

19. A method for making a polymer composition comprising forming a blend composition comprising:

a. a thermoplastic polymer;

b. a laser direct structuring additive; and

c. a reinforcing filler;

wherein the blend composition has a flexural modulus of greater than about 3 GPa and a tensile modulus of greater than about 3 GPa.

20. The method of claim 19, wherein the blend composition further comprises a plasticizer, a stabilizer, an anti-static agent, a flame-retardant, an impact modifier, a colorant, an antioxidant, or a mold release agent, or a combination thereof.

21. The method of claim 19, wherein the blend composition is formed by twin screw extrusion.

22. An article of manufacture comprising the polymer composition of claim 1.

23. The article manufacture of claim 22, wherein the article comprises a computer device, a household appliance, a decoration device, an electromagnetic interference device, a printed circuit, a Wi-Fi device, a Bluetooth device, a GPS device, a cellular antenna device, a smart phone device, an automotive device, a military device, an aerospace device, a medical device, a hearing aid, a sensor device, a security device, a shielding device, an RF antenna device, or an RFID device.

24. An article of manufacture comprising the polymer composition of claim 16.

25. The article manufacture of claim 24, wherein the article comprises a computer device, a household appliance, a decoration device, an electromagnetic interference device, a printed circuit, a Wi-Fi device, a Bluetooth device, a GPS device, a cellular antenna device, a smart phone device, an automotive device, a military device, an aerospace device, a medical device, a hearing aid, a sensor device, a security device, a shielding device, an RF antenna device, or an RFID device.