Polyamide composition

Abstract

A polyamide composition is provided that contains at least one polyamide characterized by a high glass transition temperature (Tg), at least one fibrous filler, and at least one additive, and can be used in the manufacture of articles and electrostatic coating applications.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority under U.S. Provisional Patent Application No. 63 / 114117 filed November 16, 2020, and European Patent Application Publication No. 21150952.6 filed January 11, 2021, each of which is incorporated herein by reference in whole for all purposes.

[0002] A polyamide composition is provided which contains at least one polyamide characterized by a high glass transition temperature (Tg), at least one fibrous filler, and at least one additive, and which can be used to manufacture articles suitable for electrostatic coating applications. [Background technology]

[0003] The paint finish of a new car is often considered the vehicle's single most noticeable visual feature. If the finish is smooth, uniform, and attractive, viewers are more likely to have a positive impression of the vehicle's quality. Conversely, if the paint finish contains defects, viewers are more likely to perceive the vehicle's overall quality as low.

[0004] Therefore, vehicle manufacturers and paint suppliers have spent vast sums of money to create enhanced paint application processes in order to improve the quality and durability of vehicle finishes and eliminate defects associated with the application of paint to vehicles.

[0005] Despite these efforts, there is still a need for a composition (also known as the "E-coat process") that exhibits excellent adhesion between the substrate and the electrostatically coated paint base coat while maintaining superior mechanical properties and a high glass transition temperature (Tg). [Overview of the project]

[0006] A composition is provided containing a polyamide polymer that exhibits excellent mechanical properties while having a high glass transition temperature, making it suitable for the E-coat process.

[0007] In the first aspect, the present invention is - At least one polyamide polymer [polymer (PA)] having a glass transition temperature (Tg) of at least 130°C, more preferably at least 150°C, as measured by DSC, in an amount of 20-85% by weight based on the total weight of the composition; - At least one type of fibrous filler [Filler (F)] in an amount of 10 to 75% by weight based on the total weight of the composition; and - At least one additive [Additive (A)] selected from the group consisting of alkaline earth metal oxides; alkaline earth metal carbonates; alkaline earth metal phosphates; alkaline earth metal sulfates; alkali metal sulfates; alkali metal carbonates; oxides of Group IIB metals of the periodic table; sulfides of Group IIB metals of the periodic table; and inorganic fillers, in an amount of 0.01% to less than 5% by weight based on the total weight of the composition; This relates to the composition [Composition (C)] contained therein. [Modes for carrying out the invention]

[0008] Preferably, the polymer (PA) has at least 50 mol% repeating units having at least one amide bond (-NH-C(=O)-).

[0009] In this specification, unless otherwise specified, the mole percent of repeating units refers to the total number of moles of repeating units in the polymer (e.g., polymer (PA)).

[0010] In some embodiments, the polyamide has at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or at least 99.5 mol% of repeating units having at least one amide bond.

[0011] In some embodiments, the polyamide polymer (PA) is formed from the polycondensation of a reaction mixture [reaction mixture (RM)] containing a diamine component and a dicarboxylic acid component. The diamine component and the dicarboxylic acid component are respectively contained in the reaction mixture. In some such embodiments, at least 50 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or at least 99 mol% repeating units of the polyamide polymer (PA) are formed from the polycondensation of the reaction mixture (RM).

[0012] Each diamine in the diamine component is distinct and may independently be either aliphatic or aromatic, and can be represented by the following formula: H2N-R1-NH2 (In the formula, - R1 optionally contains a bond and one or more heteroatoms (e.g., O, N, or S), and is a halogen, hydroxy(-OH), sulfo(-SO3M), C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C 15 Aryl oxy, and C6~C 15 C1-C11 are optionally substituted with one or more substituents selected from the group consisting of aryl atoms. 15 Alkyl and C6-C 30 Selected from the group consisting of aryls; - M is selected from the group consisting of H, Na, K, Li, Ag, Zn, Mg, and Ca).

[0013] Preferably, the aliphatic diamine is diamine-propane ("3"), 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane ("D"), 1,6-diaminohexane ("HMDA"), 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine, 1,7-diamine The following are selected from the group consisting of noheptane, 1,8-diaminooctane, 2,2,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 2,5-dimonotetrahydrofuran, and N,N-bis(3-aminopropyl)methylamine.

[0014] Aliphatic diamines also include alicyclic diamines.

[0015] Preferred alicyclic diamines are selected from the group consisting of isophorone diamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis-p-aminocyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), 1,4-bis(aminomethyl)cyclohexane ("1,4-BAC"), bis(3-methyl-4-aminocyclohexyl)methane ("MACM"), and bis(4-aminocyclohexyl)methane ("PACM").

[0016] Preferably, the aliphatic diamine is selected from the group consisting of 1,3-diaminopropane ("3"), 1,4-diaminobutane, 1,5-diaminopentane, HMDA, 2-methyl-1,5-diaminopentane ("D"), 1,3-BAC, 1,4-BAC, PACM, MACM, and isophorone diamines.

[0017] Preferred aromatic diamines are selected from the group consisting of m-phenylenediamine ("MPD"), p-phenylenediamine ("PPD"), 3,4'-diaminodiphenyl ether ("3,4'-ODA"), 4,4'-diaminodiphenyl ether ("4,4'-ODA"), p-xylylenediamine ("PXDA"), and m-xylylenediamine ("MXDA").

[0018] More preferably, the aromatic diamine is selected from the group consisting of PXDA and MXDA.

[0019] Each dicarboxylic acid in the dicarboxylic acid component is distinct and may independently be either aliphatic or aromatic and is represented by the following formula: [Chemical formula] (In the formula, - R2 optionally contains one or more heteroatoms (such as O, N, or S) and is optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy (-OH), sulfo (-SO3M), C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C 15 aryloxy, and C6-C 15 aryl and is selected from the group consisting of C1-C 20 alkyl, phenyl, indanyl, and naphthyl; - M is independently selected from the group consisting of H, Na, K, Li, Ag, Zn, Mg, and Ca).

[0020] Preferred aliphatic dicarboxylic acids are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid ("6"), 2,4,4-trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid ("12"), tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid. <0000l00> Aliphatic dicarboxylic acids also include alicyclic dicarboxylic acids.

[0022] Preferred alicyclic dicarboxylic acids are selected from the group consisting of 1,4-cyclohexanedicarboxylic acid ("CHDA"), adipic acid ("6"), and sebacic acid ("10"). More preferably, the aliphatic dicarboxylic acid is CHDA.

[0023] Preferred aromatic dicarboxylic acids are selected from the group consisting of isophthalic acid ("IA"), terephthalic acid ("TA"), naphthalenedicarboxylic acid ("NDA") (e.g., naphthalene-2,6-dicarboxylic acid ("2,6-NDA")), 4,4'-bibenzoic acid, 2,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)-ketone, 4,4'-bis(4-carboxyphenyl)sulfone, 2,2-bis(3-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)ketone, and bis(3-carboxyphenoxy)benzene.

[0024] More preferably, the aromatic dicarboxylic acid is selected from the group consisting of IA, TA, and 2,6-NDA.

[0025] Each repeating unit formed by the polycondensation of the reaction mixture (RM) is distinct and can be independently represented by the following equation: [ka] (In the formula, R1, R2, and M are as defined above.)

[0026] Those skilled in the art will recognize that each repeating unit is formed by the dehydrogenation of a diamine and the dehydroxylation of a dicarboxylic acid.

[0027] In some embodiments, the polymer (PA) is - At least one diamine component selected from aliphatic, alicyclic diamines, and mixtures thereof, - At least a dicarboxylic acid component selected from aliphatic, alicyclic, aromatic dicarboxylic acids, and mixtures thereof, It is a condensation product of [the two products].

[0028] In some embodiments, the polymer (PA) is - At least one diamine component selected from the group consisting of 1,3-diaminopropane ("3"), 1,3-diaminobutane, 1,4-diaminobutane, 2-methyl-1,5-diaminopentane ("D"), 2,5-dimethylhexamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine, 3-methylhexamethylenediamine, 1,6-diaminohexane ("HMDA" or "6"), 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), 1,4-bis(aminomethyl)-cyclohexane ("1,4-BAC"), bis(3-methyl-4-aminocyclohexyl)methane ("MACM"), bis(4-aminocyclohexyl)methane ("PACM"), and mixtures thereof; - A dicarboxylic acid component selected from the group consisting of terephthalic acid ("TA"), isophthalic acid ("IA"), 1,4-cyclohexanedicarboxylic acid ("CHDA"), dodecanediic acid ("12"), sebacic acid ("10"), undecanediic acid, and mixtures thereof; It is a condensation product of [the two products].

[0029] In some embodiments, the polymer (PA) is - A diamine component containing at least one diamine selected from the group consisting of 1,3-diaminopropane ("3"), 1,3-diaminobutane, 1,4-diaminobutane, 1,6-diaminohexane ("HMDA" or "6"), bis(3-methyl-4-aminocyclohexyl)methane ("MACM"), bis(4-aminocyclohexyl)methane ("PACM"), and mixtures thereof; - A dicarboxylic acid component containing at least one dicarboxylic acid selected from the group consisting of terephthalic acid ("TA" or "T"), isophthalic acid ("IA" or "I"), 1,4-cyclohexanedicarboxylic acid ("CHDA"), dodecanedioic acid ("12"), and mixtures thereof; It is formed from polycondensation of a reaction mixture (RM) containing.

[0030] In some embodiments, the polymer (PA) is selected from the group consisting of 46 / 6T; [6 / 3] / T; MACM / 12; [PACM / MACM] / [I / 12]; 6T / DT; [4,6,D] / [T / I]; 6T / 6I; [6 / BAC] / [T / CHDA].

[0031] Preferably, the polymer (PA) may have a number average molecular weight Mn in the range of 1,000 g / mol to 40,000 g / mol, such as 2,000 g / mol to 35,000 g / mol, or 4,000 to 30,000 g / mol. The number average molecular weight Mn can be measured by gel permeation chromatography (GPC) using ASTM D5296 with polystyrene standards.

[0032] Preferably, the polymer (PA) has a glass transition temperature (T g ) of at least 130 °C, preferably at least 135 °C. In some embodiments, the polymer (PA) has a T g of 190 °C or less, 180 °C or less, or 170 °C or less. In some embodiments, the polymer (PA) has a T g of 135 °C to 190 °C, 140 °C to 190 °C, 145 °C to 185 °C, 150 °C to 185 °C, 150 °C to 180 °C, or 150 °C to 170 °C. Tg This can be measured according to ASTM D3418.

[0033] Preferably, the polymer (PA) has a melting point (T) of 360°C or less, more preferably 350°C or less, and even more preferably 340°C or less, as determined using a differential scanning calorimeter (DSC) in accordance with ASTM D3418. m ) has.

[0034] Preferably, the polymer (PA) has a melting point (T) of at least 280°C, more preferably at least 295°C, and even more preferably at least 300°C, as determined using a differential scanning calorimeter (DSC) in accordance with ASTM D3418. m ) has.

[0035] Preferably, composition (C) contains the polymer (PA) in an amount of 25 to 80% by weight, more preferably 30 to 75% by weight, and even more preferably 35 to 70% by weight, based on the total weight of composition (C).

[0036] Composition (C) further comprises at least one fibrous filler [Filler (F)] in an amount of 10 to 75% by weight based on the total weight of the composition.

[0037] As used herein and in the following claims, “fibrous filler [filler (F)]” is a material having length, width, and thickness, wherein the average length is considerably greater than both the width and thickness. Preferably, such a material has an aspect ratio defined as the average ratio of at least 5 between the length and the minimum width and thickness.

[0038] Preferably, the filler (F) is selected from at least one of glass fibers, carbon fibers, synthetic polymer fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, and steel fibers. Glass fibers and carbon fibers are most preferred.

[0039] Fibers can be in the form of whiskers, short fibers, continuous fibers, sheets, plies, or combinations thereof.

[0040] Furthermore, the continuous fibers can employ any of the following configurations: unidirectional, multidimensional, nonwoven, woven, knitted, stitched, wound, and braided, as well as swirl mats, felt mats, and chopped mats. The fiber toes can be fixed in place in such configurations by cross-toe stitches, weft-inserted stitches, or small amounts of resin such as sizing.

[0041] As used herein, "continuous fiber" refers to a fiber having a length greater than 10 mm.

[0042] According to one embodiment, the filler (F) is carbon fiber.

[0043] Carbon fibers useful for the present invention can be obtained by heat treatment and thermal decomposition of different polymer precursors, such as rayon, polyacrylonitrile (PAN), aromatic polyamide, or phenolic resin. Suitable carbon fibers can also be obtained from pitch-based materials. Various carbon fibers known to those skilled in the art are available from commercial sources.

[0044] In some embodiments, the carbon fiber is either a standard modulus carbon fiber or an intermediate modulus carbon fiber. Standard modulus carbon fiber has a tensile modulus of 227 GPa to 235 GPa. Intermediate modulus carbon fiber has a tensile modulus of 282 GPa to 289 GPa.

[0045] The carbon fibers may be unused carbon fibers or recycled (used or post-industrial) carbon fibers (thermally decomposed or excessive).

[0046] In some embodiments, the carbon fibers have an average length of at least 1 mm, at least 3 mm, at least 4 mm, at least 5 mm, or at least 6 mm. In some embodiments, the glass fibers have an average length of 10 mm or less. In some embodiments, the carbon fibers have an average length of 1 mm to 10 mm, 3 mm to 10 mm, 4 mm to 10 mm, 5 mm to 10 mm, or more than 6 mm to 10 mm.

[0047] In another embodiment, the filler (F) is glass fiber.

[0048] Glass fibers may have a circular cross-section, or a non-circular cross-section including oval, elliptical, or rectangular shapes (so-called "flattened glass fibers").

[0049] Advantageously, the glass fibers used in composition (C) of the present invention are flattened glass fibers.

[0050] In some embodiments, the flattened glass fibers have an aspect ratio of at least 2, preferably at least 2.2, more preferably at least 2.4, and even more preferably at least 3. In addition to or instead of this, in some embodiments, the aspect ratio of the glass fibers is at most 8, preferably at most 6, and more preferably at most 4.

[0051] The aspect ratio is defined as the ratio of the longest cross-sectional diameter of a glass fiber to the shortest cross-sectional diameter of the same fiber.

[0052] In some preferred embodiments, the flattened glass fibers have an aspect ratio of 2 to 6, preferably 2.2 to 4.

[0053] Glass fibers can be added as continuous fibers or chopped glass fibers.

[0054] Glass fibers typically have an equivalent diameter of 5 μm to 20 μm, preferably 5 μm to 15 μm, and more preferably 7 μm to 12 μm.

[0055] All types of glass fibers, including A, C, D, E, M, ECR, S, R, and T glass fibers (described in Chapter 5.2.3, pages 43-48 of the Additives for Plastics Handbook, 2nd ed., John Murphy), or any mixture thereof or mixture thereof can be used. E-glass fibers and S-glass fibers are most preferred.

[0056] Preferably, composition (C) contains the filler (F) in an amount of 10 to 70% by weight, more preferably 20 to 65% by weight, based on the total weight of composition (C).

[0057] According to a preferred embodiment, when the filler (F) is selected from carbon fibers, the amount of filler (F) in composition (C) is 2 to 55% by weight, more preferably 5 to 50% by weight, and even more preferably 8 to 45% by weight, based on the total weight of composition (C).

[0058] According to a preferred embodiment, when the filler (F) is selected from glass fibers, the amount of filler (F) in composition (C) is 25 to 75% by weight, more preferably 35 to 65% by weight, based on the total weight of composition (C).

[0059] According to another preferred embodiment, the filler (F) comprises, more preferably, a mixture of carbon fibers and glass fibers.

[0060] According to this embodiment, the total amount of filler (F) in composition (C) is preferably 7 to 40% by weight based on the total weight of composition (C).

[0061] Preferably, the weight ratio of carbon fibers to glass fibers (weight of carbon fibers in composition (C) / weight of glass fibers in composition (C)) is at least 0.05, at least 0.15, at least 0.2, at least 0.5, at least 0.75, or at least 1. In some embodiments in which composition (C) includes carbon fibers and glass fibers, the weight ratio of carbon fibers to glass fibers is 4 or less, 3 or less, 2 or less, or 1 or less. In some embodiments of composition (C) comprising carbon fibers and glass fibers, the weight ratio of carbon fibers to glass fibers is 0.05-4, 0.05-3, 0.05-2, 0.05-1, 0.15-4, 0.15-3, 0.15-2, 0.15-1, 0.2-5, 0.2-4, 0.2-3, 0.2-1, 0.5-4, 0.5-3, 0.5-2, 0.5-1, 1-4, 1-3, or 1-2.

[0062] Composition (C) further comprises at least one additive (A) in an amount of 0.01% to less than 5% by weight, based on the total weight of the composition.

[0063] Preferably, the compound (A) is selected from the group consisting of alkaline earth metal oxides (most preferably CaO), alkaline earth metal carbonates (most preferably CaCO3), alkaline earth metal phosphates (most preferably Ca3(PO4)2); alkaline earth metal sulfates; alkali metal sulfates (most preferably Na2SO4), alkali metal carbonates (most preferably Na2CO3); group IIB metal oxides (most preferably ZnO); group IIB metal sulfides (most preferably ZnS); and inorganic fillers (most preferably wollastonite, talc, and zeolite).

[0064] Preferably, composition (C) contains additive (A) in an amount of preferably 0.05% to less than 3% by weight, more preferably 0.10% to less than 2% by weight, and even more preferably less than 1% by weight, based on the total weight of composition (C).

[0065] Composition (C) may comprise only one additive (A) or a mixture of additives (A). A more preferred embodiment is in which composition (C) comprises only one of the additives (A) described above.

[0066] Optionally, composition (C) may include additional components such as pigments, dyes, toughening agents, UV stabilizers, heat stabilizers, antioxidants, acid scavengers, processing aids, nucleating agents, lubricants, flame retardants, smoke suppressants, antistatic agents, antiblocking agents, and carbon black.

[0067] If one or more of the above-mentioned components are present, their total concentration is preferably less than 10% by weight, more preferably less than 5% by weight, and most preferably less than 2% by weight, based on the total weight of the polymer composition (C).

[0068] The composition is advantageously prepared by melt-blending the at least one polymer (PA) with the at least one filler (F) and the at least one additive (A).

[0069] Preferably, the mixing of the polymer (PA), the at least one filler (F), and at least one additive (A) is carried out by dry blending and / or melt kneading. More preferably, the mixing of the polymer (PA), the at least one filler (F), and at least one additive (A) is carried out by melt kneading, particularly in a continuous or batch device.

[0070] Preferably, the components are supplied to a single-screw or twin-screw extruder, a stirrer, a single-screw or twin-screw kneader, or a melt mixer such as a Banbury mixer, and the addition step may be the simultaneous addition of all components or a batch-type stepwise addition.

[0071] When raw materials are added gradually in a batch process, a portion of the polymeric and / or nonpolymeric raw materials are added first, and then melt-mixed with the remaining polymeric and nonpolymeric raw materials to be added thereafter until a well-mixed composition is obtained.

[0072] If the filler (F) or additive (A) exhibits a long physical shape (e.g., long fibers and continuous fibers), stretch extrusion or pultrusion may be used to prepare the reinforced composition.

[0073] Composition (C) is advantageously used in the manufacture of articles.

[0074] Preferably, the article is formed by applying a process suitable for thermoplastic resins to composition (C), such as extrusion molding, injection molding, blow molding, rotational molding, or compression molding.

[0075] Articles containing the composition (C) defined above are also provided.

[0076] Composition (C), in which the filler (F) is selected from carbon fibers or a mixture of carbon fibers and glass fibers, is advantageously used to manufacture articles suitable for electrostatic painting, such as painted articles for use in automotive applications.

[0077] For the sake of brevity, a composition (C) in which the filler (F) consists of carbon fibers or a mixture of carbon fibers and glass fibers will hereafter be referred to as "composition (C1)" in this specification.

[0078] An article comprising a composition [composition (C1)] is provided, which is, - Glass transition temperature (T) of at least 130°C, more preferably at least 150°C, as measured by DSC. g At least one polyamide polymer [polymer (PA)] having ) is included in 20 to 85% by weight of the total weight of the composition; - At least one fibrous filler [Filler (F)] selected from carbon fibers or a mixture of carbon fibers and glass fibers, in an amount of 10 to 75% by weight based on the total weight of the composition; - At least one additive [Additive (A)] selected from the group consisting of alkaline earth metal oxides; alkaline earth metal carbonates; alkaline earth metal phosphates; alkaline earth metal sulfates; alkali metal sulfates; alkali metal carbonates; oxides of Group IIB metals of the periodic table; sulfides of Group IIB metals of the periodic table; and inorganic fillers, in an amount of 0.01% to less than 5% by weight based on the total weight of the composition; Contains.

[0079] The carbon fibers and / or glass fibers in composition (C1) have the properties defined above for composition (C) and can be used in the amounts defined above for composition (C).

[0080] Furthermore, methods for coating articles using the composition (C1) defined above are also provided, including electrostatic coating, fluid powder immersion coating, spray coating, and electrodeposition coating.

[0081] Preferably, the method for coating the substrate is carried out by electrostatic coating.

[0082] The present invention is illustrated in more detail below herein by the examples contained in the following experimental section; however, the examples are illustrative only and should not be construed as limiting the scope of the invention. [Examples]

[0083] Experiment Section Materials and methods Polyamide 1:PA6, T / 1,3-BAC, T / 6,CHDA / 1,3-BAC,CHDA (Tg=165℃ and Tm=330℃), the comonomers are as follows: - Hexamethylenediamine (70% by weight, from Ascend Performance Materials) - 1,3-bis(aminomethyl)cyclohexane (from Mitsubishi Gas Chemical Company) - Terephthalic acid (from Flint Hills Resources) - 1,4-Cyclohexanedicarboxylic acid (from Eastman Chemical Company) Polyamide 2: Radipol(registered trademark) S24 PA6 was obtained from Radici Group. The nucleating agent, Mistron® Vapor R (talc), was obtained from Imerys Performance Materials. Filler 1: Tenax(registered trademark)-JHT C493 (carbon fiber) was obtained from Teijin. Filler 2: Chop Vantage® HP3610 (circular E-glass fiber with a diameter of 10 μm) was obtained from Nippon Electric Glass. The toughening agent, Royaltuf® 498 maleic anhydride graft EPDM, was obtained from Addivant. The denaturing agent, VitaCal O (calcium oxide), was obtained from Mississippi Lime. Additive Package 1: Contains pigment (carbon black CPTA-25759) and heat stabilizer (HS pellet blend) - CPTA-35759 masterbatch of carbon black and polyamide obtained from Clariant; HS pellet blend heat stabilizer for polyphthalamide manufactured by Ajay North America. Additive package 2: Contains olefin heat stabilizer (Naugard® 445 aromatic amine), obtained from Addivant.

[0084] DSC (Differential Scanning Calorimetry) The glass transition temperature (Tg) of the composition was measured using DSC with the following specifications: - Equipment: TA Instruments DSC Q20-2 - Nitrogen carrier gas with a purity of 99.998% - Flow rate: 50ml / min - Method: ASTM D3418-15 - Method record: (1: Equilibrate at 30.00°C (2: Increase temperature to 350.00°C at 20.00°C / min) (3: Isothermate for 1.00 minutes (4: Mark end of cycle 1) (5: Increase temperature to 0.00°C at 20.00°C / min) (6: Mark end of cycle 2) (7: Increase temperature to 360.00°C at 20.00°C / min) (8: Mark end of cycle 3) (9: End of method.

[0085] Melt stability Melt stability was performed using an LCR-7000 capillary rheometer. The material was loaded into the capillary rheometer and kept in the barrel with minimal shear for 1200 seconds. -1 The melt viscosity was measured at barrel times of 5 minutes and 10 minutes. Melt stability is given as the ratio of the viscosity at 5 minutes to the viscosity at 10 minutes (T5 / T10).

[0086] Paintability test The test was performed three times on a panel with a 0.8 mm thick coating film on top. The scribing tool was an Olfa® knife that used a template with a blade spacing of 2 mm or 3 mm. The adhesion evaluation scale is as follows: 0 → The edges of the cut are perfectly smooth, and none of the squares in the grid are separated. 1. Peeling of small flakes of coating at the cross-cut intersection. Up to 5% of the cross-cut area was affected. 2. The coating peeled off along the edges and / or at the intersections of the cuts. A minimum of 5% and a maximum of 15% of the cross-cut area was affected. 3. The coating peeled off in large ribbon-like strips, either partially or entirely, along the edges of the cut, and / or partially or entirely, in various parts of the square. A minimum of 15% and a maximum of 35% of the cross-cut area was affected. 4 → The coating peeled off along the degree of the large ribbon cut, and / or some squares peeled off partially or completely. A minimum of 35% and a maximum of 65% of the cross-cut area was affected. Crosscut regions exceeding 5-65% were affected. To pass the test, the initial adhesive strength had to be evaluated as 0. After immersion in water (24 hours in deionized water at 60±1℃), a score of 0 was considered "pass," a score of 1 was considered "barely pass," and a score of 2 or higher was considered "fail."

[0087] Synthesis of Polyamide 1 Polyamide 1 was prepared in an autoclave reactor equipped with a distillation line fitted with a pressure control valve. 498 g of 70% hexamethylenediamine, 165 g of 1,3-bis(aminomethyl)cyclohexane, 635 g of terephthalic acid, 20 g of 1,4-cyclohexanedicarboxylic acid, 355 g of deionized water, 7.2 g of glacial acetic acid, and 0.32 g of phosphoric acid were added to the reactor. The reactor was sealed, purged with nitrogen, and heated to 260°C. The generated steam was slowly released to maintain an internal pressure of 120 psig. The temperature was increased to 335°C. The reactor pressure was reduced to atmospheric pressure while the reaction mixture was maintained at 335°C for 60 minutes. The polymer was removed from the reactor and used in the preparation of compound formulations.

[0088] Example (A): Preparation and testing of the composition The compositions detailed in Table 1 below were prepared by mixing the listed components in predetermined amounts using a Coperian ZSK-26TSE co-directional kneading extruder.

[0089] [Table 1]

[0090] The thermal properties and paintability of the above composition were measured according to the method described above. The results are summarized in Table 2 below.

[0091] [Table 2]

[0092] The results in Table 2 clearly show that the composition of the present invention (E-1) has significantly improved coating properties compared to compositions without modifiers (control, CE-1, and CE-3), and at the same time exhibits a high Tg.

[0093] The mechanical properties of compositions that passed the paintability test after immersion in water for 24 hours were evaluated. The results are summarized in Table 3 below.

[0094] [Table 3]

[0095] The results in Table 3 clearly show that composition (E-1) of the present invention maintained excellent mechanical properties. The comparative composition (CE-4) containing a large amount of toughening agent 2 showed acceptable paintability, but its mechanical properties were adversely affected.

[0096] Example (B): Preparation and testing of the composition The compositions detailed in Table 4 below were prepared by mixing the listed components in predetermined amounts using a Coperian ZSK-26TSE co-directional kneading extruder.

[0097] [Table 4]

[0098] The mechanical properties of the above composition were evaluated. The results are summarized in Table 5 below.

[0099] [Table 5]

[0100] The results in Table 5 clearly demonstrate that the composition of the present invention (E-2) maintained a superior balance of mechanical properties compared to the control composition.

[0101] If any disclosure of patents, patent applications, and published materials incorporated herein by reference conflicts with any description of this application to such an extent that it could obscure any term, the description herein shall prevail.

[0102] While only certain features of the present invention are illustrated and described herein, those skilled in the art will likely come up with numerous modifications and changes. It should be understood that the appended claims are intended to cover all such modifications and changes that fall within the spirit of the invention.

Claims

1. - Glass transition temperature (T) of at least 130°C ｇ At least one polyamide polymer [polymer (PA)] having a melting point (T m) of at least 280°C, wherein T g and T m are determined using a differential scanning calorimeter (DSC) according to ASTM D3418, The polymer (PA) is [6 / BAC] / [T / CHDA] [Here, T represents terephthalic acid; CHDA represents 1,4-cyclohexanedicarboxylic acid; and BAC represents bis(aminomethyl)cyclohexane.] The composition contains at least one polyamide polymer [polymer (PA)] in an amount of 20 to 85% by weight, based on the total weight of the composition; - At least one fibrous filler [Filler (F)] selected from glass fibers, carbon fibers, or mixtures thereof, in an amount of 10 to 75% by weight based on the total weight of the composition; - At least one additive [Additive (A)] selected from the group consisting of alkaline earth metal oxides; alkaline earth metal carbonates; alkaline earth metal phosphates; alkali metal sulfates and alkali metal carbonates, in an amount of 0.05% to less than 3% by weight based on the total weight of the composition. The composition containing [Composition (C)].

2. The aforementioned polymer (PA) - Number-average molecular weight (Mn) in the range of 1,000 g / mol to 40,000 g / mol (determined by gel permeation chromatography (GPC) using ASTM D5296 with polystyrene standards); and / or - Glass transition temperature (T) of at least 130°C and 190°C or less ｇ ) (measured according to ASTM D3418); and / or - A melting point (T) of 360°C or less and at least 280°C or less. ｍ (Determined using a differential scanning calorimeter (DSC) in accordance with ASTM D3418); The composition (C) according to claim 1, having the following characteristics.

3. The additive (A) is selected from the group consisting of CaO; CaCO ３ ; Ca ３ (PO ４ ) ２ ; Na ２ SO ４ ; Na ２ CO3, and is the composition (C) according to claim 1 or 2.

4. The composition (C) according to any one of claims 1 to 3, wherein the amount of additive (A) is 0.10% by weight to less than 2% by weight based on the total weight of the composition (C).

5. The composition (C) according to any one of claims 1 to 4, wherein the filler (F) contains glass fibers.

6. The aforementioned filler (F) - Carbon fibers in an amount of 2 to 55% by weight based on the total weight of the composition (C); or - A mixture of carbon fibers and glass fibers in an amount of 7 to 40% by weight based on the total weight of composition (C), wherein the weight ratio of carbon fibers to glass fibers is at least 0.05 and 4 or less; A composition (C) according to any one of claims 1 to 5, comprising:

7. The composition (C) according to any one of claims 1 to 6, wherein the polymer (PA) has a melting point (T m) of at least 295°C, and T m is determined using a differential scanning calorimetry (DSC) according to ASTM D3418.

8. An article comprising the composition (C) according to any one of claims 1 to 7.

9. A method for coating the article according to claim 8, carried out by a fluid powder immersion coating method, a spray method, and an electrodeposition coating method.

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