Polyamide composition

Abstract

The invention relates to a polyamide composition. The polyamide composition comprises (A) from 30% to 97% by weight, based on the total weight of the polyamide composition, of at least one semi-crystalline semi-aromatic polyamide, (B) from 2% to 50% by weight of at least one white pigment, (C) from 0.1% to 2% by weight of at least one phosphorus-containing heat stabilizer, (D) from 0.1% to 4.5% by weight, based on the total weight of the polyamide composition, of (A) from 30% to 97% by weight of at least one semi-crystalline semi-aromatic polyamide, (B) from 2% to 50% by weight of at least one white pigment, (C) from 0.1% to 2% by weight of at least one phosphorus-containing heat stabilizer, at least one basic salt having a pH higher than 7 and optionally from 0% to 50% by weight of (E) at least one filler. According to the invention, excellent initial reflectivity is shown, and the reflectivity is reduced slightly after long-time thermal aging at a high test temperature. In addition, it has been found that the polyamide composition maintains balanced mechanical properties. The invention also relates to an LED component made of the polyamide composition. The LED component may be manufactured or assembled by a reflow soldering process.

Description

Technical Field

[0001] The present invention relates to a polyamide composition for preparing LED components. Background Art

[0002] Plastic materials are widely used in fields that require resistance to yellowing, such as outdoor housings for consumer parts, automotive exterior parts, or high-reflection applications, and more particularly for manufacturing light-emitting diode (LED) components. Among them, polyamides, especially semi-aromatic polyamides, have been widely used as low-cost and easily processed materials to replace ceramics for LED components, such as housings, reflectors, and reflector plates, where excellent heat resistance and high light reflectivity are desired. One problem that has persisted with polyamide compositions for LED applications is that they tend to turn yellow when exposed to heat during manufacturing or under environmental conditions during use.

[0003] In recent years, surface mount technology (SMT) has developed rapidly. Fundamentally, this technology involves a component assembly technology for producing electronic circuits, where components are directly mounted or placed on the surface of a printed circuit board (PCB) using a batch reflow soldering process. SMT has the advantages of miniaturizing electronic components, having a higher packaging density, a high welding process efficiency, and a lower cost than the through-hole plating insertion process, which has led SMT to play a crucial role in leading the development of electronic products towards miniaturization and lightweight. However, the disadvantage of SMT is that the processing temperature is higher than 250 °C, which results in a significant reduction in reflectivity in LED applications.

[0004] US 7009029 describes a thermoplastic polyphthalamide (PPA) molding composition with high reflectivity, which contains well-controlled white pigment titanium dioxide with an average particle size of 0.1 to 0.5 μm.

[0005] WO 2013026779A describes a polyamide composition that has improved reflectivity after thermal aging by using additive metal oxides and titanium dioxide. When the amount of titanium dioxide is 10 - 30 wt%, the effect is promising. The polyamide composition can also contain a filler, preferably in an amount higher than 5 wt%. The reflectivity ratio is tested after 10 minutes at 260 °C. However, an aging time of 10 minutes does not meet the requirements of manufacturers.

[0006] CN 105602243A describes a polyamide composition that has a white pigment, a reinforcing filler, and a stabilizer package having elements magnesium and element phosphorus. It has been found that when the ratio of magnesium to phosphorus is controlled within the range of 0.1 - 1000, the initial whiteness of the polyamide composition can reach 90 or higher, and the whiteness can be maintained at 80 or higher after aging at 180 °C for 4 hours.

[0007] These improvements still do not meet the actual applications, especially when the aging temperature is very high (such as in the reflow soldering process) (250 °C or higher) or the aging time is very long (500 h or longer). There are still some gaps in the yellowing resistance performance compared with traditional thermosetting materials or ceramic materials. Therefore, it is quite necessary and has market value to develop a plastic composition with better reflectivity performance after molding and thermal aging. Summary of the Invention

[0008] The inventors of the present invention have tried to solve the above problems and found that the combination of semi-aromatic polyamide, white pigment, a heat stabilizer blend containing a phosphorus compound, and an inorganic or organic salt with a pH value higher than 7 shows excellent initial reflectivity and a small decrease in reflectivity after long-term thermal aging at a high test temperature. In addition, it has been found that the polyamide composition maintains balanced mechanical properties.

[0009] The present invention also provides an LED component made of the polyamide composition. The LED component can be manufactured or assembled by the reflow soldering process. Detailed Description of the Invention

[0010] Unless otherwise defined, all technical and scientific terms used herein have the meanings commonly understood by those skilled in the art to which the present invention pertains. The basic definitions or descriptions given above in a general sense or within a preferred range apply to the final product and, accordingly, to the starting materials and intermediates.

[0011] These basic definitions can be combined with each other as needed, that is, including combinations between the general definitions and / or their respective preferred ranges and / or embodiments.

[0012] All examples and preferred examples disclosed herein can be combined as needed, which are also considered to be covered within the scope of the present invention.

[0013] The terms "a / an" and "the" can be used interchangeably with the term "at least one". The phrases "at least one" and "comprising at least one" followed by a list refer to any one of the items in the list and any combination of two or more items in the list. Unless otherwise stated, all numerical ranges include their endpoints and non-integer values between the endpoints.

[0014] The term "about" refers to a range of numbers that those skilled in the art consider equivalent to the stated value when achieving the same function or result.

[0015] Unless otherwise stated, all percentages (%) are "percentages by weight".

[0016] Unless otherwise specified, the term "unit" refers to the repeating unit that constitutes the polyamide.

[0017] As used herein, the term "PA" refers to polyamide. The term "PA* / PA**" refers to a copolymer of PA* and PA**.

[0018] Disclosed is a polyamide composition for preparing an LED component, the polyamide composition comprising (A) at least one semi-crystalline semi-aromatic polyamide in an amount of 30% to 97% by weight based on the total weight of the polyamide composition, (B) at least one white pigment in an amount of 2% to 50% by weight, (C) at least one phosphorus-containing heat stabilizer in an amount of 0.1% to 2% by weight, (D) at least one basic salt with a pH higher than 7 in an amount of 0.1% to 4.5% by weight, and optionally (E) at least one filler in an amount of 0% to 50% by weight.

[0019] The term "semi-crystalline polyamide" herein should be understood as a semi-aromatic polyamide having crystalline domains as evidenced by the presence of a melting peak with a melting enthalpy of at least 5 J / g, which melting enthalpy is measured by differential scanning calorimetry (DSC) according to ISO11357 at a heating rate of 10 K / min.

[0020] The semi-crystalline semi-aromatic polyamide in the present invention comprises dicarboxylic acid units, diamine units, and optionally units derived from other monomers such as amino acids and / or lactam units, and these dicarboxylic acid units or diamine units have aromatic groups. For example, the semi-aromatic polyamide comprises aromatic dicarboxylic acid units and aliphatic diamine units, or aliphatic and / or alicyclic dicarboxylic acid units and aromatic diamine units.

[0021] The aromatic dicarboxylic acid units can typically be derived from aromatic dicarboxylic acids and / or aromatic dicarboxylic acid chlorides. The aliphatic dicarboxylic acid units can typically be derived from aliphatic dicarboxylic acids and / or aliphatic dicarboxylic acid chlorides. The alicyclic dicarboxylic acid units can typically be derived from alicyclic dicarboxylic acids and / or alicyclic dicarboxylic acid chlorides.

[0022] The aliphatic or aromatic diamine units can typically be derived from aliphatic diamines or aromatic diamines, respectively.

[0023] The amount of these other monomers is preferably 0 to 20 mol%, preferably 0 to 15 mol%, more preferably 0 to 10 mol% based on the total units constituting the semi-crystalline semi-aromatic polyamide.

[0024] The aromatic dicarboxylic acids in the present invention preferably contain 8 to 20 carbon atoms, more preferably 8 to 14 carbon atoms, such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and / or biphenyldicarboxylic acid, and more preferably are terephthalic acid, a mixture of terephthalic acid and isophthalic acid, naphthalenedicarboxylic acid, a mixture of terephthalic acid and naphthalenedicarboxylic acid.

[0025] The aliphatic dicarboxylic acids in the present invention preferably contain 4 to 36 carbon atoms, more preferably 6 to 36 carbon atoms, most preferably 6 to 20 carbon atoms or 36 carbon atoms, such as 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, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanoic acid, hexadecanedioic acid, octadecanedioic acid, dimer acid having 36 carbon atoms and mixtures thereof, and more preferably are adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and mixtures thereof.

[0026] The alicyclic dicarboxylic acids in the present invention preferably contain 4 to 20 carbon atoms, more preferably 8 to 20 carbon atoms, and more preferably contain a carbon backbone selected from the group consisting of cyclohexane, cyclopentane, cyclohexylmethane, dicyclohexylmethane, bis(methylcyclohexyl) and mixtures thereof, and most preferably are 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.

[0027] The aliphatic diamines in the present invention may be straight-chain aliphatic diamines or branched-chain aliphatic diamines, preferably straight-chain aliphatic diamines. The aliphatic diamines preferably contain 4 to 36 carbon atoms, more preferably 6 to 22 carbon atoms or 36 carbon atoms, and most preferably 4 to 14 carbon atoms, such as 4, 6, 8, 9, 10, 11, 12, 13, and 14 carbon atoms. Examples of straight-chain aliphatic diamines are 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-eicosanediamine, 1,22-docosanediamine, 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 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, and mixtures thereof. Examples of branched-chain 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.

[0028] The aromatic diamines in the present invention are preferably selected from the group consisting of: m-xylenediamine (MXD), p-xylenediamine (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'-biphenyldiamine, bis(4-methylaminophenyl)methane, 2,2'-bis(4-methylaminophenyl)propane, and mixtures thereof, more preferably MXD and / or PXD.

[0029] The suitable amino acids in the present 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.

[0030] Suitable lactams in the present invention preferably contain 4 to 12 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of lactams are 2-pyrrolidone (γ-butyrolactam), 2-piperidone (δ-valerolactam), ε-caprolactam, octanolactam, decanolactam, undecanolactam, heptanolactam, and / or laurolactam, preferably ε-caprolactam and / or undecanolactam.

[0031] In a preferred embodiment of the present invention, the semi-crystalline semi-aromatic polyamide comprises dicarboxylic acid units and diamine units, and 0 to 20 mol% of units derived from amino acids and / or lactams, based on the total moles of the units constituting the semi-crystalline semi-aromatic polyamide;

[0032] i. wherein the dicarboxylic acid units are derived from aromatic dicarboxylic acids and / or aromatic dicarboxylic acid chlorides (a-1), or a combination of aromatic dicarboxylic acids and / or aromatic dicarboxylic acid chlorides (a-1) and other dicarboxylic acids (a-2) including aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids. Based on the total moles of the dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aromatic dicarboxylic acids and / or aromatic dicarboxylic acid chlorides (a-1) is preferably 60 - 100 mol%, and the amount of the other dicarboxylic acids (a-2) is preferably 0 - 40 mol%;

[0033] The diamine units are derived from aliphatic diamines (b-1), or a combination of aliphatic diamines (b-1) and aromatic diamines (b-2). Based on the total moles of the diamine units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aliphatic diamines (b-1) is preferably 80 - 100 mol%, and the amount of the aromatic diamines (b-2) is preferably 0 - 20 mol%; or

[0034] ii. wherein the dicarboxylic acid units are derived from aliphatic dicarboxylic acids or a combination of aliphatic dicarboxylic acids and alicyclic dicarboxylic acids. Based on the total moles of the dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aliphatic dicarboxylic acids is preferably 80 - 100 mol%, and the amount of the alicyclic dicarboxylic acids is preferably 0 - 20 mol%;

[0035] The diamine units are derived from aromatic diamines, or a combination of aromatic diamines and aliphatic diamines. Based on the total moles of the diamine units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aromatic diamines is preferably 80 - 100 mol%, and the amount of the aliphatic diamines is preferably 0 - 20 mol%.

[0036] In a preferred embodiment, the semi-crystalline semi-aromatic polyamide comprises dicarboxylic acid units and diamine units, wherein the dicarboxylic acid units are derived from aromatic dicarboxylic acids and / or aromatic dicarboxylic acid chlorides (a-1), or a combination of aromatic dicarboxylic acids and / or aromatic dicarboxylic acid chlorides (a-1) and other dicarboxylic acids (a-2) including aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids. The aromatic dicarboxylic acid (a-1) is terephthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, a combination of terephthalic acid and isophthalic acid, or a combination of terephthalic acid and naphthalenedicarboxylic acid; based on the total moles of the dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) is preferably 60 - 100 mol%, more preferably 80 - 100 mol%, further preferably 90 - 100 mol%, and most preferably 95 - 100 mol%; based on the total moles of the dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide, the amount of the other dicarboxylic acid (a-2) is preferably 0 - 40 mol%, more preferably 0 - 20 mol%, further preferably 0 - 10 mol%, and most preferably equal to or less than 5 mol%;

[0037] The diamine units are derived from aliphatic diamines (b-1), or a combination of aliphatic diamines and aromatic diamines (b-2). Based on the total moles of the diamines constituting the semi-crystalline semi-aromatic polyamide, the amount of the aliphatic diamine (b-1) is preferably 80 - 100 mol%, more preferably 90 - 100 mol%, and most preferably 95 - 100 mol%; based on the total moles of the diamine units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aromatic diamine (b-2) is preferably 0 - 20 mol%, more preferably 0 - 10 mol%, and most preferably 0 - 5 mol%.

[0038] In a preferred embodiment, the semi-crystalline semi-aromatic polyamide comprises dicarboxylic acid units and diamine units, the dicarboxylic acid units are derived from aromatic dicarboxylic acids (a-1) and 0 - 10 mol%, more preferably 0 - 5 mol% of other dicarboxylic acids (a-2), wherein the aromatic dicarboxylic acid (a-1) comprises 10 - 40 mol%, more preferably 15 - 30 mol%, and most preferably 20 - 30 mol% of isophthalic acid and 60 - 90 mol%, more preferably 70 - 85 mol%, and most preferably 70 - 80 mol% of at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid, preferably terephthalic acid or a combination of terephthalic acid and naphthalenedicarboxylic acid; the other dicarboxylic acid (a-2) is an aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid; the mole percentages are based on the total moles of the dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide;

[0039] 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 moles of the diamine units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aliphatic diamine (b-1) is preferably equal to 90 - 100 mol%, more preferably 95 - 100 mol%; the amount of the aromatic diamine (b-2) is preferably 0 - 10 mol%, more preferably 0 - 5 mol%.

[0040] In a more preferred embodiment, the aliphatic dicarboxylic acid of the other dicarboxylic acid (a-2) is preferably adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanoic acid, hexadecanedioic acid, and octadecanedioic acid, more preferably adipic acid, sebacic acid, and / or dodecanedioic acid.

[0041] In a more preferred embodiment, the aliphatic diamine (b-1) is a linear aliphatic diamine (b-1a) or a combination of a linear aliphatic diamine and a branched aliphatic diamine (b-1b). The linear 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 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.

[0042] Examples of the semi-crystalline semi-aromatic polyamide are polyamide MXD6, polyamide PXD6, polyamide MXD9, polyamide PXD9, polyamide MXD10, and / or polyamide PXD10.

[0043] The polyamide in the present invention may include a polyamide copolymer or a blend of two or more polyamides and their copolymers.

[0044] The semi-crystalline semi-aromatic polyamide is suitably represented by the following symbols

[0045] -R represents one or more of a linear aliphatic diamine and a branched aliphatic diamine

[0046] -T represents terephthalic acid

[0047] -I represents isophthalic acid

[0048] -A represents one or more of aromatic diamines

[0049] -Y represents one or more of aliphatic dicarboxylic acids

[0050] -V represents one or more of lactams

[0051] Suitable semi-crystalline semi-aromatic polyamides can be represented by PA RT, PA RT / RI, PA RT / BT, PA RT / BT / RI / BI, which contain:

[0052] - 60 - 100 mol% of (T), 0 - 40 mol% of (I), preferably 60 - 85 mol% of (T), 15 - 40 mol% of (I), more preferably 65 - 80 mol% of (T), 20 - 35 mol% of (I); based on the total moles of (T)+(I); and

[0053] - 100 mol% of (R), where R is preferably a linear or branched aliphatic polyamide having 4 to 36 carbon atoms, more preferably 6 to 18 carbon atoms.

[0054] Examples of these polyamides include PA 4T / 4I, PA 4T / 6I, 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, PA4T / 6T / DT, PA 4T / 10T / DT, PA 4T / 4I / 6T / 6I / DT / DI, PA6T / 12T / 6I / 12I, PA 6T / 10T / 6I, PA4T / 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. Here, D is 2 - methylpentamethylenediamine or 3 - methyl - 1,5 - pentanediamine, or a mixture thereof, and the amount of D is 0 - 20 mol%, preferably 0 - 10 mol% of the total moles of (R).

[0055] In a preferred embodiment, PA 6T / 6I contains 65 - 80 mol% of (T), 20 - 35 mol% of (I).

[0056] In a preferred embodiment, PA 6T / 10T contains 10 - 60 mol% of (6T), 40 - 90 mol% of (10T), preferably 10 - 40 mol% of (6T), 60 - 90 mol% of (10T).

[0057] In a preferred embodiment, PA 6T / 10T / 6I comprises 60 - 90 mol% of (6T), 5 - 40 mol% of (6I), and 5 - 45 mol% of (10T).

[0058] In a preferred embodiment, PA 6T / 10T / 6 comprises 60 - 85 mol% of (6T), 15 - 40 mol% of (10T), and 5 - 15 mol% of caprolactam.

[0059] Suitable semi-crystalline semi-aromatic polyamides can be represented by PA RT / RY, PA RT / V, PA RT / RI / RY, or PA RT / RI / V, which comprise:

[0060] - 60 - 100 mol% of (T), 0 - 40 mol% of (I); 0 - 10 mol% of (V), preferably 0 - 5 mol% of (V); 0 - 80 mol% of (Y), preferably 0 - 60 mol% of (Y), more preferably 0 - 40 mol% of (Y); based on the total moles of (T)+(I)+(V)+(Y); R is preferably a linear aliphatic polyamide having 9 to 36 carbon atoms, more preferably having 9 to 18 carbon atoms. Examples of these polyamides include PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, PA 5T / 510, PA4T / 410, PA 6T / 610, PA6T / 612, PA 6T / 1012, PA 9T / 612, PA 9T / 1012, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA6T / 6I / 66, PA 10T / 12, PA 10T / 11, and PA 6T / 6I / 12, preferably PA 6T / 6, PA 6T / 610, or PA 6T / 612.

[0061] In a preferred embodiment, PA RT / RY comprises 60 - 100 mol% of (T), 0 - 40 mol% of (Y), where R is 1,6 - hexanediamine, 1,9 - nonanediamine, 1,10 - decanediamine, and Y is dodecanedioic acid.

[0062] The semi-crystalline semi-aromatic polyamides in the present invention have a melting temperature (Tm) of 250°C - 350°C, preferably 280°C - 320°C, and most preferably 305°C - 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 at a heating rate of 10 K / min according to ISO11357.

[0063] The semi-crystalline semi-aromatic polyamide in the present invention preferably has an inherent viscosity of 50-150 ml / g, which is measured in sulfuric acid with a concentration of 96 wt% according to the ISO307-2007 method.

[0064] In a preferred embodiment, the semi-crystalline 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.

[0065] The semi-crystalline semi-aromatic polyamide can be produced using conventionally known methods such as melt polymerization or solution polymerization.

[0066] The semi-crystalline semi-aromatic polyamide disclosed herein should not be limited to those prepared from virgin crude oil monomers and can be fully or at least partially bio-based or derived from waste streams or recycling activities, i.e., the polyamide used in this application can be based on renewable materials, secondary raw materials or recycled raw materials. For example, PA 6T / 6, PA6T / 12, PA 6T / 6I / 6, PA 6T / 66, 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, PA10T / 11 and PA 6T / 6I / 12 used as component (A) in this application can be prepared or obtained or derived from monomers obtained in the remonomerization process.

[0067] The amount of the semi-crystalline semi-aromatic polyamide in the present invention is 30% to 97% by weight, preferably 40% to 85% by weight, more preferably 45% to 80% by weight, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% by weight; based on the total weight of the polyamide composition.

[0068] White pigment

[0069] The white pigment in the present invention is preferably titanium oxide, zinc 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, calcium sulfate, zinc sulfide, aluminum phosphate, magnesium carbonate and mixtures thereof. Among these white pigments, titanium oxide is preferred.

[0070] The white pigment is not limited by size or form and can be in the form of particles, whiskers or fibers, preferably particles.

[0071] White pigments can be surface-treated with coupling agents by existing methods, such coupling agents as silane coupling agents, titanium coupling agents, acrylic-silane-based coupling agents, epoxy-silane-based coupling agents, and amino-silane-based coupling agents, such as vinyltriethoxysilane, polydimethylsiloxane, 2-aminopropyltriethoxysilane, 2-glycidoxypropyltriethoxysilane, etc., and their combinations.

[0072] In a preferred embodiment, the white pigment is titanium oxide, which exhibits better light reflectivity and light stability. The particle size of titanium oxide is preferably 100 - 500 nm, more preferably 200 - 400 nm. Titanium dioxide can also be treated with inorganic surface treatment agents. The surface treatment of titanium oxide can improve the wettability with polyamide. Examples of inorganic surface treatment agents can be selected from the group consisting of: alumina, silica, zirconia, sodium silicate, sodium aluminate, sodium aluminosilicate, zinc oxide, mica, etc. Inorganic surface treatment agents can be used alone or in combination.

[0073] The amount of the white pigment in the present invention is preferably 2% to 50% by weight, more preferably 10% to 50% by weight, further preferably 20% to 50% by weight, and most preferably 20% to 40% by weight, such as 20%, 25%, 30%, 35%, 40% by weight; based on the total weight of the polyamide composition.

[0074] Phosphorus-containing heat stabilizer

[0075] It has been found that compared with other heat stabilizers, phosphorus-containing heat stabilizers provide better optical properties and heat resistance for polyamide compositions. Phosphorus-containing heat stabilizers are selected from the group including but not limited to: organic phosphinates, inorganic hypophosphites, organic phosphonates, inorganic phosphonates, organic phosphites, and their mixtures, and organic phosphonates and organic phosphinates are preferred.

[0076] The organic phosphonates in the present invention are metal salts or ammonium salts of phosphonic acids or their derivatives. The metal can be an alkali metal, an alkaline earth metal, and other common metals. Examples of the metal are sodium, potassium, lithium, magnesium, calcium, barium, aluminum, and their mixtures, and preferably sodium, potassium, or magnesium. Derivatives of phosphonic acids can be alkyl- or aryl-substituted phosphonic acids. The alkyl preferably has 1 to 6 carbon atoms. Preferred phosphonic acid derivatives are phenyl phosphonate, diphenyl phosphonate, ethyl phosphonate, and diethyl phosphonate.

[0077] In a preferred embodiment, the organic phosphonates are selected from the group consisting of: sodium phosphonate, potassium phosphonate, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate, and ammonium phosphonate.

[0078] The inorganic phosphonates in the present invention conform to the following general formula: [(HO)PO2] 2- p / 2 Kat or [(HO)2PO] - p Kat p+ , where Kat is a cation of p valence, especially a cation of an alkali metal or alkaline earth metal, an ammonium cation, and / or a cation of Fe, Zn or especially Al, including the cations Al(OH) or Al(OH)2, and p is 1, 2, 3 or 4. Preferably, the inorganic phosphonate is aluminum phosphite [Al(H2PO3)3].

[0079] The inorganic hypophosphites in the present invention are metal salts or ammonium salts of hypophosphites. The metal can be an alkali metal, an alkaline earth metal, and other common metals. Examples of the metal are sodium, potassium, lithium, magnesium, calcium, barium, aluminum and mixtures thereof, preferably sodium, potassium or magnesium.

[0080] In a preferred embodiment, the inorganic hypophosphites are selected from the group consisting of: sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, magnesium hypophosphite, calcium hypophosphite, and ammonium hypophosphite.

[0081] The organic hypophosphonates in the present invention are metal salts having formula I.

[0082]

[0083] Where Ar can be a C6 to C 18 aryl, and X is a metal cation selected from Na, Ca, Mg, Al or Zn. The C6 to C 18 aryl can be unsubstituted or substituted by substituents such as: C1-C 10 alkyl, C3-C 10 cycloalkyl, C1-C 10 alkoxy, C3-C 10 cycloalkoxy, C1-C 10 alkylthio, C3-C 10 cycloalkylthio, C1-C 10 alkylamino, C3-C 10 cycloalkylamine, C6-C 18 aryl, C6-C 18 aryloxy, C6-C 18 arylthio, C6-C 18 arylamino, halogen, etc., and combinations thereof. Preferably, the C6 to C 18 aryl can be C6 to C16 Aryl, preferably C6 to C 14 Aryl, more preferably C6 to C 12 Aryl, most preferably phenyl or naphthyl. Preferably, the phosphonite is sodium phenylphosphinate.

[0084] In a preferred embodiment of the present invention, the phosphorus-containing heat stabilizer is an organic phosphonite and an organic phosphonate, which further exhibit better yellowing resistance and higher hydrolysis resistance at high temperatures.

[0085] In a preferred embodiment of the present invention, the organic phosphonite is sodium phenylphosphinate.

[0086] In a preferred embodiment of the present invention, the organic phosphonate is sodium phosphonate and potassium phosphonate.

[0087] The phosphorus-containing heat stabilizer is not limited by size. A preferred specific size is 100 to 600 μm.

[0088] The amount of the phosphorus-containing heat stabilizer in the present invention is preferably 0.1% to 2% by weight, more preferably 0.1% to 1% by weight, and most preferably 0.2% to 0.8% by weight, such as 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% by weight; based on the total weight of the polyamide composition.

[0089] Alkaline salt

[0090] The basic salt in the present invention is also known as a basic salt, which is a salt formed as a product of incomplete neutralization of a strong base and a weak acid. The basic salt is basically composed of an ionic assembly of a positively charged cation and a negatively charged anion, where the cation comes from the positively charged cation of the strong base and the anion comes from the negatively charged anion of the weak acid.

[0091] A strong base is a basic chemical compound that can remove a proton from the molecule of even a very weak acid in an acid-base reaction. The strong base is preferably a hydroxide of an alkali metal, an alkaline earth metal, and an ammonium salt, such as lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH), magnesium hydroxide (Mg(OH)2), calcium hydroxide (Ca(OH)2), strontium hydroxide (Sr(OH)2), barium hydroxide (Ba(OH)2), and tetramethylammonium hydroxide (N(CH3)4OH). Therefore, the positively charged cation of the basic salt in the present invention can be selected from the group consisting of: lithium ion (Li + )), sodium ion (Na + )), potassium ion (K + )), rubidium ion (Rb), cesium ion (Cs), magnesium ion (Mg 2+) Calcium ion (Ca 2+ ) Strontium ion (Sr 2+ ) Barium ion (Ba 2 + ) And tetramethylammonium ion (N(CH3)4 + ), preferably alkaline earth metal ions such as magnesium ion, calcium ion and barium ion, more preferably calcium ion and barium ion.

[0092] A weak acid is an acid that does not completely dissociate into its constituent ions when dissolved in a solution. The weak acid is preferably an inorganic weak acid and an organic acid. Examples of inorganic weak acids are hydrofluoric acid (HF), nitrous acid (HNO2), sulfurous acid (H2SO3), carbonic acid (H2CO3) and phosphoric acid (H3PO4). Examples of organic acids are formic acid (HCOOH), acetic acid (CH3COOH), benzoic acid (C6H5COOH), citric acid (HOC(CO2H)(CH2CO2H)2), oxalic acid (C2H2O4), acrylic acid (CH2=CHCOOH) and phosphoric acid (H3PO4). The organic acid can also be in the form of a polymer, such as polyacrylic acid with a weight average molecular weight of about 3000 - 100000. When the organic acid is in the form of a polymer, the molecular weight and the synthesis method are not limited.

[0093] Therefore, the negatively charged anions of the basic salts in the present invention can be selected from the group consisting of: formate (HCOO - ), acetate (CH3COO - ), carbonate (CO3 2- ), citrate (HOC(COO - )(CH2COO - )2), fluoride ion (F - ), nitrite (NO 2- ), benzoate (C6H5COO - ), sulfite (SO3 2- ), acrylate (CH2=CHCOO - ), dihydrogen phosphate ([H2PO4] - ), hydrogen phosphate ([HPO4] 2- ) and phosphate ([PO4] 3- ).

[0094] The basic salts in the present invention have a pH value higher than 7, which is defined and measured according to ISO 23496 - 2019.

[0095] In a preferred embodiment of the present invention, the basic salt is selected from the group consisting of, but not limited to, the following: calcium carbonate, strontium carbonate, barium carbonate, sodium acrylate, calcium acrylate, potassium acrylate, sodium polyacrylate, calcium polyacrylate, potassium polyacrylate, sodium acetate, calcium acetate, barium acetate, potassium acetate, sodium citrate, calcium citrate, barium citrate, sulfite, bisulfate, silicate, metaaluminate, phosphate, and mixtures thereof.

[0096] In a preferred embodiment of the present invention, the basic salt is calcium carbonate, barium carbonate, sodium polyacrylate, calcium polyacrylate, and barium polyacrylate.

[0097] The particle size of the basic salt is not limited, and is preferably from 0.05 μm to 50 μm, and more preferably from 0.1 μm to 10 μm.

[0098] Examples of calcium carbonate include calcite, aragonite, natural calcium carbonate (heavy calcium carbonate), and synthetic calcium carbonate (precipitated calcium carbonate). Among them, calcite and aragonite are preferred.

[0099] Surprisingly, it was found that the basic salt contributes greatly to the thermal stability of the polyamide composition. Acidic salts or neutral salts have no effect on the improvement of thermal stability. Some basic salts are also used as inorganic fillers in the polyamide composition. However, the amount of the basic salt in the present invention should be controlled within a specific range. When the amount exceeds 4.5%, the increase in the effect on thermal stability is not obvious, and the mechanical properties of the polyamide composition decrease rapidly.

[0100] The amount of the basic salt in the present invention is preferably from 0.1% to 4.5% by weight, more preferably from 0.5% to 4% by weight, and most preferably from 1% to 3% by weight; based on the total weight of the polyamide composition.

[0101] The polyamide composition in the present invention may contain from 0% to 50% by weight of a filler. The filler may be a fibrous filler, a specific filler, and a plate-like filler.

[0102] The fibrous filler in the present invention is preferably selected from the group consisting of: glass fiber, wollastonite, carbon fiber, metal fiber, mineral fiber, potassium titanate, aluminum borate, and more preferably is glass fiber, ground glass fiber, chopped glass fiber, carbon fiber, potassium titanate, and / or wollastonite.

[0103] Preferably, the glass fiber may be E-glass fiber, A-glass fiber, D-glass fiber, AR-glass fiber, C-glass fiber, S-glass fiber. The cross-section of the glass fiber may be circular or non-circular, and is preferably circular.

[0104] The fibrous filler is preferably surface-treated with a silane coupling agent, such as a vinylsilane-based coupling agent, an acrylicsilane-based coupling agent, an epoxysilane-based coupling agent, and an aminosilane-based coupling agent, preferably an aminosilane-based coupling agent. The silane coupling agent can be dispersed in the sizing agent. Examples of the sizing agent are acrylic compounds, acrylic / maleic acid derivative-modified compounds, epoxy compounds, urethane compounds, urethane / maleic acid derivative-modified compounds, and urethane / amine-modified compounds.

[0105] The fibrous filler in the polyamide composition preferably has an average length of 2 - 500 μm, preferably 200 - 300 μm, more preferably 220 - 240 μm. The diameter or major axis of the cross-section of the fibrous filler is preferably 5 - 40 μm, preferably 10 - 25 μm.

[0106] Alternatively, the filler is used in the form of particles. The specific filler can have a variety of particle sizes, ranging from particles in the form of dust to coarse particles. The specific filler used can include organic or inorganic particles. Examples that can be used are inorganic particles such as kaolin, chalk, wollastonite, talc, silicate, graphite, mica, vermiculite, montmorillonite, glass particles (e.g., glass beads).

[0107] The amount of the filler in the present invention is preferably 10% to 50% by weight, more preferably 10% to 30% by weight, most preferably 10% to 20% by weight; based on the total weight of the polyamide composition.

[0108] The polyamide composition in the present invention can optionally contain at least one additive (F), such as a lubricant, an antioxidant, a release agent, an impact modifier, a compatibilizer, a light stabilizer such as a UV stabilizer, a plasticizer, a surfactant, a nucleating agent, a coupling agent, an antimicrobial agent, an antistatic agent, and any combination thereof.

[0109] For the purposes of the present invention, the additives can be used in conventional amounts. For example, the polyamide composition can contain at least one additive in an amount of 0.01% to 10% by weight based on the total weight of the polyamide composition.

[0110] The polyamide composition may contain, for example, an antioxidant. Suitable antioxidants are aromatic amine-based antioxidants, hindered phenol-based antioxidants, and phosphite-based antioxidants, especially hindered phenol-based antioxidants. Examples of hindered phenol-based 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-ethanediyl), 2,4-bis[(octylthio)methyl]-o-cresol, octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, C7-C9-branched alkyl 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate, 2,4-bis[(dodecylthio)methyl]-o-cresol, 4,4'-butylidenebis-(3-methyl-6-tert-butylphenol), octadecyl 3,5-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-butylanilino)-1,3,5-triazine, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-1,6-hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzamide].

[0111] The amount of antioxidant (when present) may be from 0.01% to 1% by weight, or from 0.1% to 0.5% by weight, based on the total weight of the polyamide composition.

[0112] The polyamide composition may contain, for example, a lubricant. Suitable lubricants are preferably esters or amides of saturated or unsaturated aliphatic carboxylic acids having 10 to 40 carbon atoms, preferably 16 to 22 carbon atoms, and saturated aliphatic alcohols or amines containing 2 to 40 carbon atoms, preferably 2 to 6 carbon atoms. The carboxylic acid may be mono- or di-functional. Examples of carboxylic acids are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, and particularly preferably stearic acid, capric acid, and also montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms). The aliphatic alcohol may be mono- to tetra-functional. Examples of aliphatic alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, and pentaerythritol, with glycerol and pentaerythritol being preferred. The aliphatic amine may be mono- to trifunctional. Examples of aliphatic amines are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and bis(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being particularly preferred herein.

[0113] Preferred esters or amides are N,N'-ethylene bis(stearamide), glycerol distearate, glycerol tristearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate. N,N'-ethylene bis(stearamide) is particularly preferred as a lubricant in the polyamide composition according to the present invention.

[0114] Mixtures of various esters or amides, or combinations of esters and amides, can also be used in any desired mixing ratio.

[0115] 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 montan wax (a mixture of straight-chain saturated carboxylic acids with a chain length of 28 to 32 carbon atoms), calcium montanate or sodium montanate, and also low molecular weight polyethylene wax and low molecular weight polypropylene wax.

[0116] The amount of the lubricant (when present) can be from 0.01% to 2% by weight, or from 0.2% to 1% by weight, based on the total weight of the polyamide composition.

[0117] The polyamide composition can, for example, comprise an impact modifier. Suitable impact modifiers can include polyolefin-based, styrene-based, and unsaturated carboxylic acid-based impact modifiers. Suitable impact modifiers can also be those modified by functional blocks such as epoxy functional blocks and / or anhydride blocks. The epoxy functional block can be a unit derived from glycidyl (meth)acrylate. The anhydride block can be a unit derived from maleic anhydride.

[0118] Suitable polyolefin-based impact modifiers can include polyolefins comprising repeating units derived from olefins having 2 to 10 carbon atoms. Examples of such olefins include ethylene, 1-butene, 1-propene, 1-pentene, 1-octene, and mixtures of ethylene and 1-octene, preferably ethylene, 1-propene, and mixtures of ethylene and 1-octene.

[0119] Suitable unsaturated carboxylic acid-based impact modifiers can 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, methacrylic acid, maleic acid, fumaric acid, glutaconic acid, itaconic acid, citraconic acid, (meth)acrylates, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate.

[0120] The impact modifier can also be a binary or ternary polymer or a core-shell structured polymer. Examples of such impact modifiers include styrene / ethylene / butene copolymer (SEBS), ethylene-methyl acrylate-glycidyl methacrylate terpolymer, ethylene / propylene / diene rubber (EPDM), and ethylene-octene copolymer.

[0121] The amount of the impact modifier (when present) can be 0.01% to 15% by weight, or 1% to 15% by weight, or 5% to 10% by weight based on the total weight of the polyamide composition.

[0122] The polyamide composition can contain, for example, plasticizers including but not limited to dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oil, and N-(n-butyl)benzenesulfonamide.

[0123] The amount of the plasticizer (when present) can be 0.01% to 15% by weight, or 1% to 15% by weight, or 5% to 10% by weight based on the total weight of the polyamide composition.

[0124] In a specific embodiment according to the present invention, the polyamide composition comprises:

[0125] 30% to 97% by weight of (A) at least one semi-crystalline semi-aromatic polyamide,

[0126] 2% to 50% by weight of (B) at least one white pigment selected from the group consisting of titanium oxide, zinc 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, calcium sulfate, zinc sulfide, aluminum phosphate, magnesium carbonate, and mixtures thereof,

[0127] 0.1% to 2% by weight of (C) at least one phosphorus-containing heat stabilizer,

[0128] 0.1% to 4.5% by weight of (D) at least one basic salt having a pH higher than 7, and optionally

[0129] 0% to 50% by weight of (E) at least one filler,

[0130] each based on the total weight of the polyamide composition.

[0131] In another preferred embodiment, the polyamide composition comprises:

[0132] 30% to 97% by weight of (A) at least one semi-crystalline semi-aromatic polyamide,

[0133] From 2% to 50% by weight of (B) at least one white pigment selected from the group consisting of titanium oxide, zinc 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, calcium sulfate, zinc sulfide, aluminum phosphate, magnesium carbonate and mixtures thereof,

[0134] From 0.1% to 2% by weight of (C) at least one phosphorus-containing heat stabilizer selected from the group consisting of organic hypophosphites, inorganic hypophosphates, organic phosphates, inorganic phosphates, organic phosphites and mixtures thereof,

[0135] From 0.1% to 4.5% by weight of (D) at least one basic salt having a pH higher than 7 selected from the group consisting of calcium carbonate, strontium carbonate, barium carbonate, sodium acrylate, calcium acrylate, potassium acrylate, sodium polyacrylate, calcium polyacrylate, potassium polyacrylate, sodium acetate, calcium acetate, barium acetate, potassium acetate, sodium citrate, calcium citrate, barium citrate, sulfites, bisulfates, silicates, metaaluminates, phosphates and mixtures thereof, and optionally

[0136] From 0% to 50% by weight of (E) at least one filler,

[0137] Each based on the total weight of the polyamide composition.

[0138] In another preferred embodiment, the polyamide composition comprises:

[0139] From 30% to 97% by weight of (A) at least one semi-crystalline semi-aromatic polyamide,

[0140] From 2% to 50% by weight of (B) at least one white pigment selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide and mixtures thereof,

[0141] From 0.1% to 2% by weight of (C) at least one phosphorus-containing heat stabilizer, said at least one phosphorus-containing heat stabilizer being an organic hypophosphite and / or an organic phosphate,

[0142] From 0.1% to 4.5% by weight of (D) at least one basic salt having a pH higher than 7 selected from the group consisting of calcium carbonate, strontium carbonate, barium carbonate, sodium polyacrylate, calcium polyacrylate, potassium polyacrylate and mixtures thereof, and optionally

[0143] From 0% to 50% by weight of (E) at least one filler,

[0144] Each based on the total weight of the polyamide composition.

[0145] In another preferred embodiment, the polyamide composition comprises:

[0146] 47% to 67% by weight of (A) at least one semi-crystalline semi-aromatic polyamide,

[0147] 30% to 50% by weight of (B) at least one white pigment selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, and mixtures thereof,

[0148] 0.5% to 1% by weight of (C) at least one phosphorus-containing heat stabilizer, which is an organic hypophosphite and / or an organic phosphonate,

[0149] 0.5% to 2% by weight of (D) at least one basic salt having a pH higher than 7 selected from the group consisting of calcium carbonate, strontium carbonate, barium carbonate, sodium polyacrylate, calcium polyacrylate, potassium polyacrylate, and mixtures thereof, and optionally

[0150] 0% to 50% by weight of (E) at least one filler,

[0151] each based on the total weight of the polyamide composition.

[0152] The polyamide composition according to the present invention can be processed into various structures or forms by conventional methods to provide articles. For example, the respective components of the polyamide composition according to the present invention can be mixed and then molded, for example, via injection and / or extrusion in a conventional mixing device such as a screw extruder, a Brabender mixer, or a Banbury mixer to form an article. The mixing temperature used herein is generally from 220 °C to 260 °C.

[0153] It will be understood that all components of the polyamide composition can be mixed simultaneously. Alternatively, some components of the polyamide composition can be premixed and then mixed with other components. For example, all starting components of the polyamide composition except the white pigment and the filler are mixed together in a stirrer and fed into a twin-screw extruder at the throat, and then the white pigment and the filler are premixed and fed downstream using a side feeder.

[0154] Accordingly, the present invention provides an LED component made of the polyamide composition. The LED component can be manufactured or assembled by a reflow soldering process.

[0155] The LED component is part of a light-emitting diode reflector. The light-emitting diode arrangement is an assembly including at least one light-emitting semiconductor diode, a current source, and a housing covering the diode or a board in which the diode is embedded. The LED component can be the housing or the board of the light-emitting diode arrangement. The housing or the board can be produced entirely or partially from the polyamide composition of the present invention. For example, one of the walls of the housing is produced from the polyamide composition.

[0156] The LED components in the present invention can be components for automotive lamps, mobile communication devices, and household applications. The components of the lamp include automotive instrument panel displays, automotive screens, turn signal lamps, brake lamps, interior and exterior lighting devices, floodlights, and floor lamps. The components of mobile electronic devices include displays of mobile phones, laptops, notebook computers, 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 smart watches), head-mounted displays, virtual reality head-mounted devices, digital cameras, global positioning system receivers, portable power supplies, and portable Wi-Fi. The components of household applications include TV backlight devices, liquid crystal displays, computer monitors, laptop computer monitors, notebook computer monitors, and displays for household applications (such as air conditioners, smart home systems, floor mopping robots, electric cookers, rice cookers, ovens, microwave ovens, washing machines, dishwashers, etc.).

[0157] Therefore, the present invention provides an article produced from the polyamide composition according to the present invention.

[0158] Preferably, the article according to the present invention has one or more of the following properties:

[0159] - A tensile stress at break greater than 41 MPa measured according to ISO 527-1-2012.

[0160] - A tensile strain at break greater than 100% measured according to ISO 527-1-2012.

[0161] - A tensile modulus greater than 4450 MPa measured according to ISO 527-1-2012.

[0162] - A Charpy notched impact strength of at least 1.8 KJ / m 2 at 23 °C measured according to ISO 179-1-2010.

[0163] - A Charpy unnotched impact strength of at least 15 KJ / m 2 at 23 °C measured according to ISO 179-1-2010.

[0164] - A heat deflection temperature greater than 242 °C measured according to Method A of ISO 75-2-2013 at 0.45 MPa.

[0165] - A melt volume rate (MVR) greater than 88 cm 3 / 10 min measured according to ISO 1133 at 325 °C and a load of 2.16 kg.

[0166] - An original reflectance greater than 96.1% measured at a wavelength of 460 nm.

[0167] - A reflectance decrease less than 4.4% measured at a wavelength of 460 nm after aging at 120 °C for 500 hours.

[0168] - A reflectance decrease less than 25.9% measured at a wavelength of 460 nm after aging at 260 °C for 30 minutes.

[0169] The reflectance of the polyamide composition is particularly well maintained after thermal aging at 260 °C for 30 minutes, which enables the polyamide composition to be used in reflow soldering processes and meet the application requirements of LED components.

[0170] Examples

[0171] The aspects of the present invention are more fully illustrated by the following examples, which are presented to illustrate certain aspects of the present invention and should not be construed as limiting thereof.

[0172] The following materials and test methods were used in the examples.

[0173] Materials:

[0174] Table 1 Materials for Examples and Comparative Examples of the Present Invention

[0175]

[0176]

[0177] Measurements:

[0178] 1. Measure the tensile stress at break, tensile strain at break, and tensile modulus of a sample with a thickness of 4 mm according to ISO 527-1-2012. Use a type 1 test specimen described in ISO 527-1-2012. Measure the Charpy notched impact strength and Charpy unnotched impact strength via edge impact according to ISO 179-1-2010. The test specimen for the Charpy unnotched test is a type 1 specimen with dimensions of 80 * 10 * 4 mm (length * width * thickness). The test specimen for the Charpy notched test is a type 1 with a notch of type A. All test specimens were conditioned at 23 °C and 50% relative humidity for 16 h. The tests were carried out in the same environment as the conditioning.

[0179] 2. Test the heat deflection temperature (HDT) at 0.45 MPa according to Method A of ISO 75-2-2013.

[0180] 3. Test the melt volume flow rate (MVR) at 325 °C and a load of 2.16 kg according to ISO1133.

[0181] 4. According to CIE 1976, reflectance-related tests were measured at a wavelength of 460 nm in D65 light source reflection mode using a sample of molded plastic sheet (60*60*2 mm) with a DC850 spectrophotometer from Datacolor company.

[0182] The test specimens used were made according to the following general procedure for preparing test specimens.

[0183] General procedure for preparing test specimens

[0184] Prepare test specimens according to the formulation shown in Table 2. Mix all raw materials except titanium dioxide (B) together in a Turbula T50A high-speed stirrer and feed them into a ZE25Ax (Berstorff) twin-screw extruder at the throat. Feed titanium dioxide downstream using a side feeder to maintain good mechanical properties. Melt-extrude the raw materials at a temperature of 320 °C, pelletize, and thus obtain a polyamide composition in the form of pellets.

[0185] Sample preparation and testing: Process the dried pellets in an injection molding machine KM130CX from Krauss Maffei with a clamping force of 130 T at a melt temperature of 320 °C and a mold temperature of 120 °C to obtain test specimens.

[0186] Measure the properties of the obtained test specimens as described above. The test results and the formulation for preparing test specimens are summarized in Table 2.

[0187] As can be seen from Table 2, Examples E1 - E6 of the present invention use a combination of a phosphorus-containing heat stabilizer and an alkaline salt. The original reflectance of E1 to E6 is higher than that of Comparative Examples C1 - C3, and the decrease in reflectance of E1 - E6 after aging at 120 °C for 500 h and after aging at 260 °C for 30 min is significantly lower than the decrease in reflectance of C1 - C2 (the decrease in reflectance of which after aging at 260 °C for 30 min is greater than 35%).

[0188] It will be apparent to those of ordinary skill in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. The embodiments and examples are intended to be considered only exemplary. Accordingly, the present invention is intended to cover such modifications and variations within the scope of the appended claims and their equivalents.

[0189] Table 2

[0190]

[0191]

[0192] E: Examples of the present invention; C: Comparative examples.

Claims

1. A polyamide composition for preparing an LED component, the polyamide composition comprising (A) at least one semi-crystalline semi-aromatic polyamide in an amount of 30% to 97% by weight based on the total weight of the polyamide composition, (B) at least one white pigment in an amount of 2% to 50% by weight, (C) at least one phosphorus-containing heat stabilizer in an amount of 0.1% to 2% by weight, (D) at least one basic salt with a pH higher than 7 in an amount of 0.1% to 4.5% by weight, and optionally (E) at least one filler in an amount of 0% to 50% by weight.

2. The polyamide composition according to claim 1, wherein the semi-crystalline semi-aromatic polyamide comprises dicarboxylic acid units and diamine units, and 0 to 20 mol% of units derived from amino acids and / or lactams based on the total moles of the units constituting the semi-crystalline semi-aromatic polyamide; i. wherein the dicarboxylic acid units are derived from aromatic dicarboxylic acids and / or aromatic dicarboxylic acid chlorides (a-1), or a combination of the aromatic dicarboxylic acids and / or aromatic dicarboxylic acid chlorides (a-1) and other dicarboxylic acids (a-2) including aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids. Based on the total moles of these dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aromatic dicarboxylic acids and / or aromatic dicarboxylic acid chlorides (a-1) is 60 - 100 mol%, and the amount of the other dicarboxylic acids (a-2) is 0 - 40 mol%; the diamine units are derived from aliphatic diamines (b-1), or a combination of aliphatic diamines (b-1) and aromatic diamines (b-2). Based on the total moles of these diamine units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aliphatic diamines (b-1) is 80 - 100 mol%, and the amount of the aromatic diamines (b-2) is 0 - 20 mol%; or ii. wherein the dicarboxylic acid units are derived from aliphatic dicarboxylic acids or a combination of aliphatic dicarboxylic acids and alicyclic dicarboxylic acids. Based on the total moles of these dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aliphatic dicarboxylic acids is 80 - 100 mol%, and the amount of the alicyclic dicarboxylic acids is 0 - 20 mol%; the diamine units are derived from aromatic diamines, or a combination of aromatic diamines and aliphatic diamines. Based on the total moles of these diamine units constituting the semi-crystalline semi-aromatic polyamide, the amount of the aromatic diamines is 80 - 100 mol%, and the amount of the aliphatic diamines is 0 - 20 mol%.

3. The polyamide composition according to claim 1 or 2, wherein, The semi-crystalline semi-aromatic polyamide is selected from the group consisting of: PA MXD6, PA PXD6, PA MXD9, PA PXD9, PA MXD10, PA PXD10, PA 4T / 4I, PA 4T / 6I, PA 5T / 5I, 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 5T / 6T / 5I / 6I, PA 5T / 4T / 5I / 4I, PA4T / 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, PA10T / 11 and PA 6T / 6I / 12.

4. The polyamide composition according to any one of claims 1-3, wherein, The white pigment is selected from the group consisting of: titanium oxide, zinc 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, calcium sulfate, zinc sulfide, aluminum phosphate, magnesium carbonate and mixtures thereof, preferably titanium oxide.

5. The polyamide composition according to any one of claims 1-4, wherein, The phosphorus-containing heat stabilizer is selected from organic hypophosphites, inorganic hypophosphates, organic phosphonates, inorganic phosphonates, organic phosphites and mixtures thereof, and organic phosphonates and organic hypophosphites are preferred.

6. The polyamide composition according to claim 5, wherein, The organic phosphonate is selected from the group consisting of: sodium phosphonate, disodium phosphonate, potassium phosphonate, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate and ammonium phosphonate, and the organic hypophosphite is a metal salt having the formula I. wherein Ar is a C6 to C 18 aryl and X is a metal cation selected from Na, Ca, Mg, Al or Zn, and the C6 to C 18 aryl is unsubstituted or substituted with the following substituents: C1-C 10 alkyl, C3-C 10 cycloalkyl, C1-C 10 alkoxy, C3-C 10 cycloalkoxy, C1-C 10 alkylthio, C3-C 10 cycloalkylthio, C1-C 10 alkylamino, C3-C 10 cycloalkylamine, C6-C 18 aryl, C6-C 18 aryloxy, C6-C 18 arylthio, C6-C 18 arylamino, halogen and combinations thereof.

7. The polyamide composition according to claim 5 or 6, wherein The phosphorus-containing heat stabilizer is sodium benzenephosphinate, sodium phosphonate and / or potassium phosphonate.

8. The polyamide composition according to any one of claims 1-7, wherein, These basic salts are selected from the group consisting of: calcium carbonate, strontium carbonate, barium carbonate, sodium acrylate, calcium acrylate, potassium acrylate, sodium polyacrylate, calcium polyacrylate, potassium polyacrylate, sodium acetate, calcium acetate, barium acetate, potassium acetate, sodium citrate, calcium citrate, barium citrate, and mixtures thereof.

9. The polyamide composition according to claim 8, wherein, These basic salts are barium carbonate, sodium polyacrylate, calcium polyacrylate and barium polyacrylate.

10. The polyamide composition according to claim 8, wherein These basic salts are calcium carbonate.

11. The polyamide composition according to any one of claims 1-10, wherein, The polyamide composition contains a lubricant, an antioxidant and / or a light stabilizer.

12. The polyamide composition according to any one of claims 1 to 11, wherein, The polyamide composition comprises 45% to 80% by weight of component (A), 20% to 40% by weight of component (B), 0.1% to 2% of component (C), and 0.5% to 4% of component (D), based on the total weight of the polyamide composition.

13. An LED component made of the polyamide composition according to any one of claims 1 - 12.

14. The LED component according to claim 13, wherein, The LED component is a housing or a board of a light - emitting diode arrangement.

15. The LED component according to claim 13 or 14, wherein, The LED component is an element of: an instrument panel display of a motor vehicle, a motor vehicle screen, a turn signal lamp, a brake lamp, an interior and exterior lighting device, a floodlight, a floor lamp, a display of a mobile phone, a laptop computer, a notebook computer, an e - book reader, a tablet computer, a pocket calculator, a portable media player, a mobile Internet device, a handheld PC, a handheld game console, a digital media player, a wearable computer, a head - mounted display, a virtual reality head - mounted device, a digital camera, a global positioning system receiver, a portable power supply, a portable Wi - Fi, a TV backlight device, a liquid crystal display, a computer monitor, a laptop computer monitor or a notebook computer monitor, a display for home applications.

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