Multipurpose polyamide polymer compositions and housings for electric vehicles made therefrom

Abstract

A polymer composition containing glass fibers and having an excellent balance of properties is disclosed. The polymer composition exhibits a comparative tracking index greater than about 400 volts and a dielectric strength greater than about 4 kV / mm. In addition, the polymer composition provides excellent surface properties even when molding long parts. The polymer composition may contain at least one stabilizer in combination with calcium phosphate, such as calcium hydroxide phosphate. In one aspect, the calcium phosphate is present in the polymer composition in the form of bone charcoal.

Description

[Technical Field]

[0001] Related Applications

[0001] This application is based on and claims priority to U.S. Provisional Application No. 63 / 442,930, filed February 2, 2023, and U.S. Provisional Application No. 63 / 592,701, filed October 24, 2023, both of which are incorporated herein by reference. [Background technology]

[0002]

[0002] With the advent of electric vehicles and the continuous advancement of other electronic components, various electrical components such as connectors and housings have become increasingly important in recent years. Electric vehicles, including hybrid vehicles, for example, typically have an electric powertrain containing an electric propulsion source, such as thousands of lithium-ion batteries, and at least one electric motor. The electric propulsion source provides high-voltage electrical current that is fed to the motor through one or more power electronics modules. As a result, electric vehicles require the use of numerous electrical connectors, housings for the connectors, and other electrical components used to carry the high-voltage electrical current.

[0003] Polyamide compositions, especially when reinforced with glass fibers, are particularly well suited for producing electrical components and housings for electric vehicles and other industrial applications. In some applications, flame retardancy is desirable. Accordingly, a variety of different flame retardant packages have been developed for blending with polyamide compositions.

[0004]

[0004] However, in other applications, high flame retardancy standards may not be necessary. However, some degree of flame retardancy, including glow-wire resistance, is always required. Other properties that may be important for certain applications include polymer compositions having high dielectric strength, high mechanical properties, and a relatively large operating temperature range, e.g., up to at least 110°C. The polymer compositions should also exhibit some degree of chemical resistance, and in certain applications may desirably be laser-markable. Summary of the Invention [Problem to be solved by the invention]

[0005] Although a variety of polyamide polymer compositions have been formulated, there remains a need for improved compositions having a superior blend of properties such as those described above. [Means for solving the problem]

[0006] Generally, the present disclosure is directed to polyamide compositions that exhibit a unique and beneficial blend of properties. Among other advantages, the polyamide compositions of the present disclosure can be formulated to exhibit glow-wire resistance, high dielectric strength, and a relatively high comparative tracking index. The compositions can be formulated without the inclusion of a flame retardant package.

[0007] For example, in one embodiment, the present disclosure is directed to a polymer composition containing at least one polyamide polymer, a plurality of inorganic fibers, and at least one stabilizer. According to the present disclosure, the polymer composition contains a phosphate, such as calcium phosphate. In one aspect, the phosphate is calcium hydroxide phosphate. The phosphate may be added as such or may be added to the composition as part of a pigment, such as a black pigment. The black pigment may include, for example, bone charcoal. In one embodiment, the pigment may be incorporated into a composition containing the phosphate, or an additional amount of the phosphate may be added separately.

[0008] The polymer composition of the present disclosure may exhibit a glow-wire burn index of about 900°C or greater, e.g., about 960°C or greater, at a wall thickness of 1.5 mm, as measured in accordance with IEC-60695-2-12:2010. The composition may also exhibit a comparative tracking index of about 400 volts or greater, e.g., about 450 volts or greater, e.g., about 500 volts or greater, e.g., about 550 volts or greater, e.g., about 600 volts or greater, as determined in accordance with IEC-60112:2003. The polymer composition may exhibit a dielectric strength of about 4 kV / mm or greater, e.g., about 5 kV / mm or greater, at end of life. Dielectric strength can be measured in accordance with ASTM test D149-09.

[0009] Although it is unclear, it is believed that phosphates, such as calcium hydroxide phosphate, affect one or more properties of the polymer composition in a beneficial manner. For example, the phosphate may be present in the polymer composition in an amount of from about 0.01% to about 4% by weight, such as from about 0.05% to about 2.4% by weight, e.g., from about 0.05% to about 1.2% by weight.

[0010] As noted above, the black pigment incorporated into the polyamide composition may contain bone charcoal from animal bones, such as mammals, and may optionally contain carbon black. The bone charcoal may be present in the polymer composition in an amount of from about 0.01% to about 4% by weight, such as from about 0.05% to about 2.4% by weight, e.g., from about 0.05% to about 1.2% by weight. The carbon black may be present in the polymer composition in a relatively small amount, such as from about 0.001% to about 1% by weight, e.g., from about 0.001% to about 0.5% by weight.

[0011] As noted above, the polymer composition may contain at least one stabilizer. In one aspect, the stabilizer may be a hindered phenolic antioxidant. For example, the hindered phenolic antioxidant may include N,N'-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)). The hindered phenolic antioxidant may be present in the polymer composition in an amount generally ranging from about 0.1% to about 0.7% by weight, for example, from about 0.2% to about 0.5% by weight.

[0012] In one aspect, the at least one stabilizer may be a phosphonate antioxidant. The phosphonate antioxidant may be present alone in the polymer composition or in combination with a hindered phenolic antioxidant. In one embodiment, the phosphonate antioxidant has the following structure: [RP(OR1)2] m (1) wherein R is a monovalent or polyvalent aliphatic, aromatic, or heteroaromatic organic radical; and R is independently a compound of structure (II):

[0013] [ka]

[0014] or the two radicals R1 are a bridging group of structure (III)

[0015] [ka]

[0016] wherein A is a direct bond, O, S, C1- 18 Alkylene (linear or branched), or C1 18 alkylidene (linear or branched); R2 is independently C1 to 12 Alkyl (linear or branched), C1~ 12Alkoxy or C5~ 12 n is 0 to 5 and m is 1 to 4. In one embodiment, R is a cyclohexyl, phenyl, phenylene, or biphenyl radical and R1 is a group of structure (II) where m is 2 and n is 2 to 3.

[0017] The at least one stabilizer may be a light stabilizer, such as a hindered amine light stabilizer, which may have the following general structure:

[0018] [ka]

[0019] wherein R1, R2, R3, and R5 are independently hydrogen, ether groups, ester groups, amine groups, amide groups, alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, cycloalkyl groups, and aryl groups, and these substituents may contain functional groups; examples of functional groups are alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes, or any combination thereof.

[0020] In one embodiment, the hindered amine light stabilizer can include an alkyl-substituted piperidyl compound. For example, the hindered amine light stabilizer can include N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide.

[0021] The polymer composition may also contain metal oxides, such as silicon dioxide particles, which may be present in the polymer composition in an amount of from about 0.001% to about 1.5% by weight, for example, from about 0.001% to about 0.3% by weight.

[0022]

[0016] The polymer composition may also contain a lubricant, which may include a partially saponified ester wax of a C22 to C36 fatty acid.

[0017] The one or more polyamides are generally present in the polymer composition in an amount of about 50% to about 90% by weight. The one or more polyamides present in the polymer composition may be one or more aliphatic polyamides, either alone or in combination with semi-aromatic or fully aromatic polyamides. Aliphatic polyamides that may be present in the polymer composition include nylon-6, nylon-6,6, copolymers thereof, or combinations thereof.

[0023] The inorganic fibers present in the polymer composition may include glass fibers. The glass fibers may be present in an amount of about 5% to about 50% by weight, for example, about 25% to about 35% by weight. In one embodiment, the glass fibers may have an average fiber length of about 150 micrometers to about 600 micrometers.

[0024]

[0019] A wide variety of polymeric articles can be molded from the polymeric compositions of the present disclosure. The polymeric compositions are particularly well suited for being molded into components of electrical devices. The electrical devices can include, for example, conductive components surrounded by a molded polymeric component formed from the polymeric composition of the present disclosure. The molded polymeric component can include a housing surrounding the conductive component.

[0025] In one embodiment, the present disclosure may be directed to producing an electrical interface for an electric vehicle. The electrical interface may include an outer cover defining an interior space. The outer cover may be made of a flame-resistant material, such as aluminum. A polymer housing may be contained within the interior space of the outer cover. The polymer housing may be formed from the polymer composition described above. The polymer housing may be, for example, a junction box, a relay box, or any suitable E-box. In one embodiment, the polymer housing may include a base plate, a housing cover attached to the base plate, and one or more holder assemblies for holding electrical connectors within the housing.

[0026]

[0021] Other features and aspects of the present disclosure are discussed in more detail below. A full and enabling disclosure of the present disclosure is set forth in more detail in the remainder of the specification, including reference to the accompanying drawings. [Brief explanation of the drawings]

[0027] [Figure 1] FIG. 1 is a perspective view of one embodiment of an electrical interface that can be made in accordance with the present disclosure. [Figure 2] FIG. 2 is a perspective view of a high voltage charging connector that may incorporate the polymer composition of the present disclosure. [Figure 3] FIG. 3 is a perspective view of a molded electrical housing made in accordance with the present disclosure that can be used to enclose a lithium ion battery. [Figure 4] FIG. 4 is a perspective view of a battery plug board that can be made in accordance with the present disclosure. [Figure 5] FIG. 5 is a perspective assembly view of one embodiment of an electrical distribution box in which the polymer composition of the present disclosure can be employed. DETAILED DESCRIPTION OF THE INVENTION

[0028] Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention. Detailed Description It will be understood by those skilled in the art that the discussion of the present invention is merely a description of exemplary embodiments and is not intended as a limitation of the broader aspects of the present invention.

[0029]

[0025] Generally, the present disclosure is directed to polyamide polymer compositions containing at least one polyamide resin in combination with reinforcing fibers. While reinforcing fibers can improve the mechanical properties of a polymer composition, the presence of reinforcing fibers can adversely affect other properties, such as the comparative tracking index. In this regard, various other additives and ingredients are included in the polymer composition to produce a polymer composition having excellent mechanical properties combined with a beneficial blend of other properties, such as a relatively high comparative tracking index. According to the present disclosure, for example, a polymer composition containing one or more polyamide polymers and reinforcing fibers may also contain at least one stabilizer, such as a blend of different stabilizers. In addition, the polymer composition may contain calcium phosphate. The calcium phosphate may be present in a colorant (e.g., a pigment) and / or may be added separately. The polymer composition may also contain one or more lubricants.

[0030] It has been discovered that polymer compositions formulated in accordance with the present disclosure not only have good comparative tracking index properties, but also produce parts with excellent surface appearance. Among particular advantages, large or long molded parts can be produced, having at least one dimension greater than about 0.25 m, e.g., greater than about 0.5 m, e.g., greater than about 0.75 m, e.g., greater than about 1 m, with excellent surface quality and exhibiting little or no warpage after molding or after being in service, and after exposure to high temperatures.

[0031]

[0027] Polymer compositions formulated according to the present disclosure can function at temperatures ranging from, for example, -40°C to greater than 110°C, e.g., up to 150°C. It is believed that the combination of calcium phosphate with at least one stabilizer, and optionally with a lubricant, may control nucleation or crystallinity so that parts made from the polymer composition do not warp in high-temperature environments. The polymer compositions may generally exhibit a comparative tracking index greater than about 400V, e.g., greater than about 450V, e.g., greater than about 500V, e.g., greater than about 550V, e.g., even greater than 600V. Indeed, it has also been discovered that polymer compositions of the present disclosure can maintain a relatively high comparative tracking index even after heat aging. For example, after 3,000 hours of heat aging at 150°C, a polymer composition or molded article made according to the present disclosure may exhibit a comparative tracking index of, for example, 600V or greater, yet still greater than about 500V, e.g., greater than about 550V.

[0032] The dielectric strength of the polymer composition, measured at end of life, may also be greater than about 4 kV / mm, for example greater than about 4.5 kV / mm, for example greater than about 5 kV / mm, for example greater than about 5.5 kV / mm, and typically less than about 10 kV / mm. The polymer composition may exhibit a glow wire resistance at a wall thickness of 1.5 mm greater than about 900°C, for example greater than about 920°C, for example greater than about 940°C, for example greater than about 960°C, and typically less than about 1,500°C. In one embodiment, when calcium phosphate is incorporated into a colorant, particularly a black pigment, polymeric articles made from the polymer composition may be laser-markable.

[0033] Among other advantages, all of the above properties can be obtained without the need to include flame retardants in the formulation. For example, in one embodiment, the polymer composition may be free of phosphorus-based flame retardants and free of metal phosphinates, such as aluminum diethylphosphinate. Even without the flame retardant, the polymer composition can be formulated to exhibit an HB flammability rating at a thickness of 0.8 mm according to Underwriters Laboratory Test 94.

[0034] Due to their excellent flame retardant properties, excellent mechanical properties, and / or excellent thermal stability properties combined with improved melt processing properties, the polymer compositions of the present disclosure are well suited for fabricating all types of articles and components. The polymer compositions are particularly well suited for producing all types of electrical components. Such components can include high-voltage powertrain connectors and / or charging connectors for electric vehicles and other devices capable of operating using lithium-ion batteries. The polymer compositions are also well suited for producing housings for containing electrical components. In one embodiment, the polymer compositions can be used to produce electrical interfaces. The electrical interfaces can be, for example, relay boxes, junction boxes, or any other suitable E-boxes. In one aspect, the polymer compositions can be used to produce polymer housings contained within the interior space of an external case. The external case can be made of a flame-retardant material, such as aluminum. The housing can have relatively large dimensions, for example, at least one dimension greater than about 0.5 m, for example, about 0.75 m to about 3 m, while possessing excellent surface properties and little warping.

[0035] Generally, any suitable polyamide can be incorporated into the polymer composition, which may, for example, include a single polyamide polymer or a mixture of different polyamide polymers.

[0036] Typically, the one or more polyamide polymers are present in the polymer composition in an amount of from about 20% to about 95% by weight, including all 1% increments therebetween. For example, the polymer composition may contain one or more polyamides in an amount greater than about 40% by weight, such as greater than about 50% by weight, such as greater than about 60% by weight, such as greater than about 65% by weight, such as greater than about 70% by weight, such as greater than about 75% by weight, such as greater than about 80% by weight, and generally less than about 90% by weight, such as less than about 85% by weight, such as less than about 80% by weight, such as less than about 75% by weight.

[0037]

[0033] Polyamides generally have CO-NH bonds in the main chain and are obtained by the condensation of diamines and dicarboxylic acids, or by the ring-opening polymerization of lactams or the self-condensation of aminocarboxylic acids. For example, polyamides may contain aliphatic repeating 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, 1,12-dodecanediamine, etc.; 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, etc.; and combinations thereof. Of course, aromatic and / or alicyclic diamines can also be used. Further, examples of dicarboxylic acid components include aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.), and aliphatic dicarboxylic acids (e.g., adipic acid, sebacic acid, etc.). Examples of lactams include pyrrolidone, aminocaproic acid, caprolactam, undecane lactam, and lauryllactam. Similarly, examples of aminocarboxylic acids include amino fatty acids, which are compounds obtained by ring-opening the aforementioned lactams with water.

[0038] In certain embodiments, "aliphatic" polyamides formed solely from aliphatic monomer units (e.g., diamine and dicarboxylic acid monomer units) are employed. Specific examples of such aliphatic polyamides include, for example, nylon-4 (poly-α-pyrrolidone), nylon-6 (polycaproamide), nylon-11 (polyundecaneamide), nylon-12 (polydodecanamide), nylon-46 (polytetramethylene adipamide), nylon-66 (polyhexamethylene adipamide), nylon-610, and nylon-612. Nylon-6 and nylon-66 are particularly preferred. In one particular embodiment, for example, nylon-6 or nylon-66 can be used alone. In other embodiments, a blend of nylon-6 and nylon-66 may be employed. When such blends are employed, the weight ratio of nylon-66 to nylon-6 is typically from 1 to about 2, in some embodiments from about 1.1 to about 1.8, and in some embodiments, from about 1.2 to about 1.6.

[0039] Aromatic monomer units may be included in polyamides, and such polyamides are considered to be semi-aromatic (containing both aliphatic and aromatic monomer units) or wholly aromatic (containing only aromatic monomer units). For example, suitable semi-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) (PA10T / 12), poly(decamethylene terephthalamide / decamethylenedecane diamide) (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) (PA12T / 1212), poly(dodecamethylene terephthalamide / caprolactam) (PA12T / 6), poly(dodecamethylene terephthalamide / hexamethylene hexanediamide) (PA12T / 66), and the like can be mentioned.

[0040] In one embodiment, the polymer composition contains predominantly aliphatic polyamide polymers which may be blended with one or more semi-aromatic or fully aromatic polyamide polymers.

[0041] The polyamides employed in the polyamide composition are typically crystalline or semi-crystalline in nature and, therefore, have measurable melting points. The melting points may be relatively high so that the composition can provide substantial heat resistance to the resulting part. For example, the polyamides may have melting points of about 220°C or higher, and in some embodiments, from about 240°C to about 325°C, and in some embodiments, from about 250°C to about 335°C. The polyamides may also have relatively high glass transition temperatures, such as about 30°C or higher, in some embodiments, from about 40°C or higher, and in some embodiments, from about 45°C to about 140°C. Glass transition temperatures and melting points can be measured using differential scanning calorimetry ("DSC") as is well known in the art, for example, by ISO test numbers 11357-2:2013 (glass transition) and 11357-3:2011 (melting).

[0042] In one embodiment, the polyamide polymer incorporated into the polymer composition may include post-industrial recycled polymer. For example, recycled polyamide polymer may be obtained from industrial fibers such as tire cord, carpet fibers, textile fibers, films, fabrics such as airbag fabric, etc. The recycled polyamide polymer, when incorporated into the polymer composition, may optionally be combined with virgin polymer. For example, the weight ratio of recycled polyamide polymer to virgin polyamide polymer may be about 1:10 to about 10:1. For example, the amount of recycled polyamide polymer incorporated into the polymer composition may be greater than about 8 wt%, such as greater than about 10 wt%, for example greater than about 12 wt%, such as greater than about 15 wt%, for example greater than about 18 wt%, such as greater than about 20 wt%, for example greater than about 22 wt%, such as greater than about 30 wt%, for example greater than about 40 wt%, for example greater than about 50 wt%, for example greater than about 70 wt%, such as greater than about 80 wt%, for example greater than about 90 wt%, such as up to 100 wt%. The recycled polyamide is generally present in an amount less than about 90 wt%, for example less than about 70 wt%, for example less than about 50 wt%, for example less than about 45 wt%, for example less than about 35 wt%, for example less than about 30 wt%, based on the total amount of polyamide polymer present.

[0043] In addition to one or more polyamide polymers, the polymer compositions of the present disclosure may contain reinforcing fibers, which may be inorganic fibers. For example, the reinforcing or inorganic fibers may be present in the polymer composition in an amount generally greater than about 5 wt %, such as greater than about 10 wt %, such as greater than about 15 wt %, such as greater than about 20 wt %, or such as greater than about 25 wt %. The reinforcing or inorganic fibers may be present in the polymer composition in an amount generally less than about 50 wt %, such as less than about 45 wt %, such as less than about 40 wt %, or such as less than about 35 wt %.

[0044]

[0040] Inorganic fibers generally have high tensile strength relative to their mass. For example, the ultimate tensile strength of the fibers is typically about 1,000 to about 15,000 MPa, and in some embodiments, about 2,000 to about 10,000 MPa, and in some embodiments, about 3,000 to about 6,000 MPa. High strength fibers may be formed from materials that also have electrically insulating properties, such as glass, ceramics (e.g., alumina or silica), as well as mixtures thereof. Glass fibers are particularly suitable, examples of which include E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass, and the like, and mixtures thereof. The inorganic fibers may have a relatively small median diameter, for example, about 50 micrometers or less, in some embodiments, about 0.1 to about 40 micrometers, and in some embodiments, about 2 to about 20 micrometers, as measured using laser diffraction techniques (e.g., using a Horiba LA-960 particle size analyzer) according to ISO 13320:2009. Such small diameter fibers are believed to allow their length to be more easily reduced during melt blending, which can further improve surface appearance and mechanical properties. After formation of the polymer composition, for example, the average length of the inorganic fibers may be relatively short, for example, about 10 to about 800 micrometers, in some embodiments, about 100 to about 700 micrometers, and in some embodiments, about 150 to about 600 micrometers. The inorganic fibers may also have a relatively high aspect ratio (average length divided by nominal diameter), such as from about 1 to about 100, in some embodiments from about 10 to about 60, and in some embodiments, from about 30 to about 50.

[0045] The polymer compositions of the present disclosure also contain a phosphate, such as a hydroxyphosphate. For example, the phosphate can be hydroxyapatite. For example, the phosphate can be an alkali metal or alkaline earth metal phosphate. In one particular embodiment, the phosphate includes calcium phosphate, such as calcium hydroxyphosphate. It is believed that phosphates can provide numerous benefits and advantages when incorporated into polymer compositions. Although unknown, it is believed that phosphates can improve surface properties, prevent warping, and, when combined with pigments, preserve the color of the polymer composition. For example, phosphates can increase color stability. One or more phosphates can be present in the polymer composition in an amount greater than about 0.1 wt %, such as greater than about 0.3 wt %, such as greater than about 0.5 wt %, such as greater than about 0.7 wt %, such as greater than about 0.9 wt %, or such as greater than about 1.1 wt %. The phosphate may be present in the polymer composition in an amount less than about 4.2 wt%, such as less than about 3 wt%, for example less than about 2.4 wt%, such as less than about 2 wt%, for example less than about 1.8 wt%, such as less than about 1.4 wt%, for example less than about 1.2 wt%, such as less than about 1 wt%.

[0046] In one embodiment, a phosphate, such as calcium hydroxide phosphate, may be included in the colorant incorporated into the polymer composition. The colorant may be, for example, a black pigment. In one embodiment, calcium phosphate or calcium hydroxide phosphate may be included in the pigment along with bone char. The bone char pigment may be produced, for example, by destructive distillation of animal bones in the absence of oxygen to form the bone char. The bone char may have an average particle size of about 0.3 micrometers to about 50 micrometers. The bone char pigment may contain about 10 to about 20 weight percent carbon and about 90 to about 80 weight percent calcium phosphate. The calcium phosphate may be incorporated into the polymer composition solely as contained in the bone char, or may be added separately to the polymer composition. In one embodiment, for example, the bone char may be incorporated into the polymer composition in combination with an additional amount of calcium phosphate.

[0047] Bone charcoal may generally be present in the polymer composition in an amount greater than about 0.1 wt%, such as greater than about 0.3 wt%, for example, greater than about 0.5 wt%, for example, greater than about 0.7 wt%, for example, greater than about 0.9 wt%, for example, greater than about 1.1 wt%. Phosphate may be present in the polymer composition in an amount less than about 6 wt%, for example, less than about 4.5 wt%, for example, less than about 2.4 wt%, for example, less than about 2 wt%, for example, less than about 1.8 wt%, for example, less than about 1.4 wt%, for example, less than about 1.2 wt%, for example, less than about 1 wt%.

[0048] In one aspect, the bone charcoal may contain about 70 to about 96% by weight of calcium hydroxyphosphate, with the remainder of the composition consisting essentially of carbon black. For example, carbon black may be present in the bone charcoal in an amount of about 4 to about 30% by weight.

[0049] As noted above, calcium hydroxyphosphate may be added to the polymer composition solely in the form of bone charcoal. Alternatively, calcium hydroxyphosphate may be added separately from the bone charcoal. In yet another embodiment, calcium hydroxyphosphate may be incorporated into the composition by adding not only bone charcoal but also an additional amount of a calcium hydroxyphosphate source.

[0050] In one aspect, the polymer composition contains calcium hydroxyphosphate in an amount of about 0.3 wt. % to about 4.2 wt. % (including all values ​​therebetween in 0.1 wt. % increments). The proportion of calcium hydroxyphosphate present in the polymer composition added in the form of bone charcoal may be in an amount of about 0 wt. % to about 100 wt. % (based on the total amount of calcium hydroxyphosphate present in the composition). For example, the proportion of calcium hydroxyphosphate contained in the polymer composition in the form of bone charcoal may be greater than about 20 wt. %, e.g., greater than about 40 wt. %, e.g., greater than about 60 wt. %, e.g., greater than about 80 wt. The proportion of calcium hydroxyphosphate present in the polymer composition in a form other than bone charcoal (e.g., pure form) may also be about 0 wt. % to about 100 wt. For example, the proportion of calcium hydroxyphosphate present in the polymer composition added other than as bone charcoal may be greater than about 20% by weight, such as greater than about 40% by weight, such as greater than about 60% by weight, such as greater than about 80% by weight, or less than about 90% by weight, such as less than about 70% by weight, such as less than about 50% by weight, such as less than about 30% by weight.

[0051] As mentioned above, carbon black may also be incorporated into the polymer composition in the form of bone charcoal. Carbon black may also be added separately to the polymer composition. The total amount of carbon black present in the polymer composition is generally greater than about 0.001 wt %, e.g., greater than about 0.01 wt %, e.g., greater than about 0.1 wt %, e.g., greater than about 0.3 wt %, e.g., greater than about 0.5 wt %, e.g., greater than about 0.7 wt %, and generally less than about 1 wt %, e.g., less than about 0.7 wt %, e.g., less than about 0.5 wt %. Carbon black can produce a polymer composition with a desirable overall black color, but carbon black can also degrade the comparative tracking index of the overall composition. However, calcium hydroxide phosphate is believed to counteract the effect of carbon black, maintaining the comparative tracking index at a relatively high level, e.g., about 600 V or greater.

[0052] Incorporation of bone charcoal into the polymer compositions of the present disclosure can also provide various functional benefits beyond use as a black pigment or supplementing the amount of calcium phosphate. For example, bone charcoal can render the polymer composition laser markable when molded into an article. For example, bone charcoal pigments can change color, such as to white, upon exposure to laser light.

[0053] The polymer composition may also contain various other components and additives. For example, the polymer composition may contain one or more stabilizers. One example of a stabilizer that may be incorporated into the polymer composition is a heat stabilizer that includes a hindered phenolic antioxidant.

[0054]

[0050] Examples of such phenolic antioxidants include, for example, calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate) (Irganox® 1425); terephthalic acid, 1,4-dithio-,S,S-bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) ester (Cyanox® 1729); triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylhydrocinnamate); hexamethylene bis(3, 5-Di-tert-butyl-4-hydroxyhydrocinnamate (Irganox® 259); 1,2-bis(3,5,di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide (Irganox® 1024); 4,4'-di-tert-octyldiphenamine (Naugalube® 438R); phosphonic acid, (3,5-di-tert-butyl-4-hydroxybenzyl)-, dioctadecyl ester (Irganox® 1093); 1,3,5-trimethyl-2 ,4,6-tris(3',5'-di-tert-butyl-4'hydroxybenzyl)benzene (Irganox® 1330); 2,4-bis(octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine (Irganox® 565); isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1135); octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1135) ) propionate (Irganox® 1076); 3,7-bis(1,1,3,3-tetramethylbutyl)-10H-phenothiazine (Irganox® LO3); 2,2'-methylenebis(4-methyl-6-tert-butylphenol) monoacrylate (Irganox® 3052); 2-tert-butyl-6-[1-(3-tert-butyl-2-hydroxy-5-methylphenyl)ethyl]-4-methylphenyl acrylate (Sumilizer® TM4039);2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (Sumilizer® GS); 1,3-dihydro-2H-benzimidazole (Sumilizer® MB); 2-methyl-4,6-bis[(octylthio)methyl]phenol (Irganox® 1520); N,N'-trimethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide (Irganox® Irganox® 1019); 4-n-octadecyloxy-2,6-diphenylphenol (Irganox® 1063); 2,2'-ethylidenebis[4,6-di-tert-butylphenol] (Irganox® 129); N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide) (Irganox® 1098); diethyl (3,5-di-tert-butyl-4-hydroxyphenyl)phosphonate (Irganox® 1098) (R) 1222); 4,4'-di-tert-octyldiphenylamine (Irganox® 5057); N-phenyl-1-naphthalenamine (Irganox® L05); tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-6-methylphenylthio)-5-methylphenyl]phosphite (Hostanox® OSP1); zinc dinonyldithiocarbamate (Hostanox® VP-ZNCS1); 3,9-bis[1,1-dimethyl-2-[(3- tert-Butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (Sumilizer® AG80); pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox® 1010); ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate (Irganox® 245);3,5-di-tert-butyl-4-hydroxytoluene (Lowinox BHT, Chemtura);

[0055] In one embodiment, the phenolic antioxidant may be N,N'-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)).

[0056]

[0052] One or more hindered phenolic antioxidants may be present in the polymer composition generally in an amount greater than about 0.01 wt%, for example greater than about 0.1 wt%, for example greater than about 0.2 wt%, for example greater than about 0.25 wt%, and generally less than about 2 wt%, for example less than about 0.8 wt%, for example less than about 0.5 wt%.

[0057] In one aspect, the polymer composition may also contain a phosphorus-containing antioxidant. Examples of phosphorus-containing antioxidants include those having the structure: [RP(OR1)2] m (1) Mention may be made of phosphonites having the formula: R is a monovalent or polyvalent aliphatic, aromatic, or heteroaromatic organic radical, such as a cyclohexyl, phenyl, phenylene, and / or biphenyl radical; R1 is independently a compound of structure (II)

[0058] [ka]

[0059] or the two radicals R1 are a bridging group of structure (III)

[0060] [ka]

[0061] Forming During the ceremony, A is a direct bond, O, S, C1~ 18 Alkylene (linear or branched), or C1 18 alkylidene (linear or branched); R2 is independently C1~ 12 Alkyl (linear or branched), C1~ 12 Alkoxy or C5~ 12 is cycloalkyl; n is 0 to 5, in some embodiments 1 to 4, and in some embodiments 2 to 3; m is 1 to 4, in some embodiments 1 to 3, and in some embodiments 1 to 2 (eg, 2).

[0062]

[0054] Particularly preferred are compounds prepared according to the preceding requirements by the Friedel-Crafts reaction of an aromatic or heteroaromatic compound, such as benzene, biphenyl, or diphenyl ether, with a phosphorus trihalide, preferably phosphorus trichloride, in the presence of a Friedel-Crafts catalyst, such as aluminum chloride, zinc chloride, or iron chloride, followed by reaction with a phenol, which is the basis of structures (II) and (III). The mixture of the phosphites produced by the above-specified reaction sequence from an excess of phosphorus trihalide and from the above-mentioned phenols is also expressly included in the present invention.

[0063] In one particular embodiment, R1 is a group of structure (II). Within this group of compounds, compounds of general structure (V):

[0064] [ka]

[0065] Particularly preferred are antioxidants of the formula: where n is as defined above. In one particular embodiment, for example, n in formula (V) is 1, and therefore the antioxidant is tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene-diphosphonate.

[0066] In one embodiment, the antioxidant may be the reaction product of 2,4-di-tert-butylphenol, phosphorus trichloride, and 1,1'-biphenyl. The phosphorus-containing antioxidant or phosphonate may be present in the polymer composition in an amount greater than about 0.01 wt.%, such as greater than about 0.05 wt.%, for example, greater than about 0.08 wt.%, for example, greater than about 0.12 wt.%, for example, greater than about 0.15 wt.%, for example, greater than about 0.18 wt.%. The phosphorus-containing antioxidant is generally present in an amount less than about 2 wt.%, for example, less than about 1 wt.%, for example, less than about 0.8 wt.%, for example, less than about 0.6 wt.%, for example, less than about 0.4 wt.%.

[0067] Another stabilizer that may be present in the polymer composition is a hindered amine light stabilizer. Examples of light stabilizers that may be incorporated into the present disclosure include benzenedicarboxamides. Light stabilizers may also include alkyl-substituted piperidyl, piperidinyl, or piperazinone compounds, or any compound derived from a substituted alkoxypiperidinyl. Other suitable HALS are those that are derivatives of 2,2,6,6-tetramethylpiperidine. Specific preferred examples of HALS include 2,2,6,6-tetramethyl-4-piperidinone, 2,2,6,6-tetramethyl-4-piperidinol, bis-(2,2,6,6-tetramethyl-4-piperidinyl)-sebacicate, a mixture of esters of 2,2,6,6-tetramethyl-4-piperidinol and a fatty acid, and bis-(2,2,6,6-tetramethyl-4-piperidinyl)-succinate. tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylic acid, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, N,N'-bis- (2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6-diamine, ~2.2'-[(2.2.6.6-tetramethyl-4-piperidinyl)-imino]-bis-[ethanol], ~5-(2.2.6.6-tetramethyl-4-piperidinyl)-2-cyclo-undecyl-oxazole), ~2,2,4,4 tetramethyl-21-oxo-7-oxa-3.20-diazadispiro[5.1. 11.2]heneicosane-20-propionic acid dodecyl ester and 2.2.4.4 tetramethyl-21-oxo-7 mixture; oxa-3,20-diazadispiro[5,1,11,2]-heneicosane-20-propionic acid; tetradecyl ester, ~diacetam 5 (CAS Registry Number: 76505-58-3), ~propanedioic acid, [(4-methoxyphenyl)methylene]-, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, ~1,3-benzenedicarboxamide, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), ~3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidine-2,5-dione, ~formamide, N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl, ~3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)-pyrrolidine-2,5-dione, 1,5-Dioxaspiro(5,5)undecane-3,3-dicarboxylic acid, bis(2,2,6,6-tetramethyl-4-peridinyl) ester, 1,5-Dioxaspiro(5,5)undecane-3,3-dicarboxylic acid, bis(1,2,2,6,6-pentamethyl-4-peridinyl) ester, Bis(1,2,2,6,6-pentamethyl-4-piperidyl)(3,5-di-t-butyl-4-hydroxybenzyl)-butylpropanedioate, Tetrakis-(1,2,2,6,6-pentamethyl-4-piperi 1,2,3,4-butanetetracarboxylic acid, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) ester, 1,2,3,4-butanetetracarboxylic acid, 1,2,3-tri(1,2,2,6,6-pentamethyl-4-piperidinyl)-4-tridecyl ester, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dione, N-2,2,6,6-tetramethyl- butyl-4-piperidinyl-N-amino-oxamide, 4-acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine, 1,5,8,12-tetrakis[2',4'-bis(1'',2'',2'',6'',6''-pentamethyl-4"-piperidinyl(butyl)amino)-1',3',5'-triazin-6'-yl]-1,5,8,12-tetraazadodecane, 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetra-methyl-piperazinone) (Good rite 3034), propanamide, 2-methyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-[(2,2,6,6-tetramethyl-4-piperidinyl)amino], oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl][2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]], poly[(6-morpholine-S-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-4 -piperidinyl)-imino]hexamethylene-[(2.2.6.6-tetramethyl-4-piperidinyl)-imino]], ~poly[(6-morpholino-s-triazine-2.4-diyl)[1.2.2.6.6-penta-methyl-4-piperidyl)imino]-hexamethylene[(2,2,6,6 tetra-methyl-4-piperidyl)imino]], ~polymethylpropyl-3-oxy-[4(2.2.6.6-tetramethyl)-piperidinyl)]-siloxane, a-methylstyrene and n-(2.2.6.6-tetramethyl-piperidinyl) Copolymer of N-stearyl-4-maleimide and N-stearyl-4-maleimide, polymer with 1,2,3,4-butanetetracarboxylic acid, 8,8,8',8'-tetramethyl-2,4,8,10-tetraoxaspiro[5,5]undecane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester, polymer with 1,2,3,4-butanetetracarboxylic acid, 8,8,8',8'-tetramethyl-2,4,8,10-tetraoxaspiro[5,5]undecane-3,9-diethanol, 2,2,6,6-tetramethyl -4-piperidinyl ester polymers, ~7-oxa-3,20-diazadispiro[5,1,11,2]heneicosan-21-one, oligomers of 2,2,4,4-tetramethyl-20-(oxiranylmethyl), ~1,3,5-triazine-2,4,6-triamine, N,N''-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]-bis[N,N''-dibutyl-N,N''-bis(1.2.2.6.6-pentamethyl-4-piperidinyl), ~1,3-propanediamine, N,N-1,2-ethanediylbis-, polymers with 2,4,6-trichloro-1,3,5-triazine, reaction products with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, ~1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-, polymers with 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butanamine, and Reaction products with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, ~2,9,11,13,15,22,24,26,27,28-decaazatricyclo[21,3,1,110,14]octacosa-1(27),10,12,14(28),23,25-hexaene-12,25-diamine, N,N'-bis(1,1,3,3-tetramethylbutyl)-2,9,15,22-tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-, ~1,1,1"-(1,3,5-triazine- Polymers with 2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,5,5-tetramethylpiperazinone), 1,1,1''-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethylenediyl)tris(3,3,4,5,5-tetramethylpiperazinone), 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-, and 2,4,6-trichloro-1,3,5-triazine , 3-bromo-1-propene, reaction products with n-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, oxidized, hydrogenated, ~ alkenes, (C20-24)-4 alpha-, polymers with maleic anhydride, reaction products with 2,2,6,6-tetramethyl-4-piperidinamine, ~ N-2,2,6,6-tetramethyl-4-piperidinyl-N-amino-oxamide; 4-acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine; HALS PB-41 or mixtures thereof.

[0068] In one particular embodiment, the hindered amine light stabilizer includes an alkyl-substituted piperidyl compound. For example, the compound may be a di- or tricarboxylic acid (ester) amide, such as N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3-benzenedicarboxamide (Nylostab® S-EED).

[0069]

[0061] One or more light stabilizers may generally be present in the composition in an amount greater than about 0.01% by weight, for example greater than about 0.05% by weight, for example greater than about 0.08% by weight, and generally less than about 2% by weight, for example less than about 1% by weight, for example less than about 0.8% by weight, for example less than about 0.5% by weight, for example less than about 0.3% by weight, for example less than about 0.2% by weight.

[0070] In one embodiment, the polyamide polymer composition may also contain a lubricant. Any suitable lubricant may be incorporated into the polymer composition. In one aspect, the lubricant may include a partially saponified ester wax. For example, the lubricant may include a partially saponified ester wax of a C22 to C36 fatty acid. The fatty acid may include, for example, montan wax. In one aspect, the lubricant may include 1-methyl-1,3-propanediyl ester. The wax may have an acid value of about 9 mg KOH / g to about 14 mg KOH / g.

[0071]

[0063] The lubricant may be present in the polymer composition generally in an amount greater than about 0.08 wt%, for example greater than about 0.1 wt%, for example greater than about 0.2 wt%, for example greater than about 0.3 wt%, for example greater than about 0.4 wt%, and generally less than about 2.5 wt%, for example less than about 2 wt%, for example less than about 1.5 wt%, for example less than about 1 wt%, for example less than about 0.8 wt%.

[0072] Another component that may optionally be included in the polymer composition is metal oxide particles, such as silicon dioxide particles. The metal oxide particles or silicon dioxide particles may be present in a relatively small amount. For example, the particles may be present in the polymer composition in an amount greater than about 0.001 wt %, such as greater than about 0.005 wt %, such as greater than about 0.008 wt %, such as greater than about 0.01 wt %, or greater than about 0.03 wt %. The particles are generally present in an amount less than about 1.5 wt %, such as less than about 1 wt %, such as less than about 0.8 wt %, such as less than about 0.5 wt %, such as less than about 0.3 wt %, or such as less than about 0.2 wt %.

[0073]

[0065] Various additional additives may be included in the polyamide composition, such as impact modifiers, compatibilizers, particulate fillers (e.g., inorganic fillers), pigments, and / or other materials added to enhance properties or processability.

[0074] In one embodiment, the polymer composition is formulated to have certain flame-controlling properties. For example, the polymer composition may exhibit slow horizontal burning on a 0.8 mm thick specimen at a burn rate of less than about 3 inches per minute, or burning ceases before the 5-inch mark. For example, the polymer composition may exhibit a UL94 HB rating. These properties can be exhibited by a polymer composition that does not contain a flame retardant. For example, in one embodiment, the polymer composition may be free of phosphorus-based flame retardants. For example, the polymer composition may be formulated to be free of metal phosphonates, such as aluminum diethylphosphonate.

[0075] Alternatively, one or more flame retardants may be incorporated into the polymer composition. For example, the polymer composition may contain a metal phosphinate in combination with a nitrogen synergist and zinc borate, as described above. The nitrogen synergist may be, for example, melamine polyphosphate.

[0076]

[0068] The polyamide, inorganic fibers, and other additives may be melt-processed or blended together. These components may be fed separately or in combination into an extruder, which may include at least one rotatably mounted screw housed within a barrel (e.g., a cylindrical barrel) and define a feed section and a melt section located downstream from the feed section along the length of the screw. Fibers may optionally be added at a location downstream from the point at which the polyamide is fed (e.g., a hopper). If desired, a flame retardant may also be added to the extruder downstream from the point at which the polyamide is fed. One or more of the extruder sections are typically heated, for example, within a temperature range of about 200°C to about 450°C, in some embodiments, about 220°C to about 350°C, and in some embodiments, about 250°C to about 350°C, to form the composition. The screw speed may be selected to achieve a desired residence time, shear rate, melt process temperature, and the like. For example, the screw speed may range from about 50 to about 800 rpm ("revolutions per minute"), in some embodiments, from about 70 to about 150 rpm, and in some embodiments, from about 80 to about 120 rpm. The apparent shear rate during melt blending is also about 100 s -1 ~about 10,000 seconds -1 and in some embodiments, in the range of about 500 seconds -1 ~about 5000 seconds -1 , in some embodiments, about 800 seconds -1 ~about 1200 seconds -1 The apparent shear rate may be in the range of 4Q / πR 3 where Q is the volumetric flow rate of the polymer melt ("m 3 / sec") and R is the radius ("m") of the capillary (e.g., extruder die) through which the molten polymer flows.

[0077] The resulting polyamide composition, regardless of the particular manner in which it is formed, may have excellent thermal properties. For example, the melt viscosity of the polyamide composition may be low enough to allow it to flow easily into mold cavities of small dimensions. In one particular embodiment, the polyamide composition is melted at a temperature of 1000 s. -1 The composition may have a melt viscosity of about 400 to about 1,000 Pascal seconds ("Pa·s"), and in some embodiments, about 450 to about 900 Pa·s, and in some embodiments, about 500 to about 800 Pa·s, measured at a shear rate of 100°C. Melt viscosity can be measured at 15°C above the melting point of the composition (e.g., 285°C) according to ISO Test No. 11443:2005.

[0078] The polyamide polymer compositions of the present disclosure can be used to produce all different types of molded members and molded parts. Examples of articles that can incorporate the polymer compositions are illustrated in Figures 1-5. Referring to Figure 1, for example, one embodiment of a junction box, relay box, or other E-box 50 is shown. The E-box 50 can form part of an electrical interface, including an optional outer cover that covers the entire assembly, as shown in Figure 1. The optional outer cover can be made, for example, from a flame-retardant material, such as aluminum, and can define an interior space. The E-box 50 can be contained within the interior space of the outer cover.

[0079] As shown, E-box 50 includes a housing cover 52 attached to a base plate 54. E-box 50 may further include various internal members 56, including a holder assembly 58. Holder assembly 58 is for holding various different electrical components, such as electrical connectors 60. E-box 50 may be made from the polymer composition of the present disclosure. For example, the entire E-box assembly may be made from the polymer composition, or various members may be made from the polymer composition.

[0080]

[0072] The E-box 50 may serve as an electrical interface to an electric vehicle. For example, the E-box 50 may serve as an energy and load management device for a battery system. The E-box 50 may be contained within the battery system of the electric vehicle, for example, located on top of a battery module.

[0081]

[0073] Referring now to Figure 2, a high-voltage charging plug or connector 10 is illustrated. As shown, charging plug 10 is in electrical communication with voltage source 12 and connected to electric vehicle 14. Charging plug or connector 10 may include a connector portion, which includes electrical pins that electrically connect with high-voltage circuitry contained within electric vehicle 14. A protective or insulating member extends from a base and surrounds at least a portion of the electrical pins contained within charging plug 10. At least the base of the protective member may be comprised of a polymer composition of the present disclosure. The polymer composition of the present disclosure may also be used to produce various other components contained within charging plug 10.

[0082] In one embodiment, the polymer compositions of the present disclosure can also be used to produce other housings containing electrical components. For example, referring to FIG. 3, a portion of a battery housing 30 is shown. The battery housing 30 may include a variety of different complex shapes, all of which can be molded from the polymer compositions of the present disclosure. Similarly, FIG. 4 illustrates a battery plug board 40 that can also be molded from the polymer compositions of the present disclosure. The battery plug board 40 can, in one embodiment, form a portion of the housing for a battery and can be used to connect the battery to an electrical connector.

[0083] In addition to the structures shown in Figures 1-4, various other electrical components, particularly those well suited for electric vehicles, can also employ the polymer compositions of the present disclosure. For example, in Figure 5, one embodiment of a battery system is shown, including, for example, a main relay 3, a main fuse 4, a shunt 5, a heating relay 6, a pre-charge relay 7, and a pre-charge resistor 8. The system can also include a relay box, which in this particular embodiment is formed from a housing including a base 1 and a top cover 2. Of course, it should be understood that the box can be a unitary member or can contain other parts. Optionally, the base 1 and / or the top cover 2 can be made from the polymer compositions of the present disclosure.

[0084]

[0076] In the illustrated embodiment, the positive circuit includes a main relay 3 and a main fuse 4 connected in series. The main fuse 4 is electrically connected to the positive output terminal (not shown) of the battery module. The upper cover 2 includes a first box cover 21 and a second box cover 25 that communicate with each other, where the first box cover 21 covers a first area and the second box cover 25 covers a second area. The first box cover 21 and the second box cover 25 can be connected to form a stepped structure so that the resulting box has a regular shape. The main fuse 4 can be connected in series with the main relay 3 via a connection string 31 to form a positive circuit, with the input string of the positive circuit fixedly supported on the first boss.

[0085]

[0077] The outer wall of the top cover 2 has inwardly recessed grooves 23 at the corners where the first box cover 21 and the second box cover 25 are connected. The groove 23 at the upper left corner of the first box cover 21 connects to the input string of the positive circuit, and the grooves 23 at the upper left and upper right corners of the second box cover 25 connect to the input and output strings of the negative circuit, respectively. The top cover 2 and the base 1 are then fixedly connected by bolts. Specifically, the diagonal positions of the receiving groove have bosses 125 and 127, and the diagonal positions of the top cover 2 are recessed inward to form mounting grooves. Preferably, a partition plate 120 is provided on the combination bosses and positioned between the input string of the heating circuit and the output string of the positive circuit to achieve physical isolation between the heating circuit and the positive circuit and improve the reliability of the distribution box. In addition, the box further includes an adapter plug 9. The positive circuit, negative circuit, heating circuit and pre-charging circuit are all connected to the external control unit via adapter plug 9 for communication, thereby avoiding chaotic wiring inside the box and reducing the amount of wiring harness used. [Example]

[0086]

[0078] The present disclosure may be better understood with reference to the following examples. Test methods for the examples Tensile modulus, tensile stress, and tensile elongation at break: Tensile properties can be tested according to ISO 527:2019 (technically equivalent to ASTM D638-14). Modulus and strength measurements may be made on the same test strip sample having a length of 80 mm, a thickness of 10 mm, and a width of 4 mm. The test temperature may be 23°C, and the test speed may be 1 or 5 mm / min.

[0087] Comparative Tracking Index ("CTI"): The comparative tracking index (CTI) can be determined in accordance with International Standard IEC 60112-2020 to provide a quantitative indication of a composition's ability to function as an electrical insulator under wet and / or contaminated conditions. In determining a composition's CTI rating, two electrodes are placed on a molded test specimen. A voltage difference is then established between the electrodes while a 0.1% aqueous ammonium chloride solution is dropped onto the specimen. The maximum voltage that five specimens can withstand without failure during a test period of 50 drops is determined. Test voltages range from 100 to 600 V in 25 V increments. The voltage value that causes failure after 50 drops of electrolyte is the "comparative tracking index." This value provides an indication of the material's relative tracking resistance. In accordance with UL 746A, a nominal part thickness of 3 mm is considered representative of performance at other thicknesses.

[0088] UL94: The specimen is supported vertically and a flame is applied to the bottom of the specimen. The flame is applied for 10 seconds, then removed until burning ceases, at which point the flame is reapplied for another 10 seconds and then removed. Two sets of five specimens are tested. Sample size is 125 mm long, 13 mm wide, and 0.8 mm thick, or as specified. The two sets are conditioned before and after aging. For unaged tests, each thickness is tested after conditioning for 48 hours at 23°C and 50% relative humidity. For aged tests, five samples of each thickness are tested after conditioning for 7 days at 70°C.

[0089] The following is one embodiment of a polymer blend according to the present disclosure.

[0090] [Table 1]

[0091] As shown above, the samples exhibited an exceptional balance of properties.

[0084] These and other modifications and variations to the present invention may be practiced by those skilled in the art without departing from the spirit and scope of the invention, as more particularly set forth in the appended claims. In addition, it is to 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 by way of example only and is not intended to limit the invention, as further set forth in the appended claims. [Explanation of symbols]

[0092] 50 E-Box 52 Housing cover 54 base plate 56 Internal parts 58 Holder Assembly 60 Electrical Connector 10 Charging plug, connector 12 Voltage Source 14 Electric Vehicles 30 Battery Housing 40 Battery Plug Board 1 base 2 Top cover 3 Main Relay 4 Main fuse 5 Shunt 6 Heating Relay 7 Pre-charge relay 8 Pre-charging resistors 9 Adapter Plug 21 First Box Cover 23 Groove 25 Second Box Cover 31 Connecting Column 120 Divider Plate 125, 127 Boss

Claims

1. 1. A polymer composition comprising at least one polyamide polymer, a plurality of inorganic fibers, at least one stabilizer, and a phosphate salt, a glow-wire flammability index of about 900°C or higher at a wall thickness of 1.5 mm when measured according to IEC-60695-2-12:2010; a comparative tracking index of about 600 volts or higher, as determined in accordance with IEC 60112:2003; and Dielectric strength of 4 kV / mm or greater The composition exhibits the following.

2. 2. The polymer composition of claim 1, wherein the phosphate comprises calcium hydroxyphosphate and is present in the composition in an amount of from about 0.01% to about 4% by weight, such as from about 0.05% to about 2.4% by weight, for example, from about 0.05% to about 1.2% by weight.

3. 3. The polymer composition of claim 1 or 2, comprising bone charcoal from animal bones.

4. 4. The polymer composition of claim 3, wherein the bone charcoal is present in the polymer composition in an amount of from about 0.01% to about 4% by weight, such as from about 0.05% to about 2.4% by weight, for example, from about 0.05% to about 1.2% by weight.

5. The polymer composition of any one of claims 1 to 4, comprising carbon black in an amount of from about 0.001% to about 1% by weight.

6. The polymer composition of any one of claims 1 to 5, wherein the at least one stabilizer comprises a hindered phenolic antioxidant.

7. 7. The polymer composition of claim 6, wherein the hindered phenolic antioxidant comprises N,N'-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)).

8. 8. The polymer composition of claim 6 or 7, wherein the hindered phenolic antioxidant is present in the polymer composition in an amount of from about 0.1 wt % to about 0.7 wt %, for example from about 0.2 wt % to about 0.5 wt %.

9. The at least one stabilizer has the following structure: [R-P(OR １ ) ２ ] ｍ (1) and a phosphonate having the formula: During the ceremony, R is a monovalent or polyvalent aliphatic, aromatic, or heteroaromatic organic radical; R １ independently represents structure (II) 【Chemistry 1】 or a compound of two radicals R １ has the structure (III) 【Chemistry 2】 and forming a bridging group of During the ceremony, A is a direct bond, O, S, C １ ~ １８ Alkylene (linear or branched), or C １ ~ １８ alkylidene (linear or branched); R ２ are independently １ ~ １２ Alkyl (linear or branched), C １ ~ １２ Alkoxy, or C ５ ~ １２ is cycloalkyl; n is 0 to 5; The polymer composition according to any one of claims 1 to 8, wherein m is 1 to 4.

10. R is a cyclohexyl, phenyl, phenylene, or biphenyl radical; R １ is a group of structure (II), wherein m is 2 and n is 2-3.

11. The at least one stabilizer comprises a light stabilizer, the light stabilizer having the following general structure: 【Transformation 3】 (In the formula, R １ , R ２ , R ３ , and R ５ are independently hydrogen, ether groups, ester groups, amine groups, amide groups, alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, cycloalkyl groups, and aryl groups, and these substituents may contain functional groups; examples of functional groups are alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes, or any combination thereof.

10. The polymer composition of claim 1, comprising one or more of:

12. 12. The polymer composition of claim 11, wherein the light stabilizer comprises an alkyl-substituted piperidyl compound.

13. The polymer composition of claim 11, wherein the light stabilizer comprises N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide.

14. 14. The polymer composition according to any one of claims 1 to 13, further comprising silicon dioxide particles present in an amount of from about 0.001 wt. % to about 1.5 wt. %, for example from about 0.001 wt. % to about 0.3 wt. %.

15. The polymer composition of any one of claims 1 to 14, further comprising a lubricant.

16. 16. The polymer composition of claim 15, wherein the lubricant comprises a partially saponified ester wax of a C22 to C36 fatty acid.

17. 17. The polymer composition of any one of claims 1 to 16, wherein the at least one polyamide polymer comprises from about 50 wt.% to about 80 wt.% of the composition, and the inorganic fibers comprise from about 5 wt.% to about 50 wt.% of the composition.

18. The polymer composition according to any one of claims 1 to 17, wherein the polymer composition does not contain a phosphorus-based flame retardant.

19. The polymer composition of any one of claims 1 to 18, wherein the polymer composition does not contain a metal phosphinate.

20. The polymer composition of claim 1 , wherein the polyamide polymer is an aliphatic polyamide polymer.

21. 21. The polymer composition of claim 20, wherein the aliphatic polyamide polymer is nylon-6, nylon-6,6, copolymers thereof, or combinations thereof.

22. 22. The polymer composition of claim 21, wherein the aliphatic polyamide polymer is present with a semi-aromatic or fully aromatic polyamide polymer.

23. 23. The polymer composition of any one of claims 1 to 22, wherein the inorganic fibers comprise glass fibers and are present in the polymer composition in an amount of about 25 wt.% to about 35 wt.%, and the glass fibers have an average fiber length of about 150 micrometers to about 600 micrometers.

24. The polymer composition of any one of claims 1 to 23, wherein the polymer composition is laser markable.

25. an exterior cover defining an interior space; and a polymer housing contained within the interior space of the outer cover; 1. An electrical interface for an electric vehicle, comprising: An electrical interface for an electric vehicle as described above, wherein the polymer housing is formed from the polymer composition of any one of claims 1 to 24.

26. 26. The electrical interface for an electric vehicle of claim 25, wherein the polymer housing comprises a junction box or a relay box.

27. 27. The electrical interface for an electric vehicle according to claim 25 or 26, wherein the outer cover comprises aluminum.

28. 28. The electrical interface for an electric vehicle of claim 25, 26, or 27, wherein the polymer housing includes a base plate attached to a housing cover, and the housing includes at least one holder assembly for holding an electrical connector.

Images