Electrical connector formed from a polymer composition having a low dielectric constant and dissipation factor

Abstract

To provide an electrical connector formed from a polymer composition that has a relatively low dielectric constant and a relatively low dissipation factor, and can still maintain excellent mechanical properties and processability (e.g., low viscosity).SOLUTION: An electrical connector (200) is disclosed that includes at least two opposing walls defining a passageway therebetween for receiving a contact pin, wherein the walls have widths of about 500 micrometers or less and are formed from a polymer composition comprising a polymer matrix containing at least one polymer having a glass-transition temperature of about 30 °C. or greater in an amount equal to or greater than 30wt.% of the composition. The polymer composition exhibits a dielectric constant of about 4 or less and a dissipation factor of about 0.02 or less as determined at 10GHz frequencies.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] Cross-reference of related questions

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 62 / 898,202, having a filing date of September 10, 2019; U.S. Provisional Patent Application No. 62 / 994,317, having a filing date of March 25, 2020; U.S. Provisional Patent Application No. 63 / 008,983, having a filing date of April 13, 2020; U.S. Provisional Patent Application No. 63 / 038,965, having a filing date of June 15, 2020; and U.S. Provisional Patent Application No. 63 / 056,848, having a filing date of July 27, 2020, the entire contents of which are incorporated herein by reference. [Background technology]

[0002]

[0002] High-frequency wireless signal communications are gaining increasing popularity. For example, the demand for faster data transmission for wireless smartphone connectivity is driving demand for high-frequency components, including those configured to operate at 5G spectrum frequencies. Components for electrically connecting 5G components, such as antennas and front-end modules, generally require small features. The trend toward miniaturization makes small, high-frequency 5G connectors even more desirable. 5G connectors can utilize a variety of materials. However, the properties of such materials may limit miniaturization and / or allow undesirable interference with the electrical connections made by the 5G connector. In particular, such materials may exhibit relatively high dielectric constants and dissipation factors, making them difficult to use in certain applications. Furthermore, such materials may not exhibit the desired balance between dielectric, thermal, and mechanical properties. Summary of the Invention [Problem to be solved by the invention]

[0003]

[0003] Therefore, a need exists for electrical connectors formed from polymer compositions that have a relatively low dielectric constant and a relatively low dissipation factor, while still maintaining excellent mechanical properties and processability (e.g., low viscosity). [Means for solving the problem]

[0004] According to one embodiment of the present invention, there is disclosed an electrical connector including at least two opposing walls defining a passage therebetween for receiving a contact pin, the opposing walls having a width of about 500 micrometers or less, the opposing walls being formed from a polymer composition including a polymer matrix containing at least one polymer having a glass transition temperature of about 30° C. or greater in an amount of about 30 wt.% or greater of the composition. The polymer composition exhibits a dielectric constant of about 4 or less and a dielectric loss tangent of about 0.02 or less, determined at a frequency of 10 GHz.

[0005] According to another embodiment of the present invention, a 5G radio frequency communication system is disclosed, the system including a radio frequency component configured to operate above about 3 GHz, the radio frequency component including a contact pin. The radio frequency component may include the contact pin and an electrical connector coupled to the radio frequency component, the electrical connector including at least two opposing walls having a passageway defined therebetween, the contact pin of the radio frequency component being received within the passageway of the electrical connector, the opposing walls having a width of about 500 micrometers or less, and the opposing walls being formed from the polymer composition defined above.

[0006]

[0006] Other features and aspects of the present invention are described in more detail below.

[0007] A full and enabling disclosure of the present invention, including the best mode thereof to one skilled in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying drawings, in which: [Brief explanation of the drawings]

[0007] [Figure 1A]

[0008] 1 is a diagram of a thin-walled electrical connector according to an aspect of the present invention. [Figure 1B]

[0009] FIG. 1B is an enlarged view of a portion of the thin-walled connector of FIG. 1A. [Figure 2]

[0010] 10 is an exploded perspective view of another embodiment of a thin-walled connector and connector receptacle formable in accordance with the present invention; [Figure 3]

[0011] 1 is a diagram of a 5G communication system including a base station, a relay station, a user computing device, and a Wi-Fi repeater. DETAILED DESCRIPTION OF THE INVENTION

[0008]

[0012] It will be understood by those skilled in the art that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the invention.

[0013] Generally, the present invention relates to thin-walled electrical connectors that can be used in 5G applications. In particular, the thin-walled electrical connectors may be formed from polymer compositions containing a polymer matrix including at least one polymer having a glass transition temperature of about 40° C. or greater. The polymer compositions have a relatively low dielectric constant (D) combined with good mechanical properties and good processability. k ) and dielectric loss tangent (D f ) can be used for such purposes.

[0009]

[0014] The electrical connector may have a variety of configurations within the scope of the present disclosure. By way of example, the electrical connector may define a plurality of passages or spaces between opposing walls. The passages may accommodate contact pins and facilitate electrical connection with a number of individual pins.

[0010]

[0015] The electrical connector may also be very compact as a result of the polymer composition from which it is formed. For example, the polymer composition may exhibit excellent flow characteristics for forming the very small features required to form the electrical connectors described herein, while also exhibiting minimal warpage upon exposure to heat. In this regard, the walls may have relatively thin respective widths "w" of about 500 micrometers or less, in some embodiments about 400 micrometers or less, in some embodiments, from about 25 micrometers to about 350 micrometers, and in some embodiments, from about 50 micrometers to about 300 micrometers.

[0011]

[0016] One particularly suitable electrical connector 100 according to an embodiment of the present invention is shown in Figure 1A. Figure 1B is an enlarged view of the electrical connector 100 of Figure 1A. As shown, an insertion passage or space 225 capable of accommodating contact pins and facilitating multiple individual electrical connections is defined between opposing walls 224. The electrical connector 100 may be very compact. More particularly, the walls 224 may have respective widths "w" that are relatively thin, such as within the ranges discussed above.

[0012]

[0017] FIG. 2 shows another embodiment of an electrical connector 200. The connector 200 may also include a board side C2 that may be attached to the surface of a circuit board P. The connector 200 may also include a wiring side C1 that is structured to connect individual wires 3 to the circuit board P by being coupled to the board side connector C2. The board side C2 may include a mating recess 10a into which the wiring side connector C1 is mated, and a first housing 10 having an elongated configuration in the width direction of the housing 10. The wiring side C1 may also include a second housing 20 that is elongated in the width direction of the housing 20. In the second housing 20, a plurality of terminal receiving cavities 22 are provided parallel to the width direction, and upper and lower terminal receiving cavities A two-tier array may be created containing cavities 22. Terminals 5 attached to the distal ends of the individual wires 3 may be received in each of the terminal-receiving cavities 22. If desired, locking portions 28 (engagement portions) may also be provided on the housing 20 to correspond to connecting members (not shown) of the plate-side connector C2.

[0013]

[0018] As discussed above, the interior walls of first housing 10 and / or second housing 20 may be relatively thin (e.g., may have a relatively small width dimension) and may be formed from the polymer composition of the present invention.

[0014]

[0019] Electrical connectors may be formed from polymer compositions having relatively low dielectric constants and dissipation factors. Providing a polymer composition with such dielectric properties can help minimize signal loss and improve performance when utilized in certain applications, such as signal transmission applications, particularly those related to 5G communications. As used herein, "5G" generally refers to high-speed data communications via radio frequency signals. 5G networks and systems can communicate data at much higher speeds than previous generations of data communications standards (e.g., "4G," "LTE"). Various standards and specifications have been published that quantify the requirements for 5G communications. As an example, the International Telecommunications Union (ITU) published the International Mobile Telecommunications-2020 ("IMT-2020") standard in 2015. The IMT-2020 standard defines various data transmission criteria for 5G (e.g., downlink and uplink data rates, latency, etc.). The IMT-2020 standard specifies uplink and downlink peak data rates as the minimum data rates for uploading and downloading data that 5G systems must support. The IMT-2020 standard sets the downlink peak data rate requirement at 20 Gbit / s and the uplink peak data rate at 10 Gbit / s.

[0015]

[0020] Another example is 3 rdThe Third Generation Partnership Project (3GPP®) recently published a new standard for 5G called "5G NR." 3GPP® published "Release 15" in 2018, defining "Phase 1" as the standardization of 5G NR. 3GPP® defines the 5G frequency band as "Frequency Range 1" (FR1), which generally includes frequencies below 6 GHz, and "Frequency Range 2" (FR2), which is the frequency band in the range of 20-60 GHz. However, as used herein, "5G frequency" can also refer to systems utilizing frequencies greater than 60 GHz, for example, in the ranges up to 80 GHz, up to 150 GHz, and up to 300 GHz. As used herein, "5G frequency" may refer to frequencies of about 2.5 GHz or higher, in some embodiments about 3.0 GHz or higher, in some embodiments about 3 GHz to about 300 GHz or higher, in some embodiments about 4 GHz to about 80 GHz, in some embodiments about 5 GHz to about 80 GHz, in some embodiments about 20 GHz to about 80 GHz, and in some embodiments about 28 GHz to about 60 GHz.

[0016]

[0021] The connectors described herein can be used in radio frequency systems that meet or may be considered "5G" standards based on standards published by 3GPP, such as Release 15 (2018), and / or the IMT-2020 standard. To achieve such high-speed data communications at high frequencies, antenna elements and arrays typically utilize small feature sizes / spacings (e.g., fine pitch technology) and / or advanced materials that can improve antenna performance. For example, feature sizes (spacings between antenna elements, widths of antenna elements), etc., typically depend on the speed at which the desired transmit and / or receive radio frequency signals propagate through the dielectric of the substrate on which the antenna elements are formed. It depends on the wavelength ("λ") (e.g., nλ / 4, where n is an integer). Additionally, beamforming and / or beamsteering can be utilized to facilitate transmission and reception across multiple frequency ranges or channels (e.g., MIMO, massive MIMO).

[0017]

[0022] The electrical connector can also reduce or prevent interference (e.g., "crosstalk") between signals transmitted to adjacent or nearby pins due to the dielectric properties of the polymer composition from which it is formed. For example, the dielectric constant of the polymer composition may be about 4 or less, in some embodiments about 3.7 or less, in some embodiments about 3.5 or less, in some embodiments about 0.5 to about 3.4, and in some embodiments about 1.0 to about 3.2, as determined by split post resonance at a frequency of 10 GHz. Furthermore, the dielectric loss tangent, which is a measure of the rate of energy loss of the polymer composition, may be about 0.02 or less, in some embodiments about 0.015 or less, in some embodiments about 0.01 or less, in some embodiments about 0.001 to about 0.01, and in some embodiments about 0.001 to about 0.006, as determined by split post resonance at a frequency of 10 GHz.

[0018]

[0023] In some embodiments, the polymer composition may utilize at least one additive that allows for a reduction in the dielectric constant of the polymer matrix. For example, the use of such an additive (e.g., hollow inorganic fillers) may reduce the dielectric constant of the polymer matrix by about 2% or more, in some embodiments, about 3% or more, in some embodiments, about 3.5% to about 50%, and in some embodiments, about 4% to about 30%. Similarly, the polymer composition may utilize at least one additive that allows for a reduction in the dielectric loss tangent of the polymer matrix. For example, the use of such an additive (e.g., hollow inorganic fillers) may reduce the dielectric loss tangent of the polymer matrix by about 2% or more, in some embodiments, about 3% or more, in some embodiments, about 3.5% to about 50%, and in some embodiments, about 4% to about 30%.

[0019]

[0024] Also, it has been conventionally believed that polymer compositions exhibiting a combination of low dielectric constant and low dielectric loss tangent do not simultaneously possess sufficiently good thermal and mechanical properties and ease of processability (i.e., low viscosity) to enable their use as electrical connectors. However, contrary to conventional thinking, it has been discovered that polymer compositions possess both excellent thermal and mechanical properties and processability.

[0020]

[0025] For example, the melting temperature of the polymer composition may be, for example, about 180°C or higher, in some embodiments about 200°C, in some embodiments about 210°C to about 400°C, and in some embodiments about 220°C to about 380°C. Even at such melting temperatures, the ratio of temperature deflection under load ("DTUL"), a measure of short-term heat resistance, to melting temperature may still remain relatively high. For example, the ratio may range from about 0.5 to about 1.00, in some embodiments about 0.6 to about 0.95, and in some embodiments about 0.65 to about 0.85. A particular DTUL value may be, for example, about 200°C or higher, in some embodiments about 200°C to about 350°C, for example, from about 210°C to about 320°C, for example, from about 230°C to about 290°C.

[0021]

[0026] The polymeric compositions may also have excellent mechanical properties that may be useful in forming molded parts. For example, the polymeric compositions may exhibit a tensile strength of about 20 MPa or greater, in some embodiments about 30 MPa or greater, in some embodiments about 40 MPa to about 300 MPa, and in some embodiments about 50 MPa to about 100 MPa. The tensile properties may be determined according to ISO Test No. 527:2012 at a temperature of 23°C. Furthermore, the polymeric compositions may exhibit a flexural strength of about 20 MPa or greater, in some embodiments about 50 MPa or greater, in some embodiments about 60 MPa to about 300 MPa, and in some embodiments about 80 MPa to about 250 MPa. The flexural properties may be determined according to ISO Test No. 178:2010 at a temperature of 23°C. Furthermore, the polymeric compositions may also have high impact strength that may be useful in forming thin substrates. For example, the polymeric compositions may exhibit a flexural strength of about 3 kJ / m 2 The above is a partial embodiment. is about 5kJ / m2 or greater, in some embodiments, about 7 kJ / m 2 or more, in some embodiments, about 8 kJ / m 2 ~about 40kJ / m 2 , and in some embodiments, about 10 kJ / m 2 ~about 25kJ / m 2 The impact strength may be determined in accordance with ISO Test No. ISO 179-1:2010 at a temperature of 23°C.

[0022]

[0027] Various embodiments of the invention will now be described in more detail. I. Polymer Composition A. Polymer matrix

[0028] Generally, any of a variety of polymers or combinations of polymers may be utilized in the polymer matrix. For example, the polymer may be semi-crystalline or crystalline in nature. In one embodiment, the polymer may be semi-crystalline. In another embodiment, the polymer may be crystalline. Additionally, in one embodiment, the polymer may be an aromatic polymer. Alternatively, in another embodiment, the polymer may be an aliphatic polymer.

[0023]

[0029] Suitable polymers may include thermoplastic polymers, such as polyolefins (e.g., ethylene polymers, propylene polymers, etc.), polyamides (e.g., aliphatic, semi-aromatic, or aromatic polyamides), polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate, liquid crystal polymers), polyarylene sulfides, polyetherimides, polyacetals (e.g., polyoxymethylene), polyphenylene oxides, polyaryl ketones (e.g., polyether ether ketone, polyether ketone ketone, etc.), polycarbonates, and blends thereof.

[0024]

[0030] Regardless, the polymers may generally be considered "high performance" polymers and, therefore, may have relatively high glass transition temperatures and / or high melting temperatures. Accordingly, such high performance polymers may impart a substantial degree of heat resistance to the polymer composition. For example, the polymers may have glass transition temperatures of about 30°C or higher, in some embodiments about 40°C or higher, in some embodiments from about 50°C to about 250°C, and in some embodiments, from about 60°C to about 150°C. The polymers may also have melting temperatures of about 180°C or higher, in some embodiments about 200°C or higher, in some embodiments from about 210°C to about 400°C, and in some embodiments, from about 220°C to about 380°C. Glass transition temperatures and melting temperatures may be determined as known in the art using differential scanning calorimetry ("DSC"), for example, by ISO Test Nos. 11357-2:2013 (glass transition temperature) and 11357-3:2011 (melting temperature).

[0025]

[0031] An example of a suitable semi-crystalline aromatic polymer is an aromatic polyester, which is the condensation product of an aromatic dicarboxylic acid having, for example, 8 to 14 carbon atoms with at least one diol. Suitable diols include, for example, neopentyl glycol, cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, and carboxylic acids of the formula HO(CH2). nOH (where n is an integer from 2 to 10). Suitable aromatic dicarboxylic acids include, for example, isophthalic acid, terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, and the like, and combinations thereof. Fused rings may be present, as in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acid. Specific examples of such aromatic polyesters include, for example, poly(ethylene terephthalate) (PET), poly(1,4-butylene terephthalate) (PBT), poly(1,3-propylene terephthalate) (PPT), poly(1,4-butylene 2,6-naphthalate) (PBN), poly(ethylene 2,6-naphthalate) (PEN), poly(1,4-cyclohexylene dimethylene terephthalate) (PCT), and copolymers and mixtures of the above.

[0026]

[0032] In one particular embodiment, the polymer may comprise polybutylene terephthalate. The polybutylene terephthalate may have a crystallinity of about 38% or greater, in some embodiments about 40% or greater, and in some embodiments, about 45% or greater. The crystallinity of the polybutylene terephthalate polymer may generally be about 70% or less, in some embodiments about 65% or less, and in some embodiments, about 60% or less. Percent crystallinity may be determined using differential scanning calorimetry (DSC). Such analysis may be performed using a PerkinElmer Pyris 6 DSC instrument. A detailed description of the calculation is available in Sichina, WJ, "DSC as a problem-solving tool: measurement of percent crystallinity of thermoplastics." Thermal Analysis Application Note (2000).

[0027]

[0033] Additionally, modifications or copolymers of polyethylene terephthalate polymers and / or polybutylene terephthalate polymers may also be used. For example, in one embodiment, a modifying acid or a modifying diol may be used to produce a modified polyethylene terephthalate polymer and / or a modified polybutylene terephthalate polymer. As used herein, the terms "modifying acid" and "modifying diol" are intended to define compounds that can form part of the acid and diol repeat units of a polyester, respectively, and that can modify the polyester to reduce its crystallinity or render the polyester amorphous. Of course, the polyester may be unmodified and contain no modifying acid or modifying diol. In either case, examples of the modifying acid component may include, but are not limited to, isophthalic acid, phthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, 1,12-dodecanedioic acid, and the like. In practice, it is often preferred to use these functional acid derivatives, such as the dimethyl, diethyl, or dipropyl esters of the dicarboxylic acids. Where practical, the anhydrides or acid halides of these acids may also be utilized.Examples of the modified diol component include, but are not limited to, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, Z,8-bis(hydroxymethyltricyclo-[5.2.1.0]-decane (wherein Z represents 3, 4, or 5); 1,4-bis(2-hydroxyethoxy)benzene Examples of suitable diols include benzene, 4,4'-bis(2-hydroxyethoxy)diphenyl ether [bis-hydroxyethyl bisphenol A], 4,4'-bis(2-hydroxyethoxy)diphenyl sulfide [bis-hydroxyethyl bisphenol S], and diols containing one or more oxygen atoms in the chain, such as diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol. Generally, these diols contain 2 to 18 carbon atoms, and in some embodiments, 2 to 8 carbon atoms. The alicyclic diols can be utilized in their cis or trans configurations, or as mixtures of both forms.

[0028]

[0034] In some embodiments, the at least one polyester or copolyester present in the polymer composition may have an intrinsic viscosity (IV) of from about 0.5 to about 0.9 dL / g, e.g., from about 0.5 to about 0.8 dL / g. In one embodiment, for example, the intrinsic viscosity of the polyester is from about 0.65 to about 0.8 dL / g.

[0029]

[0035] Polyarylene sulfides are also suitable semi-crystalline aromatic polymers. The polyarylene sulfides utilized in the composition generally have the formula: -[(Ar 1 ) n -X] m -[(Ar 2 ) i -Y] j -[(Ar3 ) k -Z] l -[(Ar 4 ) o -W] p - (In the formula, Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently arylene units of 6 to 18 carbon atoms; W, X, Y, and Z are independently divalent linking groups selected from -SO2-, -S-, -SO-, -CO-, -O-, -C(O)O-, or alkylene or alkylidene groups of 1 to 6 carbon atoms, where at least one of the linking groups is -S-; n, m, i, j, k, l, o, and p are independently 0, 1, 2, 3, or 4, provided that their total is 2 or greater. It has the repeating unit:

[0030]

[0036] Arylene unit Ar 1 , Ar 2 , Ar 3 and Ar 4 may be optionally substituted or unsubstituted. Advantageous arylene units are phenylene, biphenylene, naphthylene, anthracene, and phenanthrene. Polyarylene sulfides typically contain more than about 30 mol%, more than about 50 mol%, or more than about 70 mol% of arylene sulfide (—S—) units. For example, polyarylene sulfides may contain at least 85 mol% of sulfide linkages directly bonded to two aromatic rings. In one particular embodiment, polyarylene sulfides as referred to herein have the phenylene sulfide structure —(CH—S) as a component thereof. n - (wherein n is an integer of 1 or greater).

[0031]

[0037] Synthetic techniques that can be used to prepare polyarylene sulfides are generally known in the art. For example, a method for producing polyarylene sulfides can include reacting a material that provides hydrosulfide ions (e.g., an alkali metal sulfide) with a dihaloaromatic compound in an organic amide solvent. The alkali metal sulfide can be, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, or a mixture thereof. If the alkali metal sulfide is a hydrate or an aqueous mixture, the alkali metal sulfide can be treated by a dehydration operation before the polymerization reaction. The alkali metal sulfide can also be generated in situ. Additionally, a small amount of alkali metal hydroxide can be included in the reaction to remove or react (e.g., to convert such impurities into harmless materials) impurities such as alkali metal polysulfides or alkali metal thiosulfates that may be present in very small amounts with the alkali metal sulfide.

[0032]

[0038] The dihaloaromatic compound may be, without limitation, o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl ether, dihalodiphenyl sulfone, dihalodiphenyl sulfoxide or dihalodiphenyl ketone. The dihaloaromatic compound may be used either alone or in any combination thereof. Specific exemplary dihaloaromatic compounds include, but are not limited to, p-dichlorobenzene; m-dichlorobenzene; o-dichlorobenzene; 2,5-dichlorotoluene; 1,4-dibromobenzene; 1,4-dichloronaphthalene; 1-methoxy-2,5-dichlorobenzene; 4,4'-dichlorobiphenyl; 3,5-dichlorobenzoic acid; 4,4'-dichlorodiphenyl ether; 4,4'-dichlorodiphenyl sulfone; 4,4'-dichlorodiphenyl sulfoxide; and 4,4'-dichlorodiphenyl ketone. The halogen atoms may be fluorine, chlorine, bromine, or iodine, and the two halogen atoms in the same dihaloaromatic compound may be the same or different. In one embodiment, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, or a mixture of two or more of these compounds is used as the dihaloaromatic compound. As known in the art, the dihaloaromatic compounds may be used to form end groups of polyarylene sulfides or to form end groups in polymerization reactions and the like. A monohalo compound (not necessarily an aromatic compound) can also be used in combination with a dihaloaromatic compound to adjust the molecular weight of the polyarylene sulfide.

[0033]

[0039] Polyarylene sulfides may be homopolymers or copolymers. For example, selective combination of dihaloaromatic compounds can produce polyarylene sulfide copolymers containing two or more different units. For example, when p-dichlorobenzene is used in combination with m-dichlorobenzene or 4,4'-dichlorodiphenyl sulfone, the polyarylene sulfide copolymers have the formula:

[0034] [ka]

[0035] and a segment having the structure of the formula:

[0036] [ka]

[0037] A segment having the structure, or formula:

[0038] [ka]

[0039] It is possible to form a polyarylene sulfide copolymer containing segments having the structure:

[0040] Polyarylene sulfides may be linear, semi-linear, branched, or crosslinked. Linear polyarylene sulfides typically contain 80 mol% or more of the repeating unit -(Ar-S)-. Such linear polymers may also contain a small amount of branching or crosslinking units, but the amount of branching or crosslinking units is typically less than about 1 mol% of the total monomer units of the polyarylene sulfide. Linear polyarylene sulfide polymers may be random copolymers or block copolymers containing the above repeating units. Semi-linear polyarylene sulfides may also have a crosslinked or branched structure in which a small amount of one or more monomers having three or more reactive functional groups are introduced into the polymer. For example, the monomer components used to form semi-linear polyarylene sulfides may include a certain amount of polyhaloaromatic compounds having two or more halogen substituents per molecule, which can be used to prepare branched polymers. Such monomers have the formula R'X nwhere each X is selected from chlorine, bromine, and iodine, n is an integer from 3 to 6, and R' is a polyvalent aromatic group of valence n which may have up to about four methyl substituents, and the total number of carbon atoms in R' is in the range of 6 to about 16. Some polyhalogens substituted with more than two halogens per molecule available for forming semi-linear polyarylene sulfides are Examples of aromatic compounds include 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3-dichloro-5-bromobenzene, 1,2,4-triiodobenzene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene, 1,3,5-trichloro-2,4,6-trimethylbenzene, 2,2',4,4'-tetrachlorobiphenyl, 2,2',5,5'-tetra-iodobiphenyl, 2,2',6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenyl, 1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene, and the like, and mixtures thereof.

[0040]

[0041] Another example of a suitable semi-crystalline polymer is a polyamide. For example, the polyamide may, in one embodiment, be an aromatic polyamide. In this regard, the aromatic polyamide may have a relatively high melting temperature, e.g., as determined using differential scanning calorimetry in accordance with ISO Test No. 11357, of about 200°C or higher, in some embodiments, about 220°C or higher, and in some embodiments, from about 240°C to about 320°C. The glass transition temperature of the aromatic polyamide is similarly generally from about 110°C to about 160°C. In another embodiment, the aromatic polyamide may be an aliphatic polyamide. In this regard, the aliphatic polyamide may also have a relatively high melting temperature, e.g., as determined using differential scanning calorimetry in accordance with ISO Test No. 11357, of about 180°C or higher, in some embodiments, about 200°C or higher, and in some embodiments, from about 210°C to about 320°C. The glass transition temperature of the aliphatic polyamide is similarly generally from about 30°C to about 170°C.

[0041]

[0042] Aromatic polyamides typically contain repeating units held together by amide linkages (NH—CO) and are synthesized by polycondensation of dicarboxylic acids (e.g., aromatic dicarboxylic acids), diamines (e.g., aliphatic diamines), and the like. For example, aromatic polyamides may contain aromatic repeating units derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxy-diacetic acid, 1,3-phenylenedioxy-diacetic acid, diphenic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and the like, as well as combinations thereof. Terephthalic acid is particularly preferred. Of course, it should be understood that other types of acid units, such as aliphatic dicarboxylic acid units and polyfunctional carboxylic acid units, may also be utilized.

[0042]

[0043] Aliphatic polyamides also typically contain repeat units held together by amide linkages (NH—CO). These polyamides may be synthesized by a variety of techniques. For example, polyamides may be formed by ring-opening polymerization, such as the ring-opening polymerization of caprolactam. These polyamides may also be synthesized by polycondensation of dicarboxylic acids (e.g., aliphatic dicarboxylic acids), diamines, and the like. For example, aromatic polyamides may contain aliphatic repeat units derived from aliphatic dicarboxylic acids, such as adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, dimer acid, cis- and / or trans-cyclohexane-1,4-dicarboxylic acid, cis- and / or trans-cyclohexane-1,3-dicarboxylic acid, and combinations thereof. Adipic acid is particularly suitable.

[0043]

[0044] The polyamide may also contain aliphatic repeat units derived from aliphatic diamines, typically having 4 to 14 carbon atoms. Examples of such diamines include linear aliphatic alkylenediamines such as 1,4-tetramethylenediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. and branched aliphatic alkylenediamines such as 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, and combinations thereof. Repeating units derived from 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine are particularly preferred. Naturally, other diamine units, such as alicyclic diamines and aromatic diamines, can also be used.

[0044]

[0045] Particularly preferred aromatic polyamides include poly(nonamethylene terephthalamide) (PA9T), poly(nonamethylene terephthalamide / nonamethylenedecanediamide) (PA9T / 910), poly(nonamethylene terephthalamide / nonamethylenedodecanediamide) (PA9T / 912), poly(nonamethylene terephthalamide / 11-aminoundecaneamide) (PA9T / 11), poly(nonamethylene terephthalamide / 12-aminododecanamide) (PA9T / 12), poly(decamethylene terephthalamide / 11-aminoundecaneamide) (PA10T / 11), poly(decamethylene terephthalamide / 12-aminododecanamide) (PA12T / 12), and poly(decamethylene terephthalamide / 11-aminoundecaneamide). do) (PA10T / 12), poly(decamethylene terephthalamide / decamethylene dodecanediamide) (PA10T / 1010), poly(decamethylene terephthalamide / decamethylene dodecanediamide) (PA10T / 1012), poly(decamethylene terephthalamide / tetramethylene hexanediamide) (PA10T / 46), poly(decamethylene terephthalamide / caprolactam) (PA10T / 6), poly(decamethylene terephthalamide / hexamethylene hexanediamide) (PA10T / 66), poly(dodecamethylene terephthalamide / dodecamethylene dodecanediamide) (poly(dodecamethylene terephthalamide / tetramethylene hexanediamide) Poly(dodecamethylene terephthalamide / dodecamethylene dodecanediamide) (PA12T / 1212), poly(dodecamethylene terephthalamide / caprolactam) (PA12T / 6), poly(dodecamethylene terephthalamide / hexamethylene hexanediamide) (PA12T / 66), polyphthalamide (PPA), and the like. Particularly suitable aliphatic polyamides may include polyamide 4,6, polyamide 5,10, polyamide 6, polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 11, polyamide 12, and the like. Still other examples of suitable aromatic polyamides are described in U.S. Pat. No. 8,324,307 to Harder et al.

[0045]

[0046] Another suitable semi-crystalline aromatic polymer that may be utilized in the present invention is polyaryletherketone. Polyaryletherketones are semi-crystalline polymers that have relatively high melting temperatures, such as from about 300°C to about 400°C, in some embodiments from about 310°C to about 390°C, and in some embodiments, from about 330°C to about 380°C. The glass transition temperature may also be from about 110°C to about 200°C. Particularly suitable polyaryletherketones are those that contain primarily phenyl moieties in combination with ketone and / or ether moieties. Examples of such polymers include polyetheretherketone ("PEEK"), polyetherketone ("PEK"), polyetherketoneketone ("PEKK"), polyetherketoneetherketoneketone ("PEKEKK"), polyetheretherketoneketone ("PEEKK"), polyether-diphenyl-ether-ether-diphenyl-ether-phenyl-ketone-phenyl, and the like, as well as blends and copolymers thereof.

[0046]

[0047] In addition to the polymers mentioned above, crystalline polymers may also be utilized in the polymer composition. Particularly preferred are liquid crystal polymers, which have a high degree of crystallinity that allows them to efficiently fill the small spaces in the mold. Liquid crystal polymers generally have a rod-like structure and are classified as "thermotropic" insofar as they can exhibit crystalline behavior in their molten state (e.g., a thermotropic nematic state). These polymers are generally similar to polyesters. The polymers have relatively high melting temperatures, such as from about 250°C to about 400°C, in some embodiments from about 280°C to about 390°C, and in some embodiments, from about 300°C to about 380°C. Such polymers may be formed from one or more types of repeat units as known in the art. Liquid crystal polymers may contain, for example, one or more aromatic ester repeat units, typically in an amount of from about 60 mol.% to about 99.9 mol.%, in some embodiments from about 70 mol.% to about 99.5 mol.%, and in some embodiments, from about 80 mol.% to about 99 mol.% of the polymer. The aromatic ester repeat units generally have the following formula (I):

[0047] [ka]

[0048] (In the formula, Ring B is a substituted or unsubstituted 6-membered aryl group (e.g., 1,4-phenylene or 1,3-phenylene), a substituted or unsubstituted 6-membered aryl group fused to a substituted or unsubstituted 5- or 6-membered aryl group (e.g., 2,6-naphthalene), or a substituted or unsubstituted 6-membered aryl group linked to a substituted or unsubstituted 5- or 6-membered aryl group (e.g., 4,4-biphenylene); Y1 and Y2 are independently O, C(O), NH, C(O)HN, or NHC(O). It can be expressed as:

[0049] Typically, at least one of Y1 and Y2 is C(O). Examples of such aromatic ester repeat units include, for example, aromatic dicarboxylic acid repeat units (in Formula I, Y1 and Y2 are C(O)), aromatic hydroxycarboxylic acid repeat units (in Formula I, Y1 is O and Y2 is C(O)), and various combinations thereof.

[0050]

[0049] For example, aromatic dicarboxylic acid repeat units derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, bis(4-carboxyphenyl)ether, bis(4-carboxyphenyl)butane, bis(4-carboxyphenyl)ethane, bis(3-carboxyphenyl)ether, bis(3-carboxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl, and halogen-substituted versions thereof, and combinations thereof, may be utilized. Particularly suitable aromatic dicarboxylic acids include, for example, terephthalic acid ("TA"), isophthalic acid ("IA"), and 2,6-naphthalenedicarboxylic acid ("NDA"). When utilized, repeat units derived from aromatic dicarboxylic acids (e.g., IA, TA, and / or NDA) each typically comprise from about 1 mol.% to about 40 mol.%, in some embodiments from about 2 mol.% to about 30 mol.%, and in some embodiments, from about 5 mol.% to about 25 mol.% of the polymer.

[0051]

[0050] Also, 4-hydroxybenzoic acid; 4-hydroxy-4'-biphenylcarboxylic acid; 2-hydroxy-6-naphthoic acid; 2-hydroxy-5-naphthoic acid; 3-hydroxy Aromatic hydroxycarboxylic acid repeat units derived from aromatic hydroxycarboxylic acids such as 4'-hydroxyphenyl-2-naphthoic acid; 2-hydroxy-3-naphthoic acid; 4'-hydroxyphenyl-4-benzoic acid; 3'-hydroxyphenyl-4-benzoic acid; 4'-hydroxyphenyl-3-benzoic acid, and the like, as well as alkyl, alkoxy, aryl, and halogen-substituted versions thereof, and combinations thereof, may be utilized. Particularly suitable aromatic hydroxycarboxylic acids are 4-hydroxybenzoic acid ("HBA") and 6-hydroxy-2-naphthoic acid (HNA). When utilized, repeat units derived from hydroxycarboxylic acids (e.g., HBA and / or HNA) typically comprise about 20 mol.% or more of the polymer, in some embodiments about 25 mol.% or more, in some embodiments about 30 mol.% or more, in some embodiments about 40 mol.% or more, in some embodiments about 50 mol.% or more, in some embodiments about 55 mol.% to 100 mol.%, and in some embodiments about 60 mol.% to about 95 mol.%.

[0052] Other repeating units can also be utilized in the polymer. For example, in certain embodiments, repeating units derived from aromatic diols such as hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl (or 4,4'-biphenol), 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, bis(4-hydroxyphenyl)ethane, and the like, as well as alkyl, alkoxy, aryl, and halogen-substituted versions thereof, and combinations thereof, can be utilized. Particularly suitable aromatic diols include, for example, hydroquinone ("HQ") and 4,4'-biphenol ("BP"). When utilized, repeat units derived from aromatic diols (e.g., HQ and / or BP) typically comprise from about 1 mol.% to about 50 mol.%, in some embodiments from about 1 mol.% to about 40 mol.%, in some embodiments from about 2 mol.% to about 40 mol.%, in some embodiments from about 5 mol.% to about 35 mol.%, and in some embodiments from about 5 mol.% to about 25 mol.% of the polymer. Repeat units such as those derived from aromatic amides (e.g., acetaminophen ("APAP")) and / or aromatic amines (e.g., 4-aminophenol ("AP"), 3-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine, etc.) may also be utilized. When utilized, repeat units derived from aromatic amides (e.g., APAP) and / or aromatic amines (e.g., AP) typically comprise from about 0.1 mol.% to about 20 mol.%, in some embodiments from about 0.5 mol.% to about 15 mol.%, and in some embodiments, from about 1 mol.% to about 10 mol.% of the polymer. It should also be understood that various other monomer repeat units may be incorporated into the polymer. For example, in certain embodiments, the polymer may contain one or more repeat units derived from non-aromatic monomers such as aliphatic or alicyclic hydroxycarboxylic acids, dicarboxylic acids, diols, amides, amines, and the like.Of course, in other embodiments, the polymer may be "fully aromatic" in that it contains no repeat units derived from non-aromatic (e.g., aliphatic or alicyclic) monomers.

[0053] Although not required, the liquid crystal polymer may be a "high naphthene" polymer so long as it contains a relatively high content of repeat units derived from naphthenic hydroxycarboxylic acids and naphthenic dicarboxylic acids, such as naphthalene-2,6-dicarboxylic acid ("NDA"), 6-hydroxy-2-naphthoic acid ("HNA"), or combinations thereof. That is, the total amount of repeat units derived from naphthenic hydroxycarboxylic acids and / or dicarboxylic acids (e.g., NDA, HNA, or combinations of HNA and NDA) is about 10 mol.% or more of the polymer, in some embodiments about 12 mol.% or more, in some embodiments about 15 mol.% or more, in some embodiments about 18 mol.% or more, in some embodiments about 30 mol.% or more, in some embodiments about 40 mol.% or more, in some embodiments about 45 mol.% or more, in some embodiments about 50 mol.% or more, and in some embodiments about 60 mol.% or more of the polymer. The "high naphthene" polymer may have a water absorption of about 55 mol.% or more, and in some embodiments, from about 55 mol.% to about 95 mol.%. Without being limited by theory, it is believed that such "high naphthene" polymers can reduce the tendency of the polymer composition to absorb water, thereby promoting stabilization of the dielectric constant and dissipation factor in the high frequency range. That is, such high naphthene polymers typically have a water absorption of about 0.015% or less, in some embodiments about 0.01% or less, and in some embodiments, from about 0.0001% to about 0.008% after 24 hours of immersion in water according to ISO 62-1:2008. The high naphthene polymers may also have a moisture absorption of about 0.01% or less, in some embodiments about 0.008% or less, and in some embodiments, from about 0.0001% to about 0.006% after exposure to a humid atmosphere (50% relative humidity) at a temperature of 23°C according to ISO 62-4:2008.

[0054] In one embodiment, for example, repeat units derived from HNA may comprise 30 mol % or more of the polymer, in some embodiments, about 40 mol % or more, in some embodiments, about 45 mol % or more, in some embodiments, 50 mol % or more, in some embodiments, about 55 mol % or more, and in some embodiments, about 55 mol % to about 95 mol %. In such embodiments, the liquid crystal polymer may contain various other monomers, such as aromatic hydroxycarboxylic acids (e.g., HBA) in an amount of about 1 mol % to about 50 mol %, in some embodiments, about 1 mol % to about 20 mol %, and in some embodiments, about 2 mol % to about 10 mol %, aromatic dicarboxylic acids (e.g., IA and / or TA) in an amount of about 1 mol % to about 40 mol %, and in some embodiments, about 5 mol % to about 25 mol %, and / or aromatic diols (e.g., BP and / or HQ) in an amount of about 1 mol % to about 40 mol %, and in some embodiments, about 5 mol % to about 25 mol %. In other embodiments, repeat units derived from NDA may comprise 10 mol % or more of the polymer, in some embodiments, about 12 mol % or more, in some embodiments, about 15 mol % or more, and in some embodiments, about 18 mol % to about 95 mol %. In such embodiments, the liquid crystal polymer may further contain various other monomers, such as aromatic hydroxycarboxylic acids (e.g., HBA) in an amount of about 20 mol % to about 60 mol %, in some embodiments, about 30 mol % to about 50 mol %, aromatic dicarboxylic acids (e.g., IA and / or TA) in an amount of about 2 mol % to about 30 mol %, in some embodiments, about 5 mol % to about 25 mol %, and / or aromatic diols (e.g., BP and / or HQ) in an amount of about 2 mol % to about 40 mol %, in some embodiments, about 5 mol % to about 35 mol %.

[0055] Additionally, although not necessarily required, the liquid crystal polymer may be a "low naphthene" polymer, so long as it contains a minimal amount of repeat units derived from naphthenic hydroxycarboxylic acids and naphthenic dicarboxylic acids, such as naphthalene-2,6-dicarboxylic acid ("NDA"), 6-hydroxy-2-naphthoic acid ("HNA"), or combinations thereof. That is, the total amount of repeat units derived from naphthenic hydroxycarboxylic acids and / or dicarboxylic acids (e.g., NDA, HNA, or combinations of HNA and NDA) is typically 10 mol.% or less of the polymer, in some embodiments about 15 mol.% or less, in some embodiments about 8 mol.% or less, in some embodiments about 6 mol.% or less, and in some embodiments, 1 mol.% to about 5 mol.% (e.g., 0 mol.%). In one particular embodiment, the liquid crystal polymer may be formed from repeat units derived from 4-hydroxybenzoic acid ("HBA"), as well as terephthalic acid ("TA") and / or isophthalic acid ("IA"), and various other optional components. The repeat units derived from 4-hydroxybenzoic acid ("HBA") may comprise from about 10 mol.% to about 80 mol.%, in some embodiments from about 30 mol.% to about 75 mol.%, and in some embodiments from about 45 mol.% to about 70% of the polymer. Similarly, the repeat units derived from terephthalic acid ("TA") and / or isophthalic acid ("IA") may comprise from about 5 mol.% to about 40 mol.%, in some embodiments from about 10 mol.% to about 35 mol.%, and in some embodiments from about 5 mol.% to about 40 mol.%, and in some embodiments from about 10 mol.% to about 35 mol.%, of the polymer. In some embodiments, they may comprise from about 15 mol.% to about 35 mol.%. Additionally, repeat units derived from 4,4'-biphenol ("BP") and / or hydroquinone ("HQ") may be utilized in amounts of from about 1 mol.% to about 30 mol.%, in some embodiments, from about 2 mol.% to about 25 mol.%, and in some embodiments, from about 5 mol.% to about 20 mol.% of the polymer. Other possible repeat units include those derived from 6-hydroxy-2-naphthoic acid ("HNA"), 2,6-naphthalenedicarboxylic acid ("NDA"), and / or acetaminophen ("APAP"). For example, in certain embodiments, repeat units derived from HNA, NDA, and / or APAP, when utilized, may each comprise from about 1 mol.% to about 35 mol.%, in some embodiments, from about 2 mol.% to about 30 mol.%, and in some embodiments, from about 3 mol.% to about 25 mol.%.

[0056] In certain embodiments, all of the liquid crystalline polymers utilized in the polymer composition are "high naphthene" polymers such as those described above. However, in other embodiments, "low naphthene" liquid crystalline polymers may be utilized in the composition, in which the total amount of repeat units derived from naphthenic hydroxycarboxylic acids and / or dicarboxylic acids (e.g., NDA, HNA, or a combination of HNA and NDA) is less than 10 mol.%, in some embodiments about 8 mol.% or less, in some embodiments about 6 mol.% or less, and in some embodiments about 1 mol.% to about 5 mol.% of the polymer. If utilized, it is generally desirable that such low naphthene polymers be present only in relatively low amounts. For example, when utilized, the low naphthene liquid crystalline polymer typically comprises from about 1 wt.% to about 50 wt.%, in some embodiments from about 2 wt.% to about 40 wt.%, in some embodiments from about 5 wt.% to about 30 wt.%, of the total amount of liquid crystalline polymer in the composition, and from about 0.5 wt.% to about 45 wt.%, in some embodiments from about 2 wt.% to about 35 wt.%, in some embodiments from about 5 wt.% to about 25 wt.% of the total composition. In contrast, the high naphthene liquid crystalline polymer typically comprises from about 50 wt.% to about 99 wt.%, in some embodiments from about 60 wt.% to about 98 wt.%, in some embodiments from about 70 wt.% to about 95 wt.%, of the total amount of liquid crystalline polymer in the composition, and from about 55 wt.% to about 99.5 wt.%, in some embodiments from about 65 wt.% to about 98 wt.%, in some embodiments from about 75 wt.% to about 95 wt.% of the total composition.

[0057] In certain embodiments, it may be desirable to utilize a blend of polymers in the polymer matrix. For example, the polymer matrix may contain a first polymer having a faster crystallization rate than a second polymer. In one embodiment, the first polymer may include polyethylene terephthalate, and the second polymer may include a polybutylene terephthalate polymer. Combining polymers with different crystallization rates can provide various advantages and benefits. For example, a slower-crystallizing polymer (e.g., polybutylene terephthalate) may tend to migrate to the surface of the part, providing good surface gloss and aesthetics, while a faster-crystallizing polymer (e.g., polyethylene terephthalate) may provide enhanced mechanical properties. When such blends are utilized, it is typically desirable for the first polymer to be present in an amount greater than the second polymer. For example, the weight ratio of the first polymer to the second polymer may be from about 1 to about 20, in some embodiments from about 2 to about 15, and in some embodiments from about 3 to about 10. For example, the first polymer may comprise from about 10 wt.% to about 40 wt.%, in some embodiments from about 15 wt.% to about 35 wt.%, and in some embodiments, from about 20 wt.% to about 30 wt.%, of the polymer composition, while the second polymer may comprise from about 1 wt.% to about 10 wt.%, in some embodiments, from about 2 wt.% to about 9 wt.%, and in some embodiments, from about 3 wt.% to about 8 wt.%.

[0058]

[0057] The polymer in the polymer matrix may comprise at least about 30 wt.%, in some embodiments at least about 40 wt.%, and in some embodiments from about 40 wt.% to about 99 wt.% of the polymer composition. 5 wt.%, in some embodiments, from about 50 wt.% to about 95 wt.%, in some embodiments, from about 60 wt.% to about 90 wt.%, and in some embodiments, from about 60 wt.% to about 85 wt.%.

[0059] B. Hollow inorganic fillers To facilitate achieving desired dielectric properties, the polymer composition may include hollow inorganic fillers. For example, these fillers may have a dielectric constant at 100 MHz of about 3.0 or less, in some embodiments about 2.5 or less, in some embodiments about 1.1 to about 2.3, and in some embodiments, about 1.2 to about 2.0. In addition, the hollow inorganic fillers may have a particular size, which can contribute to the strength of the polymer composition and, due to their hollow nature, may allow the polymer composition to have a reduced weight and / or density.

[0060] Generally, hollow inorganic fillers have an internal hollow space or cavity and may be synthesized using techniques known in the art. Hollow inorganic fillers may be made from conventional materials. For example, hollow inorganic fillers may include alumina, silica, zirconia, magnesia, glass, fly ash, borates, phosphates, ceramics, and the like. In one embodiment, hollow inorganic fillers may include hollow glass fillers, hollow ceramic fillers, and mixtures thereof. In one embodiment, the hollow inorganic filler comprises a hollow glass filler.

[0061] The hollow glass filler may be made from soda-lime borosilicate glass, soda-lime glass, borosilicate glass, sodium borosilicate glass, sodium silicate glass, or aluminosilicate glass. In this regard, in one embodiment, the glass composition may be, but is not limited to, at least about 65 wt. % SiO, 3-15 wt. % NaO, 8-15 wt. % CaO, 0.1-5 wt. % MgO, 0.01-3 wt. % AlO, 0.01-1 wt. % KO, and optionally other oxides (e.g., LiO, FeO, TiO, BO). In another embodiment, the composition may be about 50-58 wt. % SiO, 25-30 wt. % AlO, 6-10 wt. % CaO, 1-4 wt. % NaO / KO, and 1-5 wt. % other oxides. Furthermore, in one embodiment, the hollow glass filler may include more alkaline earth metal oxide than alkali metal oxide. For example, the weight ratio of alkaline earth metal oxide to alkali metal oxide may be greater than 1, in some embodiments, greater than about 1.1, in some embodiments, from about 1.2 to about 4, and in some embodiments, from about 1.5 to about 3. Notwithstanding the above, it should be understood that the composition of the glass may vary depending on the type of glass utilized and still provide the benefits desired by the present invention.

[0062] The hollow inorganic filler may have at least one dimension having an average value of about 1 micrometer or greater, in some embodiments about 5 micrometers or greater, in some embodiments about 8 micrometers or greater, in some embodiments about 1 micrometer to about 150 micrometers, in some embodiments about 10 micrometers to about 150 micrometers, and in some embodiments about 12 micrometers to about 50 micrometers. In one embodiment, such average value is d 50 It may be referred to as the value.

[0063] Additionally, the hollow inorganic filler may have a D of about 3 micrometers or greater, in some embodiments about 4 micrometers or greater, in some embodiments from about 5 micrometers to about 20 micrometers, and in some embodiments from about 6 micrometers to about 15 micrometers. 10 The hollow inorganic filler may have a D of about 10 micrometers or greater, in some embodiments about 15 micrometers or greater, in some embodiments from about 20 micrometers to about 150 micrometers, and in some embodiments, from about 22 micrometers to about 50 micrometers. 90 may have

[0064] In this regard, the hollow inorganic filler may be present in a size distribution that may be Gaussian, normal, or non-normal. In one embodiment, the hollow inorganic filler may have a Gaussian size distribution. In another embodiment, the hollow inorganic filler may have a normal size distribution. In a further embodiment, the hollow inorganic filler may have a non-normal size distribution. Examples of non-normal size distributions can include unimodal and multimodal (e.g., bimodal) size distributions.

[0065]

[0064] When referring to the above dimensions, such dimensions may be any dimensions. However, in one embodiment, such dimensions refer to diameters. For example, such values ​​for dimensions refer to the average diameter of the spheres. Dimensions such as average diameters may be determined according to 3M QCM 193.0. In this regard, in one embodiment, hollow inorganic fillers may refer to hollow spheres, such as hollow glass spheres. For example, hollow inorganic fillers may have an average aspect ratio of approximately 1. Generally, the average aspect ratio may be about 0.8 or greater, in some embodiments about 0.85 or greater, in some embodiments about 0.9 to about 1.3, and in some embodiments about 0.95 to about 1.05.

[0066] Additionally, the hollow inorganic fillers may have relatively thin walls to aid in the dielectric properties and weight reduction of the polymer composition, with the wall thickness being about 50% or less, in some embodiments about 40% or less, in some embodiments about 1% to about 30%, and in some embodiments about 2% to about 25% of the average dimension, e.g., average diameter, of the hollow inorganic fillers.

[0067]

[0066] Furthermore, the hollow inorganic filler may have a specific true density that allows for easy handling and can provide a polymer composition with reduced weight. Generally, true density refers to the quotient obtained by dividing the mass of a hollow filler sample by the true volume of the hollow filler mass, and the true volume is referred to as the total volume of the hollow filler. In this regard, the true density of a hollow inorganic filler is about 0.1 g / cm 3 or more, in some embodiments, about 0.2 g / cm 3 or more, in some embodiments, about 0.3 g / cm 3 More than ~ approx. 1.2g / cm 3 , and in some embodiments, about 0.4 g / cm 3 More than ~ approx. 0.9g / cm 3 True density may be determined according to 3M QCM 14.24.1.

[0068] Even when fillers are hollow, they may possess mechanical strength that allows them to maintain their structural integrity and reduces the likelihood of the fillers breaking during processing and / or use. In this regard, the isotactic crush resistance of hollow inorganic fillers (i.e., at least 80 vol.%, e.g., at least 90 vol.%, of the hollow filler survives) may be about 20 MPa or greater, in some embodiments about 100 MPa or greater, in some embodiments about 150 MPa to about 500 MPa, and in some embodiments about 200 MPa to about 350 MPa. Isotactic crush resistance may be determined according to 3M QCM 14.1.8.

[0069] The alkalinity of the hollow inorganic filler may be about 1.0 meq / g or less, in some embodiments about 0.9 meq / g or less, in some embodiments about 0.1 meq / g to about 0.8 meq / g, and in some embodiments about 0.2 meq / g to about 0.7 meq / g. The alkalinity may be determined according to 3M QCM 55.19. To produce a relatively low alkalinity, the hollow inorganic filler may be treated with a suitable acid, such as phosphoric acid.

[0070]

[0069] Furthermore, the hollow inorganic filler may also include a surface treatment to help provide better compatibility with the polymer and / or other components in the polymer composition. By way of example, the surface treatment may be silanization. In particular, the surface treatment may include, but is not limited to, aminosilane, epoxysilane, etc.

[0071] The hollow inorganic filler may comprise, for example, about 1 wt.% or more, in some embodiments about 4 wt.% or more, in some embodiments about 5 wt.% to about 40 wt.%, and in some embodiments about 10 wt.% to about 30 wt.% of the polymer composition. Furthermore, to provide beneficial properties, the weight ratio of polymer to hollow inorganic filler may be about 0.1 or more, in some embodiments about 1 or more, in some embodiments about 1.5 or more, in some embodiments about 0.1 to about 10, in some embodiments about 1 to about 10, in some embodiments about 2 to about 10, in some embodiments about 2 to about 6, and in some embodiments about 2 to about 5.

[0072] C. Dielectric filler Additionally, dielectric fillers may be utilized in the polymer composition to improve its properties. For example, the dielectric filler may also reduce the dielectric constant of the polymer composition. Furthermore, the dielectric filler may also contribute to improving other properties of the polymer composition. For example, the dielectric filler may also improve the thermal and mechanical properties of the polymer composition. These dielectric fillers may be dielectric inorganic fillers, dielectric organic fillers, or mixtures thereof. In one embodiment, the dielectric filler may be an inorganic dielectric filler. In another embodiment, the dielectric filler may be an organic dielectric filler. In a further embodiment, the dielectric filler may be a mixture of an inorganic dielectric filler and an organic dielectric filler. Furthermore, in one embodiment, these dielectric fillers may be solid fillers that do not have internal voids. These dielectric fillers may comprise about 1 wt.% or more of the polymer composition, in some embodiments, about 2 wt.% or more, in some embodiments, about 3 wt.% to about 40 wt.%, and in some embodiments, about 5 wt.% to about 25 wt.%. Furthermore, because hollow inorganic fillers and dielectric fillers each have unique properties, their combination within a specific ratio can provide a polymer composition with beneficial properties, such as a desired balance between dielectric, thermal, and / or mechanical properties. In this regard, the weight ratio of hollow inorganic filler to dielectric filler can be about 0.1 or greater, in some embodiments, from about 0.1 to about 10, in some embodiments, from about 0.1 to about 5, in some embodiments, from about 0.5 to about 4, and in some embodiments, from about 1 to about 2.

[0073] The specific properties of the dielectric filler may vary as desired. For example, in one embodiment, the dielectric filler may be a fibrous filler. Fibrous fillers typically include fillers having a high tensile strength relative to their mass. For example, the ultimate tensile strength of the fibers (determined in accordance with ASTM D2101) is typically from about 1,000 to about 15,000 megapascals ("MPa"), in some embodiments from about 2,000 MPa to about 10,000 MPa, and in some embodiments from about 3,000 MPa to about 6,000 MPa. To help maintain the desired dielectric properties, such high-strength fibers may be formed from materials generally of an insulating nature, such as glass, ceramic, or mineral (e.g., alumina or silica), aramid (e.g., Kevlar® sold by EI duPont de Nemours, Wilmington, Delaware), mineral, polyolefin, polyester, and the like. In one embodiment, the fibrous filler may include glass fiber, mineral fiber, or mixtures thereof. For example, in one embodiment, the fibrous filler may comprise glass fibers. Particularly suitable glass fibers may include E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass, and the like. In another embodiment, the fibrous filler may comprise mineral fibers. Mineral fibers include silicates, such as neosilicates, sorosilicates, inosilicates (e.g., calcium inosilicates such as wollastonite; calcium magnesium inosilicates such as tremolite; calcium magnesium iron inosilicates such as actinolite; magnesium iron inosilicates such as anthophillite), phyllosilicates (e.g., aluminum phyllosilicates such as palygorskite), tectosilicates, and the like; sulfates such as calcium sulfate (e.g., dehydrated or anhydrous gypsum); mineral wool (e.g., rock or Inosilicates such as wollastonite fiber available from Nyco Minerals under the trade name NYGLOS® (e.g., NYGLOS® 4W or NYGLOS® 8) are particularly suitable.

[0074] Furthermore, while fibrous fillers may have a variety of different sizes, fibers having a specific aspect ratio may contribute to improved mechanical properties of polymer compositions. That is, fibrous fillers having an aspect ratio (average length divided by nominal diameter) of about 2 or greater, in some embodiments about 4 or greater, in some embodiments about 5 to about 50, and in some embodiments about 8 to about 40 may be particularly beneficial. Such fibrous fillers may have a weight-average length of, for example, about 10 micrometers or greater, in some embodiments about 25 micrometers or greater, in some embodiments about 50 micrometers to about 800 micrometers, and in some embodiments about 60 micrometers to about 500 micrometers. Also, such fibrous fillers may have a volume-average length of, for example, about 10 micrometers or greater, in some embodiments about 25 micrometers or greater, in some embodiments about 50 micrometers to about 800 micrometers, and in some embodiments about 60 micrometers to about 500 micrometers. The fibrous filler may similarly have a nominal diameter of about 5 micrometers or greater, in some embodiments about 6 micrometers or greater, in some embodiments about 8 micrometers to about 40 micrometers, and in some embodiments, about 9 micrometers to about 20 micrometers. The relative amount of fibrous filler may also be selectively controlled to help achieve desired mechanical and thermal properties without adversely affecting other properties of the polymer composition, such as its flowability and dielectric properties. In this regard, the fibrous filler may have a dielectric constant at a frequency of about 6 or less, in some embodiments about 5.5 or less, in some embodiments about 1.1 to about 5, and in some embodiments about 2 to about 4.8.

[0075]

[0074] The fibrous filler may be modified or unmodified and may be sized or chemically treated, for example, to improve adhesion to plastics. In some cases, glass fibers may be sized to protect them, smooth them, and improve adhesion between the fibers and the matrix material. If present, the sizing may include silanes, film formers, lubricants, wetting agents, adhesives, optional antistatic agents and plasticizers, emulsifiers, and optionally further additives. In one particular embodiment, the sizing may include silanes. Specific examples of silanes are aminosilanes, such as 3-trimethoxysilylpropylamine, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(3-trimethoxysilanylpropyl)ethane-1,2-diamine, 3-(2-aminoethyl-amino)propyltrimethoxysilane, and N-[3-(trimethoxysilyl)propyl]-1,2-ethane-diamine.

[0076] If desired, the dielectric filler may also include a particulate filler. Particulate fillers may also be utilized in the polymer composition as a dielectric filler to help achieve desired properties and / or color. Particulate clay minerals may be particularly suitable for use in the present invention. Examples of such clay minerals include, for example, talc (Mg3SiO4). 10 (OH2), halloysite (Al2Si2O5(OH)4), kaolinite (Al2Si2O5(OH)4), illite ((K,H3O)(Al,Mg,Fe)2(Si,Al)4O 10 [(OH)2,(H2O)]), montmorillonite (Na,Ca) 0.33 (Al,Mg)2SiO 10 (OH)2.nH2O), vermiculite ((MgFe,Al)3(Al,Si)4O 10 (OH)2.4H2O), palygorskite ((Mg,Al)2Si4O 10 (OH).4(H2O)), pyrophyllite (Al2Si4O 10(OH)2), etc., and combinations thereof. Still other particulate fillers can be used instead of or in addition to clay minerals. For example, other suitable fillers such as mica, diatomaceous earth, etc. Particulate silicate fillers may also be utilized. For example, mica may be a particularly suitable mineral for use in the present invention. As used herein, the term "mica" refers to muscovite (KAl2(AlSi3)O 10 (OH)2), biotite (K(Mg,Fe)3(AlSi3)O 10 (OH)2), phlogopite (KMg3(AlSi3)O 10 (OH)2), red mica (K(Li,Al) 2-3 (AlSi3)O 10 (OH)2), glauconite (K,Na)(Al,Mg,Fe)2(Si,Al)4O 10 (OH)2), and combinations thereof. Other types of mineral particulate fillers, such as silica, alumina, and the like, can also be utilized.

[0077]

[0076] The particulate filler may be in modified or unmodified form and may be treated, for example, to improve properties. In some examples, the particulate filler may be fluorinated, for example, as a coating. Fluorinated additives may be utilized to improve processing of polymer compositions, for example, by providing better mold filling, internal lubrication, mold release, etc. In certain embodiments, the fluorinated additive may include a fluoropolymer containing a hydrocarbon backbone polymer in which some or all of the hydrogen atoms are substituted with fluorine atoms. The backbone polymer may be polyolefinic and formed from fluorine-substituted unsaturated olefin monomers. The fluoropolymer may be a homopolymer of such fluorine-substituted monomers or a copolymer of fluorine-substituted monomers, or a mixture of fluorine-substituted and non-fluorine-substituted monomers. In addition to fluorine atoms, the fluoropolymer may be substituted with other halogen atoms, such as chlorine and bromine atoms. Representative monomers suitable for forming the fluoropolymers used in the present invention are tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluoroethyl vinyl ether, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, etc., and mixtures thereof. Specific examples of suitable fluoropolymers include polytetrafluoroethylene, perfluoroalkyl vinyl ether, poly(tetrafluoroethylene-co-perfluoroalkyl vinyl ether), fluorinated ethylene propylene copolymer, ethylene tetrafluoroethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, etc., and mixtures thereof. The fluorinated additive may contain only the fluoropolymer, or may include other components, such as those that aid its ability to be uniformly dispersed in the polymer composition. For example, in one embodiment, the fluorinated additive may include a fluoropolymer in combination with a plurality of carrier particles. For example, in such an embodiment, the fluoropolymer may be coated on carrier particles, such as the particulate fillers described above.

[0078] D. Functional compounds If desired, functional compounds can also be utilized in the polymer composition, particularly to facilitate reducing the melt viscosity of the polymer composition. For example, the functional compound can be a functional aromatic compound, a non-aromatic functional compound, or a mixture thereof. For example, in one embodiment, the polymer composition can include a non-aromatic functional compound. Such compounds can serve various purposes, such as reducing the melt viscosity. One such non-aromatic functional compound is water. If desired, water can be added in a form that generates water under process conditions. For example, water can be added as a hydrate that effectively "lose" water under process conditions (e.g., elevated temperatures). Such hydrates include alumina trihydrate, copper sulfate pentahydrate, barium chloride dihydrate, calcium sulfate dehydrate, and the like. and combinations thereof. In one particular embodiment, the hydrate may comprise alumina trihydrate. When utilized, functional compounds such as hydrates may comprise about 0.001 wt.% or more, in some embodiments about 0.005 wt.% or more, in some embodiments, from about 0.005 wt.% to about 2 wt.%, and in some embodiments, from about 0.01 wt.% to about 1 wt.% of the polymer composition.

[0079] E. Laser Activatable Additives The polymer composition may be "laser activatable" in the sense that it contains an additive that can be activated by a laser direct structuring ("LDS") process. In such a process, the additive is exposed to a laser that causes the liberation of metal. The laser thereby patterns the conductive elements in the part, leaving behind a roughened surface containing embedded metal particles. These particles act as nuclei for crystal growth during a subsequent plating process (e.g., copper plating, gold plating, nickel plating, silver plating, zinc plating, tin plating, etc.).

[0080]

[0079] The laser activatable additive generally comprises a spinel crystal, which may comprise two or more metal oxide cluster configurations within a definable crystal formation. For example, the entire crystal formation may have the following general formula: AB2O4 (In the formula, A is a metal cation having a valence of 2, such as cadmium, chromium, manganese, nickel, zinc, copper, cobalt, iron, magnesium, tin, titanium, etc., and combinations thereof; B is a metal cation having a valence of 3, such as chromium, iron, aluminum, nickel, manganese, tin, and combinations thereof. may have

[0081] Typically, A in the above formula provides the primary cation component of the first metal oxide cluster, and B provides the primary cation component of the second metal oxide cluster. These oxide clusters may have the same or different structures. For example, in one embodiment, the first metal oxide cluster has a tetrahedral structure, and the second metal oxide cluster has an octahedral structure. Nevertheless, the clusters can combine to provide a single identifiable crystalline structure with enhanced sensitivity to electromagnetic radiation. Examples of suitable spinel crystals include, for example, MgAl2O4, ZnAl2O4, FeAl2O4, CuFe2O4, CuCr2O4, MnFe2O4, NiFe2O4, TiFe2O4, FeCr2O4, MgCr2O4, and the like. Copper chromium oxide (CuCr2O4) is particularly suitable for use in the present invention and is available from Shepherd Color Co. under the designation "Shepherd Black 1GM."

[0082]

[0081] The laser activatable additive may comprise from about 0.1 wt.% to about 30 wt.%, in some embodiments from about 0.5 wt.% to about 20 wt.%, and in some embodiments, from about 1 wt.% to about 10 wt.% of the polymer composition.

[0083] F. Other Additives A wide variety of additional additives may also be included in the polymer composition, such as lubricants, thermally conductive fillers, pigments, antioxidants, stabilizers, surfactants, waxes, flame retardants, anti-sag additives, nucleating agents (e.g., boron nitride), flow modifiers, coupling agents, antimicrobial agents, pigments or other colorants, impact modifiers, and other materials added to improve properties and processability. Such optional materials may be utilized in the polymer composition in conventional amounts and in accordance with conventional processing techniques. When utilized, for example, such additives typically comprise from about 0.05 wt.% to about 5 wt.%, and in some embodiments, from about 0.1 wt.% to about 1 wt.%, of the polymer composition.

[0084] In one embodiment, the polymer composition may include a lubricant. For example, the lubricant may include a polyolefin wax (e.g., a polyethylene wax), an amide wax, a fatty acid ester wax, or the like. In one embodiment, the lubricant may include a polyolefin wax (e.g., a polyethylene wax), an amide wax, a fatty acid ester wax, or the like. The lubricant may also include a triolefin wax. The lubricant may also be a fatty acid ester wax. Fatty acid ester waxes can be obtained, for example, by oxidative bleaching of crude natural waxes followed by esterification of the fatty acids with alcohols. The alcohol may in some cases have 1 to 4 hydroxyl groups and 2 to 20 carbon atoms. When the alcohol is polyfunctional (e.g., 2 to 4 hydroxyl groups), alcohols with 2 to 8 carbon atoms are particularly desirable. Particularly suitable polyfunctional alcohols include dihydric alcohols (e.g., ethylene glycol, propylene glycol, butylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanediol), trihydric alcohols (e.g., glycerol and trimethylolpropane), and tetrahydric alcohols (e.g., pentaerythritol and erythritol). Aromatic alcohols such as o-, m-, and p-tolylcarbinol, chlorobenzyl alcohol, bromobenzyl alcohol, 2,4-dimethylbenzyl alcohol, 3,5-dimethylbenzyl alcohol, 2,3,5-cumobenzyl alcohol, 3,4,5-trimethylbenzyl alcohol, p-cuminyl alcohol, 1,2-phthalyl alcohol, 1,3-bis(hydroxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, pseudocumenyl glycol, mesitylene glycol, and mesityleneglycerol may also be suitable. Fatty acid esters particularly suitable for use in the present invention are derived from montan wax. For example, Licowax® OP (Clariant) contains montanic acid partially esterified with butylene glycol and partially saponified with calcium hydroxide. Thus, Licowax® OP contains a mixture of montanic acid esters and calcium montanate. Other Montan acid esters that may be utilized include, for example, Licowax® E, Licowax® OP, and Licolub® WE 4 (all manufactured by Clariant), which are Montan acid esters obtained as a secondary product from the oxidative refining of raw Montan wax.Licowax® E and Licolub® WE 4 contain montanic acid esterified with ethylene glycol or glycerin.

[0085] In one embodiment, the polymer composition may include a black pigment. The black pigment typically includes a plurality of carbon black particles, such as furnace black, channel black, acetylene black, or lamp black. The carbon black particles may have any desired shape, such as granules or flakes. The average particle size (e.g., diameter) may range, for example, from about 1 to about 200 nanometers, in some embodiments from about 5 to about 150 nanometers, and in some embodiments, from about 10 to about 100 nanometers. Furthermore, it is typically desirable for the carbon black particles to be relatively pure, such as containing polycyclic aromatic hydrocarbons (e.g., benzo[a]pyrene, naphthalene, etc.) in an amount of about 1 parts per million ("ppm") or less, and in some embodiments, about 0.5 ppm or less. For example, the black pigment may contain benzo[a]pyrene in an amount of about 10 parts per billion ("ppb") or less, and in some embodiments, about 5 ppb or less.

[0086] If desired, the black pigment may include a carrier resin capable of encapsulating the carbon black particles, thereby providing various benefits. For example, the carrier resin may improve the ability of the particles to be handled and incorporated into the base polymer composition. While any known carrier resin may be utilized for this purpose, in certain embodiments, the carrier resin may be the same polymer utilized in the polymer matrix of the polymer composition. If desired, the carrier resin may be pre-blended with the carbon black particles to form a pigment masterbatch, which may then be combined with the polymer. If utilized, the carrier resin typically comprises from about 50 wt.% to about 95 wt.%, in some embodiments from about 60 wt.% to about 90 wt.%, and in some embodiments from about 70 wt.% to about 85 wt.%, of the masterbatch, and the carbon black particles typically comprise from about 5 wt.% to about 50 wt.% of the masterbatch. %, in some embodiments, from about 10 wt.% to about 40 wt.%, and in some embodiments, from about 15 wt.% to about 30 wt.%. Of course, other ingredients may also be incorporated into the masterbatch.

[0087] II. Formation The components used to form the polymer composition may be combined together using any of a variety of different techniques known in the art. For example, in one particular embodiment, the polymer, optional hollow inorganic filler and / or dielectric filler, and other optional additives are melt-processed as a mixture in an extruder to form the polymer composition. The mixture may be melt-mixed in a single-screw or multi-screw extruder at a temperature of about 250°C to about 450°C. In one embodiment, the mixture can be melt-processed in an extruder containing multiple temperature zones. The temperature of each zone is typically set within about -60°C to about 25°C of the melting temperature of the polymer. By way of example, the mixture can be melt-processed using a twin-screw extruder, such as a Leistritz 18mm co-rotating, fully intermeshing twin-screw extruder. A versatile screw design can be used to melt-process the mixture. In one embodiment, the mixture containing all of the components can be fed into the feed throat of the first barrel by a metering feeder. In another embodiment, different components can be added at different addition points in the extruder, as is known. For example, the polymer can be applied to a feed port, and certain additives (e.g., hollow inorganic fillers, dielectric fillers, and / or other optional additives) can be added downstream at the same or different temperature zones. In either case, the resulting mixture can be melted, mixed, and then extruded through a die. The extruded polymer composition can then be quenched in a water bath to solidify, pelletized in a pelletizer, and then dried.

[0088]

[0087] The melt viscosity of the polymer composition is generally low enough to flow easily into a mold cavity and form a small sized circuit board. For example, in one particular embodiment, the polymer composition has a melt viscosity of 1,000 s -1The polymer may have a melt viscosity of about 5 Pa·s or greater, in some embodiments about 10 Pa·s or greater, in some embodiments about 10 Pa·s to about 500 Pa·s, in some embodiments about 5 Pa·s to about 150 Pa·s, in some embodiments about 5 Pa·s to about 100 Pa·s, in some embodiments about 10 Pa·s to about 100 Pa·s, in some embodiments about 15 to about 90 Pa·s, and in some embodiments about 20 Pa·s to about 60 Pa·s, determined at a shear rate of 100° C. above the melt temperature of the polymer. The melt viscosity may be determined in accordance with IEC 11443:2005.

[0089] The polymer composition may also have a relatively low density, for example, a density of about 3 g / cm 3 or less, in some embodiments, about 2.5 g / cm 3 or less, in some embodiments, about 0.1 g / cm 3 ~About 2g / cm 3 , and in some embodiments, about 0.5 g / cm 3 ~Approx. 1.6g / cm 3 The density may be determined according to ISO 1183.

[0090] Additionally, polymer compositions are described in U.S. Pat. No. 6,495,616, which is incorporated herein by reference, and have the following formula: X=100×[(100 / ρ0+α / ρ1+β / ρ3)-(100+α+β) / ρ](α / ρ1-α / ρ2) (wherein α represents the amount of hollow inorganic filler (parts by weight based on 100 parts by weight of polymer), β represents the amount of dielectric (e.g., fibrous) filler (parts by weight based on 100 parts by weight of polymer), ρ represents the specific gravity of the polymer, ρ represents the true specific gravity of the hollow inorganic filler, ρ represents the material specific gravity of the hollow inorganic filler, ρ represents the specific gravity of the dielectric (e.g., fibrous) filler, and ρ represents the specific gravity of an ASTM No. 4 dumbbell (having a thickness of 2.5 mm) obtained by injection molding the polymer composition. In one embodiment, X is between 10 and 50. In other embodiments, X may be less than 10 or greater than 50. For example, in one embodiment, X may be less than 10. In other embodiments, X may be greater than 50.

[0091] III. Molded parts

[0090] After formation, the polymer composition can be molded into a desired shape for a particular application. Typically, molded parts are formed using a one-component injection molding process in which dried and preheated plastic granules are injected into a mold. In one embodiment, the molded part or shape can be the electrical connector described above. The electrical connector can be particularly useful in 5G radio frequency systems.

[0092]

[0091] Referring to FIG. 3, for example, a 5G communication system 300 One embodiment of the present invention includes a base station 302, one or more relay stations 304, one or more user computing devices 306, one or more Wi-Fi repeaters 308 (e.g., "femtocells"), and / or a 5G antenna system. 300 The base station 302 may include other suitable antenna components. The relay station 304 may be configured to relay or "repeat" signals between the base station 302 and the user computing device 306 and / or relay station 304 to facilitate communication with the base station 302 by the user computing device 306 and / or other relay station 304. The base station 302 may include a MIMO antenna array 310 configured to receive and / or transmit radio frequency signals 312 with the relay station 304, a Wi-Fi repeater 308, and / or directly with the user computing device 306. The user computing device 306 is not necessarily limited by the present invention and includes devices such as 5G smartphones.

[0093] The MIMO antenna array 310 may utilize beam steering to focus or direct the radio frequency signals 312 toward the relay station 304. For example, the MIMO antenna array 310 may be configured to adjust an elevation angle 314 relative to a heading angle 316 defined in the XY and / or ZY planes, as well as relative to the Z direction.

[0094] Similarly, the relay station 304, the user computing device 306, and the Wi-Fi repeater 308 One or more of the devices 304, 306, 308 may utilize beam steering to directionally tune the sensitivity and / or power transmission of the devices 304, 306, 308 relative to the MIMO antenna array 310 of the base station 302 (e.g., by adjusting one or both of the relative elevation and / or azimuth angles of the respective devices) to improve reception and / or transmission capabilities for the MIMO antenna array 310.

[0095] Electrical connectors may be utilized to communicatively couple various elements of the base station 302, relay station 304, and / or user computing device 306. For example, the base station 302, relay station 304, and / or user computing device 306. Such antennas and / or antenna arrays may be communicatively coupled to one or more integrated circuits, processors, memories, etc. For example, a front-end module may be used to control the transmission and / or reception of radio frequency signals using the antennas and / or antenna arrays. Electrical connectors may communicatively couple any of the above devices.

[0096]

[0095] The present invention can be better understood with reference to the following examples. [Example]

[0097] Test Method Melt viscosity: Melt viscosity (Pa·s) was measured using a Dynisco LCR7001 capillary rheometer at a shear rate of 1,000 s -1 and may be determined according to ISO Test No. 11443:2005 at a temperature 15°C above the melt temperature (e.g., about 350°C). The rheometer orifice (die) had a diameter of 1 mm, a length of 20 mm, an L / D ratio of 20.1, and an entrance angle of 180°. The barrel diameter was 9.55 mm + 0.005 mm, and the rod length was 233.4 mm.

[0098] Melting Temperature: The melting temperature ("Tm") may be determined by differential scanning calorimetry ("DSC") as known in the art. The melting temperature is the differential scanning calorimetry (DSC) peak melting temperature as determined by ISO Test No. 11357-2:2013. Based on the DSC procedure, samples were heated and cooled at 20°C per minute, as described in ISO Standard 10350, using DSC measurements performed on a TA Q2000 instrument.

[0099] Deflection Temperature Under Load ("DTUL"): Deflection temperature under load may be determined in accordance with ISO Test No. 75-2:2013 (technically equivalent to ASTM D648-07). More specifically, a test specimen sample 80 mm long, 10 mm thick, and 4 mm wide may be subjected to an edgewise three-point bend test at a specified load (maximum external fiber stress) of 1.8 megapascals. The specimen is lowered into a silicone oil bath and the temperature is increased at 2°C per minute until the specimen deflects 0.25 mm (0.32 mm per ISO Test No. 75-2:2013).

[0100] Tensile Modulus, Tensile Stress, and Tensile Elongation: Tensile properties may be tested according to ISO Test No. 527:2012 (technically equivalent to ASTM D638-14). Modulus and strength measurements may be performed on the same test specimen sample, 80 mm long, 10 mm thick, and 4 mm wide. The test temperature may be about 23°C, and the test speed may be 1 or 5 mm / min.

[0101] Flexural modulus, flexural stress and flexural elongation: Flexural properties were measured according to ISO test No. 178 The test may be performed in accordance with ASTM D790-10 (technically equivalent to ASTM D790-10). The test may be performed on a 64 mm support span. The test may be performed on the center of an uncut ISO 3167 multipurpose bar. The test temperature may be approximately 23°C, and the test speed may be 2 mm / min.

[0102]

[0101] Unnotched and notched Charpy impact strength: Charpy properties are measured according to ISO Testing may be performed in accordance with Test No. ISO 179-1:2010 (technically equivalent to ASTM D256-10, Method B). This test may be performed using a Type 1 specimen size (80 mm length, 10 mm width, and 4 mm thickness). When testing notched impact strength, the notch may be a Type A notch (0.25 mm base radius). Specimens may be cut from the center of the multipurpose bar using a single-tooth milling machine. The test temperature may be approximately 23°C.

[0103]

[0102] Dielectric constant ("Dk") and dissipation factor ("Df"): The dielectric constant (or relative static The dielectric constant and dissipation factor are calculated from Baker-Jarvis et al., IEEE Trans. on Dielectric and Electrical Insulation, 5(4), 571 (1998) and Krupka et al., Proc. th International Conference on Dielectric Materials: Measurements and Applications, IEEE The dielectric constant was determined using a known split-post dielectric resonance method, such as that described in Conference Publication No. 430 (September 1996). More specifically, a plate-shaped sample measuring 80 mm x 80 mm x 1 mm was inserted between two fixed dielectric resonators. The resonators measured the dielectric constant components on the surface of the sample. Five samples were The split-post resonator can be used to perform dielectric measurements in the low gigahertz range, for example, 1 GHz, 2 GHz, or 10 GHz.

[0104] Example 1

[0103] Samples 1 to 5 were prepared using liquid crystal polymers (LCP1 or LCP2), hollow glass spheres, and mica, wollastonite, glass powder, and / or glass fiber. LCP1 was formed from 43% HBA, 9% TA, 29% HQ, and 20% NDA. LCP2 was formed from 48% HNA, 2% HBA, 25% BP, and 25% TA. The hollow glass spheres had an average diameter of 18 micrometers. The glass powder had a dielectric constant of 4.8 determined at a frequency of 1 GHz. Additionally, the utilized glass fiber had an initial length of either 3 mm or 4 mm. The polymer composition may also contain polyethylene lubricant, alumina trihydrate, pigments, and / or various other minor additives. Compounding was performed using a 25 mm single-screw extruder.

[0105] [Table 1]

[0106] The samples were then tested for thermal and mechanical properties. The results are shown in Table 2 below. Write it down.

[0107] [Table 2]

[0108] Example 2 Sample 7 was composed of 62% HNA, 2% HBA, 18% TA, and 18% BP. The composite was formulated to contain 100 wt.% LCP3 for use in connectors. Samples were injection molded into plaques (60 mm x 60 mm) and tested for thermal and mechanical properties. The results are listed below.

[0109] [Table 3]

[0110] Example 3

[0106] Samples 8 to 15 were prepared using liquid crystal polymer (LCP2), milled and / or flat The formulations were made from various combinations of spun glass fiber strands (aspect ratio = 4), mica (MICA1 and MICA2), and silica. MICA1 had an average particle size of 25 micrometers, and MICA2 had an average particle size of 60 micrometers. The experiment was carried out using a 8 mm single screw extruder. The parts were injection molded and the samples were cut into plaques (60 mm x 60 mm).

[0111] [Table 4]

[0112]

[0107] Samples 8-15 were tested for thermal and mechanical properties. The results are shown in the table below. Posted.

[0113] [Table 5]

[0114] Example 4

[0108] Sample 16 was prepared using liquid crystal polymers (LCP2 and LCP4), hollow glass spheres, and glass beads. It is made from glass powder, glass fiber and alumina trihydrate. LCP4 is 60% HBA The glass powder was composed of 4% HNA, 18% TA, and 18% BP. The glass powder had a dielectric constant of 4.8 determined at a frequency of 1 GHz. Compounding was carried out using a 25 mm single screw extruder.

[0115] [Table 6]

[0116] The samples were then tested for thermal and mechanical properties. The results are shown in Table 7 below. Write it down.

[0117] [Table 7]

[0118]

[0110] These and other modifications and variations of the present invention are intended to be understood as including all such modifications and variations without departing from the spirit and scope of the present invention. The present invention can be practiced by those skilled in the art without departing from the spirit or scope of the present invention. Furthermore, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those skilled in the art will appreciate that the foregoing description is merely illustrative, and thus does not limit the invention as further described in the appended claims.

Claims

1. 1. An electrical connector comprising at least two opposing walls defining a passage therebetween for receiving a contact pin, the opposing walls having a width of about 500 micrometers or less, and the opposing walls being formed from a polymer composition comprising a polymer matrix containing at least one polymer having a glass transition temperature of about 30°C or greater in an amount of about 30 wt.% or greater of the composition, the polymer composition exhibiting a dielectric constant of about 4 or less and a dielectric loss tangent of about 0.02 or less, determined at a frequency of 10 GHz.

2. 10. The electrical connector of claim 1, wherein the polymer composition exhibits a dielectric constant of less than or equal to about 3.5 and a dissipation factor of less than or equal to about 0.005, determined at a frequency of 10 GHz.

3. 3. The electrical connector of claim 1, wherein the opposing walls have a width of about 200 to about 400 micrometers.

4. 4. The electrical connector of claim 1, wherein the polymer comprises a polyolefin, a polyamide, a polyester, a polyarylene sulfide, a polyaryl ketone, or a mixture thereof.

5. 5. The electrical connector of claim 1, wherein the polymer comprises a polyester including a liquid crystal polymer.

6. 6. The electrical connector of claim 5, wherein the thermotropic crystalline polymer is an aromatic polyester containing repeating units derived from 4-hydroxybenzoic acid.

7. 6. The electrical connector of claim 5, wherein the thermotropic liquid crystal polymer has a total amount of repeat units derived from naphthenic hydroxycarboxylic acids and / or naphthenic dicarboxylic acids of about 10 mol. % or more.

8. 6. The electrical connector according to claim 5, wherein the thermotropic liquid crystal polymer has a total amount of repeating units derived from naphthalene-2,6-dicarboxylic acid of about 10 mol. % or more.

9. 6. The electrical connector according to claim 5, wherein the liquid crystal polymer contains repeating units derived from 6-hydroxy-2-naphthoic acid in an amount of about 30 mol % or more.

10. 6. The electrical connector according to claim 5, wherein the liquid crystal polymer contains repeating units derived from 6-hydroxy-2-naphthoic acid in an amount of about 50 mol % or more.

11. 6. The electrical connector of claim 5, wherein the thermotropic liquid crystalline polymer is present in an amount of about 50 wt. % to about 85 wt. %.

12. 12. The electrical connector of claim 1, wherein the polymer composition further comprises at least one hollow inorganic filler having a dielectric constant of about 3.0 or less at a frequency of 100 MHz.

13. 13. The electrical connector of claim 1, wherein the polymer composition further comprises at least one dielectric filler comprising a fibrous filler, a particulate filler, or a mixture thereof.

14. 14. The electrical connector according to claim 1, wherein the polymer composition further comprises at least one hollow inorganic filler having a dielectric constant of less than or equal to about 3.0 at a frequency of 100 MHz and at least one dielectric filler, and the weight ratio of the at least one hollow inorganic filler to the at least one dielectric filler is from about 0.1 to about 10.

15. 15. The electrical connector of claim 14, wherein the weight ratio of said at least one polymer to said at least one hollow inorganic filler is from about 0.1 to about 10.

16. 15. The electrical connector of claim 14, wherein said at least one hollow inorganic filler comprises hollow glass spheres.

17. 17. The electrical connector of claim 16, wherein the hollow glass spheres have an aspect ratio of about 0.8 to about 1.

2.

18. 17. The electrical connector of claim 16, wherein the hollow glass spheres have an average diameter of about 1 micrometer to about 150 micrometers.

19. 17. The electrical connector of claim 16, wherein the wall thickness of the hollow glass spheres is no more than about 40% of the average diameter of the hollow glass spheres.

20. 15. The electrical connector of claim 14, wherein the at least one hollow inorganic filler is present in an amount of about 5 wt. % to about 40 wt. %.

21. 14. The electrical connector of claim 13, wherein the fibrous filler comprises glass fibers.

22. 14. The electrical connector of claim 13, wherein the fibrous filler comprises wollastonite.

23. 14. The electrical connector of claim 13, wherein the particulate filler comprises mica.

24. 14. The electrical connector of claim 13, wherein the at least one dielectric filler is present in an amount of about 3 wt. % to about 40 wt. %.

25. The polymer composition is －１ 25. The electrical connector of claim 1, having a melt viscosity of about 10 to about 100 Pa·s determined at a shear rate of 0.15 to 0.5 and a temperature 20° C. above the melting temperature of the at least one polymer.

26. 26. The electrical connector of any of claims 1 to 25, wherein the polymer composition further comprises a laser activatable additive.

27. a radio frequency component configured to operate above about 3 GHz, the radio frequency component including a contact pin; and 27. An electrical connector coupled to a radio frequency component, the electrical connector including at least two opposing walls defining a passageway therebetween, a contact pin of the radio frequency component being received within the passageway of the electrical connector, the opposing walls having a width of about 500 micrometers or less, and the opposing walls being formed from the polymer composition of any of claims 1 to 26.

1. A 5G radio frequency communication system comprising:

28. 28. The 5G radio frequency communication system of claim 27, wherein the radio frequency components are configured to operate above 28 GHz.

29. 28. The 5G radio frequency communication system of claim 27, wherein the radio frequency components include at least one of a front end module or an antenna.

30. 28. The 5G radio frequency communication system of claim 27, wherein the radio frequency component is included in at least one of a base station, a user computing device, a relay station, a repeater, or a 5G smartphone.

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