Thermoplastic materials having high dielectric constant
Incorporating metallic or metal-coated non-metallic mineral fibers into thermoplastic materials addresses the challenge of achieving high Dk and low Df with maintained mechanical properties and prevents equipment wear, resulting in effective wireless communication applications.
Patent Information
- Application Number
- PCT/CN2025/071516
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-01-10
- Filing Date
- 2025-01-09
- Publication Date
- 2025-07-17
AI Technical Summary
Developing thermoplastic materials with high dielectric constant (Dk) and low dissipation factor (Df) while maintaining desirable mechanical properties and avoiding equipment wear during processing is challenging, as high dosages of conventional ceramic fillers cause mechanical property deterioration and wear issues.
Incorporating a small amount of metallic fibers or metal-coated non-metallic mineral fibers into thermoplastic materials, which enhances Dk without significantly increasing Df and reduces wear on processing equipment.
The thermoplastic composition achieves a high Dk and low Df with improved mechanical properties, such as toughness, without causing equipment wear during processing.
Smart Images

Figure PCTCN2025071516-FTAPPB-I100001 
Figure PCTCN2025071516-FTAPPB-I100002 
Figure PCTCN2025071516-FTAPPB-I100003
Abstract
Description
THERMOPLASTIC MATERIALS HAVING HIGH DIELECTRIC CONSTANTFIELD OF INVENTION
[0001] The present invention relates to a thermoplastic composition comprising a thermoplastic resin component and an inorganic filler component, which exhibits a high dielectric constant and a low dissipation factor. The present invention also relates to use of the thermoplastic composition in wireless communication applications such as in base station antennas and high-frequency electronic devices, and to articles prepared from the thermoplastic composition.BACKGROUND OF THE INVENTION
[0002] Materials having a high dielectric constant (Dk) and low dissipation factor (also referred to as loss tangent, Df) are advantageous for wireless communication applications such as antennas and high-frequency electronic devices. A high dielectric constant enables a reduction in size of the target devices such as antenna, while a low dissipation factor minimizes energy loss (e.g., heat) and / or maximizes energy radiated.
[0003] Certain high-Dk thermoplastic materials have been developed with incorporation of dielectric fillers, such as ceramic fillers. However, a high dosage is generally required for such ceramic fillers, which may inevitably cause deteriorated mechanical properties, especially toughness. Further, the ceramic fillers generally have a relatively high density and Mohs hardness. For that reason, the high dosage of ceramic fillers may also result in a wear problem in compounding equipment during the processing of the thermoplastic materials. However, a relatively lower content of the ceramic filler will provide very limited Dk enhancement.
[0004] For example, EP3591004 A1 describes a thermoplastic composition having a dielectric constant (Dk) of from 3.0 to 8.0 between 1 and 5 gigahertz (GHz) , which comprises from 15 wt%to 70 wt%of a dielectric filler. The dielectric filler as disclosed in the patent application includes a ceramic filler, particularly titanium dioxide (TiO2) , barium titanate (BaTiO3) or a combination thereof.
[0005] KR100627248 B1 describes a high-Dk polymer composite comprising barium titanate with a carboxyl functional group introduced with surface modification as the dielectric filler. The content of the surface-modified barium titanate in the high dielectric polymer composite may be from 20 to 60 vol%.
[0006] It is also known that incorporation of carbon nanotubes filler into thermoplastic materials can give rise to significant increase of dielectric constant (Dk) , which however may result in an undesirable increase in dissipation factor (Df) , even to a higher extent.
[0007] For example, WO2022181696 A1 describes a resin composition including a thermoplastic resin and a carbon nanotube. The resin composition has a dielectric constant (Dk) of 4.50 or larger and dissipation factor (Df) of up to 0.10 or larger, at a frequency of 76.5 GHz.
[0008] It is still very challenging to develop thermoplastic materials which have a high dielectric constant (Dk) and a low dissipation factor (Df) , while desirable mechanical and processing properties of the materials are maintained.SUMMARY OF THE INVENTION
[0009] It is an object of the present invention to provide a thermoplastic material having a high dielectric constant (Dk) and a low dissipation factor (Df) , which preferably has desirable mechanical properties (e.g., toughness) , and will not cause wear problem of compounding equipment during the processing.
[0010] It was surprisingly found by the inventors that the object can be achieved by incorporation of a small amount of metallic fiber or metal coated non-metallic mineral fiber into thermoplastic materials, which allows a high Dk without excessive increase in Df.
[0011] Metallic fibers and metal coated non-metallic mineral fibers are known, which have been proposed as conductive fillers in thermoplastic materials to improve the performance related to the electrically conductive property, such EMI shielding. Use of metallic fibers or metal coated non-metallic mineral fibers in thermoplastic materials for improving the performance related to the dielectric property is not known in the art.
[0012] Accordingly, in the first aspect, the present invention provides a thermoplastic composition, comprising
[0013] (A) a thermoplastic resin component,
[0014] (B) one or more filler components, consisting of
[0015] (B1) from 1%to 7%by weight of a metallic fiber and from 10%to 60%by weight of a non-metallic mineral filler, and / or
[0016] (B2) from 1%to 10%by weight of a metal coated non-metallic mineral fiber and from 0 to 60 %by weight of non-metallic mineral filler, and
[0017] (C) from 0 to 10%by weight of an additional additive component,
[0018] each amount being based on the total weight of the thermoplastic composition.
[0019] In some embodiments of the first aspect, the present invention provides a thermoplastic composition, comprising
[0020] (A) a thermoplastic resin component, selected from
[0021] (A1) polyesters,
[0022] (A2) polyamides, or
[0023] a combination thereof,
[0024] (B) one or more filler components, consisting of
[0025] (B1) from 1%to 7%by weight of a metallic fiber and from 10%to 60%by weight of a non-metallic mineral fiber, and / or
[0026] (B2) from 1%to 10%by weight of a metal coated non-metallic mineral fiber and from 0 to 60 %by weight of non-metallic mineral fiber, and
[0027] (C) from 0 to 10%by weight of an additional additive component,
[0028] each amount being based on the total weight of the thermoplastic composition.
[0029] In some exemplary embodiments of the first aspect, the present invention provides a thermoplastic composition, comprising
[0030] (A) a thermoplastic resin component, selected from
[0031] (A1) polyesters,
[0032] (A2) polyamides, or
[0033] a combination thereof,
[0034] (B) one or more filler components, consisting of
[0035] (B1) from 2%to 5%by weight of a metallic fiber and from 20%to 40%by weight of a non-metallic mineral fiber, and / or
[0036] (B2) from 2%to 6%by weight of a metal coated non-metallic mineral fiber and from 0 to 40%by weight of non-metallic mineral fiber, and
[0037] (C) 0 to 5%by weight of an additional additive component,
[0038] each amount being based on the total weight of the thermoplastic composition.
[0039] In the second aspect, the present invention relates to use of the thermoplastic composition as described herein in wireless communication applications, such as in base station antennas and high-frequency electronic devices.
[0040] In the third aspect, the present invention relates to a method for producing articles, particularly articles in wireless communication applications, such as base station antennas and high-frequency electronic devices, by using the thermoplastic composition as described herein.
[0041] In the fourth aspect, the present invention relates to articles produced using the thermoplastic composition as described herein, particularly articles in wireless communication applications, such as base station antennas and high-frequency electronic devices.DETAILED DESCRIPTION OF THE INVENTION
[0042] The present invention will be described in detail hereinafter. It is to be understood that the present invention can be embodied in many different ways and shall not be construed as limited to the embodiments set forth herein.
[0043] The singular forms “a” , “an” and “the” include plural referents unless the context clearly dictates otherwise. The terms “comprise” , “comprising” , etc. are used interchangeably with “contain” , “containing” , etc. and are to be interpreted in a non-limiting, open manner. That is, e.g., further components or elements can be present. The expressions “consists of” or “consisting of” or cognates can be embraced within “comprises” or “comprising” or cognates.
[0044] Different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred may be combined with any other feature or features described generally or indicated as being preferred.
[0045] Herein, any reference to “some embodiments” means that a particular component, amount, composition or feature described in connection with the embodiments is included in some exemplary embodiments of the present invention. Thus, appearance of the phrase “in some embodiments” or similar phrases in various places throughout the description are not necessarily all referring to the same embodiments, but may. Furthermore, the component, amount, composition or feature may be combined in any suitable manners as would be apparent to the skilled person from the disclosure in more embodiments.
[0046] Thermoplastic Composition
[0047] In the first aspect, the present invention provides a thermoplastic composition, comprising
[0048] (A) a thermoplastic resin component,
[0049] (B) one or more filler components, consisting of
[0050] (B1) from 1%to 7%by weight of a metallic fiber and from 10%to 60%by weight of a non-metallic mineral filler, and / or
[0051] (B2) from 1%to 10%by weight of a metal coated non-metallic mineral fiber and from 0 to 60 %by weight of non-metallic mineral filler, and
[0052] (C) from 0 to 10%by weight of an additional additive component,
[0053] each amount being based on the total weight of the thermoplastic composition.
[0054] (A) Thermoplastic Resin
[0055] There is no particular restriction to the thermoplastic resin component useful for the thermoplastic composition according to the present invention. Suitable examples of the thermoplastic resin component may include, but are not limited to, polyesters, polyamides, or a combination thereof.
[0056] (A1) Polyester
[0057] Suitable polyesters for the thermoplastic composition according to the present invention may be any of known thermoplastic polyester resins.
[0058] A typical group of polyesters are polyesters based on an aromatic dicarboxylic acid and an aliphatic or aromatic dihydroxy compound, particularly based on an aromatic dicarboxylic acid and an aliphatic dihydroxy compound.
[0059] Examples of the aromatic dicarboxylic acids for deriving those polyesters are 2, 6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, or any combinations thereof, preferably terephthalic acid. Those aromatic dicarboxylic acids may have one or more substituents on the aromatic ring, e.g. by halogen, such as chlorine or bromine, or by C1-C4-alkyl, such as methyl, ethyl, iso-or n-propyl, or n-, iso-or tert-butyl. Up to 30 mol%, preferably not more than 10 mol%, of the aromatic dicarboxylic acids may be replaced by aliphatic or cycloaliphatic dicarboxylic acids, such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
[0060] Examples of the aliphatic dihydroxy compounds are aliphatic or cycloaliphatic diols having from 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, for example 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol and neopentyl glycol, or any combinations thereof.
[0061] Particularly, polyalkylene terephthalates are useful as the thermoplastic resin component in the thermoplastic composition according to the present invention. Preferably, the polyalkylene terephthalates are those based on terephthalic acid or substituted terephthalic acid and aliphatic diols having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, for example 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol and neopentyl glycol, or any combinations thereof.
[0062] Among those, particular preference is given to polyethylene terephthalate (PET) , polypropylene terephthalate (PPT) and polybutylene terephthalate (PBT) , or any combinations thereof. Preference is also given to PET and / or PBT which may comprise, as other monomer units, up to 1%by weight, preferably up to 0.75%by weight, of 1, 6-hexanediol and / or 2-methyl-1, 5-pentanediol.
[0063] The viscosity number of the polyesters (A) is generally in the range from 50 to 220, preferably from 80 to 160 cm3 / g, as measured in 0.5%strength by weight solution in a phenol / o-dichlorobenzene mixture in a weight ratio of 1 : 1 at 25 ℃ in accordance with ISO 1628.
[0064] Another typical group of polyesters are polycarbonates, which are well-known polymers comprising structural unit (s) of one or more dihydroxy compounds, e.g., dihydroxy aromatic compounds, joined by carbonate linkages, and may be homopolycarbonates, copolycarbonates, and (co) polyester carbonates.
[0065] Generally, the polycarbonates may be homopolycarbonates or copolycarbonates based on the bisphenols of the general formula (I) :
[0066] HO-Z-OH (I)
[0067] wherein Z is a divalent organic radical having 6 to 30 carbon atoms, which contains one or more aromatic groups.
[0068] The bisphenols according to the general formula (I) may be dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, indane bisphenols, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides and α, α′-bis (hydroxyphenyl) diisopropylbenzenes. Derivatives of those bisphenols via alkylation or halogenation on their aromatic rings are also examples of bisphenols according to the general formula (I) .Particularly, examples of bisphenols according to the general formula (I) may include, but are not limited to, hydroquinone, resorcinol, 4, 4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (3, 5-dimethyl-4-hydroxyphenyl) methane, bis (3, 5-dimethyl-4-hydroxyphenyl) sulfone, 1, 1-bis (3, 5-dimethyl-4-hydroxyphenyl) -p / m-diisopropylbenzene, 1, 1-bis (4-hydroxyphenyl) -1-phenyl-ethane, 1, 1-bis (3, 5-dimethyl-4-hydroxyphenyl) cyclohexane, 1, 1-bis (4-hydroxyphenyl) -3-methylcyclohexane, 1, 1-bis (4-hydroxyphenyl) -3, 3-dimethylcyclohexane, 1, 1-bis (4-hydroxyphenyl) -4-methylcyclohexane, 1, 1-bis (4-hydroxyphenyl) cyclohexane, 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane, 2, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 2, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2, 2-bis (4-hydroxyphenyl) propane (i.e. bisphenol A) , 2, 2-bis (3-chloro-4-hydroxyphenyl) propane, 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 2, 4-bis (3, 5-dimethyl-4-hydroxy-phenyl) -2-methylbutane, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (i.e. bisphenol M) , α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene and indanebisphenol.
[0069] Among those, preference is given to homopolycarbonates based on bisphenol A, homopolycarbonates based on 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane, or copolycarbonates based on the two monomers, bisphenol A and 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane.
[0070] (A2) Polyamide
[0071] Suitable polyamides for the thermoplastic composition according to the present invention may be any of known thermoplastic polyamide resins.
[0072] A typical group of polyamides are those having repeating units of formula (II) :
[0073] in which
[0074] R1 is a hydrocarbylene group having from 3 to 29 carbon atoms, preferably from 5 to 17 carbon atoms, more preferably from 5 to 11 carbon atoms.
[0075] Particularly, R1 in formula (II) is an alkylene or cycloalkylene group, more preferably an alkylene group, having a number of carbon atoms as described herein.
[0076] The polyamide having repeating units of formula (II) is typically derived from at least one aliphatic monomer selected from the group consisting of (1) lactams having from 4 to 30 carbon atoms and (2) amino acids having from 4 to 30 carbon atoms.
[0077] Suitable lactams preferably have from 6 to 18 carbon atoms, more preferably from 6 to 12 carbon atoms. Examples of the lactams may include, but are not limited to, caprolactam, caprylolactam, caprinolactam, undecanolactam, laurolactam, or any combinations thereof.
[0078] Suitable amino acids preferably have from 6 to 18 carbon atoms, more preferably from 6 to 12 carbon atoms. Examples of the amino acids may include, but are not limited to, 2-aminoadipic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or any combinations thereof.
[0079] Another typical group of polyamides are those having repeating units of formula (III) :
[0080] in which
[0081] R2 is a hydrocarbylene group having from 4 to 24 carbon atoms, preferably from 4 to 18, and R3 is a hydrocarbylene group having from 4 to 30 carbon atoms, preferably from 4 to 20.
[0082] Particularly, R2 in formula (III) is an alkylene or cycloalkylene group, preferably an alkylene group, having a number of carbon atoms as described herein. Alternatively or additionally, R3 in formula (III) is an alkylene, cycloalkylene or arylene group, preferably an alkylene or arylene group, having a number of carbon atoms are described herein.
[0083] The polyamide having repeating units of formula (III) is typically derived from monomers which are selected from the group consisting of (1) a combination of dicarboxylic acids having from 6 to 32 carbon atoms and diamines having from 4 to 24 carbon atoms and (2) a combination of dicarboxylic acid chlorides having from 6 to 32 carbon atoms and diamines having from 4 to 24 carbon atoms.
[0084] Suitable aliphatic diamines preferably have from 4 to 24 carbon atoms, more preferably from 4 to 18 carbon atoms, for example 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms. The aliphatic diamines may be linear or branched aliphatic diamines. Examples of the aliphatic diamines may include, but are not limited to, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 1, 13-tridecanediamine, 1, 14-tetradecanediamine, 1, 16-hexadecanediamine, 1, 18-octadecanediamine, 1, 20-eicosanediamine, 1, 22-docosanediamine, 2-methylpentane-1, 5-diamine, 3-methylpentane-1, 5-diamine, 2, 5-dimethylhexane-1, 6-diamine, 2, 4-dimethylhexane-1, 6-diamine, 3, 3-dimethylhexane-1, 6-diamine, 2, 2-dimethylhexane-1, 6-diamine, 2, 2, 4-trimethylhexane-1, 6-diamine, 2, 4, 4-trimethylhexane-1, 6-diamine, 2, 3-dimethylheptane-1, 7-diamine, 2, 4-dimethylheptane-1, 7-diamine, 2, 5-dimethylheptane-1, 7-diamine, 2, 2-dimethylheptane-1, 7-diamine, 2-methyloctane-1, 8-diamine, 1, 3-dimethyloctane-1, 8-diamine, 1, 4-dimethyloctane-1, 8-diamine, 2, 4-dimethyloctane-1, 8-diamine, 3, 4-dimethyloctane-1, 8-diamine, 4, 5-dimethyloctane-1, 8-diamine, 2, 2-dimethyloctane-1, 8-diamine, 3, 3-dimethyloctane-1, 8-diamine, 4, 4-dimethyloctane-1, 8-diamine, 2, 4-diethylhexane-1, 6-diamine, 5-methylnonane-1, 9-diamine, or any combinations thereof.
[0085] Suitable dicarboxylic acids may be aliphatic or aromatic and have from 6 to 32, preferably 6 to 22 carbon atoms, for example 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Examples of the dicarboxylic acids may include, but are not limited to, adipic acid, pimelic acid, sebacic acid, undecanedioic acid, dodecandioic acid, tridecanedioic acid, tetradecandioic acid, pentadecandioic acid, hexadecanedioic acid, octadecandioic acid, terephthalic acid, isophthalic acid, or any combinations thereof.
[0086] Suitable dicarboxylic acid chlorides may be aliphatic or aromatic and have from 6 to 32, preferably 6 to 22 carbon atoms, for example 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Examples of the dicarboxylic acid chlorides may include, but are not limited to, adipoyl dichloride, heptanedioyl dichloride, azelaoyl dichloride, sebacoyl dichloride, undecanedioyl dichloride, lauroyl dichloride, or any combinations thereof.
[0087] For example, the polyamides may be at least one selected from the group consisting of PA6, PA7, PA8, PA9, PA11, PA12, PA410, PA510, PA513, PA515, PA46, PA56, PA66, PA69, PA510, PA 512, PA514, PA610, PA612, PA613, PA614, PA618, PA636, PA88, PA810, PA812, PA1010, PA1012, PA1014, PA1018, PA1210, PA1212, PA1214, PA1218, PA1313, PA1410, PA1412, PA1414, PA1418, PA4T, PA6T, PA9T, PA10T, PA11T, or any combinations thereof.
[0088] Useful polyamide may also be a blend of polyamides as described above or a copolymerized polyamide (co-polyamide) . There is no limitation to the type of the co-polyamide, which may be for example a block copolymer, a random copolymer, a graft copolymer or an alternating copolymer. Examples of the co-polyamide may include, but are not limited to, PA6 / PA66, PA6 / PA636, PA6 / PA510, PA6 / PA610, PA6 / PA612, PA6 / PA1010, PA66 / PA410, PA66 / PA510, PA66 / PA610, PA66 / PA612, PA66 / PA1010, PA6 / 6T (mole ratio of 6 to 6T from 1: 99 to 99: 1) , PA66 / 6T (mole ratio of 66 to 6T from 1: 99 to 99: 1) , PA6T / 6I (mole ratio of 6T: 6I from 99: 1 to 65: 35) .
[0089] In some embodiments according to the present invention, the polyamide having the repeating units of formula (I) as described herein is particularly useful. Among those, preference is given to polyamide having the repeating units of formula (I) in which R1 having 5 to 11 carbon atoms.
[0090] The polyamides may have any suitable molecular weights without being limited. Preferably, the relative viscosity of the polyamide is from 1.8 to 4.0, as measured in 96 %by weight sulfuric acid at 25℃.
[0091] Generally, the component (A) may be present in the thermoplastic composition according to the present invention in an amount of from 40%to 99%by weight, for example from 45%to 97%by weight or from 50%to 97%by weight, based on the total weight of the thermoplastic composition.
[0092] Particularly, in some embodiments wherein the thermoplastic composition according to the present invention comprises the filler component (B1) as described herein, the component (A) may be present in an amount of from 45%to 89%by weight, from 50%to 85%by weight or from 60 to 80%by weight, based on the total weight of the thermoplastic composition.
[0093] Alternatively, in some other embodiments wherein the thermoplastic composition according to the present invention comprises the filler component (B2) as described herein, the component (A) may be present in an amount of from 45%to 97%by weight, from 50%to 97%by weight, or from 60 to 97%by weight, based on the total weight of the thermoplastic composition.
[0094] (B) Filler
[0095] The thermoplastic composition according to the present invention may comprise one or more filler components (B) , which consist of (B1) from 1%to 7%by weight of a metallic fiber and from 10%to 60%by weight of a non-metallic mineral filler, and / or (B2) from 1%to 10%by weight of a metal coated non-metallic mineral fiber and from 0 to 60 %by weight of non-metallic mineral filler, each amount being based on the total weight of the thermoplastic composition.
[0096] It will be undertood that the thermoplastic composition according to the present invention may comprise any non-metallic mineral fillers in a total amount of no more than 60%by weight, no more than 55%by weight, no more than 50%by weight, or no more than 40%by weight, based on the total weight of the thermoplastic composition.
[0097] (B1) Filler Component
[0098] Suitable metallic fibers for the filler component (B1) may be for example steel fibers, stainless steel fibers, copper fibers, brass fibers, bronze fibers, aluminum fibers, chromium fibers, nickel fibers, silver fibers, titanium fibers, or any combinations thereof. The combination of those fibers may be mixed fibers or alloy fibers, for example fibers made of any two or more metals as mentioned.
[0099] Among those, preference is given to steel fibers and stainless steel fibers. For the purpose of the present invention, commercially available metallic fibers may be used without restrictions. It will be understood that the commercially available metallic fibers may contain certain non-metal substances originating the production of the metallic fibers.
[0100] Preferably, the metallic fiber for the filler component (B1) may be used in an amount of from 1%to 6%by weight, or from 2%to 5%by weight, based on the total weight of the thermoplastic composition.
[0101] Suitable non-metallic mineral filler for the filler component (B1) may be of various types without particular restrictions, such as fibers, whiskers, platelets and particles. Amount those, non-metallic mineral fibers are particularly suitable as the non-metallic mineral filler in the filler component (B1) . Examples of the non-metallic mineral fibers may include, but are not limited to glass fibers, basalt fibers, carbon fibers, alumina fibers, asbestos fibers, boron fibers, ceramic fibers, kenaf fibers, jute fibers, bamboo fibers, flax fibers, hemp fibers, bagasse fibers, cellulosic fibers, silica fibers, silicon carbide fibers, sisal fibers, coir fibers, or any combinations thereof, among which glass fibers, basalt fibers, carbon fibers, or any combinations thereof are preferable.
[0102] Preferably, the non-metallic mineral filler may be used in an amount of from 15%to 55%by weight, from 20%to 50%by weight, or from 20%to 40%by weight, based on the total weight of the thermoplastic composition.
[0103] In some embodiments, the one or more filler components (B) in thermoplastic composition according to the present invention may consist of the filler component (B1) , i.e., the metallic fiber and the non-metallic mineral filler in respective amounts as described above.
[0104] (B2) Filler Component
[0105] Suitable metal coated non-metallic mineral fibers for the filler component (B2) may be metallized non-metallic mineral fibers, which have a core of non-metallic mineral fiber and a coating of metal partially or fully on the surface of the non-metallic mineral fibers. The metal as the coating may be selected from the group consisting of aluminum, iron, copper, silver, nickel, manganese, zirconium, chromium, tin, titanium, zinc, gold, platinum, palladium, or any combinations or alloys thereof. Among those, preference is given to aluminum, nickel or silver. The non-metallic mineral fiber as the core may be selected from the group consisting of glass fibers, basalt fibers, carbon fibers, alumina fibers, asbestos fibers, boron fibers, ceramic fibers, kenaf fibers, jute fibers, bamboo fibers, flax fibers, hemp fibers, bagasse fibers, cellulosic fibers, silica fibers, silicon carbide fibers, sisal fibers, coir fibers, or any combinations thereof. Among those, preference is given to glass fibers, basalt fibers, carbon fibers, or any combinations thereof.
[0106] Preferably, the metal coated non-metallic mineral fibers may have a metal content of from 5%to 70%by weight, preferably from 30%to 60%by weight, more preferably from 40%to 55%by weight, based on the total weight of the metal coated non-metallic mineral fibers.
[0107] For the purpose of the present invention, the metal coated non-metallic mineral fibers may be commercially available or produced in accordance with known methods.
[0108] Preferably, the metal coated non-metallic mineral fibers may be used in an amount of from 1%to 8%by weight, or from 2%to 6%by weight, based on the total weight of the thermoplastic composition.
[0109] Optionally, a non-metallic mineral filler may be used in combination with the metal coated non-metallic mineral fiber as the filler component (B2) , which may be of various types without particular restrictions, such as fibers, whiskers, platelets and particles, preferably non-metallic mineral fibers. Examples of the non-metallic mineral fibers may include, but are not limited to glass fibers, basalt fibers, carbon fibers, alumina fibers, asbestos fibers, boron fibers, ceramic fibers, kenaf fibers, jute fibers, bamboo fibers, flax fibers, hemp fibers, bagasse fibers, cellulosic fibers, silica fibers, silicon carbide fibers, sisal fibers, coir fibers, or any combinations thereof, among which glass fibers, basalt, carbon fibers or any combinations thereof are preferable.
[0110] Preferably, the non-metallic mineral filler may be used in an amount of no more than 55%by weight, for example no more than 50%by weight, or no more than 40%by weight, based on the total weight of the thermoplastic composition.
[0111] When the non-metallic mineral filler is used in combination with the metal coated non-metallic mineral fiber as the filler component (B2) , the non-metallic mineral filler may be comprised preferably in an amount of from 15%to 55%by weight, from 20%to 50%by weight, or from 20%to 40%by weight, based on the total weight of the thermoplastic composition.
[0112] There is no particular restriction to the fiber length and the fiber diameter of any fibers described for the filler component herein. For example, chopped fibers having a length in the range of from 1 to 10 mm, preferably from 2 to 6 mm, or continuous fibers may be used as starting material of the filler. The fibers will be broken down during processing, for example kneading the thermoplastic composition, to a length of a few hundreds of microns as present in the obtained moldings. The fiber diameter is generally in the range of from 3 to 35 μm, for example from 7 to 13 μm or from 15 to 30 μm. The fibrous fillers may have a cross section with a conventional aspect ratio, for example in the range of from 1 : 1 to 5 : 1.
[0113] In some embodiments, the one or more filler components (B) in thermoplastic composition according to the present invention may consist of the filler component (B2) , i.e., the metal coated non-metallic mineral fibers and the optional non-metallic mineral filler in respective amounts as described above.
[0114] (C) Additives
[0115] Optionally, the thermoplastic composition according to the present invention may comprise an additional additive component, for example, antioxidant, lubricant, nucleating agent, colorant, UV absorber, hindered amine light stabilizer, release agent, anti-dripping agent, impact modifier, compatibilizing agent, plasticizer, surfactant, flame retardant, flame retardant synergist, coupling agent, antimicrobial agent, antistatic agents or any combinations thereof.
[0116] The additional additive, if comprised, may be present in conventional amounts. For example, the thermoplastic composition may comprise the additional additive in a total amount of no higher than 10%by weight, or no higher than 5%by weight, or no higher than 3%by weight, based on the total weight of the thermoplastic composition.
[0117] For example, the thermoplastic composition according to the present invention comprises an antioxidant. There is no particular restriction to the antioxidant useful for the thermoplastic composition according to present invention, which may be selected from any known antioxidants, for example hindered phenol antioxidants, phosphite antioxidants, phosphonites antioxidants, aromatic amine antioxidants, or any combinations thereof. Examples of useful commercially available UV absorbers may include, but are not limited to, 1098 (N, N′- (hexane-1, 6-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanamide] ) , 1010 (pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) ) , (2, 4-bis [ (dodecylthio) methyl] -o-cresol) , (2, 2-thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate] ) , 168 (tris (2, 4-di-tert-butylphenyl) phosphite) , S-9228 (bis (2, 4-dicumylphenyl) pentaerythritol diphosphite) , TNPP (trisnonylphenol phosphite) , 627 (bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphonite) , S-9228PC (bis (2, 4-dicumylphenyl) pentaerythritol diphosphite) , P-EPQ (tetrakis (2, 4-di-tert-butylphenyl) [1, 1-biphenyl] -4, 4’-diyl bisphosphonite) .
[0118] The antioxidant, if comprised, may be present in an amount of from 0.01%to 5%by weight, for example from 0.1%to 2%by weight, based on the total weight of the thermoplastic composition.
[0119] For example, the thermoplastic composition according to the present invention comprises a lubricant. There is no particular restriction to the lubricant useful for the thermoplastic composition according to present invention, which may be selected from any known lubricants, for example, long-chain fatty acids and salts thereof such as stearic acid or behenic acid and salts thereof, esters or amides of saturated or unsaturated aliphatic carboxylic acids such as long-chain fatty acids, and waxes such as natural waxes, montan waxes, paraffin waxes, polyethylene waxes and polypropylene waxes.
[0120] The lubricant, if comprised, may be present in an amount of from 0.1%to 5%by weight, for example from 0.1%to 2%by weight, based on the total weight of the thermoplastic composition.
[0121] For example, the thermoplastic composition according to the present invention comprises a nucleating agent. There is no particular restriction to the nucleating agent useful for the thermoplastic composition according to present invention, which may be selected from any known nucleating agents, for example talc, boron nitride, mica, kaolin, alkali metal or alkali earth metal carbonates, bicarbonates or sulfates, alkali metal titanates, silicon nitride, and molybdenum disulfide.
[0122] The nucleating agent, if comprised, may be present in an amount of from 0.01%to 5%by weight, preferably from 0.01%to 2%by weight, based on the total weight of the thermoplastic composition.
[0123] For example, the thermoplastic composition according to the present invention may comprise a UV absorber. There is no particular restriction to the UV absorbers useful for the thermoplastic composition according to present invention, which may be selected from any known UV absorbers, for example hydroxyphenyl benzotriazoles, hydroxyphenyl triazines, benzophenones, cyanoacrylates, benzoxazinones, benzylidene malonates, and salicylate esters, or any combinations thereof. Examples of useful commercially available UV absorbers may include, but are not limited to, 328 (2- (2′-hydroxy-3′, 5′-di-tert-amylphenyl) benzotriazole) , 360 (2, 2′-methylene bis [6- (2H-benzotriazol-2-yl) -4-1, 1, 3, 3-tetramethylbutyl) phenol] ) , 900 (2- [2-hydroxy-3, 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole) , 1577 ED (2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxyphenol) , 1600 (2, 4-bis-biphenyl-6- [2-hydroxy-4- (2-ethylhexyloxy) phenyl] -1, 3, 5-triazine) , UV-531 (2-hydroxy-4-cctyloxy benzophenone) , UV-1164 (2- (4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazin-2-yl) -5- (octyloxy) phenol.
[0124] The UV absorber, if comprised, may be present in an amount of from 0.05%to 5%by weight, preferably from 0.1%to 2%by weight, based on the total weight of the thermoplastic composition.
[0125] For example, the thermoplastic composition according to the present invention may comprise a hindered amine light stabilizer (HALS) . There is no particular restriction to the hindered amine light stabilizers useful for the thermoplastic composition according to present invention, which may be selected from any known hindered amine light stabilizers, for example the monomeric, oligomeric and polymeric compounds based on 2, 2, 6, 6-tetramethylpiperidine. Examples of useful commercially available UV absorbers may include, but are not limited to, 944 (poly- {6- [ (1, 1, 3, 3-tetramethylbutyl) amino-1, 3, 5-triazine-2, 4-diyl] [ (2, 2, 6, 6-tetramethyl-4-piperidyl) imino] -1, 6-hexanediyl [ (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) } ) , 2020 (1, 6-hexanediamine, N, N’-bis (2, 2, 6, 6-tetramethyl-4-piperidinyl) -polymer with 2, 4, 6-trichloro-1, 3, 5-triazine, reaction products with N-butyl-1-butanamine and N-butyl-2, 2, 6, 6-tetramethyl-4-piperidinamine) , 123 (bis (1-octyloxy-2, 2, 6, 6-tetramethyl-4-piperidinyl) sebacate) , 770 (bis (2, 2, 6, 6-tetramethyl-4-piperidinyl) sebacate) , 292 (bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate) , UV-3529 (1, 6-hexanediamine, N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidinyl) -, polymer with morpholine-2, 4, 6-trichloro-1, 3, 5-triazine) .
[0126] The hindered amine light stabilizer, if comprised, may be present in an amount of from 0.05%to 3%by weight, preferably from 0.1%to 1%by weight, based on the total weight of the thermoplastic composition.
[0127] Formulations
[0128] It will be understood that any options with respect to species and / or amounts as described herein generally or with preference for the components A) , B) and C) may be combined in any way without a restriction. For example, a combination of a general range of the amount of one component with any preferable ranges of the amounts of other components, or a combination of a preferable range of the amount of one component with general ranges of the amounts of the other components, and so on are included in the present invention.
[0129] Following formulations will be described as examples of the thermoplastic composition according to the present invention.
[0130] In some embodiments, the thermoplastic composition according to the present invention comprises
[0131] (A) a thermoplastic resin component, selected from
[0132] (A1) polyesters,
[0133] (A2) polyamides, or
[0134] a combination thereof,
[0135] (B) one or more filler components, consisting of
[0136] (B1) from 1%to 7%by weight of a metallic fiber and from 10%to 60%by weight of a non-metallic mineral fiber, and / or
[0137] (B2) from 1%to 10%by weight of a metal coated non-metallic mineral fiber and from 0 to 60 %by weight of non-metallic mineral fiber, and
[0138] (C) from 0 to 10%by weight of an additional additive component,
[0139] each amount being based on the total weight of the thermoplastic composition.
[0140] In some further embodiments, the thermoplastic composition according to the present invention comprises
[0141] (A) a thermoplastic resin component, selected from
[0142] (A1) polyesters,
[0143] (A2) polyamides, or
[0144] a combination thereof,
[0145] (B) one or more filler components, consisting of
[0146] (B1) from 1%to 6%by weight of a metallic fiber and from 15%to 55%by weight of a non-metallic mineral fiber, and / or
[0147] (B2) from 1%to 8%by weight of a metal coated non-metallic mineral fiber and from 0 to 55%by weight of non-metallic mineral fiber, and
[0148] (C) from 0 to 10%by weight of an additional additive component,
[0149] each amount being based on the total weight of the thermoplastic composition.
[0150] In yet further embodiments, the thermoplastic composition according to the present invention comprises
[0151] (A) a thermoplastic resin component, selected from
[0152] (A1) polyesters,
[0153] (A2) polyamides, or
[0154] a combination thereof,
[0155] (B) one or more filler components, consisting of
[0156] (B1) from 1%to 6%by weight of a metallic fiber and from 20%to 50%by weight of a non-metallic mineral fiber, and / or
[0157] (B2) from 1%to 8%by weight of a metal coated non-metallic mineral fiber and from 0 to 50%by weight of non-metallic mineral fiber, and
[0158] (C) from 0 to 10%by weight of an additional additive component,
[0159] each amount being based on the total weight of the thermoplastic composition.
[0160] In some preferable embodiments, the thermoplastic composition according to the present invention comprises
[0161] (A) a thermoplastic resin component, selected from
[0162] (A1) polyesters,
[0163] (A2) polyamides, or
[0164] a combination thereof,
[0165] (B) one or more filler components, consisting of
[0166] (B1) from 2%to 5%by weight of a metallic fiber and from 20%to 40%by weight of a non-metallic mineral fiber, and / or
[0167] (B2) from 2%to 6%by weight of a metal coated non-metallic mineral fiber and from 0 to 40%by weight of non-metallic mineral fiber, and
[0168] (C) 0 to 5%by weight of an additional additive component,
[0169] each amount being based on the total weight of the thermoplastic composition.
[0170] In some particular embodiments, the thermoplastic composition according to the present invention comprises
[0171] (A) a thermoplastic resin component, selected from
[0172] (A1) polyalkylene terephthalates or polycarbonates,
[0173] (A2) polyamides, or
[0174] a combination thereof,
[0175] (B) one or more filler components, consisting of
[0176] (B1) from 1%to 7%by weight of a steel fiber or stainless steel fiber and from 10%to 60% by weight of a glass fiber, and / or
[0177] (B2) from 1%to 10%by weight of a metal coated non-metallic mineral fiber and from 0 to 60%by weight of glass fiber, wherein the metal coated non-metallic mineral fiber is selected from aluminum coated non-metallic mineral fibers, nickel coated non-metallic mineral fibers, or silver coated non-metallic mineral fibers, or any combinations thereof, and
[0178] (C) 0 to 10%by weight of an additional additive component,
[0179] each amount being based on the total weight of the thermoplastic composition.
[0180] In some further particular embodiments, the thermoplastic composition according to the present invention comprises
[0181] (A) a thermoplastic resin component, selected from
[0182] (A1) polyalkylene terephthalates or polycarbonates,
[0183] (A2) polyamides, or
[0184] a combination thereof,
[0185] (B) one or more filler components, consisting of
[0186] (B1) from 1%to 6%by weight of a steel fiber or stainless steel fiber and from 15%to 55% by weight of a glass fiber, and / or
[0187] (B2) from 1%to 8%by weight of a metal coated non-metallic mineral fiber and from 0 to 55%by weight of glass fiber, wherein the metal coated non-metallic mineral fiber is selected from aluminum coated non-metallic mineral fibers, nickel coated non-metallic mineral fibers, or silver coated non-metallic mineral fibers, or any combinations thereof, and
[0188] (C) 0 to 10%by weight of an additional additive component,
[0189] each amount being based on the total weight of the thermoplastic composition.
[0190] In some other particular embodiments, the thermoplastic composition according to the present invention comprises
[0191] (A) a thermoplastic resin component, selected from
[0192] (A1) polyalkylene terephthalates or polycarbonates,
[0193] (A2) polyamides, or
[0194] a combination thereof,
[0195] (B) one or more filler components, consisting of
[0196] (B1) from 1%to 6%by weight of a steel fiber or stainless steel fiber and from 20%to 50% by weight of a glass fiber, and / or
[0197] (B2) from 1%to 8%by weight of a metal coated non-metallic mineral fiber and from 0 to 50%by weight of glass fiber, wherein the metal coated non-metallic mineral fiber is selected from aluminum coated non-metallic mineral fibers, nickel coated non-metallic mineral fibers, or silver coated non-metallic mineral fibers, or any combinations thereof, and
[0198] (C) 0 to 10%by weight of an additional additive component,
[0199] each amount being based on the total weight of the thermoplastic composition.
[0200] Preferably, the thermoplastic composition according to the present invention comprises
[0201] (A) a thermoplastic resin component, selected from
[0202] (A1) polyalkylene terephthalates or polycarbonates,
[0203] (A2) polyamides, or
[0204] a combination thereof,
[0205] (B) one or more filler components, consisting of
[0206] (B1) from 2%to 5%by weight of a steel fiber or stainless steel fiber and from 20%to 40% by weight of a glass fiber, and / or
[0207] (B2) from 2%to 6%by weight of a metal coated non-metallic mineral fiber and from 0 to 40%by weight of glass fiber, wherein the metal coated non-metallic mineral fiber is selected from aluminum coated non-metallic mineral fibers, nickel coated non-metallic mineral fibers, or silver coated non-metallic mineral fibers, or any combinations thereof, and
[0208] (C) 0 to 5%by weight of an additional additive component,
[0209] each amount being based on the total weight of the thermoplastic composition.
[0210] Preferably, in any of the embodiments of the formulations as described above, the metal coated non-metallic mineral fibers have a metal content of from 5%to 70%by weight, preferably from 30%to 60%by weight, more preferably from 40%to 55%by weight, based on the total weight of the metal coated non-metallic mineral fibers.
[0211] In any of the embodiments of the formulations as described above, the filler component (B2) may not include the non-metallic mineral filler, or may include the non-metallic mineral filler in an amount of from 15%to 55%by weight, from 20%to 50%by weight, or from 20%to 40%by weight, based on the total weight of the thermoplastic composition.
[0212] It shall be understood that, in any of the embodiments of the formulations as described above, the thermoplastic composition according to the present invention may comprise any non-metallic mineral fillers in a total amount of no more than 60%by weight, for example no more than 55%by weight, no more than 50%by weight, or no more than 40%by weight, based on the total weight of the thermoplastic composition.
[0213] The thermoplastic composition according to the present invention may be processed by any conventional methods without particular restrictions. The method usually includes at least the step of compounding the components as described herein. Compounding per se is a technique which is well known to the skilled person in the art of polymer processing and manufacturing, and comprises preparing plastic materials by mixing and / or blending the components in a molten state. The mixing may be carried out at a rotational speed ranging from 200 rpm to 320 rpm. It is understood in the art that compounding is distinct from blending or mixing processes conducted at temperatures lower than a temperature at which the components become molten. Compounding may, for example, be used to form a masterbatch composition. Compounding may, for example, involve adding a masterbatch composition to a polymer to form a further polymer composition. The compounding may be carried out at a temperature of from 220 ℃to 350 ℃.
[0214] The thermoplastic composition according to the present invention may be processed and shaped into a desired form of articles, for example by molding such as compression molding, injection molding, stretch blow molding, injection blow molding, hollow molding, extrusion, casting or thermoforming.
[0215] The thermoplastic composition according to the present invention may have a dielectric constant (Dk) of at least 3.0, and a dissipation factor (Df) of less than 0.05, preferably less than 0.03, as measured at a frequency of 2.5 GHz in accordance with GB / T 12636-1990.
[0216] Use of the Thermoplastic Composition
[0217] The thermoplastic composition according to the present invention has a high Dk and a low Df, while exhibiting desirable mechanical properties, particularly toughness. The thermoplastic composition according to the present invention will not cause the wear problem in the compounding equipment due to the small dosage of the metallic fiber or metal coated non-metallic mineral fiber as a filler.
[0218] Accordingly, in the second aspect, the present invention relates to use of the thermoplastic composition as described herein in wireless communication applications, such as in base station antennas and high-frequency electronic devices.
[0219] Further, in the third aspect, the present invention relates to a method for producing articles, particularly articles in wireless communication applications, such as base station antennas and high-frequency electronic devices, by using the thermoplastic composition as described herein.
[0220] Articles
[0221] Accordingly, in the fourth aspect, the present invention relates to articles produced using the thermoplastic composition as described herein, particularly articles in wireless communication applications, such as base station antennas and high-frequency electronic devices.
[0222] Embodiments
[0223] Various embodiments are listed below. It will be understood that the embodiments listed below can be combined with all aspects and other embodiments in accordance with the scope of the invention.
[0224] 1. A thermoplastic composition, which comprises
[0225] (A) a thermoplastic resin component,
[0226] (B) one or more filler components, consisting of
[0227] (B1) from 1%to 7%by weight of a metallic fiber and from 10%to 60%by weight of a non-metallic mineral filler, and / or
[0228] (B2) from 1%to 10%by weight of a metal coated non-metallic mineral fiber and from 0 to 60 %by weight of non-metallic mineral filler, and
[0229] (C) from 0 to 10%by weight of an additional additive component,
[0230] each amount being based on the total weight of the thermoplastic composition.
[0231] 2. The thermoplastic composition according to Embodiment 1, wherein the thermoplastic resin component is selected from (A1) polyesters, (A2) polyamides, or a combination thereof.
[0232] 3. The thermoplastic composition according to Embodiment 1, wherein the non-metallic mineral filler is non-metallic mineral fiber.
[0233] 4. The thermoplastic composition according to any of preceding Embodiments, wherein the metallic fiber is comprised in an amount of from 1%to 6%by weight, or from 2%to 5%by weight, based on the total weight of the thermoplastic composition.
[0234] 5. The thermoplastic composition according to any of preceding Embodiments, wherein the metallic fiber is selected from steel fibers, stainless steel fibers, copper fibers, brass fibers, bronze fibers, aluminum fibers, chromium fibers, nickel fibers, silver fibers, titanium fibers, or any combinations thereof, preferably steel fibers or stainless steel fibers.
[0235] 6. The thermoplastic composition according to any of preceding Embodiments, wherein the metal coated non-metallic mineral fiber is comprised in an amount of from 1%to 8% by weight, or from 2%to 6%by weight, based on the total weight of the thermoplastic composition.
[0236] 7. The thermoplastic composition according to any of preceding Embodiments, wherein the metal coated non-metallic mineral fiber has a core of non-metallic mineral fiber and a coating of metal partially or fully on the surface of the core of non-metallic mineral fibers.
[0237] 8. The thermoplastic composition according to Embodiment 7, wherein the coating of metal is selected from the group consisting of aluminum, iron, copper, silver, nickel, manganese, zirconium, chromium, tin, titanium, zinc, gold, platinum, palladium, or any combinations or alloys thereof, preferably aluminum, nickel or silver.
[0238] 9. The thermoplastic composition according to Embodiment 7 or 8, wherein the core of non-metallic mineral fiber is selected from the group consisting of glass fibers, basalt fibers, carbon fibers, alumina fibers, asbestos fibers, boron fibers, ceramic fibers, kenaf fibers, jute fibers, bamboo fibers, flax fibers, hemp fibers, bagasse fibers, cellulosic fibers, silica fibers, silicon carbide fibers, sisal fibers, coir fibers, or any combinations thereof, preferably glass fibers, basalt fibers, carbon fibers, or any combinations thereof.
[0239] 10. The thermoplastic composition according to any of preceding Embodiments, wherein the metal coated non-metallic mineral fiber has a metal content of from 5%to 70%by weight, preferably from 30%to 60%by weight, more preferably from 40%to 55%by weight, based on the total weight of the metal coated non-metallic mineral fiber.
[0240] 11. The thermoplastic composition according to any of preceding Embodiments, wherein the non-metallic mineral filler in (B1) is comprised in an amount of from 15%to 55%by weight, from 20%to 50%by weight, or from 20%to 40%by weight, based on the total weight of the thermoplastic composition.
[0241] 12. The thermoplastic composition according to any of preceding Embodiments, wherein the non-metallic mineral filler in (B2) is comprised in an amount of no more than 55%by weight, no more than 50%by weight, or no more than 40%by weight, based on the total weight of the thermoplastic composition.
[0242] 13. The thermoplastic composition according to any of preceding Embodiments, wherein the non-metallic mineral filler in (B2) , when present, is comprised in an amount of from 15% to 55%by weight, from 20%to 50%by weight, or from 20%to 40%by weight, based on the total weight of the thermoplastic composition.
[0243] 14. The thermoplastic composition according to any of preceding Embodiments, which comprises any non-metallic mineral fillers in a total amount of no more than 60%by weight, for example no more than 55%by weight, no more than 50%by weight, or no more than 40%by weight, based on the total weight of the thermoplastic composition.
[0244] 15. The thermoplastic composition according to any of preceding Embodiments, which comprises 0 to 5%by weight of the additional additive component, based on the total weight of the thermoplastic composition.
[0245] 16. The thermoplastic composition according to any of preceding Embodiments, which has a dielectric constant (Dk) of at least 3.0, and a dissipation factor (Df) of less than 0.05, preferably less than 0.03, as measured at a frequency of 2.5 GHz in accordance with GB / T 12636-1990.
[0246] 17. Use of the thermoplastic composition according to any of preceding Embodiments 1 to 16 in wireless communication applications, such as in base station antennas and high-frequency electronic devices.
[0247] 18. A method for producing articles, particularly articles in wireless communication applications, such as base station antennas and high-frequency electronic devices, by using the thermoplastic composition according to any of preceding Embodiments 1 to 16.
[0248] 19. Articles, particularly articles in wireless communication applications, such as base station antennas and high-frequency electronic devices, produced using the thermoplastic composition according to any of preceding Embodiments 1 to 16.
[0249] EXAMPLES
[0250] Aspects of the present invention will be more fully illustrated by the following Examples, which are set forth to illustrate certain aspects of the present invention and are not to be construed as limiting thereof.
[0251] Materials
[0252] Preparation of Test Specimens
[0253] Test specimens were prepared in accordance with the formulations as shown in Tables 1, 2 and 3 below.
[0254] The compounding was carried out by a Coperion ZSKMC18 twin-screw extruder, with screw diameter of 18 mm and barrel length of 72 cm. All raw materials except the glass fibers (GFs) were mixed and fed into the throat, while the GFs were fed at downstream using a side feeder. The raw materials were melt-extruded under a temperature of 260 ℃ (when the matrix resin is PBT or PA6) , or 290℃ (when the matrix resin is PC) , and pelletized to obtain a thermoplastic composition in a pellet form. The screw speed is 300 rpm.
[0255] The dried pellets were processed in an injection molding machine Haitian MA900 at a melt temperature of 280 ℃ (when the matrix resin is PBT or PA6) , or 310℃ (when the matrix resin is PC) , and then at a mold temperature of 60 ℃ to give test specimens.
[0256] Measurements and Test Methods
[0257] Tensile stress at break and tensile strain at break for specimens having a thickness of 4 mm were measured according to ISO 527-1-2012. Test specimens of type 1 described in ISO 527-1-2012 were used.
[0258] Tensile strength, tensile modulus and elongation at break were measured for specimens having a thickness of 4 mm on the testing machine Z050 (Zwick Roell, Germany) according to ISO 527-1-2012. Test specimens of type 1 described in ISO 527-1-2012 were used.
[0259] Charpy notched impact strength and Charpy unnotched impact strength were measured on the testing machine HIT25P (Zwick Roell, Germany) according to ISO 179-1-2010 via edgewise impact. The test specimens for Charpy unnotched test is type 1 specimen with the dimensions of 80 mm x 10 mm x 4 mm (length × width × thickness) . The test specimens for Charpy notched test are type 1 with notched type A, prepared using automated specimen notching machine Notching ToolTM A-4 (Toyoseiki, Japan) .
[0260] All the test specimens were conditioned at 23 ℃ and 50%relative humidity for 16 hours. The tests were conducted under the same atmosphere as conditioning.
[0261] The dielectric properties, Dk and Df, were measured according to standard SJ20512-1995. The specimen size is 60 mm × 60 mm × 2 mm (length × width × thickness) . The test was performed at Chengdu Enchi Microwave Technology Co., Ltd., using COTRLD518 fixture and Agilent 8363B vector network analyzer.
[0262] The formulations and results for the thermoplastic compositions as tested are summarized in Tables 1, 2, and 3.
[0263] Table 1
[0264] Table 2
[0265] Table 3
[0266] N* means specimen does not break during the test.
[0267] As can be seen from the Tables, a rather high amount of the dielectric filler BaTiO3 (i.e., 10 wt%or even up to 30 wt%) is required to improve the Dk of the PBT materials (R3 and R4) , which however results in a significant deterioration of mechanical performance (e.g., toughness) . The deterioration of mechanical properties cannot be effectively remedied even with incorporation of 30 wt%glass fiber as a reinforcement filler (R5) . Additionally, the high dosage of the dielectric filler BaTiO3 resulted in a wear problem in the compounding equipment during the processing of the thermoplastic materials, due to its high Mohs hardness.
[0268] In contrast, a much lower amount of steel fiber filler or Al-BF filler provided a comparable or even higher Dk of the PBT materials (E1, E3, E5 and E7) than that of the PBT materials R3 and R4, while providing less loss of the mechanical properties of the PBT materials reinforced with glass fiber (E2, E4, E6 and E8) . Additionally, the wear problem of compounding equipment during the processing of the thermoplastic materials was effectively prevented, since those fillers have lower hardness and used in much lower amounts.
[0269] As can also be seen from the Tables, incorporation of a small amount of the WMCNT filler in the PBT material significantly improved the Dk by about 3 times, which however resulted in an excessive increase in Df by about 28 times (R2 vs. R6) .
[0270] It was found that incorporation of a small amount of steel fiber resulted in a slight increase in Df of the PBT material while providing an improvement of Dk (E1 and E3 vs. R1) . Surprisingly, further incorporation of a glass fiber reinforcement filler resulted in less extent of increase in Df while providing further improvement of Dk (E1 vs. E2; E3 vs. E4) . Incorporation of a small amount of Al-BF also provided an improvement of Dk, while resulting in no change of Df (E5 and E7 vs. R1) . Further incorporation of a glass fiber reinforcement filler even resulted in a decrease in Df while providing further improvement of Dk (E6 vs. E5; E8 vs. E7) .
[0271] Additionally, with respect to PA6 as the matrix resin, it was also found that addition of a small amount of Al-BF resulted in a slight increase in Df of the PA material while providing an improvement of Dk (E9 and E11 vs. R7) . However, it was surprising that the obtained PA material could achieve a further significant improvement on Dk, when a proper amount of a glass fiber reinforcement filler is further added (E10 vs. E9; E12 vs. E11) . When it comes to PC as the matrix resin, the obtained PC material also showcased the same phenomenon on the change of Dk and Df (E13 vs. R9; E14 vs. E13) .
[0272] Per the test results set forth above, it can be seen that the thermoplastic composition according to the present application could achieve a high dielectric constant (Dk) and a low dissipation factor (Df) as well as satisfied mechanical properties (e.g., toughness) simultaneously, without occurrence of the wear problem of compounding equipment during the processing.
[0273] It will be apparent to one of ordinary skill in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the present invention. It is intended that the embodiments and examples be considered as exemplary only.
[0274] Thus, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents.
Claims
1.A thermoplastic composition, which comprises(A) a thermoplastic resin component,(B) one or more filler components, consisting of(B1) from 1%to 7%by weight of a metallic fiber and from 10%to 60%by weight of a non-metallic mineral filler, and / or(B2) from 1%to 10%by weight of a metal coated non-metallic mineral fiber and from 0 to 60 %by weight of non-metallic mineral filler, and(C) from 0 to 10%by weight of an additional additive component,each amount being based on the total weight of the thermoplastic composition.2.The thermoplastic composition according to claim 1, wherein the thermoplastic resin component is selected from (A1) polyesters, (A2) polyamides, or a combination thereof.3.The thermoplastic composition according to claim 1, wherein the non-metallic mineral filler is non-metallic mineral fiber.4.The thermoplastic composition according to any of preceding claims, wherein the metallic fiber is comprised in an amount of from 1%to 6%by weight, or from 2%to 5%by weight, based on the total weight of the thermoplastic composition.5.The thermoplastic composition according to any of preceding claims, wherein the metallic fiber is selected from steel fibers, stainless steel fibers, copper fibers, brass fibers, bronze fibers, aluminum fibers, chromium fibers, nickel fibers, silver fibers, titanium fibers, or any combinations thereof, preferably steel fibers or stainless steel fibers.6.The thermoplastic composition according to any of preceding claims, wherein the metal coated non-metallic mineral fiber is comprised in an amount of from 1%to 8%by weight, or from 2%to 6%by weight, based on the total weight of the thermoplastic composition.7.The thermoplastic composition according to any of preceding claims, wherein the metal coated non-metallic mineral fiber has a core of non-metallic mineral fiber and a coating of metal partially or fully on the surface of the core of non-metallic mineral fibers.8.The thermoplastic composition according to claim 7, wherein the coating of metal is selected from the group consisting of aluminum, iron, copper, silver, nickel, manganese, zirconium, chromium, tin, titanium, zinc, gold, platinum, palladium, or any combinations or alloys thereof, preferably aluminum, nickel or silver.9.The thermoplastic composition according to claim 7 or 8, wherein the core of non-metallic mineral fiber is selected from the group consisting of glass fibers, basalt fibers, carbon fibers, alumina fibers, asbestos fibers, boron fibers, ceramic fibers, kenaf fibers, jute fibers, bamboo fibers, flax fibers, hemp fibers, bagasse fibers, cellulosic fibers, silica fibers, silicon carbide fibers, sisal fibers, coir fibers, or any combinations thereof, preferably glass fibers, basalt fibers, carbon fibers, or any combinations thereof.10.The thermoplastic composition according to any of preceding claims, wherein the metal coated non-metallic mineral fiber has a metal content of from 5%to 70%by weight, preferably from 30%to 60%by weight, more preferably from 40%to 55%by weight, based on the total weight of the metal coated non-metallic mineral fiber.11.The thermoplastic composition according to any of preceding claims, wherein the non-metallic mineral filler in (B1) is comprised in an amount of from 15%to 55%by weight, from 20%to 50%by weight, or from 20%to 40%by weight, based on the total weight of the thermoplastic composition.12.The thermoplastic composition according to any of preceding claims, wherein the non-metallic mineral filler in (B2) is comprised in an amount of no more than 55%by weight, no more than 50%by weight, or no more than 40%by weight, based on the total weight of the thermoplastic composition.13.The thermoplastic composition according to any of preceding claims, wherein the non-metallic mineral filler in (B2) , when present, is comprised in an amount of from 15%to 55%by weight, from 20%to 50%by weight, or from 20%to 40%by weight, based on the total weight of the thermoplastic composition.14.The thermoplastic composition according to any of preceding claims, which comprises any non-metallic mineral fillers in a total amount of no more than 60%by weight, for example no more than 55%by weight, no more than 50%by weight, or no more than 40%by weight, based on the total weight of the thermoplastic composition.15.The thermoplastic composition according to any of preceding claims, which comprises 0 to 5%by weight of the additional additive component, based on the total weight of the thermoplastic composition.16.The thermoplastic composition according to any of preceding claims, which has a dielectric constant (Dk) of at least 3.0, and a dissipation factor (Df) of less than 0.05, preferably less than 0.03, as measured at a frequency of 2.5 GHz in accordance with GB / T 12636-1990.17.Use of the thermoplastic composition according to any of preceding claims 1 to 16 in wireless communication applications, such as in base station antennas and high-frequency electronic devices.18.A method for producing articles, particularly articles in wireless communication applications, such as base station antennas and high-frequency electronic devices, by using the thermoplastic composition according to any of preceding claims 1 to 16.19.Articles, particularly articles in wireless communication applications, such as base station antennas and high-frequency electronic devices, produced using the thermoplastic composition according to any of preceding claims 1 to 16.
Citation Information
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