Stabilizing component for polyamide resin compositions

Abstract

A polyamide resin is disclosed that includes one or more polyamides and a stabilizer component that includes a copper complex and a copper salt for improving the heat aging performance of an article. The combination of the copper complex and the copper salt preserves the mechanical properties of the article.

Description

[Technical field]

[0001] Priority claim

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 246,371, filed September 21, 2021, which is incorporated herein by reference.

[0002]

[0001] The present invention relates to a polyamide resin composition, and more particularly to a polyamide resin composition having a stabilizing component that exhibits excellent mechanical properties. [Background technology]

[0003]

[0002] Polyamide resins have a good balance of mechanical properties, moldability and chemical resistance and can be used in a variety of engineering plastics applications, including fasteners, circuit breakers, terminal blocks, connectors, automotive parts, furniture parts, home appliance parts, cable ties, sporting goods, gun stocks, window thermal insulation, aerosol valves, food film packaging, automotive / vehicle parts, textiles, industrial textiles, carpets, and electrical / electronic components.

[0004]

[0003] Despite their wide variety of applications, polyamides are susceptible to environmental conditions that degrade their performance characteristics. Generally, polyamides have a service temperature range of -40°C to 85°C. At temperatures below -40°C, polyamides become very brittle. Furthermore, at higher temperatures, polyamides suffer from a number of problems. For example, polyamides become brittle and discolor. Furthermore, desirable mechanical properties of polyamides, such as tensile strength and impact resistance, generally decrease with exposure to high temperatures.

[0005]

[0004] In order to improve the mechanical properties of polyamide, reinforcing fillers such as glass fillers are added, but this leads to disadvantages, for example, when the content of reinforcing fillers is high, the surface appearance of the parts or components made from reinforced polyamide is very poor, and difficulties arise in the injection molding process.

[0006]

[0005] In particulate applications, there is an increasing need to further improve the heat resistance of polyamides that are exposed to high temperatures during their life cycle. To improve performance, certain heat stabilizers are used to provide additional heat protection up to 125°C. Even with the use of these stabilizers, other performance properties can be degraded, which is undesirable.

[0007] For example, the addition of conventional heat stabilizer packages has been shown to be moderately effective against thermal oxidative damage, but typically these heat stabilizer packages merely delay the damage. Furthermore, conventional stabilizer packages have been found to be ineffective over higher temperature ranges, e.g., over certain temperature gaps.

[0008]

[0007] While many of these stabilizer packages may provide improved performance at some temperatures, each stabilizer package often exhibits additional drawbacks unique to it. For example, stabilizer packages utilizing iron-based stabilizers are known to require high precision in the average particle size of the iron compounds, which creates manufacturing challenges. Additionally, these iron-based stabilizer packages exhibit stability issues, e.g., polyamides may degrade during various manufacturing stages. As a result, residence times at various stages of the manufacturing process must be carefully monitored. Similar issues exist for polyamides utilizing zinc-based stabilizers.

[0009]

[0008] US Pub. No. 2020 / 0299507 describes a composition comprising 70 to 91 weight % of at least one semi-crystalline polyamide, 5 to 25 weight % of at least one polyolefin having epoxy, anhydride or acid functional groups introduced by grafting or copolymerization, 3 to 20 weight % of at least one plasticizer, 0.05 to 5 weight % of at least one stabilizer based on a copper complex, and at least one catalyst, the composition being free of alkali metal halides and oligo- or polycarbodiimides.

[0010]

[0009] US Pub. No. 2014 / 0041159 describes a cable tie made from a polyamide composition formed from a low viscosity polyamide-6 and a nucleating agent including an organic material, e.g., an organic polymer, and an inorganic metal material, e.g., a metal oxide, a silicate.

[0011]

[0010] EP Pub. No. 1,121,388 describes a stabilized polyamide composition which is characterized in that it contains at least one copper complex and at least one organic halogen compound as stabilizers.

[0012]

[0011] Semi-aromatic polyamides are thermoplastics with a range of properties suitable for certain high temperature applications. US Patent No. 10,854,869 discloses a compound comprising a semi-aromatic polyamide component containing terephthalamide and / or isophthalamide repeat units, an impact modifier component containing a modified polyolefin elastomer, one or more synergistic blends of sterically hindered phenolic stabilizers and phosphonates, one or more relatively high molecular weight organic phosphite stabilizers, and a finely divided talc nucleating agent.

[0013] Therefore, in view of the references, there remains a need for improved polyamide resin compositions having stabilizers that improve the service temperature range without compromising performance. Summary of the Invention [Problem to be solved by the invention]

[0014]

[0013] A polyamide resin composition is provided having a dual heat stabilizer system that has good retention performance over time at high temperatures. The retention performance can include at least one of tensile strength, elongation, and impact strength. The dual heat stabilizer system is beneficial in retaining these initial properties. In one embodiment, at least one of these performance values ​​is retained after 2500 hours at a temperature of 150°C. In one embodiment, the polyamide resin composition retains at least 80% of its initial tensile strength after 1500 hours at a temperature of 140°C to 160°C. In one embodiment, the polyamide resin composition retains at least 5% of its initial elongation after 1500 hours at a temperature of 140°C to 160°C. In one embodiment, the polyamide resin composition retains at least 25% of its initial impact strength after 3000 hours at a temperature of 140°C to 160°C. [Means for solving the problem]

[0015] In one aspect, the disclosure describes a polyamide resin composition comprising a resin component containing 75% or more by weight of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms ("first polyamide") and 25% or less by weight of a polyamide containing caprolactam ("second polyamide"), and a stabilizer component containing a copper complex and a copper salt, the amount of copper provided by the copper complex and the copper salt being in a weight ratio of 10:90 to 90:10. In one embodiment, the resin component is present in an amount of more than 70% by weight, particularly 70 to 99.5% by weight, based on the total weight of the polyamide resin composition. The stabilizer component may be present in an amount of 0.1 to 15% by weight, based on the total weight of the polyamide resin composition. In one embodiment, the copper complex includes a ligand and / or a halogenated organic compound such as a bromine-based compound. The ligand may be a phosphine, mercaptobenzimidazole, acetylacetonate, glycine, ethylenediamine, oxalate, diethylenediamine, triethylenetetraamine, ethylenediaminetetraacetic acid, pyridine, diphosphone, dipyridyl, or mixtures thereof. The copper complex may be in an amount of 0.1 to 5 wt% based on the total weight of the polyamide resin composition. In one embodiment, the copper salt may be cuprous iodide, cuprous cyanide, cupric acetate, cupric stearate, or mixtures thereof. The copper salt further comprises an alkali metal halide, such as lithium iodide, sodium iodide, or potassium iodide, or mixtures thereof. The total halogen loading may be 5 wt% or less based on the total weight of the polyamide resin composition. The copper salt may be in an amount of 1 to 5 wt% based on the total weight of the polyamide resin composition. In one embodiment, the resin component comprises 75-100% of a polyamide containing an aliphatic diamine having 6 or more carbon atoms, preferably 6 carbon atoms, and an aliphatic diacid having 6 or more carbon atoms, preferably 6 carbon atoms (the "first polyamide"). In one embodiment, the resin component may also comprise 0-25% of a polyamide containing caprolactam (the "second polyamide"). In some embodiments, the resin composition further comprises a lubricant, a dye, a pigment, an optical brightener, a UV stabilizer, or a combination thereof.The polyamide resin composition is preferably an unfilled composition, meaning that no fillers or other reinforcing materials are used (0% filler content). Additionally, the polyamide resin composition does not contain polyolefins, plasticizers and / or impact modifiers. The stabilizer component contributes to maintaining or retaining acceptable mechanical performance, including maintaining / retaining at least 80% of initial tensile strength, at least 5% of initial elongation, and / or at least 25% of initial impact strength after 1500 hours at a temperature of 140°C to 160°C. In some embodiments, articles formed from the polyamide resin composition include fasteners, circuit breakers, terminal blocks, connectors, automotive interior parts, automotive engine parts, furniture parts, appliance parts, cable ties, sporting goods, gun stocks, window thermal insulation, aerosol valves, food film packaging, or electrical / electronic components.

[0016]

[0015] In one aspect, the disclosure describes a cable tie made from a polyamide resin composition, the polyamide resin composition including a resin component containing 75% or more by weight of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms (the "first polyamide") and 25% or less by weight of a polyamide containing caprolactam (the "second polyamide"), and a stabilizer component containing a copper complex and a copper salt, wherein the amount of copper provided by the copper complex and the copper salt is in a weight ratio of 10:90 to 90:10. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Introduction

[0016] The present invention relates to a polyamide resin composition having improved heat resistance. In one embodiment, the polyamide resin composition includes a stabilizer component containing copper provided by two different copper sources. In some embodiments, the stabilizer component includes a copper complex having bound copper and further includes a copper salt. The stabilizer component can be used with polyamide resin compositions that are unfilled and do not contain reinforcing fillers, talc, or glass fibers.

[0018]

[0017] The stabilizer component is particularly effective in providing heat resistance to temperatures up to 160°C, particularly temperatures between 140°C and 160°C, and in retaining acceptable mechanical properties in terms of tensile strength, elongation, and / or impact strength over an extended period of time, allowing the polyamide resin composition having the stabilizer component to be used in a variety of applications that are exposed to high temperatures during their life cycle.

[0019] Resin Component

[0018] The polyamide resin composition has as its main component a resin component in an amount of 70 to 99.5% by weight, for example 71 to 99% by weight, 75 to 99% by weight, 80 to 99% by weight, 85 to 99% by weight, 90 to 99% by weight, or 95 to 99% by weight, based on the total weight of the polyamide resin composition.

[0020] In one embodiment, the resin component includes 75% or more by weight of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms, sometimes referred to as a first polyamide, and 25% or less by weight of a polyamide containing caprolactam, sometimes referred to as a second polyamide. In a preferred embodiment, the resin component includes 75% or more by weight of the first polyamide and 25% or less by weight of the second polyamide. The first polyamide and the second polyamide may be separate polyamides or may be copolymerized with another polyamide. In general, polyamides can be formed by condensation of diamines or diacids and / or by ring opening of lactams. In some embodiments, the resin component does not include aromatic or cyclic diacids or diamines. Furthermore, diacids or diamines having 5 or fewer carbon atoms are particularly undesirable.

[0021] In one embodiment, the resin component comprises 75 wt% or more of the first polyamide, for example, more than 77 wt%, more than 80 wt%, more than 85 wt%, more than 87 wt%, more than 90 wt%, more than 91 wt%, more than 95 wt%, or more than 97 wt%. This is based on the total weight of the resin component, not including the stabilizer component or other additives described herein. In terms of ranges, the resin component comprises 75-100 wt%, for example, 75-99.5 wt%, 75-98.5 wt%, 75-97.5 wt%, 75-95 wt%, 75-90 wt%, or 75-87 wt% of the polyamide containing the aliphatic diamine having 6 or more carbon atoms and the aliphatic diacid having 6 or more carbon atoms. When the resin component comprises 100 wt% of the first polyamide, the resin composition does not comprise the second polyamide or other types of polyamides, such as aromatic or cyclic.

[0022]

[0021] The polyamide may include an aliphatic diamine having 6 or more carbon atoms, including hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, hexadecanediamine, octadecenediamine, octadecenediamine, eicosanediamine, docosanediamine, or mixtures thereof. Preferably, the aliphatic diamine is hexanediamine, and at least 90% of the aliphatic diamine having 6 or more carbon atoms is hexanediamine. In some embodiments, the aliphatic diamine is unmodified. Additionally, cycloaliphatic and aromatic diamines may be excluded from the resin component.

[0023]

[0022] The polyamide may include an aliphatic diacid having 6 or more carbon atoms, including adipic acid, heptanedioic acid, octanedioic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenedioic acid, eicosane diacid, docosane diacid, or mixtures thereof. Preferably, the aliphatic diacid is adipic acid, and at least 90% of the aliphatic diacid having 6 or more carbon atoms is adipic acid. In some embodiments, the aliphatic diacid is unmodified. Additionally, cycloaliphatic diacids and aromatic diacids are excluded from the resin component.

[0024] In one embodiment, the resin component comprises a polyamide based on hexamethylenediamine and adipic acid, referred to as poly[imino(1,6-dioxohexamethylene)iminohexamethylene] or polyamide 66 (PA66). In one embodiment, the resin component comprises 75% or more by weight of PA66, such as greater than 77%, greater than 80%, greater than 85%, greater than 87%, greater than 90%, greater than 91%, greater than 95%, or greater than 97% by weight. In terms of ranges, the resin component comprises 75-99.5% by weight of PA66, such as 75-98.5%, 75-97.5%, 75-95%, 75-90%, or 75-87% by weight.

[0025]

[0024] The first polyamide may contain an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms and have an amine end group (AEG) level ranging from 50 μeq / gram to 90 μeq / gram. Amine end groups are defined as the amount of amine ends (-NH2) present in the polyamide. Methods for calculating AEG are well known. In some embodiments, AEG levels may be in the range of 50 μeq / gram to 90 μeq / gram, e.g., 55 μeq / gram to 85 μeq / gram, 60 μeq / gram to 90 μeq / gram, 70 μeq / gram to 90 μeq / gram, 74 μeq / gram to 89 μeq / gram, 76 μeq / gram to 87 μeq / gram, 78 μeq / gram to 85 μeq / gram, 60 μeq / gram to 80 μeq / gram, 62 μeq / gram to 78 μeq / gram, 65 μeq / gram to 75 μeq / gram, or 67 μeq / gram to 73 μeq / gram.

[0026]

[0025] The resin component may also contain 25% or less by weight of a polyamide ("second polyamide") containing caprolactam, e.g., less than 22%, less than 20%, less than 15%, less than 10%, or less than 5% by weight. In terms of ranges, the resin component may contain the second polyamide in an amount of 0-25% by weight, e.g., 5-22%, 5-20%, 10-20%, or 15-20% by weight. When the resin component does not contain any second polyamide containing caprolactam, the resin component mainly contains a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms. In other embodiments, the resin component includes a combination of a first polyamide and a second polyamide, or a copolymer thereof, and the resin component may include the second polyamide in an amount of 1 to 25 wt%, e.g., 5 to 22 wt%, 5 to 20 wt%, 10 to 20 wt%, or 15 to 20 wt%.

[0027]

[0026] In one embodiment, the weight ratio of the first polyamide to the second polyamide (i.e., the weight ratio of the polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms to the polyamide containing caprolactam) is 75 / 25 to 100 / 0, particularly 75 / 25 to 90 / 15, 75 / 25 to 85 / 15, or 80 / 20 to 85 / 15. If the amount of the second polymer is large, the processability may be reduced.

[0028] The caprolactam-containing polyamide is preferably predominantly caprolactam and contains more than 90%, for example more than 95% or more than 97% caprolactam. A preferred caprolactam-containing polyamide is poly(azepan-2-one), also known as polyamide 6 (PA6). The second polyamide may include other polyamides containing γ-butyrolactam, capryllactam, lauryllactam, or combinations thereof. Suitable polyamide-6 materials are generally formed by reacting caprolactam with aminocaproic acid under suitable temperature conditions to initiate polymerization. Different PA6s can be produced by varying the reaction time and / or temperature, by including catalysts, and by forming various end groups. Commercially available PA6 is available from a variety of manufacturers, including Vydyne PA6 from Ascend Performance Materials, Aegis™ polyamide-6 products available from Honeywell, Nylon polyamide-6 products available from DuPont, Ube polyamide-6 products available from Ube Industries, Amilan polyamide-6 products available from Toray, and Leona polyamide-6 products available from Asahi Kasei.

[0029] In some embodiments, the resin component includes a polyamide having a melting temperature of 250° C. or less, e.g., 240° C. or less, 235° C. or less, 230° C. or less, 225° C. or less, 220° C. or less, 215° C. or less, 210° C. or less, or 205° C. or less. The melting temperature of the polyamide may be 175° C. or more, e.g., 180° C. or more, 190° C. or more, 200° C. or more, or 210° C. or more.

[0030]

[0029] The polyamides used in the resin component preferably have a number average molecular mass Mn of 20,000 or more, for example 30,000 or more or 40,000 or more, advantageously between 20,000 and 80,000. The weight average molecular mass Mw of the polyamide is generally greater than 40,000, advantageously between 50,000 and 100,000, and may in some embodiments range up to 200,000.

[0031] In one embodiment, the polyamide used in the resin composition may have a relative viscosity (RV) of 5-200, for example, 10-100, 10-75, 20-75, 20-70, 30-60, or 40-60.

[0032] Stabilizer ingredients In one embodiment, the stabilizer component comprises copper. The copper is preferably provided by at least two different copper sources ("dual copper stabilizer"). In one embodiment, the stabilizer component comprises at least one copper complex and at least one copper salt. The different copper sources may be taken together to constitute a heat stabilizer package. This stabilizer package enables the polyamide resin composition to retain its mechanical properties after heat aging.

[0033] For purposes of the disclosed embodiment, the stabilizer component is copper-based and does not include cerium-based stabilizers or melamine-based stabilizers.

[0034] The copper complex may include bound copper. The copper may be bound by a ligand. In some embodiments, the ligand of the copper complex may be a phosphine, mercaptobenzimidazole, acetylacetonate, glycine, ethylenediamine, oxalate, diethylenediamine, triethylenetetraamine, ethylenediaminetetraacetic acid, pyridine, diphosphone, dipyridyl, or mixtures thereof. The phosphine may specifically include an alkyl phosphine, such as tributylphosphine, or an aryl phosphine, such as triphenylphosphine (TPP). In a preferred embodiment, the ligand is triphenylphosphine, mercaptobenzimidazole, or mixtures thereof.

[0035] The amount of copper in the copper complex may be 10-1000wppm, for example, 10-800wppm, 10-500wppm, 20-500wppm, 20-400wppm, 20-300wppm, 20-250wppm, 20-200wppm, 20-150wppm, or 50-150wppm, based on the total weight of the polyamide resin composition. In one embodiment, the stabilizer works efficiently when the total amount of copper is less than 1000wppm, for example, less than 950wppm, less than 900wppm, less than 800wppm, less than 500wppm, less than 400wppm, less than 300wppm, less than 250wppm, less than 200wppm, or less than 150wppm. To provide an effective amount of copper, the complex may have more than 10 wppm copper, such as more than 50 wppm, more than 75 wppm, more than 100 wppm, more than 150 wppm, more than 200 wppm, or more than 250 wppm copper.

[0036] In some embodiments, the copper complex further comprises a halogenated organic compound. Suitable halogenated organic compounds may include bromine-based compounds and / or aromatic compounds. The halogenated organic compound may be decabromodiphenyl, decabromodiphenyl ether, bromostyrene oligomer, chlorostyrene oligomer, polydibromostyrene, tetrabromobisphenyl-A, tetrabisphenyl-A derivative, chlorodimethane dibenzo(a,e)cyclooctene derivative, or a mixture thereof. In one embodiment, the molar ratio of copper:halogen is 1:1 to 1:3000, for example, 1:1 to 1:1000, 1:1 to 1:500, 1:2 to 1:500, 1:2 to 1:100, 1:2 to 1:50, or 1:1.5 to 1:15.

[0037]

[0036] Commercially available copper complexes include Bruggolen® H3386, Bruggolen® H3376, Bruggolen® H3344, and Bruggolen® H3350 available from Bruggemann.

[0038] In one embodiment, the copper salt may include a halide salt or an organic salt. Suitable halide salts may include cuprous chloride, cuprous bromide, cuprous fluoride, cuprous iodide, or mixtures thereof. In a preferred embodiment, the copper salt is cuprous iodide. In some embodiments, the copper salt may be a carboxylic acid having 2 to 18 carbon atoms, such as cupric acetate, cupric naphthenate, cupric caprate, cupric laurate, and cupric stearate; cupric thiocyanate; cupric nitrate; copper(II) acetylacetonate; cuprous oxide(I); and cupric oxide(II). In one embodiment, the copper salt may be cuprous iodide, cuprous cyanide, cupric acetate, cupric stearate, or mixtures thereof. The above copper salts may be used alone or in combination.

[0039]

[0038] In some embodiments, the copper salt may further include an alkali metal halide. The alkali metal halide may include a fluoride, bromide, or iodide of lithium, sodium, or potassium. Among them, potassium iodide is preferable. Such an alkali metal halide may be used independently or in combination with the copper salt. The use of such an alkali metal halide improves the dispersibility of the copper salt in the polyamide resin composition, thereby improving the weather resistance of the composition.

[0040]

[0039] The alkali metal halide is preferably used in an amount such that the number of halogen atoms of the alkali metal halide per copper atom of the copper salt is in the range of 0.3 to 4, particularly 0.3 to 3.0, 0.3 to 2.5, 0.3 to 2.0, or 0.4 to 2.0.

[0041] In some embodiments, the total halogen loading in the composition is 5 wt% or less, e.g., less than 4 wt%, less than 3 wt%, less than 2.5 wt%, less than 2 wt%, less than 1.5 wt%, less than 1.0 wt%, or less than 0.5 wt%, based on the total weight of the polyamide resin composition. As described herein, the composition allows manufacturers to use reduced levels of stabilizers, which provide process improvements while realizing significant cost advantages.

[0042] In one embodiment, the stabilizer component contains a copper complex and a copper salt, and the weight ratio of the copper provided by the copper complex to the copper provided by the copper salt is 10:90 to 90:10, for example, 20:80 to 80:20, 25:75 to 75:25, 30:70 to 70:30, 40:60 to 60:40, 45:55 to 55:45, or 50:50. When added in such a ratio, the stabilizer component is thermally stable, does not cause degradation of the first or second polyamide during processing, and does not affect the composition during the manufacturing process. In one embodiment, the copper provided by the copper complex and the copper provided by the copper salt may be substantially equal. In some cases, the amount of copper supplied from the copper salt is greater than the amount of copper supplied from the copper complex, and the weight ratio of copper supplied from the copper complex to copper supplied from the copper salt is 10:90 to 50:50, for example, 20:80 to 50:50, 25:75 to 50:50, 30:70 to 50:50, 40:60 to 50:50, or 45:55 to 50:50.

[0043] In some embodiments, the total amount of the double copper stabilizer added is 0.1-15 wt%, for example, 0.25-15 wt%, 0.25-10 wt%, 0.25-9 wt%, 0.25-8 wt%, 0.25-7 wt%, 0.25-5 wt%, 0.3-5 wt%, 0.3-4 wt%, 0.3-3 wt%, 0.3-2.5 wt%, 0.3-2 wt%, 0.3-1.5 wt%, or 0.3-1 wt% based on the total weight of the polyamide resin composition. Thus, in one embodiment, a polyamide resin composition is provided, which comprises a resin component containing 75 wt% or more of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms, and 25 wt% or less of a polyamide containing caprolactam, and a stabilizer component containing a copper complex and a copper salt, and the total amount of the stabilizer component added is 0.1-15 wt%.

[0044]

[0043] In some embodiments, the total amount of copper complex added is 0.1-5 wt% based on the total weight of the polyamide resin composition, for example, 0.1-4.5 wt%, 0.1-4 wt%, 0.1-3.5 wt%, 0.15-3 wt%, 0.15-2.5 wt%, 0.15-2 wt%, 0.15-1.5 wt%, 0.15-1 wt%, or 0.2-0.5 wt%. Thus, in one embodiment, there is provided a polyamide resin composition comprising a resin component containing 75 wt% or more of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms, and 25 wt% or less of a polyamide containing caprolactam, and a stabilizer component containing a copper complex and a copper salt, and the total amount of copper complex added is 0.1-5 wt%.

[0045]

[0044] In some embodiments, the total amount of copper salt added is 0.1-5 wt% based on the total weight of the polyamide resin composition, for example, 0.1-4.5 wt%, 0.1-4 wt%, 0.1-3.5 wt%, 0.25-3 wt%, 0.25-2.5 wt%, 0.25-2 wt%, 0.25-1.5 wt%, or 0.25-1 wt%. Thus, in one embodiment, there is provided a polyamide resin composition comprising a resin component containing 75 wt% or more of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms, and 25 wt% or less of a polyamide containing caprolactam, and a stabilizer component containing a copper complex and a copper salt, and the total amount of copper salt added is 0.1-5 wt%.

[0046] In terms of total copper, the stabilizer components together provide between 100-6000 wppm copper, for example, 500-5000 wppm, 500-4500 wppm, 500-4000 wppm, 500-3500 wppm, 500-3000 wppm, or 1000-3000 wppm. If total copper is added at low levels, for example less than 100 wppm, the thermal protection effect is reduced.

[0047] The stabilizer component can be compounded with or separately from the polyamide resin component, melt mixed, extruded, and pelletized. In one embodiment, the stabilizer component, the copper complex and the copper salt, and either the copper complex or the copper salt can be added as a masterbatch. The masterbatch can include a polyamide such as the resin component, i.e., a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms, a polyamide containing caprolactam, or a copolymer thereof. In a preferred embodiment, the copper salt is added as a masterbatch to aid processing. The masterbatch can include 1-15 wt. % copper salt and 75-99% polyamide, particularly a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms.

[0048] Other Additives

[0047] In the embodiments disclosed herein, the polyamide resin composition does not contain polyolefins, including polymers containing olefin units such as ethylene, propylene, butylene, or octane, or polyolefins functionalized with epoxy, anhydride, or acid functional groups. Polyolefins may be impact modifiers, and impact modifiers are excluded from the polyamide resin composition disclosed herein. Other impact modifiers that are not polyolefins are also excluded from the polyamide resin composition disclosed herein. Some types of impact modifiers may improve impact strength and stiffness, but may reduce tensile strength performance.

[0049]

[0048] The disclosed polyamide resin compositions, in some embodiments, are unfilled (0% filler). In some cases, the polyamide resin compositions are neat compositions, e.g., no fillers, such as glass, carbon fiber, particulate fillers, mineral fillers, etc., are present in the composition.

[0050]

[0049] The polyamide resin composition may contain certain additives that do not impair the heat stabilizing properties or other mechanical properties. Suitable additives may include lubricants, dyes, pigments, optical brighteners, UV stabilizers or mixtures thereof. For purposes of the disclosed embodiments, additives do not include plasticizers in addition to the impact modifiers mentioned above.

[0051]

[0050] Various lubricants may be suitable for use with embodiments of the present invention. Examples of suitable lubricants include stearamides such as ethylene-bis-stearamide, stearates such as zinc stearate, magnesium stearate, calcium stearate, sodium stearate, and polydimethylsiloxane. Particularly suitable additives include zinc stearate and / or ethylene-bis-stearamide. The disclosed polyamide resin composition can effectively produce polyamide structures without the need for large amounts of lubricants typically present in conventional polyamides, thereby improving production efficiency. In some embodiments, the polyamide resin composition may include 20 wt% or less of lubricant, e.g., 15 wt% or less, 10 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2.5 wt% or less, 2 wt% or less, or 1.5 wt% or less.

[0052] Colorants such as pigment and / or dye additives may also be present. Suitable pigments may include, for example, inorganic pigments such as metal oxides and mixed metal oxides, such as zinc oxide, titanium dioxide, iron oxide, and the like; sulfides, such as zinc sulfide; aluminates; sodium sulfosilicates, sulfates, chromates, and the like; carbon black; zinc ferrite; ultramarine; Pigment Brown 24; Pigment Red 101; Pigment Yellow 119; organic pigments, such as azo, diazo, quinacridone, perylene, naphthalenetetracarboxylic acid, flavanthrone, isoindolinone, tetrachloroisoindolinone, anthraquinone, anthanthrone, dioxazine, phthalocyanine, azo lake, and the like; Pigment Blue 60, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Green 7, Pigment Yellow 147, and Pigment Yellow 150, or a combination comprising at least one of the foregoing pigments.

[0053]

[0052] Light stabilizers and / or ultraviolet (UV) stabilizers may also be used. Suitable light stabilizer additives may include, for example, benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxybenzophenone, or a combination comprising at least one of the aforementioned light stabilizers.

[0054] The polyamide composition of the present invention can be obtained by thoroughly mixing the various components in a single or twin screw extruder at a temperature sufficient to maintain the polyamide resin in a molten state. Typically, the mixture is extruded into a rod which is then chopped to form granules or pellets. The additives may be added together or separately by mixing the polyamide hot or cold. The granules or pellets can be further processed into a powder, for example by grinding with liquid nitrogen.

[0055] Performance characteristics

[0054] The polyamide resin composition described above exhibits surprising performance against heat aging. For example, the polyamide composition exhibits excellent tensile performance at high temperatures of 140°C to 160°C. This allows articles made from the polyamide resin composition to have excellent performance. These performance parameters are exemplary, and the examples support other performance parameters contemplated by the present disclosure.

[0056]

[0055] Additionally, the polyamide resin compositions have been shown to retain mechanical properties upon heat aging, such that, for example, tensile strength remains surprisingly high over time and at elevated temperatures. In contrast, polyamides that do not contain the disclosed stabilizer components exhibit a decrease in tensile strength over time and at elevated temperatures.

[0057] In some embodiments, the retention of tensile strength after heat aging, measured after 1500 hours at a temperature of 140°C to 160°C, is at least 80% of the initial tensile strength, e.g., at least 85%, at least 90%, at least 92%, at least 95%, at least 97.5%, or at least 99%. Thus, the addition of the stabilizer component provides heat stabilization over a long period of time without compromising mechanical strength. In other embodiments, the tensile strength after heat aging at 140°C to 160°C for 1500 hours may be greater than the initial tensile strength, e.g., greater than 100%, e.g., greater than 101%, greater than 102%, greater than 103%, greater than 104%, greater than 105%, greater than 110%, or even greater than 114%.

[0058] In some embodiments, the retention of tensile strength after heat aging is at least 80% of the initial tensile strength, measured after 2000 hours at a temperature of 140°C to 160°C. Thus, the addition of the stabilizer component provides heat stabilization over long periods of time without compromising mechanical strength. In some embodiments, the retention of tensile strength after heat aging is at least 85%, e.g., at least 90%, at least 92%, at least 95%, at least 97.5%, or at least 99%, of the initial tensile strength after 2000 hours at a temperature of 140°C to 160°C. In other embodiments, the tensile strength after 2000 hours of heat aging at 140°C to 160°C may be greater than the initial tensile strength, and such values ​​are also contemplated as the retention of tensile strength. Thus, in some embodiments, the tensile strength after 2000 hours may be greater than 100% of the initial tensile strength, such as greater than 101%, greater than 102%, greater than 103%, greater than 104%, greater than 105%, greater than 110%, or greater than 114%.

[0059] In some embodiments, the retention of tensile strength after heat aging is at least 80% of the initial tensile strength, measured after 3000 hours at a temperature of 140°C to 160°C. Thus, the addition of the stabilizer component provides heat stabilization over long periods of time without compromising mechanical strength. In some embodiments, the retention of tensile strength after heat aging is at least 85%, e.g., at least 90%, at least 92%, at least 95%, at least 97.5%, or at least 99%, of the initial tensile strength after 3000 hours at a temperature of 140°C to 160°C. In other embodiments, the tensile strength after 3000 hours of heat aging at 140°C to 160°C may be greater than the initial tensile strength, and such values ​​are also contemplated as the retention of tensile strength. Thus, in some embodiments, the tensile strength after 3000 hours may be greater than 100% of the initial tensile strength, e.g., greater than 101%, greater than 102%, greater than 103%, greater than 104%, greater than 105%, greater than 110%, or greater than 114%.

[0060] In some embodiments, the retention of elongation after heat aging is at least 5% of the initial elongation measured after 1500 hours at a temperature of 140° C. to 160° C. In some embodiments, the retention of elongation after heat aging is at least 25% of the initial elongation after 1500 hours at a temperature of 140° C. to 160° C., e.g., at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 99%. In other embodiments, the elongation after heat aging for 1500 hours at 140° C. to 160° C. may be greater than the initial elongation, and such values ​​are also contemplated as retention of elongation. Thus, in some embodiments, the elongation after 1500 hours may be greater than 100% of the initial elongation, such as greater than 101%, greater than 102%, greater than 103%, greater than 104%, greater than 105%, greater than 110%, or greater than 114%.

[0061] In some embodiments, the retention of elongation after heat aging is at least 5% of the initial elongation measured after 2000 hours at a temperature between 140° C. and 160° C. In some embodiments, the retention of elongation after heat aging is at least 20% of the initial elongation measured after 2000 hours at a temperature between 140° C. and 160° C., e.g., at least 25%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 99%.

[0062] In some embodiments, the retention of elongation after heat aging is at least 5% of the initial elongation measured after 3000 hours at a temperature between 140° C. and 160° C. In some embodiments, the retention of elongation after heat aging is at least 5% of the initial elongation measured after 3000 hours at a temperature between 140° C. and 160° C., e.g., at least 7%, at least 10%, at least 12%, at least 15%, at least 20%, at least 25%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 99%.

[0063]

[0062] A polyamide resin composition having PA6, for example, in an amount of 1 to 25% by weight, may have a higher initial elongation than a composition without PA6 or a composition having less than 1% by weight of PA6. In some embodiments, the retention of elongation after heat aging of the polyamide resin composition having PA6, measured after 1500 hours at a temperature of 140°C to 160°C, is at least 5% of the initial elongation. In some embodiments, the retention of elongation after heat aging of the polyamide resin composition having PA6, measured after 1500 hours at a temperature of 140°C to 160°C, is at least 25% of the initial elongation, for example, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 99%. In other embodiments, the elongation after heat aging for 1500 hours at 140°C to 160°C may be greater than the initial elongation, and such a value is also contemplated as the retention of elongation. Thus, in some embodiments, the elongation after 1500 hours may be greater than 100% of the initial elongation, such as greater than 101%, greater than 102%, greater than 103%, greater than 104%, greater than 105%, greater than 110%, or greater than 114%.

[0064] In some embodiments, the retention of elongation after heat aging of the polyamide resin composition with PA6 is at least 5% of the initial elongation measured after 2000 hours at a temperature of 140° C. to 160° C. In some embodiments, the retention of elongation after heat aging of the polyamide resin composition with PA6 is at least 7.5% of the initial elongation, for example, at least 10%, at least 15%, at least 20%, at least 25%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 99%, measured after 2000 hours at a temperature of 140° C. to 160° C.

[0065] In some embodiments, the retention of elongation after heat aging of the polyamide resin composition having PA6 is at least 5% of the initial elongation measured after 3000 hours at a temperature of 140° C. to 160° C. In some embodiments, the retention of elongation after heat aging of the polyamide resin composition having PA6 is at least 5% of the initial elongation measured after 3000 hours at a temperature of 140° C. to 160° C., for example, at least 6%, at least 7%, at least 8%, at least 10%, at least 15%, at least 20%, at least 25%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 99%.

[0066] In some embodiments, the retention of impact strength after heat aging, particularly the retention of unnotched Charpy impact strength, measured after 3000 hours at a temperature of 140° C. to 160° C., is at least 25% of the initial impact strength. In some embodiments, the retention of impact strength after heat aging after 1500 hours at a temperature of 140° C. to 160° C. is at least 10% of the initial impact strength, such as at least 15%, at least 20%, at least 25%, at least 30%, at least 40%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 99%. In other embodiments, the impact strength after 1500 hours of heat aging at 140° C. to 160° C. may be greater than the initial impact strength, and such values ​​are also contemplated as the retention of impact strength. Thus, in some embodiments, the impact strength after 1500 hours may be greater than 100% of the initial impact strength, e.g., greater than 101%, greater than 102%, greater than 103%, greater than 104%, greater than 105%, greater than 110%, or greater than 114%.

[0067] In some embodiments, the retention of impact strength after heat aging is at least 25% of the initial impact strength measured after 2000 hours at a temperature between 140° C. and 160° C. In some embodiments, the retention of impact strength after heat aging is at least 10%, e.g., at least 15%, at least 20%, at least 25%, at least 30%, at least 40%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 99% of the initial impact strength after 2000 hours at a temperature between 140° C. and 160° C.

[0068] In some embodiments, the retention of impact strength after heat aging is at least 25% of the initial impact strength measured after 3000 hours at a temperature between 140° C. and 160° C. In some embodiments, the retention of impact strength after heat aging is at least 10%, e.g., at least 15%, at least 20%, at least 25%, at least 30%, at least 40%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 99% of the initial impact strength after 3000 hours at a temperature between 140° C. and 160° C.

[0069] Purpose The resulting polyamide composition can be utilized to produce various molded articles, fibers, and films. The articles can be produced, for example, by conventional injection molding, extrusion, blow molding, press molding, compression molding, or gas-assisted molding techniques. In certain embodiments, the polyamide composition may be used to produce electronic cable ties by injection molding techniques. The polyamide resin composition of the present invention can be molded, for example, by injection molding, into automobile exterior trim parts that can be used in an uncoated state, such as automobile door mirror stays, fashion rails, door handles, and handrail parts, and building materials. Examples of articles that can be produced using the provided polyamide compositions include those used in electrical and electronic applications (for example, but not limited to, circuit breakers, terminal blocks, connectors, etc.), automotive applications (for example, but not limited to, air handling systems, radiator end tanks, fans, shrouds, etc.), furniture and appliance parts, electrical wire positioning devices such as cable ties, and the like.

[0070] In one embodiment, the polyamide resin composition containing the stabilizer component can be used to manufacture electronic cable ties by injection molding techniques. The polyamide composition of the present invention can be used to manufacture a variety of different cable tie configurations, including self-locking and reusable ones.

[0071] In some embodiments, any or some of the components disclosed herein may be considered optional. In some cases, the disclosed compositions may expressly exclude any or some of the aforementioned additives herein, for example, via claim language. For example, the claim language may be amended to state that the disclosed compositions, material processes, etc. do not utilize or include one or more of the aforementioned additives, for example, the disclosed materials do not include flame retardants or gloss agents. As another example, the claim language may be amended to state that the disclosed materials do not include aromatic polyamide components.

[0072]

[0071] As used herein, the limits "greater than" and "less than" may be inclusive of the numbers associated with them. Stated differently, "greater than" and "less than" may be interpreted as "greater than or equal to" and "less than or equal to." It is contemplated that this language may, in turn, be modified in the claims to include "or equal to." For example, "greater than 4.0" may be interpreted as "greater than or equal to 4.0" and, in turn, may be so modified in the claims.

[0073] It should be understood that the above-disclosed variations and other features and functions, or alternatives thereof, may be combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations, or improvements may be subsequently made by those skilled in the art that are also intended to be encompassed within the scope of the following claims or their equivalents. EXAMPLES

[0074]

[0073] Next, the present embodiment will be described in more detail with reference to the following examples and comparative examples, although the present embodiment is not limited to these examples.

[0075]

[0074] The raw materials and measurement methods used in the examples and comparative examples are shown below. The raw materials for the polyamide resin component are as follows: Poly[imino(1,6-dioxohexamethylene)iminohexamethylene], commercially available as poly(hexamethylene adipamide) (PA66),

[0076] Poly(azepan-2-one), commercially available as poly(hexano-6-lactam) (PA6), and

[0077] An example of a commercially available stanylpolyamide (PA46) (manufactured by DSM) is poly[imino(1,6-dioxohexamethylene)iminotetramethylene].

[0076]

[0078] Raw materials for the stabilizer component can include Bruggolen® H3386 (manufactured by Bruggemann) and CuI / KI.

[0077]

[0079] The inventive examples were prepared by combining the ingredients as shown in Table 1 and mixing in a twin screw extruder. Note that in these examples, no fillers or impact modifiers were used, but this is not limiting. Also, in inventive examples 1-4, no other polyamides were used. PA46 was used in comparative example A. The polymer was melted, additives were added to the melt, and the resulting mixture was extruded and pelletized. Percentages are expressed as weight %.

[0078] [Table 1]

[0079]

[0080] The pellets were molded into panels. Each mixture was melt mixed and extruded into strands using a vented extruder. The strands were cooled in a water bath, chopped, and dried to prepare pelletized molding materials. The molding materials were injection molded into test panels. The panels were heat aged at multiple temperatures (at various temperatures and heat aging times) and the retention of tensile strength, tensile elongation, and impact resilience was measured.

[0080]

[0081] Tensile strength was measured according to standard test method ISO 527-2 (2012). Elongation was measured according to standard test method ASTM D882-18 (2018). Unnotched Charpy impact strength was measured according to ISO standard 179 (2010).

[0081]

[0082] Tables 2 and 3 show that Example 3 has superior tensile and impact strength retention compared to Comparative Example A, a PA46 composition containing 225 wppm copper, which uses only CuI / KI stabilizers rather than a dual stabilizer package. Example 3 has an initial tensile strength of 82.6 MPa and an unnotched Charpy impact strength of 189.0 kJ / m 2 The initial tensile strength of Comparative Example A was 96.34 MPa, and the unnotched Charpy impact strength was 156.05 kJ / m 2 The test was carried out at high temperature for a long period of time.

[0082] [Table 2]

[0083] [Table 3]

[0084]

[0083] Although PA46 showed good heat resistance and moldability, there were problems leading to degradation. It was shown that heat resistance contributes to the degradation of mechanical properties over time, even when stabilizers were added. At 140°C, Comparative Example A shows a significant decrease in impact strength after 2000 hours compared to Example 3. This trend continues at higher temperatures. Surprisingly and unexpectedly, the retention of mechanical properties of Example 3, which combines PA66 and PA6 with stabilizer components, is significantly improved.

[0085]

[0084] Examples 1 and 2, which used dual copper stabilizers, showed improved retention compared to polyamide resins with only a single copper source. Comparative Example B was a PA66 resin containing a copper heat stabilizer providing approximately 150 wppm copper. For Comparative Example B, a single copper heat stabilizer, namely H3386, was used. The superior results in tensile and impact strength retention for Examples 1 and 2 compared to Comparative Example B are shown in Tables 4-6. Example 1 had an initial tensile strength of 77.2 MPa, an elongation (%) of 22.4, and an unnotched Charpy impact strength of 186.3 kJ / m 2 The initial tensile strength of Example 2 was 84.2 MPa, the elongation (%) was 25.9, and the unnotched Charpy impact strength was 185.1 kJ / m 2 The initial tensile strength of Comparative Example B was 84.4 MPa, the elongation (%) was 25.4, and the unnotched Charpy impact strength was 175.6 kJ / m 2 The test was carried out at high temperature for a long time. From this result, it was found that the performance in a short time of less than 1500 hours tended to be equivalent regardless of the temperature, but when the test was continued for a long time, as shown in Tables 4 to 6, when the tensile reduction rate, elongation retention rate, and impact strength were taken into consideration, unexpectedly, contrary to expectations, Examples 1 and 2 had superior performance to Comparative Example B.

[0086] [Table 4]

[0087] [Table 5]

[0088] [Table 6]

[0089]

[0085] Tables 4-6 show that the polyamide resins having the stabilizer components disclosed herein in Examples 1 and 3 exhibit superior retention of tensile strength, elongation, and impact strength compared to Comparative Example B, especially at elevated temperatures and over extended periods of time.

[0090] Examples 3 and 4 show that the further addition of PA6 with the stabilizer component having two different copper sources has improved retention compared to polyamide resins having only one copper source. Comparative Example C is a copolymer of PA66 and PA6 in the same ratio as Examples 3 and 4. Comparative Example C contains a copper heat stabilizer providing about 150 wppm copper. Tables 7-9 show superior results in tensile and impact strength retention of polyamide resins having the stabilizer components disclosed herein in Examples 3 and 4 compared to Comparative Example C. The incorporation of PA6 improves initial elongation values. Example 3 has an initial tensile strength of 78.1 MPa, an elongation (%) of 38.0, and an unnotched Charpy impact strength of 189.9 kJ / m 2 Example 4 had an initial tensile strength of 79.5 MPa, an elongation (%) of 43.1, and an unnotched Charpy impact strength of 188.6 kJ / m 2 Comparative Example C had an initial tensile strength of 78.69 MPa, an elongation (%) of 40.4, and an unnotched Charpy impact strength of 186.5 kJ / m 2 The test was carried out at high temperature for a long time. As a result, the performance in a short time of less than 1500 hours tended to be equivalent regardless of the temperature, but when the test was continued for a long time, as shown in Tables 7 to 9, unexpectedly and contrary to expectations, when the tensile reduction rate, elongation retention rate, and impact strength were taken into consideration, Examples 3 and 4 showed superior performance compared to Comparative Example C0.

[0091] [Table 7]

[0092] [Table 8]

[0093] [Table 9]

[0094]

[0087] Tables 7-9 show that the polyamide resins having the stabilizer components disclosed herein in Examples 3 and 4 exhibit superior retention of tensile strength, elongation, and impact strength over time, especially at elevated temperatures, as compared to Comparative Example C.

[0095] Embodiment

[0088] As used hereinafter, any reference to a series of embodiments will be understood to refer separately to each of those embodiments (e.g., "embodiments 1-4" will be understood to mean "embodiments 1, 2, 3, or 4").

[0096]

[0089] Embodiment 1 is a polyamide resin composition comprising a resin component containing 75 weight % or more of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms, and 25 weight % or less of a polyamide containing caprolactam, and a stabilizer component containing a copper complex and a copper salt, wherein the amount of copper supplied by the copper complex and the copper salt is in a weight ratio of 10:90 to 90:10, more preferably 40:60 to 60:40.

[0097]

[0090] Embodiment 2 is the composition of embodiment 1, wherein the copper complex comprises a ligand and / or a halogenated organic compound.

[0098]

[0091] Embodiment 3 is the composition of embodiment 2, wherein the ligand is a phosphine, mercaptobenzimidazole, acetylacetonate, glycine, ethylenediamine, oxalate, diethylenediamine, triethylenetetraamine, ethylenediaminetetraacetic acid, pyridine, diphosphone, dipyridyl, or mixtures thereof.

[0099]

[0092] Embodiment 4 is the composition of embodiment 3, wherein the phosphine is tributylphosphine, triphenylphosphine, or a mixture thereof.

[0100]

[0093] Embodiment 5 is the composition of embodiments 2-4, wherein the halogenated organic compound is a bromine-based compound.

[0101]

[0094] Embodiment 6 is the composition of embodiments 1 to 5, wherein the copper complex has a total amount of copper that is 10 to 1000 wppm based on the total weight of the copper complex.

[0102]

[0095] Embodiment 7 is the composition of embodiments 1 to 6, wherein the copper salt is cuprous iodide, cuprous cyanide, cupric acetate, cupric stearate, or a mixture thereof.

[0103]

[0096] Embodiment 8 is the composition of embodiments 1 to 7, wherein the copper salt further comprises an alkali metal halide.

[0104]

[0097] Embodiment 9 is the composition of embodiment 8, wherein the alkali metal halide is lithium iodide, sodium iodide, or potassium iodide, or a mixture thereof.

[0105]

[0098] Embodiment 10 is the composition of embodiments 1-9, wherein the total halogen loading is 5 weight percent or less, based on the total weight of the polyamide resin composition.

[0106]

[0099] Embodiment 11 is the composition of embodiments 1 to 10, wherein the resin component comprises 75 to 100% of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms.

[0107]

[0100] Embodiment 12 is the composition of embodiments 1 to 11, wherein the resin component comprises 0-25% of a polyamide containing caprolactam.

[0108]

[0101] Embodiment 13 is the composition of embodiments 1 to 12, wherein the resin component is in an amount of 70 to 99.5 weight percent based on the total weight of the polyamide resin composition.

[0109]

[0102] Embodiment 14 is the composition of embodiments 1-13, wherein the stabilizer component is in an amount of 0.1 to 15 weight percent, based on the total weight of the polyamide resin composition.

[0110]

[0103] Embodiment 15 is the composition of embodiments 1 to 14, wherein the copper complex is in an amount of 0.1 to 5 weight percent based on the total weight of the polyamide resin composition.

[0111]

[0104] Embodiment 16 is the composition of embodiments 1 to 15, wherein the copper salt is in an amount of 0.1 to 5 weight percent based on the total weight of the polyamide resin composition.

[0112]

[0105] Embodiment 17 is the composition of embodiments 1-16, wherein the resin composition further comprises a lubricant, a dye, a pigment, an optical brightener, a UV stabilizer, or a combination thereof.

[0113]

[0106] Embodiment 18 is the composition of embodiments 1 to 17, wherein the resin composition is an unfilled composition, ie, no fillers or other reinforcing materials are used.

[0114]

[0107] Embodiment 19 is the composition of embodiments 1 to 18, wherein the resin composition does not contain a polyolefin.

[0115]

[0108] Embodiment 20 is the composition of embodiments 1 through 19, wherein the resin composition does not contain an impact modifier.

[0116]

[0109] Embodiment 21 is the composition of embodiments 1 to 20, wherein the resin composition does not contain a plasticizer.

[0117]

[0110] Embodiment 22 is the composition of embodiments 1 to 21, wherein the polyamide resin composition maintains at least 80% of its initial tensile strength after 1500 hours at a temperature between 140°C and 160°C.

[0118]

[0111] Embodiment 23 is the composition of embodiments 1 to 22, wherein the polyamide resin composition maintains at least 5% of the initial elongation after 1500 hours at a temperature of 140°C to 160°C.

[0119]

[0112] Embodiment 24 is the composition of embodiments 1 to 23, wherein the polyamide resin composition maintains at least 25% of its initial impact strength after 3000 hours at a temperature between 140°C and 160°C.

[0120]

[0113] Embodiment 25 is an article formed from the polyamide resin composition of embodiments 1 to 24.

[0121]

[0114] Embodiment 26 is the article of embodiment 25, wherein the article is a fastener, a circuit breaker, a terminal block, a connector, an automotive interior part, an automotive engine part, a furniture part, an appliance part, a cable tie, a sporting goods, a gun stock, a window thermal barrier, an aerosol valve, a food film packaging, or an electrical / electronic component.

[0122]

[0115] Embodiment 27 is a cable tie made from a polyamide resin composition, the polyamide resin composition comprising a resin component containing 75 weight % or more of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms, and 25 weight % or less of a polyamide containing caprolactam, and a stabilizer component containing a copper complex and a copper salt, wherein the amount of copper supplied by the copper complex and the copper salt is in a weight ratio of 10:90 to 90:10.

[0123]

[0116] Embodiment 28 is the cable tie of embodiment 27, wherein the copper complex comprises a ligand and / or a halogenated organic compound.

[0124]

[0117] Embodiment 29 is the cable tie of embodiment 28, wherein the ligand is a phosphine, mercaptobenzimidazole, acetylacetonate, glycine, ethylenediamine, oxalate, diethylenediamine, triethylenetetraamine, ethylenediaminetetraacetic acid, pyridine, diphosphone, dipyridyl, or mixtures thereof.

[0125]

[0118] Embodiment 30 is the cable tie of embodiment 29, wherein the phosphine is tributylphosphine, triphenylphosphine, or a mixture thereof.

[0126]

[0119] Embodiment 31 is the cable tie of embodiments 28-29, wherein the halogenated organic compound is a bromine-based compound.

[0127]

[0120] Embodiment 32 is the cable tie of any of embodiments 27 to 31, wherein the copper complex has a total amount of copper that is 10 to 1000 wppm based on the total weight of the copper complex.

[0128]

[0121] Embodiment 33 is the cable tie of embodiments 27 to 32, wherein the copper salt is cuprous iodide, cuprous cyanide, cupric acetate, cupric stearate, or a mixture thereof.

[0129]

[0122] Embodiment 34 is the cable tie of embodiments 27 to 33, wherein the copper salt further comprises an alkali metal halide.

[0130]

[0123] Embodiment 35 is the cable tie of embodiment 34, wherein the alkali metal halide is lithium iodide, sodium iodide, or potassium iodide, or a mixture thereof.

[0131]

[0124] Embodiment 36 is the cable tie of any of embodiments 27 to 35, wherein the total halogen loading is 5 weight percent or less, based on the total weight of the polyamide resin composition.

[0132]

[0125] Embodiment 37 is a cable tie of embodiments 27 to 36, in which the resin component contains 75 to 100% polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms.

[0133]

[0126] Embodiment 38 is the cable tie of embodiments 27 to 37, wherein the resin component contains 0 to 25% of polyamide containing caprolactam.

[0134]

[0127] Embodiment 39 is the cable tie of embodiments 27 to 38, wherein the resin component is in an amount of 70 to 99.5 wt % based on the total weight of the polyamide resin composition.

[0135]

[0128] Embodiment 40 is the cable tie of embodiments 27 to 39, wherein the stabilizer component is in an amount of 0.1 to 15 weight percent, based on the total weight of the polyamide resin composition.

[0136]

[0129] Embodiment 41 is the cable tie of embodiments 27 to 40, wherein the copper complex is in an amount of 0.1 to 5 weight percent based on the total weight of the polyamide resin composition.

[0137]

[0130] Embodiment 42 is the cable tie of any of embodiments 27 to 41, wherein the copper salt is in an amount of 0.1 to 5 weight percent based on the total weight of the polyamide resin composition.

[0138]

[0131] Embodiment 43 is the cable tie of embodiments 27 to 42, wherein the resin composition further comprises a lubricant, a dye, a pigment, an optical brightener, a UV stabilizer, or a combination thereof.

[0139]

[0132] Embodiment 44 is the cable tie of embodiments 27 to 43, wherein the resin composition is an unfilled composition, ie, no fillers or other reinforcing materials are used.

[0140]

[0133] Embodiment 45 is the cable tie of embodiments 27 to 44, wherein the resin composition does not contain a polyolefin.

[0141]

[0134] Embodiment 46 is the cable tie of embodiments 27 to 45, wherein the resin composition does not contain an impact modifier.

[0142]

[0135] Embodiment 47 is the cable tie of embodiments 27 to 46, wherein the resin composition does not contain a plasticizer.

[0143]

[0136] Embodiment 48 is the cable tie of any of embodiments 27 to 47, wherein the polyamide resin composition maintains at least 80% of its initial tensile strength after 1500 hours at a temperature of 140°C to 160°C.

[0144]

[0137] Embodiment 49 is the cable tie of any of embodiments 27 to 48, wherein the polyamide resin composition maintains at least 5% of its initial elongation after 1,500 hours at a temperature of 140°C to 160°C.

[0145]

[0138] Embodiment 50 is the cable tie of embodiments 27 to 49, wherein the polyamide resin composition maintains at least 25% of its initial impact strength after 3000 hours at a temperature of 140°C to 160°C.

Claims

1. a resin component containing 75% by weight or more of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms, and 25% by weight or less of a polyamide containing caprolactam; and a stabilizer component containing a copper complex and a copper salt, wherein the amount of copper provided by the copper complex and the copper salt is in a weight ratio of 10:90 to 90:10; A polyamide resin composition comprising:

2. The copper complex is Ligand and / or Halogenated organic compounds Including, the ligand is a phosphine, mercaptobenzimidazole, acetylacetonate, glycine, ethylenediamine, oxalate, diethylenediamine, triethylenetetraamine, ethylenediaminetetraacetic acid, pyridine, diphosphone, dipyridyl, or a mixture thereof; the phosphine is tributylphosphine, triphenylphosphine, or a mixture thereof; The halogenated organic compound is a bromine-based compound; The composition of claim 1.

3. 10. The composition of claim 1, wherein the copper complex has a total amount of copper that is 10 to 1000 wppm based on the total weight of the copper complex.

4. 10. The composition of claim 1, wherein the copper salt is cuprous iodide, cuprous cyanide, cupric acetate, cupric stearate, or a mixture thereof.

5. 10. The composition of claim 1, wherein the copper salt further comprises an alkali metal halide, the alkali metal halide being lithium iodide, sodium iodide, or potassium iodide, or a mixture thereof.

6. 10. The composition of claim 1, wherein the total halogen loading is 5 wt% or less, based on the total weight of the polyamide resin composition.

7. 10. The composition of claim 1, wherein the resin component comprises 75 to 100% of a polyamide containing an aliphatic diamine having 6 or more carbon atoms and an aliphatic diacid having 6 or more carbon atoms, and the resin component comprises 0 to 25% of a polyamide containing caprolactam.

8. 2. The composition of claim 1, wherein the resin component is in an amount of 70 to 99.5 wt % based on the total weight of the polyamide resin composition, and the stabilizer component is in an amount of 0.1 to 15 wt % based on the total weight of the polyamide resin composition.

9. 2. The composition of claim 1, wherein the copper complex is present in an amount of 0.1 to 5% by weight based on the total weight of the polyamide resin composition.

10. 2. The composition of claim 1, wherein the copper salt is in an amount of 0.1 to 5 wt %, based on the total weight of the polyamide resin composition.

11. The composition of claim 1 , wherein the resin composition further comprises a lubricant, a dye, a pigment, an optical brightener, a UV stabilizer, or a combination thereof.

12. The composition of claim 1 , wherein the resin composition is an unfilled composition.

13. 13. The composition of any one of claims 1 to 12, wherein the polyamide resin composition retains at least 80% of its initial tensile strength after 1500 hours at a temperature of 140°C to 160°C.

14. 13. The composition of any one of claims 1 to 12, wherein the polyamide resin composition maintains at least 5% of its initial elongation after 1500 hours at a temperature of 140°C to 160°C.

15. 13. The composition of any one of claims 1 to 12, wherein the polyamide resin composition retains at least 25% of its initial impact strength after 3000 hours at a temperature of 140°C to 160°C.