Filler composition and use thereof in polyamide-based materials

Abstract

The present invention relates to a polyamide-based composition comprising, based on the total weight of the polyamide-based composition, from 30% to 84.9% by weight of (A) at least one semi-aromatic polyamide, from 15% to 40% by weight of (B) at least one white pigment and from 0.1% to 30% by weight of (C) at least one crystalline whisker, the mass ratio of the white pigment to the crystalline whisker being from 7 to 1: 1.

Description

Technical Field

[0001] This invention relates to a filler composition and its use in reducing the molding shrinkage of polyamide-based compositions for LED applications, improving the anti-yellowing properties and mechanical properties (e.g., especially tensile modulus) of the polyamide-based compositions. Furthermore, this invention relates to polyamide-based compositions comprising the filler composition. It also includes methods for preparing such polyamide-based compositions and articles prepared therefrom. Background Technology

[0002] In recent years, the light source market has expanded rapidly, especially the light-emitting diode (LED) market, which encompasses a wide range of applications such as LED housings, sockets, reflectors, and reflector panels. One of the key technical requirements for materials leading to LED applications is excellent resistance to yellowing when exposed to heat and light during manufacturing and end-use, particularly at high temperatures (e.g., 240°C to 260°C) for short periods (e.g., 30 min) or at medium temperatures (e.g., 100°C to 120°C) for extended periods (e.g., 500 h). Given molding feasibility and end-use requirements, low molding shrinkage and good mechanical properties, especially high tensile modulus and strength, are also crucial. With advancements in formulation technology, thermoplastic polyamide-based (e.g., polyphthalamide (PPA)-based) compositions have been found to generally meet the corresponding fundamental requirements for LED applications and are widely used in the LED market as an alternative to ceramics.

[0003] With advancements in the modification of polyamide-based materials used to fabricate LED components, much effort has focused on improving colorfastness and mechanical properties. For example, US20130281587A1 discloses a polyamide resin composition comprising (A) a polyamide resin, (B) a white pigment, (C) a sodium phosphate salt, and optionally (D) a filler, such as glass fiber, wherein (C) the sodium phosphate salt contributes to heat and water resistance and eliminates acids generated during molding to improve heat discoloration and hydrolytic stability, and (D) the filler is used to improve the formability and mechanical properties of the composition. JP4525917B2 discloses a polyamide resin composition for molding LED reflectors and an LED reflector, the composition comprising (A) a polyamide resin, (B) titanium dioxide, (C) magnesium hydroxide and (D) a reinforcing material selected from the group consisting of fiber fillers and needle fillers, wherein (C) magnesium hydroxide will suppress discoloration (such as yellowing) and whiteness reduction after heat treatment, and (D) the reinforcing material will provide benefits in improving the intensity, strength and heat resistance of the molded article obtained from the composition.

[0004] However, besides the aforementioned existing technologies, simultaneously achieving improved mechanical properties (e.g., tensile modulus), lower molding shrinkage, and excellent reflectivity performance (e.g., high initial reflectivity and good reflectivity retention after thermal aging) via a relatively low-cost method remains a considerable challenge. The aforementioned technologies cannot meet the requirements for LED applications under harsh conditions, such as continuous operation at 240°C to 260°C or higher for a predetermined period in reflow soldering processes, or continuous use at 100°C to 120°C for 500 hours. Therefore, a gap still exists compared to traditional thermosetting or ceramic materials. There is an urgent need to develop a thermoplastic polyamide-based composition that meets the above requirements and achieves widespread application in the LED field. Summary of the Invention

[0005] The present invention provides a filler composition comprising a white pigment and crystalline whiskers.

[0006] In addition, the present invention relates to the use of the filler composition in polyamide-based materials used in the preparation of LED components.

[0007] Surprisingly, it was found that polyamide-based compositions containing the above-mentioned filler compositions can exhibit significantly reduced dimensional shrinkage during the injection molding process, and can simultaneously achieve a balance of improved mechanical properties (especially tensile modulus), maintenance of initial reflectivity, and suppression of reflectivity degradation when exposed to high temperatures (e.g., 240°C to 260°C) for short periods (e.g., 30 min) or to medium temperatures (e.g., 100°C to 120°C) for long periods (e.g., 500 h).

[0008] This article also provides methods for preparing such polyamide-based compositions and articles prepared therefrom.

[0009] The present invention also provides an LED component made of a polyamide-based composition. It can be manufactured or assembled by a reflow soldering process. Detailed Implementation

[0010] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The definitions or descriptions of groups given above in general terms or within preferred ranges apply to the final product and correspondingly to starting materials and intermediates. These radical definitions may be combined with each other as needed, i.e., combinations of general definitions and / or corresponding preferred ranges and / or embodiments.

[0011] All embodiments and preferred embodiments disclosed herein may be combined as needed and are also considered to be covered within the scope of this invention.

[0012] The terms “one” and “the” are used interchangeably with the term “at least one”. The phrases “at least one of…” and “including at least one of…” followed by a list refer to any single item in the list and any combination of two or more items in the list. Unless otherwise stated, all numerical ranges include non-integer values ​​between their endpoints.

[0013] The term “about” refers to a range of numerical values ​​that a person skilled in the art would consider equivalent to the value in the context of achieving the same function or result.

[0014] Unless otherwise stated, all percentages (%) are "weight percentages".

[0015] Unless otherwise stated, the term "unit" refers to the repeating unit that constitutes a polyamide.

[0016] As used herein, the term "PA" refers to polyamide. The term "PA* / PA**" refers to a copolymer of PA* and PA**.

[0017] The present invention discloses a filler composition comprising a white pigment and crystalline whiskers, wherein the mass ratio of the white pigment to the crystalline whiskers is 7~1:1, preferably 7~3:1.

[0018] The white pigment in this invention may include, but is not limited to, titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, magnesium hydroxide, zirconium hydroxide, zinc sulfate, zinc sulfide, aluminum phosphate, calcium carbonate, magnesium carbonate, and mixtures thereof.

[0019] Preferably, the white pigment can be surface-treated with a coupling agent by existing methods, such as silane coupling agents, titanium coupling agents, acrylate silane coupling agents, epoxy silane coupling agents, and amino silane coupling agents, such as vinyltriethoxysilane, polydimethylsiloxane, 2-aminopropyltriethoxysilane, 2-epoxypropoxypropyltriethoxysilane, and combinations thereof.

[0020] In a preferred embodiment, the white pigment is titanium dioxide, which exhibits better light reflectivity and photostability. The particle size of the titanium dioxide is preferably from 100 nm to 500 nm, more preferably from 200 nm to 400 nm. Titanium dioxide can also be treated with an inorganic surface treatment agent. Surface treatment of titanium dioxide can improve its wettability with alkaline resins (e.g., polyamides). Examples of inorganic surface treatment agents include the group consisting of alumina, silica, zirconium oxide, sodium silicate, sodium aluminate, sodium aluminosilicate, zinc oxide, mica, etc. Inorganic surface treatment agents can be used alone or in combination.

[0021] The crystal whiskers in this invention may include, but are not limited to, potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium sulfate whiskers, and combinations thereof.

[0022] In a preferred embodiment, the crystal whiskers are calcium sulfate whiskers or potassium titanate whiskers.

[0023] Preferably, the crystal whiskers are calcium sulfate whiskers with an aspect ratio of 5 to 40.

[0024] Preferably, the crystal whiskers are potassium titanate whiskers with an aspect ratio of 5 to 50.

[0025] In a preferred embodiment, crystal whiskers can be treated with a surface treatment agent using existing methods to improve their compatibility with basic resins (e.g., polyamides) and the dispersion of the crystal whiskers in a polyamide-based resin matrix. Examples of surface treatment agents may include, but are not limited to, silane coupling agents (such as silanes, epoxysilanes, etc.), titanium coupling agents, organic acids, polyols, silicones, and combinations thereof.

[0026] The present invention also relates to a polyamide-based composition, comprising, based on the total weight of the polyamide-based composition, 30% to 84.9% by weight of (A) at least one semi-aromatic polyamide, 15% to 40% by weight of (B) at least one white pigment, and 0.1% to 30% by weight of (C) at least one crystalline whisker.

[0027] The mass ratio of white pigment to crystal whiskers is 7~1:1, preferably 7~3:1.

[0028] The semi-aromatic polyamides of this invention comprise dicarboxylic acid units, diamine units, and optionally units derived from other monomers, such as amino acid and / or lactam units, and the dicarboxylic acid units or diamine units have aromatic groups. For example, semi-aromatic polyamides comprise aromatic dicarboxylic acid units and aliphatic diamine units, or aliphatic and / or alicyclic dicarboxylic acid units and aromatic diamine units.

[0029] Aromatic dicarboxylic acid units are typically derived from aromatic dicarboxylic acids and / or aromatic dicarboxyl chlorides. Aliphatic dicarboxylic acid units are typically derived from aliphatic dicarboxylic acids and / or aliphatic dicarboxyl chlorides. Alicyclic dicarboxylic acid units are typically derived from alicyclic dicarboxylic acids and / or alicyclic dicarboxyl chlorides.

[0030] Aliphatic or aromatic diamine units can typically be derived from aliphatic or aromatic diamines, respectively.

[0031] Based on the total unit constituting the semi-aromatic polyamide, the amount of other monomers is preferably 0 mol% to 20 mol%, preferably 0 mol% to 15 mol%, and more preferably 0 mol% to 10 mol.

[0032] The aromatic dicarboxylic acid in this invention preferably contains 8 to 20 carbon atoms, more preferably 8 to 14 carbon atoms, such as terephthalic acid, isophthalic acid, naphthalic acid and / or biphenyl acid, more preferably terephthalic acid, a mixture of terephthalic acid and isophthalic acid, naphthalic acid, a mixture of terephthalic acid and naphthalic acid.

[0033] The aliphatic dicarboxylic acids of this invention preferably contain 4 to 36 carbon atoms, more preferably 5 to 36 carbon atoms, most preferably 5 to 20 carbon atoms or 36 carbon atoms, such as 5, 6, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 and / or 36 carbon atoms. Examples of aliphatic dicarboxylic acids are succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid, dimer acids having 36 carbon atoms, and mixtures thereof, more preferably adipic acid, azelaic acid, sebacic acid, dodecanoic acid, and mixtures thereof.

[0034] The alicyclic dicarboxylic acid of the present invention preferably comprises 4 to 20 carbon atoms, more preferably 8 to 20 carbon atoms, and even more preferably comprises a carbon backbone selected from the group consisting of cyclohexane, cyclopentane, cyclohexylmethane, dicyclohexylmethane, bis(methylcyclohexyl), and mixtures thereof, and most preferably selected from the group consisting of cis and trans-cyclopentane-1,3-dicarboxylic acid, cis and trans-cyclopentane-1,4-dicarboxylic acid, cis and trans-cyclohexane-1,2-dicarboxylic acid, cis and trans-cyclohexane-1,3-dicarboxylic acid, cis and trans-cyclohexane-1,4-dicarboxylic acid, and mixtures thereof.

[0035] The aliphatic diamine in this invention can be a straight-chain aliphatic diamine or a branched-chain aliphatic diamine, preferably a straight-chain aliphatic diamine. The aliphatic diamine preferably contains 4 to 36 carbon atoms, more preferably 4 to 22 carbon atoms or 36 carbon atoms, and most preferably 4 to 14 carbon atoms, such as 4, 5, 6, 8, 9, 10, 11, 12, 13, and 14 carbon atoms. Examples of straight-chain aliphatic diamines include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 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-eicosenediamine, and 1,22-tetradecanediamine. Alkanediamines and mixtures thereof, preferably 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine and mixtures thereof, more preferably 6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine and mixtures thereof. Examples of branched aliphatic diamines are 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4-dimethyloctanediamine, and mixtures thereof, preferably 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and mixtures thereof.

[0036] The aromatic diamines in this invention are preferably selected from the group consisting of: m-phenylenediamine (MXD), p-phenylenediamine (PXD), bis(4-aminophenyl)methane, 3-methylbenzidine, 2,2-bis(4-aminophenyl)propane, 1,1-bis(4-aminophenyl)cyclohexane, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 1,2-diaminonaphthalene, 1,3-diaminonaphthalene, 1,4-diaminonaphthalene, 2,3-diaminotoluene, N,N'-dimethyl-4,4'-phenylenediamine, bis(4-methylaminophenyl)methane, 2,2'-bis(4-methylaminophenyl)propane, and mixtures thereof, more preferably MXD and / or PXD.

[0037] Suitable amino acids in this invention preferably contain 4 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, such as 9, 10, 11, 12, or 13 carbon atoms. Examples of amino acids are 4-aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and mixtures thereof.

[0038] In this invention, suitable lactams preferably contain 4 to 12 carbon atoms, more preferably 5 to 12 carbon atoms. Examples of lactams are 2-pyrrolidone (γ-butyrolactam), 2-piperidinone (δ-pentanolactam), ε-caprolactam, octanolactam, decanolactam, undecanolactam, heptanolactam, and / or dodecalactam, preferably ε-caprolactam and / or undecanolactam.

[0039] In a preferred embodiment of the invention, the semi-aromatic polyamide comprises dicarboxylic acid units and diamine units, as well as 0 mol% to 20 mol% of units derived from amino acids and / or lactams based on the total molar number of units constituting the semi-aromatic polyamide.

[0040] i. wherein the dicarboxylic acid unit is derived from an aromatic dicarboxylic acid and / or an aromatic dicarboxyl chloride (a-1), or a combination of an aromatic dicarboxylic acid and / or an aromatic dicarboxyl chloride (a-1) with other dicarboxylic acids (a-2), including aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids. Based on the total molar number of dicarboxylic acid units constituting the semi-aromatic polyamide, the amount of aromatic dicarboxylic acid and / or aromatic dicarboxyl chloride (a-1) is preferably 60 mol% to 100 mol%, and the amount of other dicarboxylic acids (a-2) is preferably 0 mol% to 40 mol%.

[0041] The diamine unit is derived from an aliphatic diamine (b-1) or a combination of an aliphatic diamine (b-1) and an aromatic diamine (b-2). Based on the total molar number of diamine units constituting the semi-aromatic polyamide, the amount of aliphatic diamine (b-1) is preferably 80 mol% to 100 mol%, and the amount of aromatic diamine (b-2) is preferably 0 mol% to 20 mol%; or

[0042] ii. The dicarboxylic acid unit is derived from an aliphatic dicarboxylic acid or a combination of an aliphatic dicarboxylic acid and an alicyclic dicarboxylic acid. Based on the total molar number of dicarboxylic acid units constituting the semi-aromatic polyamide, the amount of aliphatic dicarboxylic acid is preferably 80 mol% to 100 mol%, and the amount of alicyclic dicarboxylic acid is preferably 0 mol% to 20 mol%.

[0043] The diamine unit is derived from an aromatic diamine, or a combination of an aromatic diamine and an aliphatic diamine. Based on the total molar number of diamine units constituting the semi-aromatic polyamide, the amount of aromatic diamine is preferably 80 mol% to 100 mol%, and the amount of aliphatic diamine is preferably 0 mol% to 20 mol%.

[0044] In a preferred embodiment, the semi-aromatic polyamide comprises a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit is derived from an aromatic dicarboxylic acid and / or an aromatic dicarboxyl chloride (a-1), or a combination of an aromatic dicarboxylic acid and / or an aromatic dicarboxyl chloride (a-1) with other dicarboxylic acids (a-2), including aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids. The aromatic dicarboxylic acid (a-1) is terephthalic acid, naphthalic acid, biphenyl phthalic acid, a combination of terephthalic acid and isophthalic acid, or a combination of terephthalic acid and naphthalic acid; based on the total molar number of dicarboxylic acid units constituting the semi-aromatic polyamide, the amount of aromatic dicarboxylic acid and / or aromatic dicarboxyl chloride (a-1) is preferably 60 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, further preferably 90 mol% to 100 mol%, and most preferably 95 mol% to 100 mol%; based on the total molar number of dicarboxylic acid units constituting the semi-aromatic polyamide, the amount of other dicarboxylic acids (a-2) is preferably 0 mol% to 40 mol%, more preferably 0 mol% to 20 mol%, further preferably 0 mol% to 10 mol%, and most preferably equal to or less than 5 mol%.

[0045] The diamine unit is derived from an aliphatic diamine (b-1), or a combination of an aliphatic diamine and an aromatic diamine (b-2). Based on the total molar number of diamines constituting the semi-aromatic polyamide, the amount of aliphatic diamine (b-1) is preferably 80 mol% to 100 mol%, more preferably 90 mol% to 100 mol%, and most preferably 95 mol% to 100 mol%; based on the total molar number of diamine units constituting the semi-aromatic polyamide, the amount of aromatic diamine (b-2) is preferably 0 mol% to 20 mol%, more preferably 0 mol% to 10 mol%, and most preferably 0 mol% to 5 mol%.

[0046] In a preferred embodiment, the semi-aromatic polyamide comprises a dicarboxylic acid unit and a diamine unit, the dicarboxylic acid unit being derived from an aromatic dicarboxylic acid (a-1) and 0 mol% to 10 mol%, more preferably 0 mol% to 5 mol% of another dicarboxylic acid (a-2), wherein the aromatic dicarboxylic acid (a-1) comprises 10 mol% to 40 mol%, more preferably 15 mol% to 30 mol%, most preferably 20 mol% to 30 mol% of isophthalic acid, and 60 mol% to 90 mol%, more preferably 70 mol% to 85 mol%, most preferably 70 mol% to 80 mol% of at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, naphthalene-2-carboxylic acid and biphenyl-2-carboxylic acid, preferably terephthalic acid or a combination of terephthalic acid and naphthalene-2-carboxylic acid; the other dicarboxylic acid in (a-2) is an aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid; the molar percentage is based on the total number of moles of the dicarboxylic acid units constituting the semi-aromatic polyamide;

[0047] The diamine unit is derived from an aliphatic diamine (b-1), or a combination of an aliphatic diamine and an aromatic diamine (b-2). Based on the total molar number of diamine units constituting the semi-aromatic polyamide, the amount of aliphatic diamine (b-1) is preferably 90 mol% to 100 mol%, more preferably 95 mol% to 100 mol%; the amount of aromatic diamine (b-2) is preferably 0 mol% to 10 mol%, more preferably 0 mol% to 5 mol%.

[0048] In a more preferred embodiment, the aliphatic dicarboxylic acid of the other dicarboxylic acid (a-2) is preferably glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, and octadecanoic acid, more preferably glutaric acid, adipic acid, sebacic acid, and / or dodecanoic acid.

[0049] In a more preferred embodiment, the aliphatic diamine (b-1) is a straight-chain aliphatic diamine (b-1a) or a combination of a straight-chain aliphatic diamine and a branched-chain aliphatic diamine (b-1b). The straight-chain aliphatic diamine (b-1a) is preferably selected from the group consisting of 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. The branched-chain aliphatic diamine (b-1b) is preferably selected from the group consisting of 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,4,4-trimethylhexamethylenediamine, and 2,2,4-trimethylhexamethylenediamine.

[0050] Examples of semi-aromatic polyamides are polyamide MXD5, polyamide PXD5, polyamide MXD6, polyamide PXD6, polyamide MXD9, polyamide PXD9, polyamide MXD10 and / or polyamide PXD10.

[0051] The polyamides in this invention may also include polyamide copolymers or blends of two or more polyamides and their copolymers.

[0052] Semi-aromatic polyamides are suitably represented by the following symbols:

[0053] -R represents one or more of straight-chain aliphatic diamines and branched-chain aliphatic diamines.

[0054] -T indicates terephthalic acid.

[0055] -I indicates isophthalic acid.

[0056] -A represents one or more aromatic diamines.

[0057] -Y represents one or more aliphatic dicarboxylic acids.

[0058] -V indicates one or more lactams.

[0059] Suitable semi-aromatic polyamides can be represented by PA RT, PA RT / RI, PA RT / BT, PA RT / BT / RI / BI, and based on the total molar number of (T)+(I), the semi-aromatic polyamide comprises:

[0060] -60 mol% to 100 mol% (T), 0 mol% to 40 mol% (I), preferably 60 mol% to 85 mol% (T), 15 mol% to 40 mol% (I), more preferably 65 mol% to 80 mol% (T), 20 mol% to 35 mol% (I); and

[0061] -100 mol% of (R), wherein R is preferably a linear or branched aliphatic polyamide having 4 to 36 carbons, more preferably having 5 to 18 carbons.

[0062] Examples of these polyamides include PA 4T / 4I, PA 4T / 6I, PA 5T, PA 5T / 5I, PA 6T, PA 6T / 6I, PA 6T / 8T, PA 6T / 10T, PA 6T / 10I, PA 9T, PA 10T, PA 12T, PA 10T / 10I, PA 6T / 9T, PA 6T / 12T, PA 4T / 6T / DT, PA 4T / 10T / DT, PA 4T / 4I / 6T / 6I / DT / DI, PA6T / 12T / 6I / 12I PA 6T / 10T / 6I, PA 4T / 6T / 4I / 6I, PA 5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA 4T / 10T / 5I / 10I, PA 4T / 6T / DT, PA 4T / 10T / DT, or PA4T / 4I / 6T / 6I / DT / DI, preferably PA6T, PA9T, PA10T, PA 6T / 6I, PA 6T / 10T, PA6T / 12T, PA 6T / 10T / 6I, PA 6T / DT, or PA 6T / DT / 6I / DI. In this document, D is 2-methylpentane-methylenediamine or 3-methyl-1,5-pentanediimide, or a mixture thereof, and the amount of D is from 0 mol% to 20 mol% of the total moles of (R), preferably from 0 mol% to 10 mol%.

[0063] In a preferred embodiment, PA 6T / 6I comprises 65 mol% to 80 mol% of (T) and 20 mol% to 35 mol% of (I).

[0064] In a preferred embodiment, PA 6T / 10T comprises 10 mol% to 60 mol% of (6T) and 40 mol% to 90 mol% of (10T), preferably 10 mol% to 40 mol% of (6T) and 60 mol% to 90 mol% of (10T).

[0065] In a preferred embodiment, PA 6T / 10T / 6I comprises 60 mol% to 90 mol% of (6T), 5 mol% to 40 mol% of (6I), and 5 mol% to 45 mol% of (10T).

[0066] In a preferred embodiment, PA 6T / 10T / 6 comprises 60 mol% to 85 mol% of (6T), 15 mol% to 40 mol% of (10T), and 5 mol% to 15 mol% of caprolactam.

[0067] Suitable semi-aromatic polyamides can be represented by PA RT / RY, PA RT / V, PA RT / RI / RY, or PA RT / RI / V, and based on the total molar number of (T)+(I)+(V)+(Y), the semi-aromatic polyamide comprises:

[0068] -60 mol% to 100 mol% (T), 0 mol% to 40 mol% (I); 0 mol% to 10 mol% (V), preferably 0 mol% to 5 mol% (V); 0 mol% to 80 mol% (Y), preferably 0 mol% to 60 mol% (Y), more preferably 0 mol% to 40 mol% (Y); R is preferably a linear aliphatic polyamide having 9 to 36 carbons, more preferably having 9 to 18 carbons. Examples of these polyamides include PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, PA5T / 510, PA4T / 410, PA 6T / 610, PA 6T / 612, PA 6T / 1012, PA 9T / 612, PA 9T / 1012, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA 10T / 12, PA 10T / 11, and PA 6T / 6I / 12, preferably PA 6T / 6, PA 6T / 610, or PA 6T / 612.

[0069] In a preferred embodiment, PA RT / RY comprises 60 mol% to 100 mol% of (T) and 0 mol% to 40 mol% of (Y), where R is 1,6-hexanediamine, 1,9-nonanediamine, or 1,10-decanediamine, and Y is dodecanoic acid.

[0070] The melting temperature (Tm) of the semi-aromatic polyamide in this invention is 250°C to 350°C, preferably 280°C to 320°C, and most preferably 305°C to 315°C. The melting temperature is defined as the temperature corresponding to the endothermic peak in the differential scanning calorimetry (DSC) curve, which is obtained by DSC according to ISO 11357-3-2018 at a heating rate of 10 K / min.

[0071] The semi-aromatic polyamide of the present invention preferably has a viscosity value of 50 ml / g to 150 ml / g, which is measured in 96% by weight sulfuric acid according to the ISO 307-2019 method.

[0072] In a preferred embodiment, the semi-aromatic polyamide is selected from polyamide MXD6, polyamide 12T, polyamide 10T, polyamide 9T, polyamide 6T / 66, polyamide 6T / DT, polyamide 66 / 6T / 6l, polyamide 6T / 6, polyamide 6T / 6I copolymers, and mixtures thereof.

[0073] Semi-aromatic polyamides can be produced using conventionally known methods such as melt polymerization or solution polymerization.

[0074] The semi-aromatic polyamides disclosed herein are not limited to those prepared from virgin crude oil monomers, and may be wholly or at least partially bio-based or derived from waste streams or recycling activities; that is, the polyamides used in this application may be based on renewable materials, secondary feedstocks, or recycled feedstocks. For example, PA 5T, PA 5T / 5I, PA 5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA 4T / 10T / 5I / 10I, PA 5T / 510, PA 6T, PA 6T / 6, PA6T / 12, PA6T / 6I / 6, PA 6T / 66, PA 6T / 610, PA 6T / 612, PA 6T / 1012, PA 9T, PA 9T / 612, PA 9T / 1012, PA10T, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA 10T / 12, PA 10T / 11 and PA are used as component (A) in this application. 6T / 6I / 12 can be prepared, obtained, or derived from monomers obtained via a re-monomerization method.

[0075] Based on the total weight of the polyamide-based composition, the amount of semi-aromatic polyamide in this invention is from 30% to 84.9% by weight, preferably from 40% to 79% by weight, more preferably from 56% to 65% by weight, such as 56%, 57%, 60%, 62%, and 65% by weight.

[0076] The white pigment in this invention may include, but is not limited to, titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, magnesium hydroxide, zirconium hydroxide, zinc sulfate, zinc sulfide, aluminum phosphate, calcium carbonate, magnesium carbonate, and mixtures thereof.

[0077] Preferably, the white pigment can be surface-treated with a coupling agent by existing methods, such as silane coupling agents, titanium coupling agents, acrylate silane coupling agents, epoxy silane coupling agents, and amino silane coupling agents, such as vinyltriethoxysilane, polydimethylsiloxane, 2-aminopropyltriethoxysilane, 2-epoxypropoxypropyltriethoxysilane, and combinations thereof.

[0078] In a preferred embodiment, the white pigment is titanium dioxide, which exhibits better light reflectivity and photostability. The particle size of the titanium dioxide is preferably from 100 nm to 500 nm, more preferably from 200 nm to 400 nm. Titanium dioxide can also be treated with an inorganic surface treatment agent. Surface treatment of titanium dioxide can improve its wettability with alkaline resins (e.g., polyamides). Examples of inorganic surface treatment agents include the group consisting of alumina, silica, zirconium oxide, sodium silicate, sodium aluminate, sodium aluminosilicate, zinc oxide, mica, etc. Inorganic surface treatment agents can be used alone or in combination.

[0079] Based on the total weight of the polyamide-based composition, the amount of white pigment in this invention is from 15% to 40% by weight, preferably from 20% to 35% by weight, more preferably from 30% to 35% by weight, such as 30%, 32%, 34%, and 35% by weight.

[0080] The crystal whiskers in this invention may include, but are not limited to, potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium sulfate whiskers, and combinations thereof.

[0081] In a preferred embodiment, the crystal whiskers are calcium sulfate whiskers or potassium titanate whiskers.

[0082] Preferably, the crystal whiskers are calcium sulfate whiskers with an aspect ratio of 5 to 40.

[0083] Preferably, the crystal whiskers are potassium titanate whiskers with an aspect ratio of 5 to 50.

[0084] In a preferred embodiment, crystal whiskers can be treated with a surface treatment agent using existing methods to improve their compatibility with basic resins (e.g., polyamides) and the dispersion of the crystal whiskers in a polyamide-based resin matrix. Examples of surface treatment agents may include, but are not limited to, silane coupling agents (such as silanes, epoxysilanes, etc.), titanium coupling agents, organic acids, polyols, silicones, and combinations thereof.

[0085] Based on the total weight of the polyamide-based composition, the amount of crystal whiskers in this invention is from 0.1% to 30% by weight, preferably from 1% to 25% by weight, more preferably from 5% to 10% by weight, such as 5% by weight, 6% by weight, 8% by weight, or 10% by weight.

[0086] The polyamide-based compositions of the present invention may optionally contain at least one additive (D), such as heat stabilizers, antioxidants, nucleating agents, acid scavengers, lubricants, light stabilizers (such as UV stabilizers), flame retardants, release agents, impact modifiers, compatibilizers, plasticizers, surfactants, coupling agents, antimicrobial agents, antistatic agents, and any combination thereof.

[0087] For the purposes of this invention, the additive can be used in conventional amounts. For example, based on the total weight of the polyamide-based composition, the polyamide-based composition may contain at least one additive in amounts ranging from 0.01% to 40% by weight.

[0088] Polyamide-based compositions may, for example, contain heat stabilizers. Suitable heat stabilizers are organic hypophosphites, inorganic hypophosphites, inorganic phosphonates, organic phosphites, and mixtures thereof, preferably inorganic phosphonates and organic hypophosphites. Examples of heat stabilizers are sodium phosphonate, potassium phosphonate, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate, ammonium phosphonate, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, magnesium hypophosphite, calcium hypophosphite, and ammonium hypophosphite, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, magnesium hypophosphite, calcium hypophosphite, ammonium hypophosphite, and sodium phenylphosphite.

[0089] Based on the total weight of the polyamide-based composition, the amount of heat stabilizer (if present) may be from 0.01% to 1% by weight, or preferably from 0.1% to 0.5% by weight.

[0090] Polyamide-based compositions may, for example, contain antioxidants. Suitable antioxidants are aromatic amine antioxidants, hindered phenolic antioxidants, and phosphite antioxidants, especially hindered phenolic antioxidants. Examples of hindered phenolic antioxidants include, but are not limited to, α-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]poly(oxy-1,2-ethylenediyl), 2,4-bis[(octylthio)methyl]-o-cresol, octyl-3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamate, 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid C7-C9 branched alkyl ester, 2,4-bis[(dodecylthio)methyl]-o-cresol, 4,4'-butylenebis-(3-methyl-6-tert-butylphenol), 3 Octadecyl 5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate, pentaerythritol tetra(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,2-thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-1,6-hexadiylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionamide].

[0091] Based on the total weight of the polyamide-based composition, the amount of antioxidant (when present) may be from 0.01% to 1% by weight, or preferably from 0.1% to 0.3% by weight.

[0092] The nucleating agent used in this article may be selected from at least one of inorganic nucleating agents and organic nucleating agents with a particle size of less than 1 μm. Preferably, the inorganic nucleating agent is at least one of talc, montmorillonite, and calcium carbonate; and the organic nucleating agent is at least one of sodium benzoate, dibenzyl sorbitol, and sodium carboxylate.

[0093] Based on the total weight of the insulating film, the amount of nucleating agent (if present) may be from 0.01% to 0.1% by weight, or preferably from 0.02% to 0.05% by weight.

[0094] The acid scavenger in this invention may be selected from at least one of magnesium oxide, zinc stannate, magnesium stannate, calcium stannate, calcium lactate, and mixtures thereof.

[0095] Based on the total weight of the insulating film, the amount of acid remover (when present) may be from 0.1% to 3% by weight, or preferably from 1% to 2% by weight.

[0096] Polyamide-based compositions may, for example, contain lubricants. Suitable lubricants are preferably esters or amides of saturated or unsaturated aliphatic carboxylic acids having 10 to 40, preferably 16 to 22 carbon atoms, and saturated aliphatic alcohols or amines having 2 to 40, preferably 2 to 6 carbon atoms. The carboxylic acid can be monobasic or dibasic. Examples of carboxylic acids are nonanoic acid, palmitic acid, lauric acid, heptadecanic acid, dodecanoic acid, benzalkonium chloride, and particularly preferably stearic acid, decanoic acid, and linalic acid (a mixture of fatty acids having 30 to 40 carbon atoms). The aliphatic alcohol can be monobasic to tetrabasic. Examples of aliphatic alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, and pentaerythritol, preferably glycerol and pentaerythritol. The aliphatic amine can be monofunctional to trifunctional. Examples of aliphatic amines are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and di(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being particularly preferred herein.

[0097] Preferred esters or amides are N,N'-ethylenedi(stearamide), glyceryl distearate, glyceryl tristearate, glyceryl monopalmitate, glyceryl trilaurate, glyceryl monobenzyl heatherate, and pentaerythritol tetrastearate. N,N'-ethylenedi(stearamide) is particularly preferred as a lubricant in the polyamide compositions according to the invention.

[0098] Mixtures of various esters or amides can also be used, or combinations of esters and amides in any desired mixing ratio can be used.

[0099] Other lubricants are preferably long-chain fatty acids (e.g., stearic acid or behenic acid), salts of these long-chain fatty acids (e.g., calcium stearate or zinc stearate), or lignite wax (a mixture of straight-chain saturated carboxylic acids with a chain length of 28 to 32 carbon atoms), calcium lignite or sodium lignite, as well as low molecular weight polyethylene wax and low molecular weight polypropylene wax.

[0100] Based on the total weight of the polyamide-based composition, the amount of lubricant (when present) may be from 0.01% to 2% by weight, or preferably from 0.2% to 1% by weight.

[0101] The polyamide-based composition may, for example, contain a UV stabilizer. There are no particular limitations on the UV stabilizer that can be used in the polyamide-based composition according to the invention, and the UV stabilizer may be selected from any known UV stabilizer, such as commercially available Nylostab S-EED FF from Clariant.

[0102] Based on the total weight of the polyamide-based composition, the amount of UV stabilizer (when present) may be from 0.01% to 1% by weight, or preferably from 0.1% to 0.5% by weight.

[0103] Preferably, the flame retardant described herein comprises a metal salt of a dialkylphosphine salt, wherein the metal salt of the dialkylphosphine salt comprises a metal salt of a phosphonic acid of formula (I), or a metal salt of a diphosphonate of formula (II), or a mixture thereof;

[0104]

[0105]

[0106] R1 and R2 may be the same or different, and are straight-chain or branched C1-C-6-alkyl, preferably straight-chain or branched C1-C4 alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl;

[0107] M or N is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, a protonated nitrogen base or a mixture thereof, preferably Mg, Ca, Al, Zn or a mixture thereof; m is an integer from 1 to 4; n is an integer from 1 to 4;

[0108] R3 is a straight chain or a branched chain C1-C. 10 -alkylene, C6-C 10 -Asaryl, C7-C 20 -alkylarylene or C7-C 20 -Arylalkylene, preferably straight-chain or branched C1-C4-alkylene or C6-C 10 -Aryl, more preferably methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, phenylmethylene, phenylethylene, phenylpropylene, or phenylbutylene.

[0109] R4 and R5 may be the same or different, and are straight-chain or branched C1-C-6-alkyl, preferably straight-chain or branched C1-C4 alkyl, more preferably methyl, ethyl or propyl; q is an integer from 1 to 4; p is an integer from 1 to 4; x is an integer from 1 to 4.

[0110] The protonated nitrogen base is preferably a protonated base of ammonia, melamine, or triethanolamine, especially NH4. + .

[0111] The metal salt of the hypophosphonic acid used to produce the hypophosphonic acid of formula (I) in this invention is preferably dimethyl hypophosphonic acid, ethylmethyl hypophosphonic acid, diethyl hypophosphonic acid, or methyl n-propyl hypophosphonic acid.

[0112] The secondary phosphonic acid used to produce the salt of the secondary phosphonic acid of formula (II) in this invention is preferably methane-di(methylphosphonic acid), ethane-1,2-di(methylphosphonic acid), hexane-1,6-di(methylphosphonic acid), benzene-1,4-di(methylphosphonic acid), methylphenylphosphonic acid, or diphenylphosphonic acid.

[0113] Examples of metal salts of phosphonates of formula (I) include calcium dimethylphosphonate, magnesium dimethylphosphonate, aluminum dimethylphosphonate, zinc dimethylphosphonate, calcium ethylmethylphosphonate, magnesium ethylmethylphosphonate, aluminum ethylmethylphosphonate, zinc ethylmethylphosphonate, calcium diethylphosphonate, magnesium diethylphosphonate, aluminum diethylphosphonate, zinc diethylphosphonate, calcium methyl-n-propylphosphonate, magnesium methyl-n-propylphosphonate, aluminum methyl-n-propylphosphonate, and zinc methyl-n-propylphosphonate. More preferably, these are aluminum diethylphosphonate, zinc diethylphosphonate, aluminum dimethylphosphonate, and zinc dimethylphosphonate.

[0114] Examples of metal salts of the secondary phosphonic acid of formula (II) include calcium methanedi(methylphosphonic acid), magnesium methanedi(methylphosphonic acid), aluminum methanedi(methylphosphonic acid), zinc methanedi(methylphosphonic acid), calcium benzene-1,4-(dimethylphosphonic acid), magnesium benzene-1,4-(dimethylphosphonic acid), aluminum benzene-1,4-(dimethylphosphonic acid), and zinc benzene-1,4-(dimethylphosphonic acid).

[0115] Flame retardants may also contain flame retardant synergists. Suitable flame retardant synergists include phosphorus synergists, nitrogen synergists, and phosphorus / nitrogen synergists.

[0116] The phosphorus synergist in this invention can be a metal salt of phosphorous acid, a polyphosphonate, a phosphazene, an organophosphate, or a mixture thereof. The metal salt of phosphorous acid comprises a structural unit of formula (III) or (IV):

[0117]

[0118]

[0119] Wherein T is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, protonated nitrogen base or mixtures thereof, preferably Al and / or Zn; r is 1 to 4; w is 1 to 4; z is 1 to 7, preferably 1 to 4.

[0120] Examples of molten salts of phosphorous acid are Al(H--2PO3)3, Al2(HPO3)3, Zn(HPO3), Al2(HPO3)3•4H2O and Al(OH)(H--2PO3)2•2H2O, with Al2(HPO3)3 being the most preferred.

[0121] The protonated nitrogen base is preferably a protonated base of ammonia, melamine, or triethanolamine, especially NH4. + .

[0122] Suitable nitrogen synergists can be melamine condensation products, such as mellamine, mellamide, melon, and mixtures thereof.

[0123] Suitable phosphorus / nitrogen synergists can be reaction products of melamine and polyphosphate, condensation products of melamine and polyphosphate, and mixtures thereof, such as melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, and mixtures thereof.

[0124] The mass ratio of the metal salt of phosphonic acid to the flame retardant synergist is preferably 60:40 to 90:10, more preferably 75:25 to 90:10, for example 85:15 or 80:20.

[0125] A suitable flame retardant could be Exolit from Clariant. ® OP series.

[0126] Flame retardant synergists can also be metal oxides, metal hydroxides, boehmite, hydrotalcite, hydrated calcium borate, metal borates (such as zinc borate), and metal hydroxystannates (such as zinc hydroxystannate). Suitable metal oxides are magnesium oxide, calcium oxide, zinc oxide, manganese oxide, tin oxide, tin oxide hydrate, and mixtures thereof. Suitable metal hydroxides are aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, and manganese hydroxide.

[0127] In a preferred embodiment, the flame retardant is a mixture of a metal salt of a dialkylphosphine salt and a metal salt of phosphorous acid containing a structural unit of formula (III) or (IV).

[0128] In a preferred embodiment, the flame retardant is a mixture of a metal salt of a dialkylphosphinate and a flame retardant synergist;

[0129] - A metal salt of a dialkylphosphinate, selected from the group consisting of aluminum diethylphosphinate, zinc diethylphosphinate, aluminum dimethylphosphinate, and zinc dimethylphosphinate, preferably aluminum diethylphosphinate, and

[0130] - The flame retardant synergist is a metal salt of phosphorous acid containing a structural unit of formula (III) or (IV), wherein the metal salt of phosphorous acid is selected from the group consisting of Al(H--2PO3)3, Al2(HPO3)3, Zn(HPO3), Al2(HPO3)3•4H2O and Al(OH)(H--2PO3)2•2H2O, preferably Al2(HPO3)3.

[0131] The mass ratio of the metal salt of phosphonic acid to the flame retardant synergist is 75:25 to 90:10.

[0132] In a preferred embodiment, the flame retardant is a mixture of a metal salt of a dialkylphosphinate and a flame retardant synergist;

[0133] - A metal salt of a dialkylphosphinate, selected from the group consisting of aluminum diethylphosphinate, zinc diethylphosphinate, aluminum dimethylphosphinate, and zinc dimethylphosphinate, preferably aluminum diethylphosphinate, and

[0134] - The flame retardant synergist is selected from the group consisting of melamine polyphosphate, melamine polyphosphate, and melamine polyphosphate.

[0135] The mass ratio of the metal salt of phosphonic acid to the flame retardant synergist is 75:25 to 90:10.

[0136] Based on the total weight percentage of the polyamide-based composition, the amount of flame retardant (when present) can be from 10% to 25% by weight, preferably from 15% to 25% by weight, such as 15%, 20%, or 25% by weight.

[0137] Polyamide-based compositions may, for example, contain impact modifiers. Suitable impact modifiers may include polyolefin-based, styrene-based, and unsaturated carboxylic acid-based impact modifiers. Suitable impact modifiers may also be those modified by functional blocks, such as epoxy functional blocks and / or anhydride blocks. Epoxy functional blocks may be units derived from glycidyl (meth)acrylate. Anhydride blocks may be units derived from maleic anhydride.

[0138] Suitable polyolefin-based impact modifiers may include polyolefins comprising repeating units derived from olefins having 2 to 10 carbon atoms. Examples of such olefins include ethylene, 1-butene, 1-propylene, 1-pentene, 1-octene, and mixtures of ethylene and 1-octene, preferably ethylene, 1-propylene, and mixtures of ethylene and 1-octene.

[0139] Suitable unsaturated carboxylic acid impact modifiers may include blocks derived from carboxylic acids and their derivatives, such as esters, imides, and amides. Suitable carboxylic acids and their derivatives are, for example, acrylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, glutaric acid, itaconic acid, citraconic acid, (meth)acrylates, (meth)acrylate, (meth)methyl acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, and (meth)acrylate isobutyl acrylate.

[0140] Impact modifiers can also be binary polymers, ternary polymers, or core-shell polymers. Examples of such impact modifiers include styrene / ethylene / butene copolymers (SEBS), ethylene-methyl acrylate-glycidyl methacrylate terpolymers, ethylene / propylene / diene rubber (EPDM), and ethylene-octene copolymers.

[0141] Based on the total weight of the polyamide-based composition, the amount of impact modifier (when present) may be from 0.01% to 15% by weight, or preferably from 1% to 15% by weight, or more preferably from 5% to 10% by weight.

[0142] The polyamide-based composition may, for example, contain plasticizers, including but not limited to dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, and N-(n-butyl)benzenesulfonamide.

[0143] Based on the total weight of the polyamide-based composition, the amount of plasticizer (when present) may be from 0.01% to 15% by weight, or preferably from 1% to 15% by weight, or more preferably from 5% to 10% by weight.

[0144] In a specific embodiment of the invention, the polyamide-based composition comprises:

[0145] From 30% by weight to 84.9% by weight of (A) at least one semi-aromatic polyamide, wherein the semi-aromatic polyamide is selected from at least one of the following: PA5T, PA 5T / 5I, PA 5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA 4T / 10T / 5I / 10I, PA5T / 510, PA 6T, PA 6T / 6I, PA 6T / 8T, PA 6T / 10T, PA 6T / 10I, PA 9T, PA 10T, PA 12T, PA10T / 10I, PA 6T / 9T, PA 6T / 12T, PA 4T / 6T / DT, PA 4T / 10T / DT, PA 4T / 4I / 6T / 6I / DT / DI, PA6T / 12T / 6I / 12I, PA 6T / 10T / 6I, PA 4T / 6T / 4I / 6I, PA 4T / 6T / DT, PA 4T / 10T / DT or PA4T / 4I / 6T / 6I / DT / DI, PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, PA4T / 410, PA 6T / 610, PA 6T / 612, PA 6T / 1012, PA 9T / 612, PA 9T / 1012, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA 10T / 12, PA 10T / 11, PA 6T / 6I / 12 and their combinations,

[0146] (B) At least one white pigment, comprising 15% to 40% by weight, wherein the white pigment is selected from the group consisting of titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, magnesium hydroxide, zirconium hydroxide, zinc sulfate, zinc sulfide, aluminum phosphate, calcium carbonate, magnesium carbonate, and any combination thereof.

[0147] From 0.1 wt% to 30 wt% of at least one crystalline whisker of (C), wherein the crystalline whisker is selected from the group consisting of potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium sulfate whiskers, and any combination thereof.

[0148] The mass ratio of white pigment to crystal whiskers is 7~1:1.

[0149] Each is based on the total weight of the polyamide-based composition.

[0150] In a specific embodiment of the invention, the polyamide-based composition comprises:

[0151] From 30% by weight to 84.9% by weight of (A) at least one semi-aromatic polyamide, wherein the semi-aromatic polyamide is selected from at least one of the following: PA5T, PA 5T / 5I, PA 5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA 4T / 10T / 5I / 10I, PA5T / 510, PA 6T, PA 6T / 6I, PA 6T / 8T, PA 6T / 10T, PA 6T / 10I, PA 9T, PA 10T, PA 12T, PA10T / 10I, PA 6T / 9T, PA 6T / 12T, PA 4T / 6T / DT, PA 4T / 10T / DT, PA 4T / 4I / 6T / 6I / DT / DI, PA6T / 12T / 6I / 12I, PA 6T / 10T / 6I, PA 4T / 6T / 4I / 6I, PA 4T / 6T / DT, PA 4T / 10T / DT or PA4T / 4I / 6T / 6I / DT / DI, PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, PA4T / 410, PA 6T / 610, PA 6T / 612, PA 6T / 1012, PA 9T / 612, PA 9T / 1012, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA 10T / 12, PA 10T / 11, PA 6T / 6I / 12 and their combinations,

[0152] (B) At least one white pigment, comprising 15% to 40% by weight, wherein the white pigment is selected from the group consisting of titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, magnesium hydroxide, zirconium hydroxide, zinc sulfate, zinc sulfide, aluminum phosphate, calcium carbonate, magnesium carbonate, and any combination thereof.

[0153] From 0.1 wt% to 30 wt% of (C) at least one crystalline whisker, selected from the group consisting of potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium sulfate whiskers, and any combination thereof, and optionally...

[0154] From 0.01% by weight to 40% by weight of (D) at least one additive, selected from the group consisting of heat stabilizers, antioxidants, nucleating agents, acid scavengers, lubricants, light stabilizers (such as UV stabilizers), mold release agents, impact modifiers, compatibilizers, plasticizers, surfactants, coupling agents, antimicrobial agents, antistatic agents, and any combination thereof.

[0155] The mass ratio of white pigment to crystal whiskers is 7~1:1.

[0156] Each is based on the total weight of the polyamide-based composition.

[0157] In a preferred embodiment of the invention, the polyamide-based composition comprises:

[0158] From 40% to 79% by weight of (A) at least one semi-aromatic polyamide, wherein the semi-aromatic polyamide is selected from at least one of the following: PA5T, PA 5T / 5I, PA 5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA 4T / 10T / 5I / 10I, PA 5T / 510, PA 6T, PA 6T / 6I, PA 6T / 8T, PA 6T / 10T, PA 6T / 10I, PA 9T, PA 10T, PA 12T, PA 10T / 10I, PA 6T / 9T, PA 6T / 12T, PA 4T / 6T / DT, PA 4T / 10T / DT, PA 4T / 4I / 6T / 6I / DT / DI, PA6T / 12T / 6I / 12I, PA 6T / 10T / 6I, PA 4T / 6T / 4I / 6I, PA 4T / 6T / DT, PA 4T / 10T / DT or PA4T / 4I / 6T / 6I / DT / DI, PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, PA4T / 410, PA 6T / 610, PA 6T / 612, PA6T / 1012, PA 9T / 612, PA 9T / 1012, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA10T / 12, PA 10T / 11, PA 6T / 6I / 12 and their combinations,

[0159] (B) At least one white pigment, comprising 20% ​​to 35% by weight of (B), wherein the white pigment is selected from the group consisting of titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, magnesium hydroxide, zirconium hydroxide, zinc sulfate, zinc sulfide, aluminum phosphate, calcium carbonate, magnesium carbonate, and any combination thereof.

[0160] From 1 wt% to 25 wt% of (C) at least one crystalline whisker, selected from the group consisting of potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium sulfate whiskers, and any combination thereof, and

[0161] The mass ratio of white pigment to crystal whiskers is 7~1:1.

[0162] Each is based on the total weight of the polyamide-based composition.

[0163] In a preferred embodiment of the invention, the polyamide-based composition comprises:

[0164] 56% to 65% by weight of (A) at least one semi-aromatic polyamide, wherein the semi-aromatic polyamide is selected from at least one of the following: PA5T, PA 5T / 5I, PA 5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA 4T / 10T / 5I / 10I, PA 5T / 510, PA 6T, PA 6T / 6I, PA 6T / 8T, PA 6T / 10T, PA 6T / 10I, PA 9T, PA 10T, PA 12T, PA 10T / 10I, PA 6T / 9T, PA 6T / 12T, PA 4T / 6T / DT, PA 4T / 10T / DT, PA 4T / 4I / 6T / 6I / DT / DI, PA6T / 12T / 6I / 12I, PA 6T / 10T / 6I, PA 4T / 6T / 4I / 6I, PA 4T / 6T / DT, PA 4T / 10T / DT or PA4T / 4I / 6T / 6I / DT / DI, PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, PA4T / 410, PA 6T / 610, PA 6T / 612, PA6T / 1012, PA 9T / 612, PA 9T / 1012, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA10T / 12, PA 10T / 11, PA 6T / 6I / 12 and their combinations,

[0165] (B) At least one white pigment, comprising 30% to 35% by weight of (B), wherein the white pigment is selected from the group consisting of titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, magnesium hydroxide, zirconium hydroxide, zinc sulfate, zinc sulfide, aluminum phosphate, calcium carbonate, magnesium carbonate, and any combination thereof.

[0166] From 5% to 10% by weight of at least one crystalline whisker of (C), the crystalline whisker being selected from the group consisting of potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium sulfate whiskers, and any combination thereof, and

[0167] The mass ratio of white pigment to crystal whiskers is 7~1:1.

[0168] Each is based on the total weight of the polyamide-based composition.

[0169] In another preferred embodiment of the invention, the polyamide-based composition comprises:

[0170] 56% to 65% by weight of (A) at least one semi-aromatic polyamide, wherein the semi-aromatic polyamide is selected from at least one of the following: PA5T, PA 5T / 5I, PA 5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA 4T / 10T / 5I / 10I, PA 5T / 510, PA 6T, PA 6T / 6I, PA 6T / 8T, PA 6T / 10T, PA 6T / 10I, PA 9T, PA 10T, PA 12T, PA 10T / 10I, PA 6T / 9T, PA 6T / 12T, PA 4T / 6T / DT, PA 4T / 10T / DT, PA 4T / 4I / 6T / 6I / DT / DI, PA6T / 12T / 6I / 12I, PA 6T / 10T / 6I, PA 4T / 6T / 4I / 6I, PA 4T / 6T / DT, PA 4T / 10T / DT or PA4T / 4I / 6T / 6I / DT / DI, PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, PA4T / 410, PA 6T / 610, PA 6T / 612, PA6T / 1012, PA 9T / 612, PA 9T / 1012, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA10T / 12, PA 10T / 11, PA 6T / 6I / 12 and their combinations,

[0171] (B) At least one white pigment, comprising 30% to 35% by weight of (B), wherein the white pigment is selected from the group consisting of titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, magnesium hydroxide, zirconium hydroxide, zinc sulfate, zinc sulfide, aluminum phosphate, calcium carbonate, magnesium carbonate, and any combination thereof.

[0172] From 5% to 10% by weight of at least one crystalline whisker of (C), the crystalline whisker being selected from the group consisting of potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium sulfate whiskers, and any combination thereof, and

[0173] The mass ratio of white pigment to crystal whiskers is 7~3:1.

[0174] Each is based on the total weight of the polyamide-based composition.

[0175] In another preferred embodiment of the invention, the polyamide-based composition comprises:

[0176] 56% to 65% by weight of (A) at least one semi-aromatic polyamide, wherein the semi-aromatic polyamide is selected from at least one of the following: PA5T, PA 5T / 5I, PA 5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA 4T / 10T / 5I / 10I, PA 5T / 510, PA 6T, PA 6T / 6I, PA 6T / 8T, PA 6T / 10T, PA 6T / 10I, PA 9T, PA 10T, PA 12T, PA 10T / 10I, PA 6T / 9T, PA 6T / 12T, PA 4T / 6T / DT, PA 4T / 10T / DT, PA 4T / 4I / 6T / 6I / DT / DI, PA6T / 12T / 6I / 12I, PA 6T / 10T / 6I, PA 4T / 6T / 4I / 6I, PA 4T / 6T / DT, PA 4T / 10T / DT or PA4T / 4I / 6T / 6I / DT / DI, PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, PA4T / 410, PA 6T / 610, PA 6T / 612, PA6T / 1012, PA 9T / 612, PA 9T / 1012, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA10T / 12, PA 10T / 11, PA 6T / 6I / 12 and their combinations,

[0177] (B) At least one white pigment, comprising 30% to 35% by weight of (B), wherein the white pigment is selected from the group consisting of titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, magnesium hydroxide, zirconium hydroxide, zinc sulfate, zinc sulfide, aluminum phosphate, calcium carbonate, magnesium carbonate, and any combination thereof.

[0178] 5% to 10% by weight of (C) at least one crystalline whisker, selected from the group consisting of potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium sulfate whiskers, and any combination thereof, and optionally...

[0179] From 0.01% by weight to 40% by weight of (D) at least one additive, selected from the group consisting of heat stabilizers, antioxidants, nucleating agents, acid scavengers, lubricants, light stabilizers (such as UV stabilizers), mold release agents, impact modifiers, compatibilizers, plasticizers, surfactants, coupling agents, antimicrobial agents, antistatic agents, and any combination thereof.

[0180] The mass ratio of white pigment to crystal whiskers is 7~3:1.

[0181] Each is based on the total weight of the polyamide-based composition.

[0182] The polyamide-based compositions according to the invention can be processed into various structures or forms by conventional methods to provide articles. For example, the components of the polyamide-based compositions according to the invention can be mixed and then molded, for example by injection and / or extrusion, in conventional mixing equipment such as screw extruders, Brabender mixers, or Banbury mixers to form articles. The mixing temperatures used herein are typically from 280°C to 320°C.

[0183] It should be understood that all components of a polyamide-based composition can be mixed simultaneously. Alternatively, some components of the polyamide-based composition can be premixed and then mixed with the other components. For example, all starting components of the polyamide-based composition, except for the white pigment and crystalline whiskers, can be mixed together in a stirrer and fed into a twin-screw extruder at the throat, then the white pigment and crystalline whiskers can be premixed and fed downstream using a side feeder.

[0184] Therefore, the present invention provides an LED component made of a polyamide-based composition. It can be manufactured or assembled using a reflow soldering process.

[0185] LED components are part of a light-emitting diode reflector. A light-emitting diode arrangement is an assembly comprising at least one light-emitting semiconductor diode, a current source, and a housing covering the diode or a plate embedding the diode. LED components can be the housing or plate of a light-emitting diode arrangement. The housing or plate can be entirely or partially manufactured from the polyamide-based composition of the present invention. For example, one wall of the housing may be manufactured from a polyamide-based composition.

[0186] The LED components in this invention can be elements of automotive lights, mobile communication devices, and home appliances. Lighting components include automotive dashboard displays, automotive screens, turn signals, brake lights, interior and exterior lighting, floodlights, and floor lamps. Mobile electronic device components include mobile phones, laptops, notebooks, e-book readers, tablet computers, pocket calculators, portable media players, mobile internet devices (MIDs), handheld PCs, handheld game consoles, digital media players, wearable computers such as smartwatches, head-mounted displays, virtual reality headsets, digital cameras, GPS receivers, portable power supplies, and portable Wi-Fi displays. Home appliance components include displays for television backlighting, liquid crystal displays, computer monitors, laptop displays, notebook computer displays, and displays for home appliances such as air conditioners, smart home systems, robot vacuums, electric cookers, rice cookers, ovens, microwave ovens, washing machines, dishwashers, etc.

[0187] Therefore, the present invention provides articles produced from polyamide-based compositions according to the present invention.

[0188] Preferably, the article according to the invention has one or more of the following properties:

[0189] - Tensile modulus greater than 4400 MPa as measured according to ISO 527-2-2012;

[0190] - Tensile stress at break greater than 42 MPa, measured according to ISO 527-2-2012;

[0191] -Measured according to ISO 179-1-2010 at 23°C, at least 10 KJ / m 2 Charpy unnotched impact strength.

[0192] -Measured according to ISO 179-1-2010 at 23°C, it should be at least 1.6 KJ / m³. 2 Charpy notch impact strength;

[0193] - Heat distortion temperature greater than 242°C, measured at 0.45 MPa according to Method B of ISO 75-2-2013;

[0194] -Measured according to ISO 1133-2-2011 at 325°C and under a 2.16 kg load, greater than 83 cm 3 / 10min MVR;

[0195] -SM with a molding shrinkage rate (perpendicular to the flow direction) less than 1.1 as measured according to ISO 294-4 n ;

[0196] -SM with a molding shrinkage rate (parallel to the flow direction) less than 1.0 as measured according to ISO 294-4. p ;

[0197] - Initial reflectivity greater than 95.11% measured at a wavelength of 460 nm;

[0198] - A decrease in reflectance of less than 21.6% was observed after aging at 260°C for 30 minutes at a wavelength of 460 nm;

[0199] - A decrease in reflectance of less than 5.0% measured at a wavelength of 460nm after aging at 120°C for 500 hours;

[0200] - A ΔE value of less than 10.57 measured at a wavelength of 460 nm after aging at 260°C for 30 minutes;

[0201] - A ΔE value less than 2.31 measured at a wavelength of 460 nm after aging at 120°C for 500 hours.

[0202] Based on the above properties, it is surprising to find that the polyamide-based compositions of the present invention can possess satisfactory mechanical properties (e.g., relatively high tensile modulus) and significantly improved resistance to molding shrinkage and yellowing, while the initial loss of reflectivity is relatively low and acceptable.

[0203] Implementation Plan

[0204] Various implementation schemes are listed below. It should be understood that the implementation schemes listed below can be combined with all aspects and other implementation schemes within the scope of the invention.

[0205] 1. A polyamide-based composition, comprising, based on the total weight of the polyamide-based composition, 30% to 84.9% by weight of (A) at least one semi-aromatic polyamide, 15% to 40% by weight of (B) at least one white pigment, and 0.1% to 30% by weight of (C) at least one crystalline whisker.

[0206] The mass ratio of white pigment to crystal whiskers is 7~1:1.

[0207] 2. The polyamide-based composition according to embodiment 1, wherein the composition has an SmO2 content measured according to ISO 294-4. n Less than 1.1.

[0208] 3. The polyamide-based composition according to embodiment 1, wherein the composition has an Sm measured according to ISO 294-4. p Less than 1.0.

[0209] 4. The polyamide-based composition according to embodiment 1, wherein the reflectance of the composition, measured at a wavelength of 460 nm after aging at 260°C for 30 minutes, decreases by less than 21.6%.

[0210] 5. The polyamide-based composition according to embodiment 1, wherein the reflectance of the composition, measured at a wavelength of 460 nm after aging at 120°C for 500 hours, decreases by less than 5.0%.

[0211] 6. The polyamide-based composition according to embodiment 1, wherein the Δ-E value of the composition measured at a wavelength of 460 nm after aging at 260°C for 30 minutes is less than 10.57.

[0212] 7. The polyamide-based composition according to embodiment 1, wherein the Δ-E value of the composition measured at a wavelength of 460 nm after aging at 120°C for 500 hours is less than 2.31.

[0213] 8. The polyamide-based composition according to any one of the foregoing embodiments, wherein the semi-aromatic polyamide comprises dicarboxylic acid units and diamine units, and units derived from amino acids and / or lactams in a total molar percentage of 0 mol% to 20 mol% based on the total molar percentage of the units constituting the semi-crystalline semi-aromatic polyamide;

[0214] i. wherein the dicarboxylic acid unit is derived from an aromatic dicarboxylic acid and / or an aromatic dicarboxyl chloride (a-1), or a combination of an aromatic dicarboxylic acid and / or an aromatic dicarboxyl chloride (a-1) with other dicarboxylic acids (a-2), including aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids, and based on the total molar number of dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide, the amount of aromatic dicarboxylic acid and / or aromatic dicarboxyl chloride (a-1) is 60 mol% to 100 mol%, and the amount of other dicarboxylic acids (a-2) is 0 mol% to 40 mol%;

[0215] The diamine unit is derived from an aliphatic diamine (b-1), or a combination of an aliphatic diamine (b-1) and an aromatic diamine (b-2), wherein, based on the total molar number of diamine units constituting the semi-aromatic polyamide, the amount of aliphatic diamine (b-1) is 80 mol% to 100 mol%, and the amount of aromatic diamine (b-2) is 0 mol% to 20 mol%; or

[0216] ii. Wherein the dicarboxylic acid unit is derived from an aliphatic dicarboxylic acid or a combination of an aliphatic dicarboxylic acid and an alicyclic dicarboxylic acid, and based on the total number of moles of dicarboxylic acid units constituting the semi-aromatic polyamide, the amount of aliphatic dicarboxylic acid is 80 mol% to 100 mol%, and the amount of alicyclic dicarboxylic acid is 0 mol% to 20 mol%;

[0217] The diamine unit is derived from an aromatic diamine, or a combination of an aromatic diamine and an aliphatic diamine, and the amount of the aromatic diamine is 80 mol% to 100 mol% and the amount of the aliphatic diamine is 0 mol% to 20 mol% based on the total number of moles of the diamine units constituting the semi-crystalline semi-aromatic polyamide.

[0218] 9. The polyamide-based composition according to embodiment 8, wherein the semi-aromatic polyamide is at least one selected from the group consisting of: PA MXD5, PA PXD5, PA MXD6, PA PXD6, PA MXD9, PA PXD9, PA MXD10, PAPXD10, PA 4T / 4I, PA 4T / 6I, PA5T, PA 5T / 5I, PA 6T, PA 6T / 6I, PA 6T / 8T, PA 6T / 10T, PA6T / 10I, PA 9T, PA 10T, PA 12T, PA 10T / 10I, PA 6T / 9T, PA 6T / 12T, PA 4T / 6T / DT, PA 4T / 10T / DT, PA 4T / 4I / 6T / 6I / DT / DI, PA6T / 12T / 6I / 12I PA 6T / 10T / 6I, PA 4T / 6T / 4I / 6I, PA5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA 4T / 10T / 5I / 10I, PA 4T / 6T / DT, PA 4T / 10T / DT or PA4T / 4I / 6T / 6I / DT / DI, PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, PA 5T / 510, PA4T / 410, PA 6T / 610, PA 6T / 612, PA 6T / 1012, PA 9T / 612, PA 9T / 1012, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA 10T / 12, PA 10T / 11 and PA 6T / 6I / 12.

[0219] 10. The polyamide-based composition according to any one of the foregoing embodiments, wherein the white pigment is at least one selected from the group consisting of: titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, magnesium hydroxide, zirconium hydroxide, zinc sulfate, zinc sulfide, aluminum phosphate, calcium carbonate, magnesium carbonate, and mixtures thereof.

[0220] 11. The polyamide-based composition according to any one of the foregoing embodiments, wherein the crystal whiskers are at least one selected from the group consisting of: potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium sulfate whiskers, and mixtures thereof.

[0221] 12. The polyamide-based composition according to any one of the foregoing embodiments, wherein component (A) is present in an amount of 40% to 79% by weight, component (B) is present in an amount of 20% to 35% by weight, and component (C) is present in an amount of 1% to 25% by weight, each based on the total weight of the polyamide-based composition.

[0222] 13. The polyamide-based composition according to any one of the foregoing embodiments, wherein component (A) is present in an amount of 56% to 65% by weight, component (B) is present in an amount of 30% to 35% by weight, and component (C) is present in an amount of 5% to 10% by weight, each based on the total weight of the polyamide-based composition.

[0223] 14. The polyamide-based composition according to any one of the foregoing embodiments, wherein the composition further comprises 0.01% to 40% by weight of (D) at least one additive selected from the group consisting of: heat stabilizers, antioxidants, nucleating agents, acid scavengers, lubricants, light stabilizers, release agents, impact modifiers, compatibilizers, plasticizers, surfactants, coupling agents, antimicrobial agents, antistatic agents, and any combination thereof.

[0224] 15. An article prepared from the polyamide-based composition of embodiment 1.

[0225] 16. The article of manufacture according to embodiment 15, wherein the article of manufacture is an LED component, the LED component being at least one selected from the group consisting of: a car body, an element of a panel or dashboard display with light-emitting diodes arranged in a manner, a car screen, turn signals, brake lights, interior and exterior lighting, floodlights, floor lamps; mobile phones, laptop computers, notebook computers, e-book readers, tablet computers, pocket calculators, portable media players, mobile internet devices, handheld PCs, handheld game consoles, digital media players, wearable computers, head-mounted displays, virtual reality headsets, digital cameras, GPS receivers, portable power supplies, portable Wi-Fi displays; television backlights, liquid crystal displays, computer monitors, laptop computer displays or notebook computer displays, displays for home appliances.

[0226] 17. A filler composition comprising a white pigment and crystalline whiskers, wherein the mass ratio of the white pigment to the crystalline whiskers is 7 to 1:1.

[0227] 18. Use of the filler composition according to embodiment 17 in a polyamide-based composition for preparing LED components, wherein, based on the total weight of the polyamide-based composition, the polyamide-based composition comprises 30% to 84.9% by weight of (A) at least one semi-aromatic polyamide, 15% to 40% by weight of (B) at least one white pigment, and 0.1% to 30% by weight of (C) at least one crystalline whisker.

[0228] Example

[0229] The invention is illustrated more fully by way of the following examples, which are set forth in order to illustrate certain aspects of the invention and should not be construed as limiting the invention.

[0230] The following materials and test methods are used in the embodiments.

[0231] Material:

[0232] Table 1. Materials used in the embodiments and comparative examples of the present invention.

[0233] acronyms / names describe A1: PA9T <![CDATA[Genestar from Kuraray Co., Ltd.]]> ® GC51010, Tm = 305 °C]]> <![CDATA[B1:TiO2]]> Titanium dioxide TIPAQUE CR-90 from Ishihara Sangyo Co., Ltd. (ISK) <![CDATA[C1: CaSO4 whisker]]> Calcium sulfate whiskers NP-S01-LT from NP Whisker <![CDATA[C2:K2Ti6O 13 whiskers Potassium titanate whiskers NP-TW2 from Fengzhu Whiskers Company C3: Glass fiber <![CDATA[ChopVantage from Nippon Electric Glass ™ HP 3660 chopped strand]]> C4: Wollastonite <![CDATA[NYGLOS from Imerys ® 4W]]> D1:HS The stabilizer is sodium phenylphosphonate (SBP) from ALPHARM. D2: AO <![CDATA[Antioxidant: Irganox from BASF Corporation ® 1098]]> D3: NU The nucleating agent is Microtalc IT Extra from ELEMENTIS. D4:AS <![CDATA[Acid scavenger, magnesium oxide Kyowamag from Kyowa Chemical Industry Co., Ltd.]] ™ MF-150]]> D5: LU1 <![CDATA[Lubricant, Luwax from BASF ® OA 5 powder]]> D6: LU2 <![CDATA[Lubricant, CRODAMIDE from Croda ™ EBS-MB-(GD)]]> D7: UV UV stabilizer, NYLOSTAB S-EED FF from Clariant.

[0234] Composition treatment:

[0235] Prepare test samples according to the formulations shown in Table 2.

[0236] All raw materials except fillers (i.e., B1: TiO2, C1: CaSO4 whiskers, C2: K2Ti6O) were used. 13 Whiskers, C3 (glass fiber), and / or C4 (wollastonite) are mixed together in a Turbula T50A high-speed mixer and fed into a ZE25Ax (Berstorff) twin-screw extruder via the throat, using a side feeder to feed filler downstream to maintain good mechanical properties. The raw material is melt-extruded at 320°C and granulated to obtain a thermoplastic polyamide-based composition in granular form.

[0237] Table 2

[0238] Components C1 E1 E2 E3 C2 C3 E4 C4 C5 A1 PA9T 56.73 56.73 56.73 56.73 56.73 56.73 56.73 56.73 56.73 <![CDATA[B1 TiO2]]> 40.00 35.00 30.00 20.00 10.00 30.00 30.00 30.00 <![CDATA[C1: CaSO4 whisker]]> 5.00 10.00 20.00 30.00 40.00 <![CDATA[C2:K2Ti6O 13 whiskers 10.00 C3: Glass fiber 10.00 C4: Wollastonite 10.00 D1:HS 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 D2: AO 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 D3: NU 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 D4:AS 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 D5: LU1 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 D6: LU2 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 D7: UV 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10

[0239] E: Embodiments of the present invention; C: Comparative examples

[0240] Sample preparation:

[0241] The dried granules were processed in a Krauss Maffei KM130CX injection molding machine with a clamping force of 130T at a melt temperature of 320°C and a molding temperature of 120°C to obtain test samples.

[0242] test:

[0243] The melt volumetric flow rate (MVR) was tested at 325°C and 2.16 kg load according to ISO 1133-2-2011.

[0244] The tensile modulus, tensile stress at break, and tensile strain at break of a 4 mm thick sample were measured according to ISO 527-2-2012. Type 1 test specimens as described in ISO 527-2-2012 were used. Charpy notched and unnotched impact strengths were tested along the edge according to ISO 179-1-2010. The unnotched Charpy test specimen was a Type 1 specimen with dimensions of 80 mm × 10 mm × 4 mm (length × width × thickness). The notched Charpy test specimen was a Type 1 specimen with a notch (Type A). All test specimens were conditioned at 23°C and 50% relative humidity for 16 hours. Testing was conducted under the same atmosphere as the conditioning conditions.

[0245] According to ISO 294-4, the molding shrinkage rate is tested using a plastic plaque (60mm × 60mm × 2mm) within 16 to 24 hours after sample preparation.

[0246] The heat distortion temperature (HDT) was tested at 0.45 MPa according to Method B of ISO 75-2-2013.

[0247] Reflectance-related tests were performed using a Datacolor 850 spectrophotometer from Datacolor Company in D65 light source reflectance mode at a wavelength of 460 nm using a molded plastic test plate (60 mm × 60 mm × 2 mm).

[0248] ΔE (total color difference, often written as ΔE or E*) is based on the ΔL*, Δa*, and Δb* color values, all of which provide a complete numerical descriptor of the color in a Cartesian coordinate system. Their meanings are as follows:

[0249] •ΔL* represents the brightness difference between the sample and the standard color.

[0250] • Δa* represents the difference in red or gray between the sample and the standard color.

[0251] •Δb* represents the blue-yellow difference between the sample and the standard color.

[0252] ΔE can be calculated using the following formula via measurement with a Datacolor 850 spectrophotometer:

[0253] .

[0254] The test samples used are prepared according to the following general procedure for preparing test samples.

[0255] Test results:

[0256] Table 3 below shows the test results of the above-described specific embodiments and comparative examples of the present invention.

[0257] Table 3

[0258] nature C1 E1 E2 E3 C2 C3 E4 C4 C5 <![CDATA[MVR(cm 3 / 10min)]]> 101 89 121 83 73 75 117 65 88 Tensile modulus (MPa) 4430 4560 4680 5130 5610 6060 5900 6520 5570 Tensile stress (MPa) 42 43 45 49 49 56 42 60 55 Tensile strain (%) 0.98 0.99 1.0 1.0 0.92 0.98 0.73 0.95 1.1 <![CDATA[Charpy impact strength, without notch (KJ / m 2 ).]]> 15 16 14 14 12 14 10 20 23 <![CDATA[Charpy impact strength, with notch (KJ / m 2 ).]]> 1.8 1.7 1.7 1.7 1.6 1.6 1.6 1.7 1.9 <![CDATA[Molding shrinkage rate, SM n (perpendicular to the flow direction)]]> 1.6 0.8 0.8 0.8 1.1 1.6 1.1 1.0 1.1 <![CDATA[Molding shrinkage rate, SM p (parallel to the flow direction)]]> 1.5 0.7 0.7 0.7 1.1 1.5 1.0 0.7 1.1 Heat distortion temperature, 0.45 MPa (°C) 241 242 248 247 253 255 258 283 257 Reflectivity (%) of the cast state at 460 nm 96.49 96.35 96.14 95.42 92.36 52.14 95.11 93.63 93.81 ΔE at 460nm after aging at 260℃ / 30min 9.20 7.31 8.60 10.57 14.62 24.48 9.60 9.62 11.98 Reflectance (%) at 460nm after aging at 260℃ for 30min 74.64 79.15 76.36 75.43 62.56 18.74 74.58 72.22 66.26 ΔE at 460nm after aging at 120℃ for 500h 2.40 1.53 1.69 2.16 3.66 16.09 2.31 2.62 2.63 Reflectance at 460nm after aging at 120℃ for 500h (%) 90.04 92.62 92.07 90.73 82.12 31.30 90.70 87.56 87.64

[0259] E: Embodiments of the present invention; C: Comparative examples

[0260] Based on the comparison of the results for C1 and C3 presented in Table 3, it can be seen that adding white pigment (e.g., TiO2) can benefit initial reflectivity and anti-yellowing properties, but has a relatively small effect on improving mechanical properties (such as tensile modulus) and heat resistance (e.g., HDT). Conversely, adding crystalline whiskers (e.g., CaSO4 whiskers) can significantly improve mechanical properties (such as tensile modulus) and heat resistance (e.g., HDT), but will have a significant negative impact on initial reflectivity and anti-yellowing properties. However, when added alone, neither white pigment (e.g., TiO2) nor crystalline whiskers (e.g., CaSO4 whiskers) can suppress molding shrinkage (including SM). n and SM p ).

[0261] Surprisingly, it was found that the combination of white pigments (e.g., TiO2) and crystalline whiskers (e.g., CaSO4 whiskers) used in the composition can exert a synergistic effect on each other to achieve relatively low SM n and SM P The following results showed an unexpected effect on improving resistance to molding shrinkage (see SMs for E1 to E3). n and SM P At the same time, it achieves excellent anti-yellowing properties (e.g., relatively low reflectance reduction and fairly low ΔE value after aging tests) and satisfactory mechanical properties (e.g., relatively high tensile modulus).

[0262] Furthermore, to achieve the aforementioned comprehensive performance, the mass ratio of white pigment (e.g., TiO2) to crystal whiskers (e.g., CaSO4 whiskers) should be strictly controlled within an appropriate range, such as 7 to 1:1, preferably 7 to 3:1. However, when the mass ratio is less than 1, the combination of white pigment (e.g., TiO2) and crystal whiskers (e.g., CaSO4 whiskers) used in the composition may negatively affect the initial reflectivity and anti-yellowing properties. For example, under the condition that the mass ratio of TiO2 to CaSO4 whiskers is 1 / 3, the C2 results presented in Table 3 show a relatively low initial reflectivity and rather poor anti-yellowing properties.

[0263] It will be apparent to those skilled in the art that various modifications and variations can be made to this invention without departing from the scope or spirit of the invention. The embodiments and examples are intended to be illustrative only. Therefore, this invention is intended to cover such modifications and variations falling within the scope of the appended claims and their equivalents.

Claims

1. A polyamide-based composition, comprising, based on the total weight of the polyamide-based composition, 30% to 84.9% by weight of (A) at least one semi-aromatic polyamide, 15% to 40% by weight of (B) at least one white pigment, and 0.1% to 30% by weight of (C) at least one crystalline whisker. The mass ratio of the white pigment to the crystal whiskers is 7 to 1:

1.

2. The polyamide-based composition according to claim 1, wherein the composition has an SM measured according to ISO 294-4. n Less than 1.

1.

3. The polyamide-based composition according to claim 1, wherein the composition has an SM measured according to ISO 294-4. p Less than 1.

0.

4. The polyamide-based composition according to claim 1, wherein the reflectance of the composition, measured at a wavelength of 460 nm after aging at 260°C for 30 minutes, decreases by less than 21.6%.

5. The polyamide-based composition according to claim 1, wherein the reflectance of the composition, measured at a wavelength of 460 nm after aging at 120°C for 500 hours, decreases by less than 5.0%.

6. The polyamide-based composition according to claim 1, wherein the Δ-E value of the composition, measured at a wavelength of 460 nm after aging at 260°C for 30 minutes, is less than 10.

57.

7. The polyamide-based composition according to claim 1, wherein the Δ-E value of the composition measured at a wavelength of 460 nm after aging at 120°C for 500 hours is less than 2.

31.

8. The polyamide-based composition according to any one of the preceding claims, wherein the semi-aromatic polyamide comprises dicarboxylic acid units and diamine units, and units derived from amino acids and / or lactams in a total molar percentage of 0 mol% to 20 mol% based on the total molar percentage of the units constituting the semi-crystalline semi-aromatic polyamide; i. wherein the dicarboxylic acid unit is derived from an aromatic dicarboxylic acid and / or an aromatic dicarboxyl chloride (a-1), or a combination of the aromatic dicarboxylic acid and / or an aromatic dicarboxyl chloride (a-1) with other dicarboxylic acids (a-2) including aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids, and based on the total molar number of the dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aromatic dicarboxylic acid and / or aromatic dicarboxyl chloride (a-1) is 60 mol% to 100 mol%, and the amount of the other dicarboxylic acid (a-2) is 0 mol% to 40 mol%. The diamine unit is derived from an aliphatic diamine (b-1), or a combination of an aliphatic diamine (b-1) and an aromatic diamine (b-2), wherein, based on the total molar number of the diamine units constituting the semi-aromatic polyamide, the amount of the aliphatic diamine (b-1) is 80 mol% to 100 mol%, and the amount of the aromatic diamine (b-2) is 0 mol% to 20 mol%; or ii. wherein the dicarboxylic acid unit is derived from an aliphatic dicarboxylic acid or a combination of an aliphatic dicarboxylic acid and an alicyclic dicarboxylic acid, and the amount of the aliphatic dicarboxylic acid is 80 mol% to 100 mol% and the amount of the alicyclic dicarboxylic acid is 0 mol% to 20 mol% based on the total molar number of the dicarboxylic acid units constituting the semi-aromatic polyamide. The diamine unit is derived from an aromatic diamine, or a combination of an aromatic diamine and an aliphatic diamine, and the amount of the aromatic diamine is from 80 mol% to 100 mol% and the amount of the aliphatic diamine is from 0 mol% to 20 mol% based on the total number of moles of the diamine units constituting the semi-crystalline semi-aromatic polyamide.

9. The polyamide-based composition according to claim 8, wherein the semi-aromatic polyamide is at least one selected from the group consisting of: PA MXD5, PA PXD5, PA MXD6, PA PXD6, PA MXD9, PA PXD9, PA MXD10, PAPXD10, PA 4T / 4I, PA 4T / 6I, PA5T, PA 5T / 5I, PA 6T, PA 6T / 6I, PA 6T / 8T, PA 6T / 10T, PA6T / 10I, PA 9T, PA 10T, PA 12T, PA 10T / 10I, PA 6T / 9T, PA 6T / 12T, PA 4T / 6T / DT, PA 4T / 10T / DT, PA 4T / 4I / 6T / 6I / DT / DI, PA6T / 12T / 6I / 12I PA 6T / 10T / 6I, PA 4T / 6T / 4I / 6I, PA5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA 4T / 10T / 5I / 10I, PA 4T / 6T / DT, PA 4T / 10T / DT or PA4T / 4I / 6T / 6I / DT / DI, PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, PA 5T / 510, PA4T / 410, PA 6T / 610, PA 6T / 612, PA 6T / 1012, PA 9T / 612, PA 9T / 1012, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA 10T / 12, PA 10T / 11 and PA 6T / 6I / 12.

10. The polyamide-based composition according to any one of the preceding claims, wherein the white pigment is at least one selected from the group consisting of: titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, magnesium hydroxide, zirconium hydroxide, zinc sulfate, zinc sulfide, aluminum phosphate, calcium carbonate, magnesium carbonate, and mixtures thereof.

11. The polyamide-based composition according to any one of the preceding claims, wherein the crystal whiskers are at least one selected from the group consisting of: potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium sulfate whiskers, and mixtures thereof.

12. The polyamide-based composition according to any one of the preceding claims, wherein the component (A) is present in an amount of 40% to 79% by weight, the component (B) is present in an amount of 20% to 35% by weight, and the component (C) is present in an amount of 1% to 25% by weight, each based on the total weight of the polyamide-based composition.

13. The polyamide-based composition according to any one of the preceding claims, wherein the component (A) is present in an amount of 56% to 65% by weight, the component (B) is present in an amount of 30% to 35% by weight, and the component (C) is present in an amount of 5% to 10% by weight, each based on the total weight of the polyamide-based composition.

14. The polyamide-based composition according to any one of the preceding claims, wherein the composition further comprises 0.01% to 40% by weight of (D) at least one additive, said additive being selected from the group consisting of: heat stabilizers, antioxidants, nucleating agents, acid scavengers, lubricants, light stabilizers, flame retardants, release agents, impact modifiers, compatibilizers, plasticizers, surfactants, coupling agents, antimicrobial agents, antistatic agents, and any combination thereof.

15. An article prepared from the polyamide-based composition according to claim 1.

16. The article of claim 15, wherein the article of claim 15 is an LED component, the LED component being at least one selected from the group consisting of: a car body, an element of a panel or dashboard display with light-emitting diodes arranged in a manner, a car screen, turn signals, brake lights, interior and exterior lighting, floodlights, floor lamps; mobile phones, laptops, notebook computers, e-book readers, tablet computers, pocket calculators, portable media players, mobile internet devices, handheld PCs, handheld game consoles, digital media players, wearable computers, head-mounted displays, virtual reality headsets, digital cameras, GPS receivers, portable power supplies, portable Wi-Fi displays; television backlights, liquid crystal displays, computer monitors, laptop computer displays or notebook computer displays, and displays for home appliances.

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