A filler composition and its use in polyamide-based material
Patent Information
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- BASF SE
- Filing Date
- 2024-07-04
- Publication Date
- 2026-05-20
AI Technical Summary
Existing polyamide-based compositions for LED applications struggle to simultaneously achieve low molding shrinkage, high mechanical properties, excellent anti-yellowing performance, and good reflectivity retention under harsh temperature conditions, while maintaining a relatively low cost.
A filler composition comprising a white pigment and a crystal whisker, with a mass ratio of 7:1 to 7:3, is incorporated into a polyamide-based material to enhance its mechanical properties, reduce molding shrinkage, and improve anti-yellowing and reflectivity performance.
The polyamide-based composition exhibits significantly reduced dimensional shrinkage during injection molding, maintains high tensile modulus and strength, and shows excellent reflectivity retention and anti-yellowing performance even under extreme temperature conditions.
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Figure PCTCN2024103597-FTAPPB-I100001 
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Abstract
Description
A Filler Composition and Its Use in Polyamide-based MaterialField of the invention
[0001] The present invention relates to a filler composition, and its use for reducing molding shrinkage, improving anti-yellowing performance, and mechanical property (e.g., especially tensile modulus) of a polyamide-based composition for LED application. Moreover, the present invention relates to a polyamide-based composition comprising said filler composition. Also included are methods for preparing such polyamide-based composition and articles therefrom.Background of the Invention
[0002] In recent years, the light-source market has expanded rapidly, especially the light emitting diode (LED) market, which contains various applications, such as LED housings, sockets, reflectors, and reflector plates. One of the key technical requirements for LED application-oriented material is excellent anti-yellowing performance when exposed to heat and light during manufacturing and end use, especially under high temperature (e.g., 240-260℃) for a short time (e.g., 30 min) or under medium temperature (e.g., 100-120℃) for a long time (e.g., 500 h) . In view of molding feasibility and end use requirments, lower molding shrinkage and good mechanical properties, especially high tensile modulus and strength, are also of great importance. With development of formulation technology, it has been found that thermoplastic polyamide-based (e.g., polyphthalamide (i.e., PPA) -based) composition could generally fulfil corresponding basic requirements of LED application, and is being widely used in LED market as an alternative solution to replace ceramics.
[0003] With development of modification on polyamide-based materials for preparing LED components, many efforts have been focused on improving discoloration resistance and mechanical properties. For example, US20130281587A1 discloses a polyamide resin composition comprising (A) polyamide resin, (B) white pigment, (C) sodium phosphate salt, and optionally (D) filler like a glass fiber, in which (C) sodium phosphate salt may be beneficial for heat resistance and water resistance, and may would eliminate acid generated during molding process to improve thermo-discoloration stability and hydrolysis stability, and (D) filler is used to improve formability and mechanical properties of the composition. JP4525917B2 discloses a polyamide resin composition for LED reflector molding and LED reflector, such composition comprises (A) polyamide resin, (B) titanium oxide, (C) magnesium hydroxide, and (D) reinforcing material selected from the group consisting of a fibrous filler and an acicular filler, in which (C) magnesium hydroxide would suppress discoloration such as yellowing and a decrease in whiteness after a heat treatment, and (D) reinforcing material would bring benefits to improve the intensity, strength and heat resistance of the molded article obtained from the composition.
[0004] Besides these above existing techniques, however, it is still a quite big challenge to acquire improved mechanical property (e.g., tensile modulus) , lower molding shrinkage, and excellent reflectivity performance (e.g., high initial reflectivity and good reflectivity retention after thermal aging) simultaneously via a relatively low cost method. The above said techniques cannot fulfil LED application under hostile conditions, such as under 240-260℃ or higher during reflow soldering process for a predetermined period, or under 100-120℃ for continueous use of 500h. Thus, there still exists gaps compared with traditional thermoset or ceramic materials. It is highly needed to develop a thermoplastic polyamide-based composition to satisfy the above requirements, and obtain extensive application in LED field.Summary of the invention
[0005] The present invention provides a filler composition comprising a white pigment and a crystal whisker.
[0006] Besides this, the present invention relates to use of said filler composition in a polyamide-based material for preparing LED components.
[0007] It is surprisingly found that a polyamide-based composition comprising the above filler composition could exhibit significantly decreased dimensional shrinkage during injection molding process, and could simultaneously achieve balanced performance on improving mechanical property (especially tensile modulus) , maintaining initial reflectivity and suppressing reflectivity deterioration when exposed to high temperature (e.g., 240-260℃) for a short time (e.g., 30 min) or to medium temperature (e.g., 100-120℃) for a long time (e.g., 500 h) .
[0008] Also provided herein are methods for preparing such polyamide-based composition and articles therefrom.
[0009] The present invention further provides a LED component made from the polyamide-based composition. It can be manufactured or assembled by reflow soldering processes.Detailed description of the invention
[0010] Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by a person skilled in the art to which the invention belongs. The radical definitions or elucidations given above in general terms or within areas of preference apply to the end products and correspondingly to the starting materials and intermediates. These radical definitions can be combined with one another as desired, i.e., including combinations between the general definition and / or the respective ranges of preference and / or the embodiments.
[0011] All the embodiments and the preferred embodiments disclosed herein can be combined as desired, which are also regarded as being covered within the scope of the present invention.
[0012] The terms “a” , “an” and “the” are used interchangeable with the term “at least one” . The phrases “at least one of” and “comprises at least one of” followed by a list refers to any one of the items in the list and any combination of two or more item in the list. All numerical ranges are inclusive of their endpoints and non-integral values between the endpoints unless otherwise stated.
[0013] The term "about" refers to a range of numbers that a person of skill in the art would consider equivalent to the recited value in the context of achieving the same function or result.
[0014] Unless otherwise identified, all percentages (%) are “percent by weight" .
[0015] The term “unit” refers to a repeated unit constituting the polyamide, unless otherwise stated.
[0016] As used herein, the term “PA” refers to polyamide. The term “PA* / PA**” refers to copolymer of PA*and PA**.
[0017] Disclosed is a filler composition comprising a white pigment and a crystal whisker, wherein a mass ratio of the white pigment to the crystal whisker is 7~1: 1, preferably 7~3: 1.
[0018] The white pigment in the present invention may include without limitation 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 the mixtures thereof.
[0019] Preferably, the white pigment can be surface treated through existing methods with a coupling agent, such as a silane coupling agent, titanium coupling agents, acrylic silane-based coupling agents, epoxysilane-based coupling agents and aminosilane-based coupling agents, such as vinyltriethoxysilane, polydimethylsiloxane, 2-aminopropyltriethoxysilane, 2-glycidoxypropyltriethoxysilane, and the like, and combinations thereof.
[0020] In one preferred embodiment, the white pigment is titanium oxide, which shows better light reflectivity and light stability. The particle diameter of titanium oxide is preferably 100-500 nm, more preferably is 200-400 nm. The titanium dioxide can also be treated by an inorganic surface treatment agent. The surface treatment for titanium oxide can improve the wettability with the basic resin (e.g., polyamide) . Examples of the inorganic surface treatment agent can be selected from the group consisting of alumina, silica, zirconia, sodium silicate, sodium aluminate, sodium aluminosilicate, zinc oxide, mica, and the like. The inorganic surface treatment agent may be used alone or in combinations thereof.
[0021] The crystal whisker in the present invention may include without limitation potassium titanate whisker, aluminum boric acid whisker, zinc oxide whisker, calcium sulfate whisker, and the like, and combinations thereof.
[0022] In one preferred embodiment, the crystal whisker is calcium sulfate whisker or potassium titanate whisker.
[0023] Preferably, the crystal whisker is calcium sulfate whisker having a length-diameter ratio of 5-40.
[0024] Preferably, the crystal whisker is potassium titanate whisker having a length-diameter ratio of 5-50.
[0025] In one preferred embodiment, the crystal whisker may be treated with surface treatment agent through existing methods to improve compatibility thereof with the basic resin (e.g., polyamide) and dispersion of the crystal whisker in the polyamide-based resin matrix. Examples of surface treatment agents may include without limitation silane coupling agents such as silane, epoxy silane and the like, titanium coupling agents, organic acids, polyols, silicones, and the like, and combinations thereof.
[0026] The present invention also relates to a polyamide-based composition comprising 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 crystal whisker, based on the total weight of the polyamide-based composition,
[0027] wherein a mass ratio of the white pigment to the crystal whisker is 7~1: 1, preferably 7~3: 1.
[0028] The 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 the dicarboxylic acid units or diamine units having aromatic groups. For example, the semi-aromatic polyamide comprises aromatic dicarboxylic acid units and aliphatic diamine units, or aliphatic and / or cycloaliphatic dicarboxylic acid units and aromatic diamine units.
[0029] The aromatic dicarboxylic acid units can be typically derived from aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride. The aliphatic dicarboxylic acid units can be typically derived from aliphatic dicarboxylic acid and / or aliphatic dicarboxylic acid chloride. The cycloaliphatic dicarboxylic acid units can be typically derived from cycloaliphatic dicarboxylic acid and / or cycloaliphatic dicarboxylic acid chloride.
[0030] The aliphatic or aromatic diamine units can be typically derived from aliphatic diamine or aromatic diamine respectively.
[0031] The other monomers are preferably in an amount of from 0 to 20 mol%, preferably from 0 to 15 mol%, more preferably from 0 to 10 mol%, based on the total units constituting the semi-aromatic polyamide.
[0032] The aromatic dicarboxylic acid in the present invention preferably comprises from 8 to 20 carbon atoms, more preferably from 8 to 14 carbon atoms, such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids and / or diphenyl dicarboxylic acids, more preferably is terephthalic acid, a mixture of terephthalic and isophthalic, naphthalene dicarboxylic acid, a mixture of terephthalic and naphthalene dicarboxylic acid.
[0033] The aliphatic dicarboxylic acid in the present invention preferably comprises from 4 to 36 carbon atoms, more preferably from 5 to 36 carbon atoms, most preferably from 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 the aliphatic dicarboxylic acid 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, more preferably is adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and mixtures thereof.
[0034] The cycloaliphatic dicarboxylic acid in the present invention preferably comprises from 4 to 20 carbon atoms, more preferably from 8 to 20 carbon atoms, more preferably comprises one carbon backbone selected from the group consisting of cyclohexane, cyclopentane, cyclohexylmethane, dicyclohexylmethane, bis (methylcyclohexyl) and mixtures thereof, most preferably is 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 the present invention could be linear aliphatic diamine or branched aliphatic diamine, preferably is linear aliphatic diamine. The aliphatic diamine preferably comprises from 4 to 36 carbon atoms, more preferably from 4 to 22 carbon atoms or 36 carbon atoms, most preferably from 4 to 14 carbon atoms, such as 4, 5, 6, 8, 9, 10, 11, 12, 13 and 14 carbon atoms. Examples of the linear aliphatic diamines are 1, 4-butane diamine, 1, 5-pentane diamine, 1, 6-hexane diamine, 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 is 1, 6-hexane diamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine and mixtures thereof, more preferably is 6-hexane diamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine and mixtures thereof. Examples of the branched aliphatic diamines are 2-methyl-1, 5-pentane diamine, 3-methyl-1, 5-pentane diamine, 2-methyl-1, 8-octanediamine, 5-methyl-1, 9-nonanediamine, 2, 4, 4-trimethylhexamethylene diamine, 2, 2, 4-trimethylhexamethylene diamine, 2, 4-dimethyloctanediamine and mixtures thereof, preferably is 2-methyl-1, 5-pentane diamine, 3-methyl-1, 5-pentane diamine, 2-methyl-1, 8-octanediamine, 2,4, 4-trimethylhexamethylene diamine, 2, 2, 4-trimethylhexamethylene diamine and mixtures thereof.
[0036] The aromatic diamine in the present invention is preferably selected from the group consisting of m-xylylenediamine (MXD) , p-xylylenediamine (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’ -bephenyldiamine, bis (4-methylaminophenyl) methane, 2, 2’ -bis (4-methylaminophenyul) propane and mixtures thereof, more preferably is MXD and / or PXD.
[0037] The suitable amino acid in the present invention preferably comprises from 4 to 20 carbon atoms, more preferably from 4 to 14 carbon atoms, such as 9, 10, 11, 12 or 13 carbon atoms. Examples of the amino acid are 4-aminobutanoic acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and mixtures thereof.
[0038] The suitable lactam in the present invention preferably comprises from 4 to 12 carbon atoms, more preferably from 5 to 12 carbon atoms. Examples of the lactam are 2-pyrrolidone (γ-butyrolactam) , 2-piperidone (δ-valerolactam) , ε-caprolactam, capryllactam, decanelactam, undecanolactam, enantholactam and / or lauryllactam, preferably is ε-caprlactam and / or undecanolactam.
[0039] In a preferred embodiment of the present invention, the 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 mole of units constituting the semi-aromatic polyamide;
[0040] i. wherein the dicarboxylic acid unit is derived from aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) , or a combination of the aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) and the other dicarboxylic acid (a-2) including aliphatic dicarboxylic acid and / or cycloaliphatic dicarboxylic acid. The aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) is preferably in an amount of 60-100 mol%, the other dicarboxylic acid (a-2) is preferably in an amount of 0-40 mol%, based on the total mole of the dicarboxylic acid units constituting the semi-aromatic polyamide;
[0041] the diamine unit is derived from aliphatic diamine (b-1) , or a combination of aliphatic diamine (b-1) and aromatic diamine (b-2) . The aliphatic diamine (b-1) is preferably in an amount of 80-100 mol%, the aromatic diamine (b-2) is preferably in an amount of 0-20 mol%, based on the total mole of the diamine units constituting the semi-aromatic polyamide; or
[0042] ii. wherein the dicarboxylic acid unit is derived from aliphatic dicarboxylic acid or a combination of aliphatic dicarboxylic acid and cycloaliphatic dicarboxylic acid. The aliphatic dicarboxylic acid is preferably in an amount of 80-100 mol%, the cycloaliphatic dicarboxylic acid is preferably in an amount of 0-20 mol%, based on the total mole of the dicarboxylic acid units constituting the semi-aromatic polyamide;
[0043] the diamine unit is derived from aromatic diamine, or a combination of aromatic diamine and aliphatic diamine. The aromatic diamine is preferably in an amount of 80-100 mol%, the aliphatic diamine is preferably in an amount of 0-20 mol%, based on the total mole of the diamine units constituting the semi-aromatic polyamide.
[0044] In one preferred embodiment, the semi-aromatic polyamide comprises dicarboxylic acid units and diamine units, wherein the dicarboxylic acid unit is derived from aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) , or a combination of the aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) and the other dicarboxylic acid (a-2) including aliphatic dicarboxylic acid and / or cycloaliphatic dicarboxylic acid. The aromatic dicarboxylic acid (a-1) is terephthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, a combination of terephthalic acid and isophthalic acid, or a combination of terephthalic acid and naphthalene dicarboxylic acid; the aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) is preferably in an amount of 60-100 mol%, more preferably 80-100 mol%, furthermore preferably 90-100 mol%, most preferably 95-100 mol%, based on the total mole of the dicarboxylic acid units constituting the semi-aromatic polyamide; the other dicarboxylic acid (a-2) is preferably in an amount of 0-40 mol%, more preferably 0-20 mol%, furthermore preferably 0-10 mol%, most preferably is equal to or less than 5 mol%, based on the total mole of the dicarboxylic acid units constituting the semi-aromatic polyamide;
[0045] the diamine unit is derived from aliphatic diamine (b-1) , or a combination of aliphatic diamine and aromatic diamine (b-2) . The aliphatic diamine (b-1) is preferably in an amount of 80-100 mol%, more preferably 90-100 mol%, most preferably 95-100 mol%, based on the total mole of the diamines constituting the semi-aromatic polyamide; the aromatic diamine (b-2) is preferably in an amount of 0-20 mol%, more preferably is 0-10 mol%, most preferably is 0-5 mol%, based on the total mole of the diamine units constituting the semi-aromatic polyamide.
[0046] In one preferred embodiment, the semi-aromatic polyamide comprises dicarboxylic acid units and diamine units, the dicarboxylic acid unit is derived from aromatic dicarboxylic acid (a-1) and 0-10 mol%, more preferably 0-5 mol%of the other dicarboxylic acid (a-2) , wherein the aromatic dicarboxylic acid (a-1) includes 10-40 mol%, more preferably 15-30 mol%, most preferably 20-30 mol%of isophthalic acid and 60-90 mol%, more preferably 70-85 mol%, most preferably 70-80 mol%of at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, naphthalene dicarboxylic acid and biphenyl dicarboxylic acid, preferably is terephthalic acid or a combination of terephthalic acid and naphthalene dicarboxylic acid; the other dicarboxylic acid is (a-2) is aliphatic dicarboxylic acid and / or cycloaliphatic dicarboxylic acid; the mole percentage is based on the total mole of the dicarboxylic acid units constituting the semi-aromatic polyamide;
[0047] the diamine unit is derived from aliphatic diamine (b-1) , or a combination of aliphatic diamine and aromatic diamine (b-2) . The aliphatic diamine (b-1) is preferably in an amount of equal to or 90-100 mol%, more preferably 95-100 mol%; the aromatic diamine (b-2) is preferably in an amount of 0-10 mol%, more preferably 0-5 mol%, based on the total mole of the diamine units constituting the semi-aromatic polyamide.
[0048] In one more preferred embodiment, the aliphatic dicarboxylic acid of the other dicarboxylic acid (a-2) is preferably glutaric acid, 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 is glutaric acid, adipic acid, sebacic acid and / or dodecanedioic acid.
[0049] In one more preferred embodiment, the aliphatic diamine (b-1) is a linear aliphatic diamine (b-1a) or the 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-butane diamine, 1, 5-pentane diamine, 1, 6-hexane diamine, 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-pentane diamine, 3-methyl-1, 5-pentane diamine, 2-methyl-1, 8-octanediamine, 2, 4, 4-trimethylhexamethylene diamine and 2, 2, 4-trimethylhexamethylene diamine.
[0050] Examples of the semi-aromatic polyamide is polyamide MXD5, polyamide PXD5, polyamide MXD6, polyamide PXD6, polyamide MXD9, polyamide PXD9, polyamide MXD10 and / or polyamide PXD10.
[0051] The polyamide in the present invention could also comprise a polyamide copolymer or a blend of two or more polyamide and its copolymer.
[0052] The semi-aromatic polyamide is suitably represented by the notations,
[0053] -R represents one or more of linear aliphatic diamine and branched aliphatic diamine,
[0054] -T represents terephthalic acid,
[0055] -I represents isophthalic acid,
[0056] -A represents one or more of aromatic diamine,
[0057] -Y represents one or more of aliphatic dicarboxylic acid,
[0058] -V represent one or more of lactam.
[0059] The suitable semi-aromatic polyamide could be represented by PA RT, PA RT / RI, PA RT / BT, PA RT / BT / RI / BI, which comprising:
[0060] -60-100 mol%of (T) , 0-40 mol%of (I) , preferably 60-85 mol%of (T) , 15-40 mol%of (I) , furthermore preferably 65-80 mol%of (T) , 20-35 mol%of (I) ; based on the total mole of (T) + (I) ; and
[0061] -100 mol%of (R) , R is preferably the linear or branched aliphatic polyamide having from 4 to 36 carbon numbers, more preferably having from 5 to 18 carbon numbers.
[0062] The 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 is PA6T, PA9T, PA10T, PA 6T / 6I, PA 6T / 10T, PA6T / 12T, PA 6T / 10T / 6I, PA 6T / DT or PA 6T / DT / 6I / DI. Herein D is 2-methylpenta-methylenediamine or 3-methyl-1, 5-pentanedimine, or a mixture thereof, and D is in an amount of 0-20 mol%, preferably 0-10 mol%of the total mole of (R) .
[0063] In one preferred embodiment, PA 6T / 6I comprises 65-80 mol%of (T) , 20-35 mol%of (I) .
[0064] In one preferred embodiment, PA 6T / 10T comprises 10-60 mol%of (6T) , 40-90 mol%of (10T) , preferably 10-40 mol%of (6T) , 60-90 mol%of (10T) .
[0065] In one preferred embodiment, PA 6T / 10T / 6I comprises 60-90 mol%of (6T) , 5-40 mol%of (6I) and 5-45 mol%of (10T) .
[0066] In one preferred embodiment, PA 6T / 10T / 6 comprises 60-85 mol%of (6T) , 15-40 mol%of (10T) , and 5-15 mol%of caprolactam.
[0067] The suitable semi-aromatic polyamide could be represented by PA RT / RY, PA RT / V, PA RT / RI / RY or PA RT / RI / V, which comprising:
[0068] -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 mole of (T) + (I) + (V) + (Y) ; R is preferably the linear aliphatic polyamide having from 9 to 36 carbon numbers, more preferably having from 9 to 18 carbon numbers. The 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, 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 is PA 6T / 6, PA 6T / 610 or PA 6T / 612.
[0069] In one preferred embodiment, PA RT / RY comprises 60-100 mol%of (T) , 0-40 mol%of (Y) , R is 1, 6-hexane diamine, 1, 9-nonanediamine, 1, 10-decanediamine, Y is dodecanedioic acid.
[0070] The semi-aromatic polyamide in the present invention has a melting temperature (Tm) of 250℃ -350℃, preferably 280℃ -320℃, most preferably 305℃ -315℃. The melting temperature is defined as a temperature corresponding to an endothermic peak in a 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 in the present invention preferably has the viscosity number of 50-150 ml / g, which is measured in sulfuric acid with a concentration of 96wt%according to ISO 307-2019 method.
[0072] In one 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 copolymer, and mixtures thereof.
[0073] The semi-aromatic polyamide can be produced using a conventionally known method such as a melt polymerization method or a solution polymerization method.
[0074] The semi-aromatic polyamide disclosed herein should not be limited to the ones prepared from virgin crude oil monomers, and could be completely or at least partially biobased or derived from waste stream or recycling activities, i.e., the polyamide used in the present application can be based on renewable materials, secondary raw materials or recycled raw materials. 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, PA 6T / 6I / 6, PA 6T / 66, PA 6T / 610, PA 6T / 612, PA 6T / 1012, PA 9T, PA 9T / 612, PA 9T / 1012, PA 10T, PA 10T / 106, PA 10T / 612, PA 10T / 1012, PA 6T / 6I / 66, PA 10T / 12, PA 10T / 11 and PA 6T / 6I / 12, used as component (A) in the present application could be prepared or obtained or derived from monomers that obtained via re-monomerisation processes.
[0075] The semi-aromatic polyamide in the present invention is in an amount of 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%, 65%by weight; based on the total weight of polyamide-based composition.
[0076] The white pigment in the present invention may include without limitation 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 the mixtures thereof.
[0077] Preferably, the white pigment can be surface treated through existing methods with a coupling agent, such as a silane coupling agent, titanium coupling agents, acrylic silane-based coupling agents, epoxysilane-based coupling agents and aminosilane-based coupling agents, such as vinyltriethoxysilane, polydimethylsiloxane, 2-aminopropyltriethoxysilane, 2-glycidoxypropyltriethoxysilane, and the like, and combinations thereof.
[0078] In one preferred embodiment, the white pigment is titanium oxide, which shows better light reflectivity and light stability. The particle diameter of titanium oxide is preferably 100-500 nm, more preferably is 200-400 nm. The titanium dioxide can also be treated by an inorganic surface treatment agent. The surface treatment for titanium oxide can improve the wettability with the basic resin (e.g., polyamide) . Examples of the inorganic surface treatment agent can be selected from the group consisting of alumina, silica, zirconia, sodium silicate, sodium aluminate, sodium aluminosilicate, zinc oxide, mica, and the like. The inorganic surface treatment agent may be used alone or in combinations thereof.
[0079] The white pigment in the present invention is in an amount of 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%, 35%by weight; based on the total weight of polyamide-based composition.
[0080] The crystal whisker in the present invention may include without limitation potassium titanate whisker, aluminum boric acid whisker, zinc oxide whisker, calcium sulfate whisker, and the like, and combinations thereof.
[0081] In one preferred embodiment, the crystal whisker is calcium sulfate whisker or potassium titanate whisker.
[0082] Preferably, the crystal whisker is calcium sulfate whisker having a length-diameter ratio of 5-40.
[0083] Preferably, the crystal whisker is potassium titanate whisker having a length-diameter ratio of 5-50.
[0084] In one preferred embodiment, the crystal whisker may be treated with surface treatment agent through existing methods to improve compatibility thereof with the basic resin (e.g., polyamide) and dispersion of the crystal whisker in the polyamide-based resin matrix. Examples of surface treatment agents may include without limitation silane coupling agents such as silane, epoxy silane and the like, titanium coupling agents, organic acids, polyols, silicones, and the like, and combinations thereof.
[0085] The crystal whisker in the present invention is in an amount of 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%, 6%, 8%, 10%by weight; based on the total weight of polyamide-based composition.
[0086] The polyamide-based composition in the present invention can optionally comprise at least one additive (D) , for example, thermal stabilizers, antioxidants, nucleating agents, acid scavengers, lubricants, photostabilizers such as UV stabilizers, flame-retardant agents, release agents, impact modifiers, compatibilizing agents, plasticizers, surfactants, coupling agents, antimicrobial agents, antistatic agents, and any combinations thereof.
[0087] For the purpose of the present invention, the additives can be used in conventional amounts. For example, the polyamide-based composition can comprise at least one additive in an amount of from 0.01%to 40%by weight, based on the total weight of the polyamide-based composition.
[0088] The polyamide-based composition can for example comprise a thermal stabilizer. Suitable thermal stabilizers are organic phosphinate, inorganic hypophosphite, inorganic phosphonate, organophosphite and the mixtures thereof, inorganic phosphonate and organic phosphinate are preferably. Examples of thermal stabilizer 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 hypophosphites sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, magnesium hypophosphite, calcium hypophosphite, ammonium hypophosphites, and sodium benzene phosphinate.
[0089] The thermal stabilizer, when present, can be in an amount of from 0.01%to 1%by weight, or preferably from 0.1%to 0.5%by weight, based on the total weight of the polyamide-based composition.
[0090] The polyamide-based composition can for example comprise an antioxidant. Suitable antioxidants are aromatic amine-based antioxidants, hindered phenol-based antioxidants and phosphite-based antioxidants, particularly 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-hydroxy-hydrocinnamate, 3, 5-bis (1, 1-dimethylethyl) -4-hydroxybenzenepropanoic acid C7-C9-branched alkyl ester, 2, 4-bis [ (dodecylthio) methyl] -o-cresol, 4, 4’ -butylidene bis- (3-methyl-6-tert-butylphenol) , 3, 5-bis (1, 1-dimethylethyl) -4-hydroxybenzenepropanoic acid octadecyl ester, pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) , triethylene glycol bis [3-(3-tert-butyl-5-methyl-4-hydrophenyl) 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-thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate] , N,N’ -1, 6-hexanediylbis [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyl-benzenepropanamide.
[0091] The antioxidant, when present, can be in an amount of from 0.01%to 1%by weight, or preferably from 0.1%to 0.3%by weight, based on the total weight of the polyamide-based composition.
[0092] The nucleating agent herein can be selected from at least one of an inorganic nucleating agent and an organic nucleating agent with the particle size of less than 1 μm.Preferably, the inorganic nucleating agent is at least one of talcum powder, montmorillonite and calcium carbonate; the organic nucleating agent is at least one of sodium benzoate, sorbitol dibenzyl ester and sodium carboxylate.
[0093] The nucleating agent, when present, can be in an amount of from 0.01%to 0.1%by weight, or preferably from 0.02%to 0.05%by weight, based on the total weight of the insulation film.
[0094] The acid scavenger in the present invention can be selected from at least one of magnesium oxide, zinc stannate, magnesium stannate, calcium stannate, calcium lactate, and the mixtures thereof.
[0095] The acid scavenger, when present, can be in an amount of from 0.1%to 3%by weight, or preferably from 1%to 2%by weight, based on the total weight of the insulation film.
[0096] The polyamide-based composition can for example comprise a lubricant. Suitable lubricant is preferably esters or amides of saturated or unsaturated aliphatic carboxylic acids having from 10 to 40, preferably from 16 to 22 carbon atoms with saturated aliphatic alcohols or amines which comprise from 2 to 40, preferably from 2 to 6 carbon atoms. The carboxylic acids can be mono-or dibasic. Examples of the 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 (amixture of fatty acids having from 30 to 40 carbon atoms) . The aliphatic alcohols can be mono-to tetrahydric. Examples of the aliphatic alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, and pentaerythritol, preference being given to glycerol and pentaerythritol. The aliphatic amines can be mono-to trifunctional. Examples of the aliphatic amines are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and di (6-aminohexyl) amine, particular preference being given here to ethylenediamine and hexamethylenediamine.
[0097] Preferred esters or amides are N, N’ -ethylenedi (stearamide) , glycerol distearate, glycerol tristearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate. N, N’ -ethylenedi (stearamide) is particularly preferred as a lubricant in the polyamide composition according to the present invention.
[0098] It is also possible to use mixtures of various esters or amides, or esters with amides in combination, in any desired mixing ratio.
[0099] The other lubricants are preferably long-chain fatty acids (e.g., stearic acid or behenic acid) , salts of these (e.g., Ca stearate or Zn stearate) , or montan waxes (mixtures of straight-chain, saturated carboxylic acids having chain lengths of from 28 to 32 carbon atoms) , Ca montanate or Na montanate, and also low-molecular-weight polyethylene waxes and low-molecular-weight polypropylene waxes.
[0100] The lubricant, when present, can be in an amount of from 0.01%to 2 %by weight, or preferably from 0.2%to 1 %by weight, based on the total weight of the polyamide-based composition.
[0101] The polyamide-based composition can for example comprise an UV stabilizer. There is no particular restriction to the UV stabilizer useful for the polyamide-based composition according to present invention, which may be selected from any known UV stabilizers, for example, commercially available Nylostab S-EED FF from Clariant.
[0102] The UV stabilizer, when present, can be in an amount of from 0.01%to 1 %by weight, or preferably from 0.1%to 0.5 %by weight, based on the total weight of the polyamide-based composition.
[0103] Preferably, the flame retardant agent herein comprises a metal salt of dialkylphosphinate comprising metal salts of phosphinic acid of formula (I) , or metal salts of diphosphinic salt of formula (II) , or the mixture thereof;
[0104] wherein R1 and R2 are identical or different and are linear or branched C1-C6-alkyl, preferable is linear or branched C1-C4 alkyl, more preferable is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and / or phenyl;
[0105] 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, preferable is Mg, Ca, Al, Zn, or a mixture thereof; m is integer of 1 to 4; n is integer of 1 to 4;
[0106] R3 is linear or branched C1-C10-alkylene, C6-C10-arylene, C7-C20-alkylarylene or C7-C20-arylalkylene, preferable is linear or branched C1-C4-alkylene or C6-C10-arylene, more preferable is methylene, ethylene, n-proylene, isopropylene, n-buytlene, tert-butylene, n-pentylene, n- octylene, n-dodecylene, phenylene, naphthylene, phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.
[0107] R4 and R5 are identical or different and are linear or branched C1-C6-alkyl, preferable is linear or branched C1-C4 alkyl, more preferable is methyl, ethyl or propyl; q is integer of 1 to 4; p is integer of 1 to 4; x is integer of 1 to 4.
[0108] Protonated nitrogen base are preferably the protonated bases of ammonia, melamine, triethanolamine, particlular is NH4+.
[0109] The phosphinic acids for the production of the metal salt of phosphinic acid of formula (I) in the present invention are preferably dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid.
[0110] The diphosphinic acid for the production of the salt of diphosphinic acid of formula (II) in the present invention are preferably methane-di (methylphosphinic acid) , ethane-1, 2-di(methylphosphinic acid) , hexane-1, 6-di (methylphosphinic acid) , benzene-1, 4-di(methylphosphinic acid) , methylphenylphosphinic acid, diphenylphosphinic acid.
[0111] Examples of metal salts of phosphinic acid of formula (I) include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphoshinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate and zinc methyl-n-propylphosphinate. Among them, aluminum diethylphosphinate, zinc diethylphosphinate, aluminum dimethylphosphinate and zinc dimethylphosphinate are more preferable.
[0112] Examples of metal salt of diphosphinic acid of formula (II) include calcium methanedi (methylphosphinate) , magnesium methanedi (methylphosphinate) , aluminum methanedi (methylphosphinate) , zinc methanedi (methylphosphinate) , calcium benzene-1, 4-(dimethylphosphinate) , magnesium benzene-1, 4- (dimethylphosphinate) , aluminum benzene-1,4- (dimethylphosphinate) and zinc benzene-1, 4- (dimethylphosphinate) .
[0113] The flame retardant agent can further comprise flame retardant synergists. The suitable flame retardant synergists include phosphorus synergists, nitrogen synergists, and phosphorus / nitrogen synergists.
[0114] The phosphorus synergist in the present invention can be metal salt of phosphorous acid, polyphosphonate, phosphazene, polyphosphonate, organophosphate, and the mixtures thereof. The metal salt of phosphorous acid comprises the structural unit of formula (III) or (IV) :
[0115] wherein T 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, preferable is Al and / or Zn; r is 1 to 4; w is 1 to 4; z is 1 to 7, preferably is 1 to 4.
[0116] Examples of melt salt of phosphorous acid are Al (H2PO3) 3, Al2 (HPO3) 3, Zn (HPO3) , Al2(HPO3) 3 ·4H2O and Al (OH) (H2PO3) 2·2H2O, preferable is Al2 (HPO3) 3.
[0117] Protonated nitrogen base are preferably the protonated bases of ammonia, melamine, triethanolamine, particlular is NH4+.
[0118] The suitbale nitrogen synergist can be melamine condensation products, such as melem, melam, melon, and the mixtures thereof.
[0119] The suitable phosphorus / nitrogen synergist can be the reaction products of melamine with polyphosphoric acid, condensation products of melamine with polyphosphoric acid, and the mixtures thereof, such as dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate, the mixtures thereof.
[0120] The metal salts of phosphinic acid and flame retardant synergist are preferably in a mass ratio of from 60: 40 to 90: 10, more preferably from 75: 25 to 90: 10, for example 85: 15, 80: 20.
[0121] The suitable flame-retardant agents could be OP series from Clariant.
[0122] The flame retardant synergist can also be metal oxide, metal hydroxide, boehmite, hydrotalcite, hydrocalumite, metal borate such as zinc borate, metal hydroxystannate such as zinc hydroxystannate. Suitable metal oxide is magnesium oxide, calcium oxide, zinc oxide, manganese oxide, tin oxide, tin oxide hydrate, and the mixtures thereof. Suitable metal hydroxide is aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, manganese hydroxide.
[0123] In one preferred embodiment, the flame-retardant agent is the mixture of metal salt of dialkylphosphinate and metal salt of phosphorous acid comprising the structural unit of formula (III) or (IV) .
[0124] In one preferred embodiment, the flame-retardant agent is the mixture of metal salt of dialkylphosphinate and flame retardant synergist,
[0125] -metal salt of dialkylphosphinate which is selected from the group consisting of aluminum diethylphosphinate, zinc diethylphosphinate, aluminum dimethylphosphinate and zinc dimethylphosphinate, preferably is aluminum diethylphosphinate, and
[0126] -flame retardant synergist is metal salt of phosphorous acid comprising the structural unit of formula (III) or (IV) , which is selected from the group consisting of Al (H2PO3) 3, Al2 (HPO3) 3, Zn(HPO3) , Al2 (HPO3) 3 ·4H2O and Al (OH) (H2PO3) 2·2H2O, preferable is Al2 (HPO3) 3,
[0127] wherein the metal salts of phosphinic acid and the flame retardant synergist are in a mass ratio of from 75: 25 to 90: 10.
[0128] In one preferred embodiment, the flame-retardant agent is the mixture of metal salt of dialkylphosphinate and flame retardant synergist,
[0129] -metal salt of dialkylphosphinate which is selected from the group consisting of aluminum diethylphosphinate, zinc diethylphosphinate, aluminum dimethylphosphinate and zinc dimethylphosphinate, preferably is aluminum diethylphosphinate, and
[0130] -flame retardant synergist is selected from the group consisting of melamine polyphosphate, melem polyphosphate, melam polyphosphate,
[0131] wherein the metal salts of phosphinic acid and the flame retardant synergist are in a mass ratio of from 75: 25 to 90: 10.
[0132] The flame-retardant agent, when present, can be in an amount of from 10%to 25%by weight, preferably from 15%to 25%by weight, such as 15%, 20%, 25%by weight, based on the total percentages by weight of the polyamide-based composition.
[0133] The polyamide-based composition can for example comprise an impact modifier. Suitable impact modifiers can include polyolefin-based, styrene-based, unsaturated carboxylic acid-based impact modifiers. Suitable impact modifiers can also be those modified by a functional block, such as epoxy functional block and / or acid anhydride block. The epoxy function block can be units derived from a glycidyl (meth) acrylate. The acid anhydride block can be units derived from maleic anhydride.
[0134] Suitable polyolefin-based impact modifiers can include polyolefins comprising repeating units derived from olefin having 2 to 10 carbon atoms. Examples of such olefins include ethylene, 1-butene, 1-propylene, 1-pentene, 1-octene and mixture of ethylene and 1-octene, preferably ethylene, 1-propylene and mixture of ethylene and 1-octene.
[0135] Suitable unsaturated carboxylic acid-based impact modifiers can include blocks derived from carboxylic acid and derivates thereof such as ester, imide and amide. Suitable carboxylic acid and derivates thereof are for example acrylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, glutaconic acid, itaconic acid, citraconic acid, (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (methyl) acrylate and isobutyl (meth) acrylate.
[0136] The impact modifier can also be a bi-or ter-polymer or a core-shell structure polymer. Examples of such impact modifier include styrene / ethylene / butylene copolymer (SEBS) , ethylene-methyl acrylate-glycidyl methacrylate terpolymer, ethylene / propylene / diene rubber (EPDM) and ethylene-octene copolymer.
[0137] The impact modifier, when present, can be in an amount of from 0.01%to 15%by weight, or preferably from 1%to 15%by weight, or more preferably from 5%to 10%by weight, based on the total weight of the polyamide-based composition.
[0138] The polyamide-based composition can for example comprise a plasticizer, including but is not limited to dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, and N- (n-butyl) benzenesulfonamide.
[0139] The plasticizer, when present, can be in an amount of from 0.01%to 15%by weight, or preferably from 1%to 15%by weight, or more preferably from 5%to 10%by weight, based on the total weight of the polyamide-based composition.
[0140] In a particular embodiment according to the present invention, the polyamide-based composition comprises:
[0141] 30%to 84.9%by weight of (A) at least one semi-aromatic polyamide, which is selected from at least one of 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, 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 any combinations thereof,
[0142] 15%to 40%by weight of (B) at least one white pigment, which 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 combinations thereof,
[0143] 0.1%to 30%by weight of (C) at least one crystal whisker, which is selected from the group consisting of potassium titanate whisker, aluminum boric acid whisker, zinc oxide whisker, calcium sulfate whisker, and any combinations thereof,
[0144] wherein a mass ratio of the white pigment to the crystal whisker is 7~1: 1,
[0145] each being based on the total weight of the polyamide-based composition.
[0146] In a particular embodiment according to the present invention, the polyamide-based composition comprises:
[0147] 30%to 84.9%by weight of (A) at least one semi-aromatic polyamide, which is selected from at least one of 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, 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 any combinations thereof,
[0148] 15%to 40%by weight of (B) at least one white pigment, which 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 combinations thereof,
[0149] 0.1%to 30%by weight of (C) at least one crystal whisker, which is selected from the group consisting of potassium titanate whisker, aluminum boric acid whisker, zinc oxide whisker, calcium sulfate whisker, and any combinations thereof, and optionally,
[0150] 0.01%to 40%by weight of (D) at least one additive, which is selected from the group consisting of thermal stabilizer, antioxidant, nucleating agent, acid scavenger, lubricant, photostabilizer such as UV stabilizer, release agent, impact modifier, compatibilizing agent, plasticizer, surfactant, coupling agent, antimicrobial agent, antistatic agent, and any combinations thereof,
[0151] wherein a mass ratio of the white pigment to the crystal whisker is 7~1: 1,
[0152] each being based on the total weight of the polyamide-based composition.
[0153] In one preferred embodiment according to the present invention, the polyamide-based composition comprises:
[0154] 40%to 79%by weight of (A) at least one semi-aromatic polyamide, which is selected from at least one of 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, 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 any combinations thereof,
[0155] 20%to 35%by weight of (B) at least one white pigment, which 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 combinations thereof,
[0156] 1%to 25%by weight of (C) at least one crystal whisker, which is selected from the group consisting of potassium titanate whisker, aluminum boric acid whisker, zinc oxide whisker, calcium sulfate whisker, and any combinations thereof, and
[0157] wherein a mass ratio of the white pigment to the crystal whisker is 7~1: 1,
[0158] each being based on the total weight of the polyamide-based composition.
[0159] In one preferred embodiment according to the present invention, the polyamide-based composition comprises:
[0160] 56%to 65%by weight of (A) at least one semi-aromatic polyamide, which is selected from at least one of 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, 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 any combinations thereof,
[0161] 30%to 35%by weight of (B) at least one white pigment, which 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 combinations thereof,
[0162] 5%to 10%by weight of (C) at least one crystal whisker, which is selected from the group consisting of potassium titanate whisker, aluminum boric acid whisker, zinc oxide whisker, calcium sulfate whisker, and any combinations thereof, and
[0163] wherein a mass ratio of the white pigment to the crystal whisker is 7~1: 1,
[0164] each being based on the total weight of the polyamide-based composition.
[0165] In another preferred embodiment according to the present invention, the polyamide-based composition comprises:
[0166] 56%to 65%by weight of (A) at least one semi-aromatic polyamide, which is selected from at least one of 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, 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 any combinations thereof,
[0167] 30%to 35%by weight of (B) at least one white pigment, which 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 combinations thereof,
[0168] 5%to 10%by weight of (C) at least one crystal whisker, which is selected from the group consisting of potassium titanate whisker, aluminum boric acid whisker, zinc oxide whisker, calcium sulfate whisker, and any combinations thereof, and
[0169] wherein a mass ratio of the white pigment to the crystal whisker is 7~3: 1,
[0170] each being based on the total weight of the polyamide-based composition.
[0171] In another preferred embodiment according to the present invention, the polyamide-based composition comprises:
[0172] 56%to 65%by weight of (A) at least one semi-aromatic polyamide, which is selected from at least one of 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, 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 any combinations thereof,
[0173] 30%to 35%by weight of (B) at least one white pigment, which 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 combinations thereof,
[0174] 5%to 10%by weight of (C) at least one crystal whisker, which is selected from the group consisting of potassium titanate whisker, aluminum boric acid whisker, zinc oxide whisker, calcium sulfate whisker, and any combinations thereof, and optionally,
[0175] 0.01%to 40%by weight of (D) at least one additive, which is selected from the group consisting of thermal stabilizer, antioxidant, nucleating agent, acid scavenger, lubricant, photostabilizer such as UV stabilizer, release agent, impact modifier, compatibilizing agent, plasticizer, surfactant, coupling agent, antimicrobial agent, antistatic agent, and any combinations thereof,
[0176] wherein a mass ratio of the white pigment to the crystal whisker is 7~3: 1,
[0177] each being based on the total weight of the polyamide-based composition.
[0178] The polyamide-based composition according to the present invention can be processed into various structures or forms by conventional methods to provide articles. For example, the individual components of the polyamide-based composition according to the present invention can be mixed and then be molded, for example via injection and / or extrusion in conventional mixing apparatus, such as screw extruders, Brabender mixers or Banbury mixers to form the articles. The mixing temperatures used herein are generally from 280℃ to 320℃.
[0179] It will be understood that all components of the polyamide-based composition can be mixed at the same time. Alternatively, some components of the polyamide-based composition can be pre-mixed and then mixed with other components. For example, all starting components of the polyamide-based composition except the white pigment and the crystal whisker are mixed together in a stirrer and fed into a twin-screw extruder at the throat, then the white pigment and the crystal whisker are pre-mixed and fed at downstream using a side feeder.
[0180] Accordingly, the present invention provides a LED component made from the polyamide-based composition. It can be manufactured or assembled by reflow soldering processes.
[0181] The LED component is a part of a light-emitting diode reflector. Light-emitting diode arrangement is an assembly comprising at least one light-emitting semiconductor diode, a current sourse, and a housing covering the diode or a plate in which the diode is embeded. The LED component can be the housing or the plate of the light-emitting diode arrangement. The housing or plate can be fully or partially produced from the polyamide-based composition in the present invention. For example, one of walls of the housing is produced from the polyamide-based composition.
[0182] The LED component in the present invention can be the element of automobile light, mobile communication equipment, and household applications. The element of light includes instrumental panel displays of automobiles, screen of automobiles, turn signals, stop lights, interior and exterior lighting, floodlights, floor lights. The element of mobile electronic equipment includes displays of mobile phones, laptops, notebooks, e-book readers, tablet computers, pocket calculators, portable media players, mobile internet devices (MID) , handheld PCs, handheld game consoles, digital media players, wearable computers such as a smart watch, head-mounted displays, virtual reality headsets, digital cameras, global positioning system receivers, portable power sources, portable Wi-Fis. The element of household applications includes the backlighting for TVs, liquid crystal displays, computer displays, laptop displays, notebook displays, displays of household applications, such as air-conditioners, intelligent housing system, mopping robots, electrical cookers, rice cookers, ovens, microwave ovens, washing machine, dish-washing machine, etc.
[0183] Accordingly, the present invention provides an article produced from the polyamide-based composition according to the present invention.
[0184] It is preferred that the articles according to the present invention have one or more of following properties,
[0185] -a tensile modulus of greater than 4400 MPa measured according to ISO 527-2-2012;
[0186] -a tensile stress at break of greater than 42 MPa measured according to ISO 527-2-2012;
[0187] -a charpy unnotched impact strength at 23℃ of at least 10 KJ / m2 measured according to ISO 179-1-2010;
[0188] -a charpy notched impact strength at 23℃ of at least 1.6 KJ / m2 measured according to ISO 179-1-2010;
[0189] -a heat deflection temperature of greater than 242℃ measured according to method B of ISO 75-2-2013 under 0.45 Mpa;
[0190] -a MVR of greater than 83 cm3 / 10min measured according to ISO 1133-2-2011 under 325℃ and 2.16kg loading;
[0191] -a SMn for molding shrinkage (normal to flow direction) of less than 1.1 measured according to ISO 294-4;
[0192] -a SMp for molding shrinkage (parallel to flow direction) of less than 1.0 measured according to ISO 294-4;
[0193] -an initial reflectivity of greater than 95.11%measured at the wavelength of 460nm;
[0194] -a reflectivity drop of less than 21.6%measured after aging at 260℃ for 30 minutes at the wavelength of 460nm;
[0195] -a reflectivity drop of less than 5.0%measured after aging at 120℃ for 500 hours at the wavelength of 460nm;
[0196] -a Delta-E value of less than 10.57 measured after aging at 260℃ for 30 minutes at the wavelength of 460nm;
[0197] -a Delta-E value of less than 2.31 measured after aging at 120℃ for 500 hours at the wavelength of 460nm.
[0198] According to the above performance, it is surprisingly found that the polyamide-based composition of the present invention could possess satisfied mechanical properties (e.g., relatively high tensile modulus) and significantly improved molding shrinkage resistance and anti-yellowing performance simultaneously with relatively lower and accepted sacrifice on initial reflectivity.
[0199] EMBODIMENTS
[0200] Various embodiments are listed below. It will be understood that the embodiments listed below can be combined with all aspects and other embodiments in accordance with the scope of the invention.
[0201] 1. A polyamide-based composition comprising 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 crystal whisker, based on the total weight of the polyamide-based composition,
[0202] wherein a mass ratio of the white pigment to the crystal whisker is 7~1: 1.
[0203] 2. The polyamide-based composition according to Embodiment 1, wherein a SMn of the composition is less than 1.1 measured according to ISO 294-4.
[0204] 3. The polyamide-based composition according to Embodiment 1, wherein a SMp of the composition is less than 1.0 measured according to ISO 294-4.
[0205] 4. The polyamide-based composition according to Embodiment 1, wherein a reflectivity drop of the composition is less than 21.6%measured after aging at 260℃ for 30 minutes at the wavelength of 460nm.
[0206] 5. The polyamide-based composition according to Embodiment 1, wherein a reflectivity drop of the composition is less than 5.0%measured after aging at 120℃ for 500 hours at the wavelength of 460nm.
[0207] 6. The polyamide-based composition according to Embodiment 1, wherein a Delta-E value of the composition is less than 10.57 measured after aging at 260℃ for 30 minutes at the wavelength of 460nm.
[0208] 7. The polyamide-based composition according to Embodiment 1, wherein a Delta-E value of the composition is less than 2.31 measured after aging at 120℃ for 500 hours at the wavelength of 460nm.
[0209] 8. The polyamide-based composition according to any of preceding Embodiments, wherein the 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 mole of units constituting the semi-crystalline semi-aromatic polyamide;
[0210] i. wherein the dicarboxylic acid unit is derived from aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) , or a combination of the aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) and the other dicarboxylic acid (a-2) including aliphatic dicarboxylic acid and / or cycloaliphatic dicarboxylic acid, the aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) is in an amount of 60-100 mol%, the other dicarboxylic acid (a-2) is in an amount of 0-40 mol%, based on the total mole of the dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide;
[0211] the diamine unit is derived from aliphatic diamine (b-1) , or a combination of aliphatic diamine (b-1) and aromatic diamine (b-2) , the aliphatic diamine (b-1) is in an amount of 80-100 mol%, the aromatic diamine (b-2) is in an amount of 0-20 mol%, based on the total mole of the diamine units constituting the semi-aromatic polyamide; or
[0212] ii. wherein the dicarboxylic acid unit is derived from aliphatic dicarboxylic acid or a combination of aliphatic dicarboxylic acid and cycloaliphatic dicarboxylic acid, the aliphatic dicarboxylic acid is in an amount of 80-100 mol%, the cycloaliphatic dicarboxylic acid is in an amount of 0-20 mol%, based on the total mole of the dicarboxylic acid units constituting the semi-aromatic polyamide;
[0213] the diamine unit is derived from aromatic diamine, or a combination of aromatic diamine and aliphatic diamine, the aromatic diamine is in an amount of 80-100 mol%, the aliphatic diamine is in an amount of 0-20 mol%, based on the total mole of the diamine units constituting the semi-crystalline semi-aromatic polyamide.
[0214] 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, PA PXD10, PA 4T / 4I, PA 4T / 6I, PA5T, 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, 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.
[0215] 10. The polyamide-based composition according to any of preceding 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 the mixtures thereof.
[0216] 11. The polyamide-based composition according to any of preceding Embodiments, wherein the crystal whisker is at least one selected from the group consisting of potassium titanate whisker, aluminum boric acid whisker, zinc oxide whisker, calcium sulfate whisker, and the mixtures thereof.
[0217] 12. The polyamide-based composition according to any of preceding Embodiments, 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, component (C) is present in an amount of 1%to 25%by weight, each being based on the total weight of the polyamide-based composition.
[0218] 13. The polyamide-based composition according to any of preceding Embodiments, 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, component (C) is present in an amount of 5%to 10%by weight, each being based on the total weight of the polyamide-based composition.
[0219] 14. The polyamide-based composition according to any of preceding Embodiments, wherein the composition further comprises 0.01%to 40%by weight of (D) at least one additive selected from the group consisting of thermal stabilizer, antioxidant, nucleating agent, acid scavenger, lubricant, photostabilizer, release agent, impact modifier, compatibilizing agent, plasticizer, surfactant, coupling agent, antimicrobial agent, antistatic agent, and any combinations thereof.
[0220] 15. An article prepared from the polyamide-based composition of Embodiment 1.
[0221] 16. The article according to Embodiment 15, wherein the article is a LED component which is at least one selected from the group consisting of a housing, a plate of a light-emitting diode arrangement, or an element of instrumental panel displays of automobiles, screen of automobiles, turn signals, stop lights, interior and exterior lighting, floodlights, floor lights, displays of mobile phones, laptops, notebooks, 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, global positioning system receivers, portable power sources, portable Wi-Fis, backlighting for TVs, liquid crystal displays, computer displays, laptop displays or notebook displays, displays of household applications.
[0222] 17. A filler composition comprising a white pigment and a crystal whisker, wherein a mass ratio of the white pigment to the crystal whisker is 7~1: 1.
[0223] 18. Use of the filler composition according to Embodiment 17 in a polyamide-based composition for preparing a LED component, wherein 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 crystal whisker, based on the total weight of the polyamide-based composition.
[0224] EXAMPLES
[0225] Aspects of the present invention are more fully illustrated by the following examples, which are set forth to illustrate certain aspects of the present invention and are not to be construed as limiting thereof.
[0226] Following materials and test methods were used in the Examples.
[0227] Materials:
[0228] Table 1 The materials used in the inventive examples and comparative examples
[0229] Composition Processing:
[0230] Test specimens were prepared in accordance with the formulations as shown in Table 2.
[0231] All raw materials except the filler (i.e., B1: TiO2, C1: CaSO4 whisker, C2: K2Ti6O13 whisker, C3:Glass fiber and / or C4: Wollastonite) are mixed together in a Turbula T50A high-speed stirrer and fed into a ZE25Ax (Berstorff) twin-screw extruder at the throat, the filler is fed at downstream using a side feeder to keep good mechanical property. The raw materials are melt-extruded under a temperature of 320℃, pelletized, thus obtaining a thermoplastic polyamide-based composition in a pellet form.
[0232] Table 2
[0233] E: Example of This Invention; C: Comparative Example
[0234] Sample preparation:
[0235] The dried pellets were processed in an injection molding machine KM130CX, from Krauss Maffei with a clamping force of 130T at melting temperature of 320℃ and molding temperature of 120℃ to get test specimens.
[0236] Testing:
[0237] Melt Volume-flow Rate (MVR) was tested according to ISO 1133-2-2011 under 325℃ and 2.16kg loading.
[0238] Tensile modulus, tensile stress at break and tensile strain at break for samples having thickness of 4 mm were measured according to ISO 527-2-2012. Test specimens of type 1 described in ISO 527-2-2012 were used. Charpy notched impact strength and Charpy unnotched impact strength was tested according to ISO 179-1-2010 via edgewise impact. The test specimens for Charpy unnotched test is type 1 specimen with the dimensions of 80 X 10 X 4mm (length X width X thickness) . The test specimens for Charpy notched test are type 1 with notched type A. All the test specimens were conditioned at 23℃ and 50%relative humidity for 16 h. The tests were conducted under the same atmosphere as conditioning.
[0239] Molding Shrinkage was tested according to ISO 294-4 using plastic plaque (60 X 60 X 2 mm) sample within 16 to 24 hours after sample completion.
[0240] Heat Deflection Temperature (HDT) was tested according to method B of ISO 75-2-2013 under 0.45 MPa.
[0241] The reflectivity related test was measure by a Datacolor 850 Spectrophotometer from Datacolor company with D65 light source reflection mode at the wavelength of 460nm using a molded plastic plaque (60 X 60 X 2 mm) sample.
[0242] Delta E (the total color difference, also commonly written as ΔE, or E*) is based on delta L*, delta a*, and delta b*color values, all of which provide a complete numerical descriptor of the color in a rectangular coordinate system. The meanings are as follows:
[0243] · delta L*represents a lightness difference between the sample and standard colors.
[0244] · delta a*represents the difference in redness or greyness between the sample and standard colors.
[0245] · delta b*denotes blueness-yellowness differences between the sample and standard colors.
[0246] Delta E could be calculated through the following formula via measurements by Datacolor 850 Spectrophotometer:
[0247] The test specimens used are made according to the following general procedure for preparing the test specimens.
[0248] Testing Results:
[0249] Table 3 provided below shows the testing results of the above specific examples of this invention and comparative examples.
[0250] Table 3
[0251] E: Example of This Invention; C: Comparative Example
[0252] According to the comparision of the results of C1 and C3 presented in Table 3, it can be seen that addition of white pigment (e.g., TiO2) could be beneficial to initial reflectivity and anti-yellowing performance, but shows relatively less influence on improving mechanical properties (such as tensile modulus) and heat resistence (e.g., HDT) , on the contrary, addition of crystal whisker (e.g., CaSO4 whisker) could improve mechanical properties (such as tensile modulus) and heat resistence (e.g., HDT) significantly, but would exert obvious negative influence on initial reflectivity and anti-yellowing performance. However, neither white pigment (e.g., TiO2) nor crystal whisker (e.g., CaSO4 whisker) could suppress the molding shringkage (including SMn and SMp) when added individually.
[0253] It was surprisingly found that a combination of white pigment (e.g., TiO2) and crystal whisker (e.g., CaSO4 whisker) used in the composition could play synergistic effects with each other to obtain unexpected influence on improving molding shrinkage resistance with relatively lower SMn and SMP (see SMn and SMP of E1 to E3) , while obtaining excellent anti-yellowing performance (e.g., relatively lower reflectivity drop and quite lower Delta-E value after aging experiments) and satisfied mechanical properties (e.g., relatively high tensile modulus) .
[0254] Furthermore, in order to achieve the above comprehensive performance, a mass ratio of the white pigment (e.g., TiO2) to the crystal whisker (e.g., CaSO4 whisker) should be restrictly controlled within a proper range, such as 7~1: 1, perferably 7~3: 1. However, the combination of white pigment (e.g., TiO2) and crystal whisker (e.g., CaSO4 whisker) used in the composition would probably exert negative influence on initial reflectivity and anti-yellowing performance when said mass ratio is below 1, for example, the result of C2 presented in Table 3 shows relatively lower initial reflectivity and quite poor anti-yellowing performance under the condition that the mass ratio of TiO2 to CaSO4 whisker is 1 / 3 .
[0255] It will be apparent to one of ordinary skill in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the present invention. It is intended that the embodiments and examples be considered as exemplary only. Thus, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents.
Claims
1.A polyamide-based composition comprising 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 crystal whisker, based on the total weight of the polyamide-based composition,wherein a mass ratio of the white pigment to the crystal whisker is 7~1: 1.2.The polyamide-based composition according to claim 1, wherein a SMn of the composition is less than 1.1 measured according to ISO 294-4.3.The polyamide-based composition according to claim 1, wherein a SMp of the composition is less than 1.0 measured according to ISO 294-4.4.The polyamide-based composition according to claim 1, wherein a reflectivity drop of the composition is less than 21.6%measured after aging at 260℃ for 30 minutes at the wavelength of 460nm.5.The polyamide-based composition according to claim 1, wherein a reflectivity drop of the composition is less than 5.0%measured after aging at 120℃ for 500 hours at the wavelength of 460nm.6.The polyamide-based composition according to claim 1, wherein a Delta-E value of the composition is less than 10.57 measured after aging at 260℃ for 30 minutes at the wavelength of 460nm.7.The polyamide-based composition according to claim 1, wherein a Delta-E value of the composition is less than 2.31 measured after aging at 120℃ for 500 hours at the wavelength of 460nm.8.The polyamide-based composition according to any of preceding claims, wherein the 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 mole of units constituting the semi-crystalline semi-aromatic polyamide;i.wherein the dicarboxylic acid unit is derived from aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) , or a combination of the aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) and the other dicarboxylic acid (a-2) including aliphatic dicarboxylic acid and / or cycloaliphatic dicarboxylic acid, the aromatic dicarboxylic acid and / or aromatic dicarboxylic acid chloride (a-1) is in an amount of 60-100 mol%, the other dicarboxylic acid (a-2) is in an amount of 0-40 mol%, based on the total mole of the dicarboxylic acid units constituting the semi-crystalline semi-aromatic polyamide;the diamine unit is derived from aliphatic diamine (b-1) , or a combination of aliphatic diamine (b-1) and aromatic diamine (b-2) , the aliphatic diamine (b-1) is in an amount of 80-100 mol%, the aromatic diamine (b-2) is in an amount of 0-20 mol%, based on the total mole of the diamine units constituting the semi-aromatic polyamide; orii. wherein the dicarboxylic acid unit is derived from aliphatic dicarboxylic acid or a combination of aliphatic dicarboxylic acid and cycloaliphatic dicarboxylic acid, the aliphatic dicarboxylic acid is in an amount of 80-100 mol%, the cycloaliphatic dicarboxylic acid is in an amount of 0-20 mol%, based on the total mole of the dicarboxylic acid units constituting the semi-aromatic polyamide;the diamine unit is derived from aromatic diamine, or a combination of aromatic diamine and aliphatic diamine, the aromatic diamine is in an amount of 80-100 mol%, the aliphatic diamine is in an amount of 0-20 mol%, based on the total mole 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, PA PXD10, PA 4T / 4I, PA 4T / 6I, PA5T, 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, 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 of 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 the mixtures thereof.11.The polyamide-based composition according to any of preceding claims, wherein the crystal whisker is at least one selected from the group consisting of potassium titanate whisker, aluminum boric acid whisker, zinc oxide whisker, calcium sulfate whisker, and the mixtures thereof.12.The polyamide-based composition according to any of 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, component (C) is present in an amount of 1%to 25%by weight, each being based on the total weight of the polyamide-based composition.13.The polyamide-based composition according to any of 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, component (C) is present in an amount of 5%to 10%by weight, each being based on the total weight of the polyamide-based composition.14.The polyamide-based composition according to any of preceding claims, wherein the composition further comprises 0.01%to 40%by weight of (D) at least one additive selected from the group consisting of thermal stabilizers, antioxidants, nucleating agents, acid scavengers, lubricants, photostabilizers, flame-retardant agents, release agents, impact modifiers, compatibilizing agents, plasticizers, surfactants, coupling agents, antimicrobial agents, antistatic agents, and any combinations thereof.15.An article prepared from the polyamide-based composition of claim 1.16.The article according to claim 15, wherein the article is a LED component which is at least one selected from the group consisting of a housing, a plate of a light-emitting diode arrangement, or an element of instrumental panel displays of automobiles, screen of automobiles, turn signals, stop lights, interior and exterior lighting, floodlights, floor lights, displays of mobile phones, laptops, notebooks, 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, global positioning system receivers, portable power sources, portable Wi-Fis, backlighting for TVs, liquid crystal displays, computer displays, laptop displays or notebook displays, displays of household applications.