Polyamide molding composition with improved heat aging resistance

Abstract

This disclosure relates to a component A comprising at least one thermoplastic polyamide in an amount of about 30% to about 99.9% by weight, and a component B comprising more than six hydroxyl groups and a number-average molecular weight M greater than 2000 g / mol. n The present invention describes a thermoplastic molding composition comprising about 0.1% to about 10% by weight of at least one polyhydric alcohol, about 0.05% to about 3% by weight of at least one sterically hindered phenol antioxidant as component C, 0% to about 3% by weight of at least one cationic polyethyleneimine branched polymer as component D, 0% to about 50% by weight of at least one fibrous and / or particulate filler as component E, and 0% to about 25% by weight of further additives as component F, wherein the total weight percentage of components A to F is 100% by weight.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 535155, filed on 29 August 2023, the entire contents of which are incorporated herein by reference.

[0002] background Thermoplastic polyamides, such as PA6 and PA66, are often used in the form of glass fiber reinforced molded compositions as materials in the design of parts that are exposed throughout their service life to elevated temperatures and / or humidity, often accompanied by thermal oxidative degradation.

[0003] Polyamide molded compositions utilize various heat-aging additives to counteract or delay thermal oxidative degradation, such as Cu-containing stabilizers, organic HALS (hindered amine light stabilizers) compounds, or combinations of sterically hindered phenols or polyhydroxy alcohols. Improving the heat aging resistance (HAR) of polyamides is highly desirable because it allows for a longer lifespan of thermally stressed components or reduces the risk of structural failure. Additionally, improved HAR can enable the use of components at higher temperatures.

[0004] The thermal aging resistance of known molding compositions remains insufficient, particularly in the case of prolonged exposure to heat. Furthermore, with the advancement of electrification, an increasing number of applications require that materials be free of any halide (e.g., copper iodide)-based stabilizer systems due to the risk of corrosion and associated failure. Therefore, none of the compositions disclosed in the cited literature satisfy a combination of good thermal stability while avoiding the use of widely used metal halide stabilizers.

[0005] Thermoplastic molding compositions free of metal halide stabilizers have been studied in the past (for example, in US Patent Application Publication No. 2023 / 0128646, which is incorporated herein by reference in its entirety). However, there still remains a need for metal halide-free thermoplastic molding compositions having improved tensile and impact property retention.

[0006] Summary In some aspects, the technology described herein relates to a thermoplastic molding composition comprising, as component A, from about 30% by weight to about 99.9% by weight of at least one thermoplastic polyamide, as component B, more than 6 hydroxyl groups and a number average molecular M n from about 0.1% to about 10% by weight of at least one polyhydric alcohol having n greater than 2000 g / mol, as component C, from about 0.05% to about 3% by weight of at least one sterically hindered phenol antioxidant, as component D, from about 0.1% to about 3% by weight of at least one cationic polyethyleneimine branched polymer, as component E, from 0% to about 50% by weight of at least one fibrous and / or particulate filler, and as component F, from 0% to about 25% by weight of further additives, wherein the total weight percent of components A to F is 100% by weight.

[0007] In some aspects, the technology described herein relates to a thermoplastic molding composition comprising from about 45% by weight to about 70% by weight of component A.

[0008] In some aspects, the technology described herein relates to a thermoplastic molding composition, wherein component A comprises polyamide 6 (PA6), polyamide 66 (PA66), polyamide 12 (PA12), polyamide 610 (PA610), polyamide 46 (PA46), or a combination thereof.

[0009] In some aspects, the technology described herein relates to a thermoplastic molding composition comprising from about 1% by weight to about 5% by weight of component B.

[0010] In some embodiments, the techniques described herein relate to thermoplastic molding compositions in which component B comprises an ethylene vinyl alcohol copolymer.

[0011] In some embodiments, the techniques described herein relate to thermoplastic molding compositions in which component C comprises a phenol substituted with one or more alkyl groups, alkoxy groups, substituted amino groups, or combinations thereof.

[0012] In some embodiments, the techniques described herein include a compound in which component C is 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octa-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl The present invention relates to a thermoplastic molding composition comprising 3,5-distearylthiotriazylamine, 2-(2'-hydroxy-3'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyldimethylamine, N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide, or a combination thereof.

[0013] In some embodiments, the techniques described herein relate to thermoplastic molding compositions comprising about 0.1% to about 1.5% by weight of component D.

[0014] In some embodiments, the techniques described herein involve a number average molecular weight M greater than approximately 1000 g / mol of component D. n This relates to a thermoplastic molding composition having the following characteristics.

[0015] In some embodiments, the techniques described herein involve a number-average molecular weight M of component D, which is approximately 1300 g / mol. n This relates to a thermoplastic molding composition having the following characteristics.

[0016] In some embodiments, the techniques described herein relate to thermoplastic molding compositions in which component D has a cation charge density of about 16 milliequivalents / g (dry solids).

[0017] In some embodiments, the techniques described herein relate to thermoplastic molding compositions comprising about 10% to about 50% by weight of component E.

[0018] In some embodiments, the techniques described herein relate to thermoplastic molding compositions in which component E comprises carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, feldspar, aramid fibers, potassium titanate fibers, kaolin, calcined kaolin, wollastonite, talc, chalk, layered nanofillers, needle-shaped nanofillers, boehmite, bentonite, montmorillonite, vermiculite, hectorite, laponite, or combinations thereof.

[0019] In some embodiments, the techniques described herein relate to thermoplastic molding compositions having a tensile strength retention rate of at least about 85% after aging at 180°C for 3000 hours.

[0020] In some embodiments, the techniques described herein relate to thermoplastic molding compositions having a tensile strength retention rate of at least about 90% after aging at 180°C for 3000 hours.

[0021] In some embodiments, the techniques described herein relate to thermoplastic molding compositions having a tensile strength retention rate of at least about 60% after aging at 180°C for 5000 hours.

[0022] In some embodiments, the techniques described herein relate to thermoplastic molding compositions having a tensile strength retention rate of at least about 70% after aging at 180°C for 5000 hours.

[0023] In some embodiments, the techniques described herein relate to thermoplastic molding compositions having a tensile elongation retention rate of at least about 55% after aging at 180°C for 3000 hours.

[0024] In some embodiments, the techniques described herein relate to thermoplastic molding compositions having a tensile elongation retention rate of at least about 65% after aging at 180°C for 3000 hours.

[0025] In some embodiments, the techniques described herein relate to thermoplastic molding compositions having a tensile elongation retention rate of at least about 40% after aging at 180°C for 5000 hours.

[0026] In some embodiments, the techniques described herein relate to thermoplastic molded compositions having a notched Izod impact strength retention of at least about 95% after aging at 180°C for 3000 hours.

[0027] In some embodiments, the techniques described herein relate to thermoplastic molding compositions having a notched Izod impact strength retention of at least about 90% after aging at 180°C for 5000 hours.

[0028] The aspects, features, benefits, and advantages of the embodiments described herein will become apparent with respect to the following description, the appended claims, and the appended drawings. [Brief explanation of the drawing]

[0029] [Figure 1] This graph shows the retention rate of tensile strength of the compositions of this disclosure after thermal aging at 180°C for 5000 hours. [Figure 2] This graph shows the retention rate of tensile elongation of the compositions of this disclosure after thermal aging at 180°C for 5000 hours. [Figure 3] This graph shows the retention rate of the notched Izod impact of the compositions of this disclosure after thermal aging at 180°C for 5000 hours.

[0030] Detailed explanation This disclosure describes thermoplastic molding compositions comprising a polyamide having improved heat aging resistance (HAR) and retaining good mechanical properties after heat aging. The components disclosed herein can act as heat stabilizers in thermoplastic polyamide molding compositions and can significantly improve heat aging resistance during prolonged exposure to heat.

[0031] In some embodiments, the thermoplastic molding composition comprises, as component A, at least one thermoplastic polyamide in an amount of about 30% to about 99.9% by weight, and as component B, a number-average molecular weight M of more than 6 hydroxyl groups and more than 2000 g / mol. n A thermoplastic molding composition is provided, comprising at least one polyhydric alcohol in about 0.1% to about 10% by weight, at least one sterically hindered phenol antioxidant in about 0.05% to about 3% by weight as component C, at least one cationic polyethyleneimine branched polymer in about 0.1% to about 3% by weight as component D, at least one fibrous and / or particulate filler in 0% to about 50% by weight as component E, and a further additive in 0% to about 25% by weight as component F, wherein the total weight percentage of components A to F is 100% by weight.

[0032] As disclosed herein, number-average molecular weight and weight-average molecular weight (M n Mw The molecular weight and polydispersity data can be obtained using gel permeation chromatography (GPC) in hexafluoroisopropanol as a solvent, calibrated with PMMA. This molecular weight measurement can be used for all components of the thermoplastic molding composition according to the present invention.

[0033] In some embodiments, the thermoplastic molding composition comprises, as component A, at least one thermoplastic polyamide in an amount ranging from about 30% by weight to about 99.9% by weight. For example, the thermoplastic molding composition may contain component A in an amount that falls within the range formed by about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 55% by weight, about 60% by weight, about 65% by weight, about 70% by weight, about 75% by weight, about 80% by weight, about 85% by weight, about 90% by weight, about 95% by weight, about 96% by weight, about 97% by weight, about 98% by weight, about 99% by weight, about 99.9% by weight, or any value that falls within the range formed by any two of the aforementioned values.

[0034] If component E or component F, or a combination thereof, is present in the thermoplastic molded composition, the maximum amount of component A is reduced by the minimum amount of each component E or component F, or a combination thereof, so that the total weight percentage of components A through F becomes 100% by weight.

[0035] The polyamide in the molding composition of the present invention generally has an intrinsic viscosity of 90 mL / g to 350 mL / g, preferably 110 mL / g to 240 mL / g, and this intrinsic viscosity is measured at 25°C in a 0.5 wt% solution in 96 wt% sulfuric acid in accordance with ISO 307.

[0036] Of particular interest are semicrystalline or amorphous resins having a molecular weight (weight average) of at least 5,000, which are described, for example, in the following U.S. Patents: U.S. Patent No. 2071250, U.S. Patent No. 2071251, U.S. Patent No. 2130523, U.S. Patent No. 2130948, U.S. Patent No. 2241322, U.S. Patent No. 2312966, U.S. Patent No. 2512606, and U.S. Patent No. 3393210.

[0037] These examples include polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryloractam, and polylaurolactam, as well as polyamides obtained through the reaction of dicarboxylic acids with diamines.

[0038] The dicarboxylic acids that can be used are alkanedicarboxylic acids having 6 to 12 carbon atoms, particularly 6 to 10 carbon atoms, and aromatic dicarboxylic acids. Examples that may be listed here are adipic acid, azelaic acid, sebacic acid, dodecanediic acid, and terephthalic acid and / or isophthalic acid.

[0039] Particularly suitable diamines are alkanediamines having 6 to 12 carbon atoms, especially 6 to 8 carbon atoms, as well as m-xylylenediamine, di(4-aminophenyl)methane, di(4-aminocyclohexyl)methane, 2,2-di(4-aminophenyl)propane, 2,2-di(4-aminocyclohexyl)propane, and 1,5-diamino-2-methylpentane.

[0040] In some embodiments, preferred polyamides include polyhexamethylene adipamide, polyhexamethylene sebakamid, and polycaprolactam, as well as nylon 6 / 6,6 copolyamide, particularly nylon 6 / 6,6 copolyamide having caprolactam units in a proportion of 5% to 95% by weight (e.g., Ultramid® C31 from BASF SE).

[0041] Other suitable polyamides can be obtained, for example, from ω-aminoalkyl nitriles, such as aminocapronitrile (PA6), and hexamethylenediamine and adiposinitrile (PA66), via a method known as direct polymerization in the presence of water, as described in West German Patent Application Publication No. 10313681, European Patent Application Publication No. 1198491, and European Patent Application Publication No. 0922065.

[0042] For example, polyamides (nylon 4,6) obtained by the condensation of 1,4-diaminobutane and adipic acid at elevated temperatures can also be cited. The process for preparing polyamides of this structure is described, for example, in European Patent Publication No. 0038094, European Patent Publication No. 0038582, and European Patent Publication No. 0039524.

[0043] Other suitable examples include polyamides obtained by copolymerization of two or more monomers as described above, and mixtures of two or more polyamides in any desired mixing ratio. Mixtures of nylon 6,6 with other polyamides, particularly blends of nylon 6 and nylon 66, as well as nylon 6 / 6,6 copolyamides and nylon 6,6 / 6 copolyamides are especially preferred.

[0044] Other copolyamides that have proven particularly advantageous are semi-aromatic copolyamides, such as PA6 / 6T and PA66 / 6T, in which the triamine content is less than 0.5% by weight, preferably less than 0.3% by weight (see European Patent Application Publication No. 0299444). Other polyamides that are resistant to high temperatures are known based on European Patent Application Publication No. 1994075 (PA6T / 6I / MXD6).

[0045] The processes described in European Patent Application Publication No. 0129195 and European Patent Application Publication No. 0129196 can be used to prepare preferred semi-aromatic copolyamides having a low triamine content.

[0046] The following list is not exhaustive, but includes the polyamide A) described and other polyamide A) for the purposes of this disclosure. AB type polymer: PA4 Pyrrolidone PA6 ε-caprolactam PA7 Ethanolactam PA8 Capryloractam PA9 9-aminopelargonic acid PA11 11-aminoundecanoic acid PA12 Laurolactam AA / BB type polymers: PA46 Tetramethylenediamine, Adipic Acid PA66 Hexamethylenediamine, Adipic Acid PA69 Hexamethylenediamine, Azelaic Acid PA610 Hexamethylenediamine, Sebacic acid PA612 Hexamethylenediamine, Decanedicarboxylic acid PA613 Hexamethylenediamine, Undecanedicarboxylic acid PA1212 1,12-Dodecanediamine, Decanedicarboxylic acid PA1313 1,13-diaminotridecane, undecanedicarboxylic acid PA6T Hexamethylenediamine, Terephthalic Acid PAMXD6 m-xylylenediamine, adipic acid AA / BB type polymers: PA6I hexamethylenediamine, isophthalic acid PA6-3-T Trimethylhexamethylenediamine, Terephthalic acid PA6 / 6T (See PA6 and PA6T) PA6 / 66 (See PA6 and PA66) PA6 / 12 (See PA6 and PA12) PA66 / 6 / 610 (See PA66, PA6, and PA610) PA6I / 6T (See PA6I and PA6T) PAPACM12 Diaminodicyclohexylmethane, Laurolactam PA6I / 6T / PACM PA6I / 6T + diaminodicyclohexylmethane PA12 / MACMI: Laurolactam, Dimethyldiaminodicyclohexylmethane, Isophthalic Acid PA12 / MACMT: Laurolactam, Dimethyldiaminodicyclohexylmethane, Terephthalic Acid PAPDA-T: Phenylenediamine, Terephthalic Acid Contains monomers.

[0047] The most preferred are PA6, PA66, PA6 / 66, and PA66 / 6.

[0048] The appropriate copolyamide is, A1) Units derived from terephthalic acid and hexamethylenediamine in amounts ranging from 20.0% to 90.0% by weight. A2) Units derived from ε-caprolactam in amounts from 0% to 50.0% by weight. A3) Units derived from adipic acid and hexamethylenediamine, ranging from 0% to 80.0% by weight. A4) Further polyamide-forming monomers in an amount of 0% to 40.0% by weight It is often composed of, The proportion of component A2), component A3), or component A4), or a mixture thereof, is at least 10.0% by weight.

[0049] Component A1) contains 20.0% to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine.

[0050] In addition to units derived from terephthalic acid and hexamethylenediamine, this copolyamide optionally contains units derived from ε-caprolactam, and / or units derived from adipic acid and hexamethylenediamine, and / or units derived from further polyamide-forming monomers.

[0051] Aromatic dicarboxylic acids (A4) contain 8 to 16 carbon atoms. Suitable aromatic dicarboxylic acids include, for example, isophthalic acid, substituted terephthalic acid and isophthalic acid, such as 3-t-butylisophthalic acid, polycyclic dicarboxylic acids, such as 4,4'- and 3,3'-diphenyldicarboxylic acid, 4,4'- and 3,3'-diphenylmethanedicarboxylic acid, 4,4'- and 3,3'-sulfodiphenylcarboxylic acid, 1,4- or 2,6-naphthalenedicarboxylic acid, and phenoxyterephthalic acid, with isophthalic acid being particularly preferred.

[0052] Further polyamide-forming monomers A4) may be derived from dicarboxylic acids having 4 to 16 carbon atoms, aliphatic or alicyclic diamines having 4 to 16 carbon atoms, and aminocarboxylic acids / corresponding lactams having 7 to 12 carbon atoms. Examples of suitable monomers of these types include, as representatives of aliphatic dicarboxylic acids, suberic acid, azelaic acid, and sebacic acid; as representatives of diamines, 1,4-butanediamine, 1,5-pentanediamine, piperazine, 4,4'-diaminodicyclohexylmethane, 2,2-(4,4'-diaminodicyclohexyl)propane, and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane or m-xylylenediamine; and as representatives of lactams / aminocarboxylic acids, caprolactam, enantractam, ω-aminoundecanoic acid, and laurolactam. Such suitable copolyamides are described in more detail in German Patent Application Publication No. 102009011668.

[0053] In some embodiments, component A includes polyamide 6 (PA6), polyamide 66 (PA66), polyamide 12 (PA12), polyamide 610 (PA610), polyamide 46 (PA46), or a combination thereof.

[0054] In some embodiments, the thermoplastic molding composition has more than six hydroxyl groups and a number-average molecular weight M greater than 2000 g / mol as component B. ncomprises from about 0.1% by weight to about 10% by weight of at least one polyhydric alcohol having. For example, the thermoplastic molding composition may comprise component B in an amount of about 0.1% by weight, about 0.2% by weight, about 0.3% by weight, about 0.4% by weight, about 0.5% by weight, about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, about 10% by weight, or any value within a range formed by any two of the foregoing values.

[0055] In some embodiments, component B comprises at least one polyhydric alcohol having more than 6 hydroxyl groups and a number average molecular weight M n having. Component B may have more than 8 or more than 10 hydroxyl groups.

[0056] In some embodiments, component B has a number average molecular weight M of more than 3000 g / mol, for example more than 5000 g / mol, or more than 10000 g / mol n . The maximum number average molecular weight is preferably 35000 g / mol, more preferably 25000 g / mol. Particularly preferred component B has a number average molecular weight of from 10000 g / mol to 30000 g / mol, more preferably from 12500 g / mol to 22500 g / mol, most preferably from 15000 g / mol to 20000 g / mol.

[0057] The weight average molecular weight M w is preferably from 10000 g / mol to 250000 g / mol, more preferably from 25000 g / mol to 120000 g / mol, particularly from 30000 g / mol to 80000 g / mol.

[0058] Component B is a polyhydric alcohol having more than 6 hydroxyl groups and a number average molecular weight M of more than 2000 g / mol nAs long as it has the properties of [the specified substance], any suitable polyhydric alcohol can be selected. An example of a suitable polyhydric alcohol is ethylene-vinyl alcohol copolymer, which is commercially available from Mitsubishi Chemical Corporation under the trade name Soarnol® or from Kuraray Corporation under the trade name EVAL®. In some embodiments, other high molecular weight polyhydric alcohols may also be suitable.

[0059] In some embodiments, component B is an ethylene-vinyl alcohol copolymer. Preferably, the ethylene unit content in the ethylene-vinyl alcohol copolymer is 10 mol% to 60 mol%, more preferably 20 mol% to 50 mol%, and particularly 25 mol% to 50 mol%.

[0060] In addition to ethylene and vinyl alcohol, residual vinyl acetate may be present in the copolymer, preferably 20 mol% or less, more preferably 10 mol% or less, and particularly 5 mol% or less. Most preferably, no residual vinyl acetate is present. Ethylene-vinyl alcohol copolymer can be obtained by partial or complete hydrolysis of ethylene-vinyl acetate copolymer.

[0061] Particularly suitable ethylene-vinyl alcohol copolymers have a number-average molecular weight M of 10,000 g / mol to 30,000 g / mol, more preferably 12,500 g / mol to 22,500 g / mol, and most preferably 15,000 g / mol to 20,000 g / mol. n It has the following characteristics. Most preferably, the ethylene-vinyl alcohol copolymer has a number average molecular weight of 18,000 g / mol M n , and weight-average molecular weight M of 50,000 g / mol w It has.

[0062] Polyhydric alcohols may also contain additional functional groups other than hydroxyl groups. However, preferably, polyhydric alcohols contain only hydroxyl groups as functional groups. Polyhydric alcohols may be linear, branched, or hyperbranched. Specifically, highly branched or hyperbranched structures consisting partially of hydroxyl functional groups, such as those described in European Patent No. 2227507 and German Patent Application Publication No. 102004051241, are also suitable for achieving the desired effect. For example, highly branched or hyperbranched polyetheramines having a hydroxyl value of 50 mg KOH / g to 1000 mg KOH / g, preferably 100 mg KOH / g to 900 mg KOH / g, and more preferably 150 mg KOH / g to 800 mg KOH / g can be used.

[0063] In some embodiments, the thermoplastic molding composition contains, as component C, at least one sterically hindered phenol antioxidant in an amount of about 0.05% to about 3% by weight. For example, the thermoplastic molding composition may contain component C in an amount that is about 0.05% by weight, about 0.1% by weight, about 0.5% by weight, about 1% by weight, about 1.5% by weight, about 2% by weight, about 2.5% by weight, about 3% by weight, or any value that falls within the range formed by any two of the aforementioned values.

[0064] In some embodiments, component C has a molecular weight greater than 500 g / mol, for example, greater than 1000 g / mol. Additionally, component C preferably has high thermal stability, for example, in a TGA (thermogravimetric analysis) experiment (heating from 40°C to 120°C at 10°C / min, isothermal holding at the latter temperature for 15 minutes, followed by heating from 120°C to 600°C at 20°C / min), it should exhibit a weight loss of up to 5%, more preferably up to 2%, when measured at 300°C under nitrogen.

[0065] Component C has at least one branched C as a sterically hindering group. 3~12 It preferably has at least one, more preferably at least two, phenol groups substituted with alkyl groups. The substituted phenol groups are covalently bonded to the structure of component C.

[0066] In principle, sterically hindered phenols suitable for use as component C are all compounds that have a phenol structure and at least one bulky group on the phenol ring. The bulky group is, for example, a branched C. 3~12 Alkyl alkyl groups, preferably branched C 3~6 An alkyl group, more preferably an isopropyl group or a tert-butyl group.

[0067] In some embodiments, preferably, for example, the formula: [ka] [In the formula, R 1 and R 2 These are, respectively, an alkyl group, a substituted alkyl group, or a substituted triazole group, and the group R 1 and R 2 They may be the same, or they may be different from each other, and R 3 [This is an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group.] The compound is used. The alkyl and alkoxy residues preferably have 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. The substituent is preferably C 1~12 Alkyl alkyl groups, more C 1~6 Alkyl alkyl group, most preferably C 1~4 It is an alkyl group. 1 ~R 3 At least one of these is preferably a bulky group as defined above.

[0068] The aforementioned type of antioxidant is described, for example, in West German Patent Application Publication No. 2702661 (U.S. Patent No. 4360617).

[0069] Another group of preferred sterically hindered phenols is provided by substituted phenylcarboxylic acids, particularly those derived from substituted phenylpropionic acid, which preferably have at least one bulky group on the phenyl group. These phenols contain at least one, preferably two, covalently bonded substituted phenylcarboxylic acid units in their structure, which preferably have at least one bulky group on the phenyl group.

[0070] Preferred phenylcarboxylic acid is phenyl-C 1~12 -carboxylic acid, more preferably phenyl-C 2~6 -It is a carboxylic acid. The phenyl group is preferably a phenol group having at least one bulky group on the phenol ring, as shown above. Therefore, the sterically hindered phenol described above is preferably C 1~12 Alkanecarboxylic acids, more preferably linear C 2~6 It is covalently bonded to an alkanecarboxylic acid.

[0071] A particularly preferred compound in this class is given by formula: [ka] [In the formula, R 4 , R 5 , R 7 , and R 8 These are C1-C8 alkyl groups that may independently have substituents (at least one of these groups is a bulky group), R 6 This is a divalent aliphatic group having 1 to 10 carbon atoms, and whose main chain may have CO bonds. It is a compound of R. 4 ~R 8 At least one of them is a bulky group as defined above.

[0072] Preferred compounds corresponding to this formula are: [ka] (Irganox® 245 manufactured by BASF SE) [ka] (Irganox® 259 manufactured by BASF SE) That is the case.

[0073] Examples of sterically hindered phenols that may be included as component C in the compositions disclosed herein are as follows: 2,2'-Methylenebis(4-methyl-6-tert-butylphenol), 1,6-Hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], Pentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox® 1010 manufactured by BASF SE), Distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,6,7-Trioxa-1-phosphabicyclo[2.2.2]octa-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearylthiotriazylamine, 2-(2'-hydroxy-3'-hydroxy C-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyldimethylamine, or combinations thereof. All of the above should be listed.

[0074] While we do not wish to be bound by theory, compounds that have proven particularly effective and are therefore preferred are 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediolbis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 259), pentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098), as well as the BASF SE products Irganox® 245 and Irganox® 1010 mentioned above, which have particularly good compatibility.

[0075] In several embodiments, sterically hindrance phenols having one or fewer sterically hindrance groups at the ortho position with respect to the phenolic hydroxyl group have been proven particularly advantageous. This is especially advantageous when evaluating color fastness during long-term storage under diffuse light.

[0076] In some embodiments, the thermoplastic molding composition contains, as component D, at least one cationic polyethyleneimine branched polymer in an amount of about 0.1% to about 3% by weight. For example, the thermoplastic molding composition may contain component D in an amount that is about 0.1% by weight, about 0.5% by weight, about 1% by weight, about 1.5% by weight, about 2% by weight, about 2.5% by weight, about 3% by weight, or any value that falls within the range formed by any two of the aforementioned values.

[0077] In some embodiments, component D has a number-average molecular weight M of any value greater than about 1000 g / mol, for example, about 1050 g / mol, about 1100 g / mol, about 1150 g / mol, about 1200 g / mol, about 1250 g / mol, about 1300 g / mol, about 1350 g / mol, about 1400 g / mol, or any value within the range formed by any two of the aforementioned values. n It has.

[0078] In some embodiments, component D has a cation charge density of any value that falls within the range of about 10 milliequivalents / g (dry solids) to about 20 milliequivalents / g (dry solids), for example, about 10 milliequivalents / g (dry solids), about 11 milliequivalents / g (dry solids), about 12 milliequivalents / g (dry solids), about 13 milliequivalents / g (dry solids), about 14 milliequivalents / g (dry solids), about 15 milliequivalents / g (dry solids), about 16 milliequivalents / g (dry solids), about 17 milliequivalents / g (dry solids), about 18 milliequivalents / g (dry solids), about 19 milliequivalents / g (dry solids), about 20 milliequivalents / g (dry solids), or any value formed by any two of the aforementioned values.

[0079] In some embodiments, the polyethyleneimine can be selected from highly branched polyethyleneimines. Highly branched polyethyleneimines are characterized by their high degree of branching (DB). The degree of branching is, for example, preferably in D2O. 13 This can be measured using C-NMR spectroscopy, as follows: DB = D + T / D + T + L [In the formula, D (dendritic) corresponds to the fraction of a tertiary amino group, L (linear) corresponds to the fraction of a secondary amino group, and T (terminal) corresponds to the fraction of a primary amino group.] It is defined as follows.

[0080] In the context of this disclosure, highly branched polyethyleneimine is polyethyleneimine having a DB in the range of 0.25 to 0.90.

[0081] In some embodiments, polyethyleneimine is selected from copolymers of ethyleneimine, for example, copolymers of ethyleneimine with at least one diamine other than ethyleneimine having two NH2 groups per molecule, such as propyleneimine, or copolymers of ethyleneimine with at least one compound having three NH2 groups per molecule, such as melamine.

[0082] Suitable compounds that can be used as component D include, but are not limited to, Lupasol® G 20 WF manufactured by BASF.

[0083] While we do not wish to be bound by theory, in some embodiments, components B and D can produce synergistic effects in the compositions of the present disclosure that enable high performance and strong retention of tensile strength, tensile elongation, and notched Izod impact. In some embodiments, compositions of the present disclosure comprising both components B and D achieve improved performance compared to compositions comprising only one of components B or D.

[0084] In some embodiments, the thermoplastic molding composition includes, as component E, at least one fibrous and / or particulate filler in an amount ranging from 0% by weight to about 50% by weight. In some embodiments, the thermoplastic molding composition includes 0% by weight of component E, so that component E is omitted. In other embodiments, the thermoplastic molding composition includes component E in an amount that falls within the range of about 1% by weight, about 5% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 50% by weight, or any value that falls within the range formed by any two of the aforementioned values.

[0085] In some embodiments, component E includes carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, feldspar, or combinations thereof. Preferred fibrous fillers that may be listed are carbon fibers, aramid fibers, and potassium titanate fibers, with glass fibers in the form of E-glass being particularly preferred. These glass fibers can be used as roving or in the commercially available form of chopped glass.

[0086] The fibrous filler may be surface-pretreated with a silane compound to improve its compatibility with thermoplastic resins. A suitable silane compound has the general formula: (X-(CH2) n )k -Si-(OC m H 2m+1 ) 4-k [In the formula, the definition of substituents is as follows: X is NH2, epoxide, or OH. n is an integer between 2 and 10, preferably between 3 and 4. m is an integer from 1 to 5, preferably from 1 to 2, and k is an integer between 1 and 3, preferably 1. It has.

[0087] Preferred silane compounds include aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, and aminobutyltriethoxysilane, as well as the corresponding silanes containing a glycidyl group as substituent X.

[0088] The amount of silane compound commonly used for surface coating is 0.01% to 2% by weight, preferably 0.025% to 1.0% by weight, and particularly 0.05% to 0.5% by weight (based on the weight of component E).

[0089] Acicular mineral fillers are also suitable. For the purposes of the present invention, the acicular mineral filler is a mineral filler having strongly developed acicular properties. One example is acicular wollastonite. The mineral preferably has an L / D (length to diameter) ratio of 8:1 to 35:1, more preferably 8:1 to 11:1. The mineral filler may be optionally pretreated with the silane compound described above, but such pretreatment is not essential.

[0090] Other possible fillers include kaolin, calcined kaolin, wollastonite, talc, and chalk, as well as layered or needle-shaped nanofillers, the amount of which these fillers is preferably 0.1% to 10%. Preferred materials for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite, and laponite. Layered nanofillers are organically modified by prior art methods to give them good compatibility with organic binders. The addition of layered or needle-shaped nanofillers to the nanocomposite of the present invention results in a further increase in mechanical strength.

[0091] In some embodiments, the thermoplastic molding composition includes a further additive as component F in an amount ranging from 0% to about 25% by weight. For example, in some embodiments, the thermoplastic molding composition may contain 0% by weight of component F so that component F is omitted, or it may contain component F in an amount that falls within the range formed by about 1% by weight, about 5% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, or any value formed by any two of the aforementioned values.

[0092] If further additives are used, the minimum amount is preferably 0.1% by weight, more preferably 0.25% by weight, and most preferably 0.5% by weight.

[0093] The thermoplastic molding composition of the present invention may include, as component F, conventional processing aids, further stabilizers, oxidation retarders, agents to counteract thermal and ultraviolet decomposition, lubricants and release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.

[0094] The thermoplastic molding compositions of this disclosure may contain, as component F, a lubricant in an amount of about 0.05% to about 3% by weight, preferably about 0.1% to about 1.5% by weight, and particularly about 0.1% to about 1% by weight.

[0095] A salt of aluminum, a salt of an alkali metal, or a salt of an alkaline earth metal, or an ester or amide of a fatty acid having 10 to 44 carbon atoms, preferably 12 to 44 carbon atoms, is preferred. The metal ion is preferably an alkaline earth metal and aluminum, with calcium or magnesium being particularly preferred.

[0096] Preferred metal salts include calcium stearate, calcium montana, and aluminum stearate. Mixtures of various salts can also be used in any desired mixing ratio.

[0097] In some embodiments, the molding composition of the present invention may include, as component F, about 0.05% to about 3% by weight, preferably about 0.1% to about 1.5% by weight, and especially about 0.1% to about 1% by weight of a copper stabilizer, preferably Cu(I) halide in a mixture with an alkali metal halide, preferably KI, particularly in a ratio of 1:4, or a sterically hindered phenol, or a mixture thereof.

[0098] In some embodiments, the carboxylic acids disclosed herein may be monobasic or dibasic. Possible examples include pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanediic acid, behenic acid, particularly preferably stearic acid, capric acid, and montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms).

[0099] In some embodiments, the aliphatic alcohols disclosed herein may be monovalent to tetravalent. Examples of alcohols include n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, and pentaerythritol, with glycerol and pentaerythritol being preferred.

[0100] In some embodiments, the aliphatic amines disclosed herein may be monovalent to trivalent. Examples of these include stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and di(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are, correspondingly, glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.

[0101] It is also possible to use various ester or amide mixtures, or combinations of esters and amides, in any desired mixing ratio.

[0102] According to a preferred embodiment of the present invention, the molding composition does not contain copper, specifically, copper stabilizers such as Cu / (I) halides, and combinations of Cu(I) halides and alkali metal halides.

[0103] More preferably, the thermoplastic molding composition of the present invention is metal halide-free. Metal halide-free systems, so-called electro-friendly systems, are of great interest because electromobility, electrification, and connectivity are increasing in almost all industries. Therefore, in some embodiments, the thermoplastic molding composition preferably does not contain metal halides, specifically copper halides and alkali metal halides. In some embodiments, metal halides are present in very small amounts. For example, metal halides may be present in amounts of about 0.001% to about 1% by weight.

[0104] Other examples of conventional additives F include elastomer polymers (often also called impact modifiers, elastomers, or rubbers) in amounts of up to about 25% by weight, preferably up to about 20% by weight.

[0105] When component D is used in the molding composition according to the present invention, the elastomer polymer disclosed herein with respect to component F is different from component D. Therefore, when the composition contains component D, the polymer of component F, in particular the elastomer polymer, is different from the polymer of component D. Similarly, the polymer of component F is different from the polymer of component B.

[0106] These elastomer polymers are very commonly copolymers preferably composed of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile, and at least two acrylates and / or methacrylates having 1 to 18 carbon atoms in the alcohol component.

[0107] This type of polymer is described, for example, in Houben-Weyl, Methoden der organischen Chemie, vol.14 / 1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), pp.392-406 and in the monograph by CB Bucknall, Toughened Plastics (Applied Science Publishers, London, UK, 1977).

[0108] Preferred types of such elastomers are those known as ethylene-propylene (EPM) rubber and ethylene-propylene-diene (EPDM) rubber. EPM rubber generally has virtually no residual double bonds, while EPDM rubber may have 1 to 20 double bonds per 100 carbon atoms.

[0109] Examples of diene monomers for EPDM rubber include conjugated dienes, e.g., isoprene and butadiene; non-conjugated dienes having 5 to 25 carbon atoms, e.g., 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, and 1,4-octadiene; cyclic dienes, e.g., cyclopentadiene, cyclohexadiene, cyclooctadiene, and dicyclopentadiene; alkenyl norbornene, e.g., 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, and 2-isopropenyl-5-norbornene; tricyclodiene, e.g., 3-methyltricyclo[5.2.1.02,6]-3,8-decadiene; and mixtures thereof. 1,5-Hexadiene, 5-Ethylidenenorbornene, and dicyclopentadiene are preferred. The diene content of the EPDM rubber is preferably 0.5% to 50% by weight, and particularly 1% to 8% by weight, based on the total weight of the rubber.

[0110] EPM rubber and EPDM rubber may preferably be grafted with reactive carboxylic acids or their derivatives. Examples of such reactive carboxylic acids or their derivatives include acrylic acid, methacrylic acid, and their derivatives, such as glycidyl (meth)acrylate, and maleic anhydride.

[0111] Copolymers of ethylene with acrylic acid and / or methacrylic acid, and / or esters of these acids constitute another group of preferred rubbers. These rubbers may contain monomers comprising dicarboxylic acids, e.g., maleic acid and fumaric acid, or derivatives of these acids, e.g., esters and anhydrides, and / or epoxy groups. These dicarboxylic acid derivatives or monomers comprising epoxy groups preferably contain dicarboxylic acid groups and / or epoxy groups and have general formula I, II, III, or IV: [ka] [In the formula, R 1 ~R 9[where m is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer from 0 to 20, g is an integer from 0 to 10, and p is an integer from 0 to 5] Monomers having the group R are incorporated into rubber by adding them to a monomer mixture. 1 ~R 9 is preferably hydrogen, m is 0 or 1, and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether, and vinyl glycidyl ether.

[0112] Preferred compounds of formulas I, II, and IV are maleic acid, maleic anhydride, and (meth)acrylates containing epoxy groups, such as glycidyl acrylate and glycidyl methacrylate, as well as esters with tertiary alcohols, such as tert-butyl acrylate. Esters with tertiary alcohols do not have a free carboxyl group, but the behavior of the ester is similar to that of a free acid, and therefore the ester is called a monomer with a latent carboxyl group.

[0113] The copolymer is advantageously composed of 50% to 98% by weight of ethylene, 0.1% to 20% by weight of monomers containing epoxy groups and / or monomers containing methacrylic acid and / or anhydride groups, with the remainder being (meth)acrylate.

[0114] A copolymer comprising 50% to 98% by weight, particularly 55% to 95% by weight of ethylene, 0.1% to 40% by weight, particularly 0.3% to 20% by weight of glycidyl acrylate and / or glycidyl methacrylate, (meth)acrylic acid and / or maleic anhydride, and 1% to 45% by weight, particularly 5% to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate is particularly preferred.

[0115] Other preferred (meth)acrylates are methyl, ethyl, propyl, isobutyl, and tert-butyl esters. Comonomers that can be used with these (meth)acrylates include vinyl esters and vinyl ethers.

[0116] The ethylene copolymers described above may be prepared by known processes, preferably by random copolymerization under high pressure and elevated temperature. Suitable processes are well known.

[0117] Other preferred elastomers are emulsion polymers whose preparation is described, for example, by Blackley in the monograph "Emulsion Polymerization." Emulsifiers and catalysts that can be used are known in themselves.

[0118] In principle, it is possible to use homogeneously structured elastomers or other elastomers having a shell structure. The shell structure is determined by the order in which the individual monomers are added. The morphology of the polymer is also affected by this addition order.

[0119] For the preparation of the rubber fraction of the elastomer, monomers that can be listed here merely as examples include acrylates, e.g., n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene, and mixtures thereof.

[0120] These monomers may be copolymerized with other monomers, such as styrene, acrylonitrile, vinyl ether, and other acrylates or methacrylates, such as methyl methacrylate, methyl acrylate, ethyl acrylate, or propyl acrylate.

[0121] The soft or rubbery phase of the elastomer (having a glass transition temperature below 0°C) may be the core, the outer shell, or (in the case of an elastomer with a structure having more than two shells) an intermediate shell. An elastomer with more than one shell may also have more than one shell composed of the rubbery phase.

[0122] When one or more hard components (with a glass transition temperature above 20°C) are involved in the structure of the elastomer in addition to the rubber phase, these hard components are generally prepared by polymerizing styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylate, or methacrylate, such as methyl acrylate, ethyl acrylate, or methyl methacrylate, as the main monomer. In addition to these main monomers, it is also possible to use other comonomers in relatively small proportions.

[0123] Possible UV stabilizers include various substituted resorcinols, salicylates, benzotriazoles, and benzophenones, and are generally used in amounts of up to approximately 2% by weight based on the molding composition.

[0124] Materials that can be added as colorants include inorganic pigments, such as titanium dioxide, ultramarine, iron oxide, and carbon black, as well as organic pigments, such as phthalocyanine, quinacridone, and perylene, and dyes, such as anthraquinone.

[0125] Materials that can be used as nucleating agents include sodium phenylphosphinate, aluminum oxide, silicon dioxide, and preferably talc.

[0126] The thermoplastic molding composition may further contain a flame retardant as component F.

[0127] The thermoplastic molding compositions of this disclosure may contain, as component F, 1.0% to 10.0% by weight, preferably 2.0% to 6.0% by weight, and particularly 3.0% to 5.0% by weight, at least one phosphazene of general formula (IX) or (X) as a flame retardant.

[0128] In some embodiments, component F comprises a mixture of cyclic phenoxyphosphazenes having three and four phenoxyphosphazene units. The weight ratio of rings containing three phenoxyphosphazene units to rings containing four phenoxyphosphazene units is preferably about 80:20. Larger rings of phenoxyphosphazene units may be present, but in smaller amounts. A suitable cyclic phenoxyphosphazene is available from Fushimi Pharmaceutical Co., Ltd. under the name Rabitle® FP-100. This cyclic phenoxyphosphazene is a matte white / yellowish solid with a melting point of 110°C, a phosphorus content of 13.4%, and a nitrogen content of 6.0%. In some embodiments, the proportion of rings having three phenoxyphosphazene units is at least 80.0% by weight.

[0129] The thermoplastic molding material preferably contains, as a flame retardant, at least one aliphatic or aromatic ester of phosphoric acid or polyphosphate in an amount of 1.0% to 6.0% by weight, preferably 2.5% to 5.5% by weight, and particularly 3.0% to 5.0% by weight.

[0130] For this reason, solid, non-migratory phosphate esters having a melting point of 70°C to 150°C are preferred. While we do not wish to be bound by theory, products derived from such phosphate esters are easy to meter and exhibit significantly less migration in molding materials. Particularly preferred examples are phosphate ester PX-200 (CAS: 139189-30-3) commercially available from Daihachi Chemical Industry, or Sol-DP commercially available from ICL-IP. Further phosphate esters with appropriate substitution of the phenyl group are conceivable if this appropriate substitution allows for achieving a preferred melting point range. General structural formulas depending on the substitution pattern at the ortho or para position of the aromatic ring are as follows: [ka] [In the formula, R 1 This is H, a methyl group, an ethyl group, or an isopropyl group, but is preferably H. n is between 0 and 7, but is preferably 0. R 2~6 is H, a methyl group, an ethyl group, or an isopropyl group, but is preferably a methyl group, and R 6 Preferably R 4 and R 5 It is identical to, m may be the same, but does not need to be the same; it can be 1, 2, 3, 4, or 5, but is preferably 2. R'' may be H, a methyl group, an ethyl group, or a cyclopropyl group, but is preferably a methyl group and H. That is correct.

[0131] It is particularly preferable that at least one aromatic ester of polyphosphate is used. Such aromatic polyphosphates are available, for example, from Daihachi Chemical Industry under the name PX-200.

[0132] The thermoplastic molding material according to the present invention may contain, as component F, at least one metal phosphinate or phosphinate described below as a flame retardant in an amount of 5.0% to 30.0% by weight, preferably 10.0% to 25.0% by weight, particularly 12.0% to 20.0% by weight, for example, about 16.0% by weight. A preferred flame retardant for component F is a metal phosphinate derived from hypophosphorous acid. For example, a metal salt of hypophosphorous acid having Mg, Ca, Al, or Zn as the metal may be used. Here, aluminum hypophosphorous acid is particularly preferred.

[0133] Phosphinates of formula (I) and / or diphosphins of formula (II) or polymers thereof are also suitable: [ka] [In the formula, R 1 and R 2 This refers to groups that are identical or distinct from each other, and represent hydrogen, linear or branched C1-C6 alkyl groups, and / or aryl groups. R 3 C1-C are linear or branched C1-C 10 - Alkylene group, or C6~C 10 - Represents an arylene group, an alkylarylene group, or an arylalkylene group. M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, and / or protonated nitrogenous bases. m=1~4, n=1~4, x=1~4, preferably m=3, x=3.

[0134] Preferably, R 1 and R 2 This refers to a group that is either identical or distinct from another, and represents hydrogen, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, and / or a phenyl group.

[0135] Preferably, R 3 This represents a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, tert-butylene group, n-pentylene group, n-octylene group or n-dodecylene group, phenylene group or naphthylene group, methylphenylene group, ethylphenylene group, tert-butylphenylene group, methylnaphthylene group, ethylnaphthylene group or tert-butylnaphthylene group, phenylmethylene group, phenylpropylene group or phenylbutylene group.

[0136] Particularly preferred, R 1 , R 2 is hydrogen, a methyl group, or an ethyl group, and M is Al, with aluminum hypophosphite being particularly preferred.

[0137] Further flame retardants include, for example, halogen-containing flame retardants. Suitable halogen-containing flame retardants are preferably bromides, such as diphenyl ether bromide, trimethylphenylindan bromide (FR1808 from DSB), tetrabromobisphenol A, and hexabromocyclododecane. Suitable flame retardants are preferably bromides, such as oligocarbonates bromide (BC52 or BC58 from Great Lakes).

[0138] Oligostyrene bromides, which are preferably used as flame retardants, have an average degree of polymerization (number average) of 3 to 90, preferably 5 to 60, as measured by vapor pressure osmosis in toluene. Cyclic oligomers are similarly suitable.

[0139] In some embodiments, halogen-containing flame retardants are not used in thermoplastic molding compositions. Suitable flame-retardant melamine compounds for component F are, for example, melamine compounds that, when added to glass fiber-filled polyamide molding materials, affect combustion behavior to reduce flammability and make them flame-retardant, thus resulting in improved properties in UL94 and glow-wire tests.

[0140] The melamine compound can be selected from, for example, melamine borate, melamine phosphate, melamine sulfate, melamine pyrophosphate, melam, melem, melon, or melamine cyanurate, or mixtures thereof. The preferred melamine cyanurate according to the present invention is preferably a reaction product of equimolar amounts of melamine and cyanuric acid / isocyanuric acid.

[0141] Further suitable compounds (often also described as salts or adducts) are melamine sulfate, melamine, melamine borate, oxalate, monophosphate, dative phosphate, and dative pyrophosphate, and melamine neopentyl glycol borate. In some embodiments, the molding material preferably does not contain polymeric melamine phosphate (CAS numbers 56386-64-2 or 218768-84-4).

[0142] This polymeric melamine phosphate should be understood to mean a polymelamine phosphate salt of a 1,3,5-triazine compound having an average degree of condensation n of 20 to 200, and having a 1,3,5-triazine content of 1.1 to 2.0 moles per mole of a 1,3,5-triazine compound selected from the group consisting of melamine, melam, melem, melon, ammelin, ammerido, 2-ureidomelamine, acetoguanamine, benzoguanamine, and diaminophenyltriazine. Preferably, the n value of such a salt is generally 40 to 150, and the ratio of the 1,3,5-triazine compound per mole of phosphorus atoms is preferably 1.2 to 1.8. Furthermore, the pH of a 10 wt% aqueous slurry of the salt produced according to European Patent No. 0095030 is generally greater than 4.5, preferably at least 5.0. pH is typically measured by adding 25 g of salt and 225 g of clean water to a 300 mL beaker at 25°C, stirring the resulting aqueous slurry for 30 minutes, and then measuring the pH. The n value mentioned above, i.e., the number-average degree of condensation, 31 Measurement may be performed by solid-state NMR. JR van Wazer, CF Callis, J. Shoolery and R. Jones, J. Am. Chem. Soc., vol.78, p.5715, 1956, discloses that the number of adjacent phosphate groups results in a unique chemical shift, which allows for a clear distinction between orthophosphates, pyrophosphates, and polyphosphates.

[0143] Similarly, a functional polymer may be used as component F, and this functional polymer may be a flame-retardant polymer. Such polymers are described in U.S. Patent No. 8,314,202 and contain a 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethane repeating unit. Further suitable functional polymers for increasing the amount of carbon residue include poly(2,6-dimethyl-1,4-phenylene oxide) (PPPO).

[0144] The thermoplastic molding composition of the present invention can be produced by a known process, which involves mixing the starting components in a conventional mixing apparatus, such as a screw extruder, Brabender mixer, or Banbury mixer, and then extruding the components. After extrusion, the extruded material can be cooled and pelletized. It is also possible to premix the individual components and then add the remaining starting materials individually and / or in the form of a mixture. The mixing temperature is generally about 230°C to about 320°C.

[0145] These materials are suitable for the manufacture of fibers, foils, and all types of molded parts. Some examples include: cylinder head covers, motorcycle covers, intake manifolds, charge air cooler caps, plug connectors, gears, cooling fan wheels, and coolant tanks.

[0146] In the electrical and electronic fields, polyamides with improved fluidity can be used to manufacture plugs, plug components, plug connectors, membrane switches, printed circuit board modules, microelectronic components, coils, I / O plug connectors, plugs for printed circuit boards (PCBs), plugs for flexible printed circuits (FPCs), plugs for flexible integrated circuits (FFCs), high-speed plug connectors, terminal strips, connector plugs, device connectors, cable harness components, circuit mounts, circuit mount components, three-dimensional injection molded circuit mounts, electrical connection elements, and mechatronic components.

[0147] Possible applications in automotive interiors include dashboards, steering column switches, seat components, headrests, center consoles, gearbox components, and door modules, while possible applications in automotive exteriors include door handles, exterior mirror components, windshield wiper components, windshield wiper protective housings, grilles, roof rails, sunroof frames, engine covers, cylinder head covers, intake pipes (especially intake manifolds), windshield wipers, and exterior body components.

[0148] While we do not wish to be constrained by theory, the combination of components B, C, and D is intended to lead to an efficient system for stabilizing polyamides above 180°C while maintaining a completely metal halide-free system. In other words, the combination of components B, C, and D provides an unexpected stabilizing effect against thermal aging. B, C, or D alone are not sufficient to produce the stabilizing effect; components B, C, and D act synergistically.

[0149] In some embodiments, the thermoplastic molding composition is completely halogen-free, and therefore does not contain halogen-containing flame retardants.

[0150] Molded articles comprising the above compositions exhibit better heat aging resistance than currently available halogenated or non-halogenated stabilizer systems disclosed. Thermoplastic components subjected to prolonged exposure to heat, such as automotive parts like cylinder head covers, can achieve a longer service life when made from the disclosed compositions. Additionally, the improved HAR can enable the use of components at higher temperatures.

[0151] In some embodiments, the thermoplastic molding composition has a tensile strength of at least about 210 MPa at 23°C, for example, at least about 210 MPa, at least about 215 MPa, at least about 220 MPa, at least about 225 MPa, etc.

[0152] In some embodiments, the thermoplastic molding composition has a tensile strength of at least about 200 MPa at 23°C after aging at 180°C for 3000 hours, for example, at least about 200 MPa, at least about 210 MPa, at least about 215 MPa, at least about 220 MPa, etc.

[0153] In some embodiments, the thermoplastic molding composition, after aging at 180°C for 3000 hours, has a tensile strength retention of at least about 50%, for example, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, about 100%, or any value within the range formed by any two of the aforementioned values.

[0154] In some embodiments, the thermoplastic molding composition has a tensile strength of at least about 150 MPa at 23°C after aging at 180°C for 5000 hours, such as at least about 150 MPa, at least about 155 MPa, at least about 160 MPa, at least about 165 MPa, at least about 170 MPa, etc.

[0155] In some embodiments, the thermoplastic molding composition has a tensile strength retention of at least about 40%, for example, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, etc., after aging at 180°C for 5000 hours.

[0156] Figure 1 is a graph of the tensile strength retention of the compositions of the present disclosure after thermal aging at 180°C for 5000 hours. As shown in Figure 1, the compositions of the present disclosure provide a tensile strength retention of at least about 70% after thermal aging.

[0157] In some embodiments, the thermoplastic molded composition has a tensile elongation at break of about 2.0% to about 4.0% at 23°C. For example, in some embodiments, the thermoplastic molded composition may have a tensile elongation at break of about 2.0%, about 2.1%, about 2.2%, about 2.3%, about 2.4%, about 2.5%, about 2.6%, about 2.7%, about 2.8%, about 2.9%, about 3.0%, about 3.1%, about 3.2%, about 3.3%, about 3.4%, about 3.5%, about 3.6%, about 3.7%, about 3.8%, about 3.9%, about 4.0%, or any value that falls within the range formed by any two of the aforementioned values.

[0158] In some embodiments, the thermoplastic molded composition, after being heat-aged at 180°C for 5000 hours, has a tensile elongation at 23°C of about 1.2% to about 2.5%, for example, about 1.2%, about 1.3%, about 1.4%, about 1.5%, about 1.6%, about 1.7%, about 1.8%, about 1.9%, about 2.0%, about 2.1%, about 2.2%, about 2.3%, about 2.4%, about 2.5%, or any value within the range formed by any two of the aforementioned values.

[0159] In some embodiments, the thermoplastic molding composition has a tensile elongation retention rate of at least about 50%, for example, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, etc., after aging at 180°C for 3000 hours.

[0160] In some embodiments, the thermoplastic molding composition has a tensile elongation retention rate of at least about 40%, for example, at least about 40%, at least about 45%, at least about 50%, etc., after aging at 180°C for 5000 hours.

[0161] Figure 2 is a graph of the tensile elongation retention of the compositions of this disclosure after thermal aging at 180°C for 5000 hours. As shown in Figure 2, the compositions of this disclosure exhibit a tensile elongation retention of at least about 50% after thermal aging for 3000 hours as described herein, and a tensile elongation retention of at least about 40% after thermal aging for 5000 hours as described herein.

[0162] In some embodiments, the thermoplastic molded composition has a notched Izod impact retention rate of at least about 95%, for example, about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, or any value within the range formed by any two of the aforementioned values, after aging at 180°C for 3000 hours. In some embodiments, the thermoplastic molded composition has a notched Izod impact retention rate of at least about 90%, for example, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, or any value within the range formed by any two of the aforementioned values, after aging at 180°C for 5000 hours.

[0163] Figure 3 is a graph of the notched Izod impact (NII) retention rates of the compositions of this disclosure after thermal aging at 180°C for 5000 hours. As shown in Figure 3, the compositions of this disclosure exhibit at least about 95% NII retention after thermal aging for 3000 hours as described herein, and at least about 90% NII retention after thermal aging for 5000 hours as described herein. [Examples]

[0164] The following thermoplastic molding compositions were prepared as shown in Table 1.

[0165] [Table 1]

[0166] Table 2 shows the tensile properties of the molded dry state tested at 23°C, as well as the percentage retention of tensile properties after the parts have undergone 3000 hours of thermal aging at 180°C. Composition 3 retains 16% and 35% additional tensile strength compared to the copper halide-based systems (Composition 1 and Composition 4, respectively), and 8% additional tensile strength compared to Composition 2.

[0167] [Table 2]

[0168] Table 3 shows the tensile elongation properties of the compositions after thermal aging at 180°C for 3000 hours. Composition 3 retains 25% and 30% additional tensile elongation compared to the copper halide-based systems (composition 1 and composition 4, respectively), and 18% additional tensile elongation compared to composition 2.

[0169] [Table 3]

[0170] Table 4 shows the tensile properties of the molded dry state tested at 23°C, as well as the percentage retention of tensile properties after the parts have undergone 5000 hours of thermal aging at 180°C. Composition 3 retains 20% and 49% additional tensile strength compared to the copper halide-based systems (Composition 1 and Composition 4, respectively), and retains 20% additional tensile strength compared to Composition 2.

[0171] [Table 4]

[0172] Table 5 shows the tensile elongation properties of the compositions after thermal aging at 180°C for 5000 hours. Composition 3 retains 19% and 29% additional tensile elongation compared to the copper halide-based systems (composition 1 and composition 4, respectively), and retains 16% additional tensile elongation compared to composition 2.

[0173] [Table 5]

[0174] Table 6 shows the notched Izod impact strengths of the compositions after thermal aging at 180°C for 3000 hours. Composition 3 retains 27% and 20% additional impact strengths compared to the copper halide-based systems (compositions 1 and 4, respectively), and 22% additional impact strength compared to composition 2.

[0175] [Table 6]

[0176] Table 7 shows the notched Izod impact strength of the compositions after thermal aging at 180°C for 5000 hours. Composition 3 retains 38% and 67% additional impact strength compared to the copper halide-based systems (compositions 1 and 4, respectively), and retains 11% additional impact strength compared to composition 2.

[0177] [Table 7]

[0178] This disclosure is not limited to the specific systems, apparatus, and methods described, as these systems, apparatus, and methods may change. The terms used herein are intended solely to describe specific versions or embodiments and are not intended to limit their scope.

[0179] As used herein, the singular forms "a," "an," and "the" include plural nouns unless the context clearly indicates otherwise. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Nothing in this disclosure should be construed as an admission that the embodiments described herein do not have prior rights to this disclosure by prior inventions. As used herein, the term "including" means "including, but not limited to."

[0180] As used herein, the term "about" means plus or minus 10% of the number in which the term is used. For example, "about 50%" means within the range of 45% to 55%.

[0181] In the detailed description above, references are made to the accompanying drawings which form part of this specification. In the drawings, unless otherwise indicated in the context, similar reference numerals typically identify similar components. The exemplary embodiments described in the detailed description, drawings and claims are not intended to be limiting. Other embodiments may be used and other modifications may be made without departing from the spirit or scope of the subject matter presented herein. It will be readily apparent that the aspects of this disclosure generally described herein and shown in the drawings can be arranged, substituted, combined, separated and designed in a wide variety of different configurations, all of which are expressly intended herein.

[0182] This disclosure should not be limited by the specific embodiments described herein, which are intended to be illustrative of various aspects. As will be apparent to those skilled in the art, many modifications and variations may be made without departing from the spirit and scope thereof. In addition to those enumerated herein, functionally equivalent methods and apparatus within the scope of this disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to be within the scope of the appended claims. This disclosure should be limited only by the terminology of the appended claims and the entire scope of the equivalents to which such claims are entitled. It should be understood that this disclosure is not limited to any particular method, reagent, compound, composition, or biological system, and these methods, reagents, compounds, compositions, or biological systems may, of course, change. It should also be understood that the terminology used herein is intended solely to describe and not to limit any particular embodiment.

[0183] With regard to the use of substantially any plural and / or singular terms herein, those skilled in the art can interpret them as plural-to-singular and / or singular-to-plural as appropriate to the context and / or use. For clarity, various singular / plural permutations may be explicitly listed herein.

[0184] Generally, it will be understood by those skilled in the art that the terms used herein, and in particular in the appended claims (e.g., the main body of the appended claims), are generally intended to be “open” terms (for example, the term “includes” should be interpreted as “includes but not limited to,” the term “has” should be interpreted as “has at least,” and the term “includes” should be interpreted as “includes but not limited to,” etc.). Various compositions, methods, and apparatuses are described using the term “includes” (to be interpreted as “includes but not limited to”) various components or processes, but compositions, methods, and apparatuses may also “essentially consist of” or “consist of” various components and processes, and such terms should be interpreted as defining essentially closed groups of members. It will further be understood by those skilled in the art that if a particular number of claims introduced is intended, such intention is explicitly stated in the claim, and if no such statement is made, such intention is not present.

[0185] For example, to aid understanding, the attached claims below may include the use of the introductory phrases “at least one” and “one or more” to introduce the claim description. However, the use of such phrases should not be interpreted as meaning that the introduction of the claim description by the indefinite article “a” or “an” means that any particular claim containing such introduced claim description is limited to embodiments containing only one such description (for example, “a” and / or “an” should be interpreted as meaning “at least one” or “one or more”). The same applies to the use of the definite article used to introduce the claim description.

[0186] Furthermore, even if a specific number is explicitly stated in an introduced claim, a person skilled in the art will recognize that such a statement should be interpreted to mean at least the number stated (for example, the mere statement “two statements” without other modifiers means at least two statements, or two or more statements). Furthermore, when idiomatic expressions similar to “at least one of A, B, and C, etc.” are used, such constructions are generally intended to mean that a person skilled in the art will understand the idiomatic expression (for example, “a system having at least one of A, B, and C” includes, but is not limited to, a system having A alone, a system having B alone, a system having C alone, a system having A and B together, a system having A and C together, a system having B and C together, and / or a system having A, B and C together, etc.). Where idiomatic expressions similar to “at least one of A, B, or C” are used, generally such constructions are intended in a sense that a person skilled in the art would understand the idiomatic expression to be (for example, “a system having at least one of A, B, or C” includes, but is not limited to, a system having A alone, a system having B alone, a system having C alone, a system having A and B together, a system having A and C together, a system having B and C together, and / or a system having A, B and C together). It will further be understood by a person skilled in the art that any substantially disjunctive word and / or phrase representing two or more alternative terms in this specification, the claims, or the drawings should be understood as construing the possibility of encompassing one of those terms, either of those terms, or both of those terms. For example, the phrase “A or B” will be understood as encompassing the possibilities of “A” or “B,” or “A and B.”

[0187] Furthermore, if any feature or aspect of the present disclosure is described by a group of Markush members, it will be recognized by those skilled in the art that the present disclosure is described by any individual member or subgroup of such member of the Markush group.

[0188] As will be understood by those skilled in the art, in terms of all purposes, such as providing written descriptions, all scopes disclosed herein also encompass all possible sub-scopes and combinations thereof. Any scope enumerated can be readily recognized as sufficiently explainable and enable to divide that scope into at least two, three, four, five, ten, etc., parts. As a non-limiting example, each scope discussed herein can be readily divided into a lower third, a middle third, and an upper third, etc. Also, as will be understood by those skilled in the art, all words such as “maximum,” “at least,” etc., mean a scope that includes the stated numerical value and can then be divided into sub-scopes as discussed above. Finally, as will be understood by those skilled in the art, a scope encompasses each individual member. Thus, for example, a group having 1 to 3 compounds means a group having 1, 2, or 3 compounds. Similarly, a group having 1 to 5 cells means a group having 1, 2, 3, 4, or 5 compounds, and so on.

[0189] The various features and functions disclosed above, as well as other features and functions, or their substitutes, may be combined with many other different systems or applications. Various substitutes, modifications, variations, or improvements in those systems or applications that are not currently foreseen or anticipated may subsequently be made by those skilled in the art, but each of these substitutes, modifications, variations, or improvements is intended to be encompassed by the disclosed embodiments.

Claims

1. A thermoplastic molding composition, Component A consists of at least one thermoplastic polyamide in an amount of approximately 30% to approximately 99.9% by weight, Component B consists of approximately 0.1% to 10% by weight of more than six hydroxyl groups and a number-average molecular weight M greater than 2000 g / mol. ｎ A polyhydric alcohol having at least one such alcohol, Component C consists of at least one sterically hindered phenol antioxidant in an amount of approximately 0.05% to approximately 3% by weight, Component D is at least one cationic polyethyleneimine branched polymer in an amount of approximately 0.1% to approximately 3% by weight, Component E is at least one fibrous and / or particulate filler in an amount of 0% to about 50% by weight, Component F is a further additive in an amount of 0% to approximately 25% by weight, Includes, The total weight percentage of components A through F is 100% by weight. Thermoplastic molding composition.

2. The thermoplastic molding composition according to claim 1, comprising approximately 45% to approximately 70% by weight of component A.

3. The thermoplastic molding composition according to claim 1, wherein component A comprises polyamide 6 (PA6), polyamide 66 (PA66), polyamide 12 (PA12), polyamide 610 (PA610), polyamide 46 (PA46), or a combination thereof.

4. The thermoplastic molding composition according to claim 1, comprising approximately 1% to approximately 5% by weight of component B.

5. The thermoplastic molding composition according to claim 1, wherein component B comprises an ethylene vinyl alcohol copolymer.

6. The thermoplastic molding composition according to claim 1, wherein component C comprises a phenol substituted with one or more alkyl groups, alkoxy groups, substituted amino groups, or combinations thereof.

7. Component C is 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octa-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearyl thio The thermoplastic molding composition according to claim 1, comprising otriadilamine, 2-(2'-hydroxy-3'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyldimethylamine, N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide, or a combination thereof.

8. The thermoplastic molding composition according to claim 1, comprising about 0.1% to about 1.5% by weight of component D.

9. Component D has a number average molecular weight M of over approximately 1000 g / mol. ｎ A thermoplastic molding composition according to claim 1, comprising the features described above.

10. Component D has a number-average molecular weight of approximately 1300 g / mol M ｎ A thermoplastic molding composition according to claim 1, comprising the features described above.

11. The thermoplastic molding composition according to claim 1, wherein component D has a cation charge density of approximately 16 milliequivalents / g (dry solids).

12. The thermoplastic molding composition according to claim 1, comprising approximately 10% to approximately 50% by weight of component E.

13. The thermoplastic molding composition according to claim 1, wherein component E comprises carbon fiber, glass fiber, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, feldspar, aramid fiber, potassium titanate fiber, kaolin, calcined kaolin, wollastonite, talc, chalk, layered nanofiller, needle-shaped nanofiller, boehmite, bentonite, montmorillonite, vermiculite, hectorite, laponite, or a combination thereof.

14. The thermoplastic molding composition according to claim 1, wherein the thermoplastic molding composition has a tensile strength retention rate of at least about 85% after aging at 180°C for 3000 hours.

15. The thermoplastic molding composition according to claim 1, wherein the thermoplastic molding composition has a tensile strength retention rate of at least about 90% after aging at 180°C for 3000 hours.

16. The thermoplastic molding composition according to claim 1, wherein the thermoplastic molding composition has a tensile strength retention rate of at least about 60% after aging at 180°C for 5000 hours.

17. The thermoplastic molding composition according to claim 1, wherein the thermoplastic molding composition has a tensile strength retention rate of at least about 70% after aging at 180°C for 5000 hours.

18. The thermoplastic molding composition according to claim 1, wherein the thermoplastic molding composition has a tensile elongation retention rate of at least about 55% after aging at 180°C for 3000 hours.

19. The thermoplastic molding composition according to claim 1, wherein the thermoplastic molding composition has a tensile elongation retention rate of at least about 65% after aging at 180°C for 3000 hours.

20. The thermoplastic molding composition according to claim 1, wherein the thermoplastic molding composition has a tensile elongation retention rate of at least about 40% after aging at 180°C for 5000 hours.

21. The thermoplastic molding composition according to claim 1, wherein the thermoplastic molding composition has at least about 95% of the notched Izod impact strength retention rate after aging at 180°C for 3000 hours.

22. The thermoplastic molding composition according to claim 1, wherein the thermoplastic molding composition has at least about 90% notched Izod impact strength retention after aging at 180°C for 5000 hours.

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