Heat-aging resistant polyamide molding composition

Abstract

1. A thermoplastic molding composition comprising: a) as component A, 30 to 99.85% by weight of at least one thermoplastic polyamide; b) as component B, 0.1 to 10% by weight of a copolymer having more than 6 hydroxyl groups and a number average molecular weight M of more than 2000 g / mol n at least one polyhydric alcohol having the formula c) 0.05 to 3% by weight of at least one sterically hindered phenol antioxidant as component C; d) as component D, 0 to 3% by weight of carboxylic acid and / or carboxylate groups having more than 3 groups and a number average molecular weight M of more than 300 g / mol n at least one polycarboxylic acid compound having the formula e) as component E, 0 to 50% by weight of at least one fibrous and / or particulate filler; f) 0 to 25% by weight of further additives as component F Including, The total mass % of components A to F is 100 mass %.

Description

[Technical Field]

[0001] The present invention relates to thermoplastic molding compositions containing polyamides having improved heat aging resistance.

[0002] Furthermore, the present invention also relates to the use of the molding compositions of the present invention for producing fibers, foils and moldings of any type, and to the fibers, foils and moldings obtained.

[0003] Furthermore, the present invention relates to mixtures comprising specific combinations of heat-aging resistant additives for polyamide molding compositions. [Background technology]

[0004] Thermoplastic polyamides such as PA6 and PA66, in the form of glass fiber reinforced molding compositions, are often used as materials in the design of parts that are exposed during their lifetime to high temperatures and / or humidity accompanied by thermo-oxidative degradation.

[0005] Various heat-aging additives, such as Cu-containing stabilizers in combination with organic HALS (hindered amine light stabilizers) compounds or sterically hindered phenols or polyhydroxy alcohols, are used in polyamide molding compositions to counteract or delay thermo-oxidative degradation. Improving the heat-aging resistance (HAR) of polyamides is highly desirable because it can extend the life of components subjected to thermal stress or reduce the risk of failure. Furthermore, improving the HAR can enable components to be used at higher temperatures.

[0006] US 2010 / 0028580 discloses a heat-resistant thermoplastic article made from a thermoplastic semi-aromatic polyamide composition containing a polyhydric alcohol such as dipentaerythritol (DPE), a sterically hindered phenol such as Irganox® 1098, a Cu heat stabilizer, and an ethylene-methacrylic acid copolymer neutralized with zinc. The use of these additives is intended to improve the heat aging performance of the polyamide composition.

[0007] EP 2 227 507 B1 describes molding compositions with highly branched or hyperbranched polyetheramines which have improved flow properties and thermal stability.

[0008] Furthermore, DE 10 2004 051 241 A1 describes molding compositions which contain highly branched or hyperbranched polycarbonates or polyesters with improved flow properties and a specific OH number, measured with KOH.

[0009] EP 2 896 656 A1 discloses polyamide resin compositions containing hydroxyl and carboxyl group-containing compounds, the preferred compound being 3,5-dihydroxybenzoic acid.

[0010] WO 2012 / 106319 A2 discloses a thermoplastic melt-mixed composition containing a heat stabilizer. The composition includes a copolymer, e.g., maleic anhydride-modified EPDM, a copper-based stabilizer system containing potassium iodide, and a low molecular weight additive, e.g., 2,6-naphthalenedicarboxylic acid. Unfortunately, the heat aging experiment provided covers a period of only 500 hours, which is not representative of most automotive applications.

[0011] EP 1 041 109 A2 discloses a polyamide composition having good fluidity, which contains a polyhydric alcohol having a melting point of 150 to 280°C, and the polyamide composition should have improved fluidity. Examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, and trimethylolethane.

[0012] EP 3 059 283 B1 discloses polyamide resin compositions with improved low-temperature heat aging resistance. These compositions contain an aliphatic compound having three or more amino groups or three or more hydroxyl groups per molecule, and a compound having two or more functional groups reactive with amino or hydroxyl groups per molecule. Suitable hydroxyl compounds are, inter alia, trimethylolpropane, pentaerythritol, or dipentaerythritol; see paragraphs

[0022] and

[0029] . The hydroxyl-containing aliphatic compound can be reacted with, for example, a compound having an epoxy group or a glycidyl group.

[0013] US 2013 / 0217814 A1 describes a polyamide and a phosphorus compound, boehmite, a polymer having more than two hydroxyl groups and a number average molecular weight (M) of about 2000 or less. n and at least one reinforcing agent.

[0014] The heat aging resistance of known molding compositions remains unsatisfactory, especially after prolonged exposure to heat. Furthermore, due to increasing electrification, more and more applications require materials that do not contain halide-based stabilizer systems (e.g., copper iodide) due to the risk of corrosion and the associated breakdown. Thus, none of the compositions disclosed in the above-cited documents meets the combination of good thermal stability while avoiding the widely used metal halide stabilizers. Some additives with low molecular weights, such as dipentaerythritol, tend to migrate from molded articles at high temperatures, leading to a loss of mechanical properties over time. [Prior art documents] [Patent documents]

[0015] [Patent Document 1] US 2010 / 0028580 [Patent Document 2] EP 2 227 507 B1 [Patent Document 3] DE 10 2004 051 241 A1 [Patent Document 4] EP 2 896 656 A1 [Patent Document 5] WO 2012 / 106319 A2 [Patent Document 6] EP 1 041 109 A2 [Patent Document 7] EP 3 059 283 B1 [Patent Document 8] US 2013 / 0217814 A1 Summary of the Invention [Problem to be solved by the invention]

[0016] It is therefore an object of the present invention to provide a thermoplastic molding composition comprising a polyamide with an improved HAR, which thermoplastic molding composition has good mechanical properties after heat ageing. [Means for solving the problem]

[0017] The purpose of this is to a) as component A, 30 to 99.85% by weight of at least one thermoplastic polyamide; b) as component B, 0.1 to 10% by weight of a copolymer having more than 6 hydroxyl groups and a number average molecular weight M of more than 2000 g / mol n at least one polyhydric alcohol having the formula c) 0.05 to 3% by weight of at least one sterically hindered phenol antioxidant as component C; d) as component D, 0 to 3% by weight of carboxylic acid and / or carboxylate groups having more than 3 groups and a number average molecular weight M of more than 300 g / mol n at least one polycarboxylic acid compound having the formula e) as component E, 0 to 50% by weight of at least one fibrous and / or particulate filler; f) 0 to 25% by weight of further additives as component F The thermoplastic molding composition according to the present invention comprises the following components A to F, and the total of the mass percentages of the components A to F is 100 mass%.

[0018] Furthermore, this purpose is b) 0.1 to 10 parts by mass of component B having more than 6 hydroxyl groups and a number average molecular weight M of more than 2000 g / mol n at least one polyhydric alcohol having the formula c) 0.05 to 3 parts by weight of at least one sterically hindered phenol antioxidant as component C; d) as component D, 0 to 3 parts by weight of a copolymer having more than 3 carboxylic acid groups and / or carboxylate groups and a number average molecular weight M of more than 300 g / mol n at least one polycarboxylic acid compound having the formula This is achieved by a mixture comprising or consisting of the above, wherein the total parts by mass of components B to D is 100 parts by mass.

[0019] In this mixture, the amounts of components B, C and D listed below as weight percent can be used as parts by weight (eg, 0.5 weight percent becomes 0.5 parts by weight).

[0020] Furthermore, the object is to use this mixture to improve the HAR of polyamides, especially after heat aging.

[0021] Furthermore, this object is achieved by a method for preparing the above-described thermoplastic molding composition by mixing components A to F.

[0022] Furthermore, this object is achieved by the use of this thermoplastic molding composition for producing any type of fiber, foil and molding, and by the fiber, foil and molding made from the above-mentioned thermoplastic molding composition. DETAILED DESCRIPTION OF THE INVENTION

[0023] According to the present invention, a copolymer having more than 6 hydroxyl groups and a number average molecular weight M of more than 2000 g / mol isn and at least one sterically hindered phenol antioxidant, and preferably having more than three carboxylic acid or carboxylate groups and a number average molecular weight M of more than 300 g / mol. n It has been found that certain combinations of at least one polycarboxylic acid compound having the formula

[0024] The number average molecular weight, mass average molecular weight (M), and β-glucan-1-phosphate dehydrogenase (β-glucan-1-phosphate dehydrogenase) were determined using gel permeation chromatography (GPC) with PMMA calibration in hexafluoroisopropanol as the solvent. n , M W ) and polydispersity data can be obtained.

[0025] This molecular weight determination can be employed for all components of the thermoplastic molding composition according to the invention.

[0026] This effect is most pronounced at molding temperatures and during the life of the molded article at elevated service temperatures, if the polyhydric alcohol component B and the polycarboxylic acid compound of component D have a sufficiently high number average molecular weight so as not to migrate out of the thermoplastic molding composition during preparation. This effect is most pronounced in thermoplastic molding compositions based primarily on polyamides.

[0027] Furthermore, it is advantageous to employ sterically hindered phenolic antioxidants that also have a sufficiently high molecular weight, preferably above 500 g / mol, in particular above 1000 g / mol, and that preferably exhibit high thermal stability as measured by TGA (thermogravimetric analysis) of less than 2% decomposition up to 300°C under nitrogen atmosphere.

[0028] The molding composition of the invention comprises as component A from 30 to 99.85% by weight, preferably from 35 to 99.4% by weight, in particular from 45 to 98.9% by weight, of at least one thermoplastic polyamide.

[0029] When components D, E, F, or combinations thereof are present in the thermoplastic molding composition, the maximum amount of component A is reduced by the minimum amount of each of components D, E, F, or combinations thereof.

[0030] The polyamides of the molding compositions of the invention generally have an intrinsic viscosity, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25°C according to ISO 307, of 90 to 350 ml / g, preferably 110 to 240 ml / g.

[0031] Semicrystalline or amorphous resins having a molecular weight (weight average) of at least 5000 are preferred, such as those described in the following U.S. Patents: 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606, and 3,393,210.

[0032] Examples of these include polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycaprylolactam and polylaurolactam, and polyamides obtained by reacting dicarboxylic acids with diamines.

[0033] Dicarboxylic acids that can be used are alkanedicarboxylic acids having 6 to 12, especially 6 to 10, carbon atoms, and aromatic dicarboxylic acids. Merely by way of example, mention may be made here of adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and terephthalic and / or isophthalic acid.

[0034] Particularly suitable diamines include alkanediamines having 6 to 12, especially 6 to 8, carbon atoms, and also 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.

[0035] Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam, in particular having a proportion of caprolactam units of 5 to 95% by weight, and also nylon-6 / 6,6 copolyamide (for example Ultramid® C31 from BASF SE).

[0036] Other suitable polyamides can be obtained from ω-aminoalkylnitriles, such as aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66), via what is known as direct polymerization in the presence of water, as described, for example, in DE-A 10313681, EP-A 1198491 and EP 922065.

[0037] Mention may also be made of polyamides (nylon-4,6) which can be obtained, for example, by condensing 1,4-diaminobutane with adipic acid at high temperature. Methods for preparing polyamides of this structure are described, for example, in EP-A 38 094, EP-A 38 582, and EP-A 39 524.

[0038] Other suitable examples are polyamides obtainable through copolymerization of two or more of the above-mentioned monomers, and mixtures of two or more polyamides in any desired mixing ratio. Particularly preferred are mixtures of nylon-6,6 with other polyamides, in particular blends of nylon-6 with nylon-66, nylon-6 / 6,6 copolyamide and nylon-6,6 / 6 copolyamide.

[0039] Other copolyamides that have proven particularly advantageous are semi-aromatic copolyamides such as PA 6 / 6T and PA 66 / 6T, which have a triamine content of less than 0.5% by weight, preferably less than 0.3% by weight (see EP-A 299 444). Other polyamides that are resistant to high temperatures are known from EP-A 19 94 075 (PA 6T / 6I / MXD6).

[0040] The processes described in EP-A 129 195 and 129 196 can be used to prepare the preferred semi-aromatic copolyamides with a low triamine content.

[0041] The following non-exhaustive list includes the polyamides A) mentioned and other polyamides A) for the purposes of the present invention and the monomers they contain: AB polymer: PA 4 Pyrrolidone PA 6 ε-caprolactam PA 7 Ethanol Lactam PA 8 Caprylolactam PA 9 9-aminopelargonic acid PA 11 11-aminoundecanoic acid PA 12 Laurolactam AA / BB polymer: PA 46 Tetramethylenediamine, Adipic Acid PA 66 Hexamethylenediamine, Adipic Acid PA 69 Hexamethylenediamine, Azelaic Acid PA 610 Hexamethylenediamine, Sebacic Acid PA 612 Hexamethylenediamine, Decanedicarboxylic acid PA 613 Hexamethylenediamine, Undecanedicarboxylic Acid PA 1212 1,12-Dodecanediamine, Decanedicarboxylic acid PA 1313 1,13-Diaminotridecane, undecanedicarboxylic acid PA 6T Hexamethylenediamine, Terephthalic Acid PA MXD6 m-xylylenediamine, adipic acid AA / BB polymer: PA 6I Hexamethylenediamine, Isophthalic Acid PA 6-3-T Trimethylhexamethylenediamine, Terephthalic Acid PA 6 / 6T (see PA 6 and PA 6T) PA 6 / 66 (see PA 6 and PA 66) PA 6 / 12 (see PA 6 and PA 12) PA 66 / 6 / 610 (see PA 66, PA 6 and PA 610) PA 6I / 6T (see PA 6I and PA 6T) PA PACM 12 Diaminodicyclohexylmethane, Laurolactam PA 6I / 6T / PACM PA 6I / 6T+Diaminodicyclohexylmethane PA 12 / MACMI Laurolactam, Dimethyldiaminodicyclohexylmethane, Isophthalic Acid PA 12 / MACMT Laurolactam, Dimethyldiaminodicyclohexylmethane, Terephthalic Acid PA PDA-T Phenylenediamine, Terephthalic Acid.

[0042] PA 6, PA 66, PA 6 / 66 and PA 66 / 6 are most preferred.

[0043] Suitable copolyamides are A1) 20.0 to 90.0 mass% of units derived from terephthalic acid and hexamethylenediamine, A2) 0 to 50.0% by mass of units derived from ε-caprolactam, A3) 0 to 80.0% by mass of units derived from adipic acid and hexamethylenediamine, A4) 0 to 40.0% by weight of further polyamide-forming monomers It consists of Here, the proportion of components A2), A3), A4) or mixtures thereof is at least 10.0% by weight.

[0044] Component A1) contains 20.0 to 90.0% by mass of units derived from terephthalic acid and hexamethylenediamine.

[0045] In addition to units derived from terephthalic acid and hexamethylenediamine, the copolyamide optionally comprises units derived from ε-caprolactam and / or units derived from adipic acid and hexamethylenediamine and / or units derived from further polyamide-forming monomers.

[0046] The aromatic dicarboxylic acids A4) contain 8 to 16 carbon atoms. Suitable aromatic dicarboxylic acids include, for example, isophthalic acid, substituted terephthalic acids and isophthalic acids 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, phenoxyterephthalic acid, with isophthalic acid being particularly preferred.

[0047] Further polyamide-forming monomers A4) may be derived from dicarboxylic acids having 4 to 16 carbon atoms and aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms, as well as from aminocarboxylic acids / corresponding lactams having 7 to 12 carbon atoms. Examples of suitable monomers of this type include suberic acid, azelaic acid and sebacic acid as representatives of aliphatic dicarboxylic acids, and 1,4-butanediamine, 1,5-pentanediamine, piperazine, 4,4'-diaminodicyclohexylmethane, 2,2-(4,4'-diaminodicyclohexyl)propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane or meta-xylylenediamine as representatives of diamines, and caprolactam, enantholactam, ω-aminoundecanoic acid and laurolactam as representatives of lactams / aminocarboxylic acids.

[0048] Suitable such copolyamides are described more particularly in DE-A-10 2009 011 668. Component B is used in an amount of 0.1 to 10% by weight, preferably 0.5 to 7.5% by weight, in particular 1 to 5% by weight.

[0049] Component B has more than 6 hydroxyl groups and a number average molecular weight M of more than 2000 g / mol. n and at least one polyhydric alcohol having the formula:

[0050] Component B preferably has more than 8, more preferably more than 10 hydroxyl groups.

[0051] Component B preferably has a number average molecular weight M of more than 3000 g / mol, more preferably more than 5000 g / mol, in particular more than 10000 g / mol. n Preferably, the maximum number average molecular weight is 35,000 g / mol, more preferably 25,000 g / mol. Specifically, a preferred component B has a number average molecular weight of 10,000 to 30,000 g / mol, more preferably 12,500 to 22,500 g / mol, and most preferably 15,000 to 20,000 g / mol.

[0052] Mass average M W is preferably 10,000 to 250,000 g / mol, more preferably 25,000 to 120,000 g / mol, and particularly preferably 30,000 to 80,000 g / mol.

[0053] Component B has more than 6 hydroxyl groups and a number average molecular weight M of more than 2000 g / mol. n The polyhydric alcohol may be selected from any suitable polyhydric alcohol so long as it has the formula:

[0054] An example of a suitable polyhydric alcohol is the ethylene-vinyl alcohol copolymer sold by Mitsubishi Chemical under the trade name Soarnol™ or by Kuraray under the trade name EVAL™. Other high molecular weight polyhydric alcohols are suitable as well.

[0055] Preferably, component B is an ethylene-vinyl alcohol copolymer. Preferably, the ethylene unit content in the ethylene-vinyl alcohol copolymer is 10 to 60 mol %, more preferably 20 to 50 mol %, particularly 25 to 50 mol %.

[0056] In addition to ethylene and vinyl alcohol, residual amounts of vinyl acetate may be present in the copolymer, preferably up to 20 mol %, more preferably up to 10 mol %, and especially up to 5 mol %. Most preferably, there is no residual vinyl acetate. Ethylene-vinyl alcohol copolymers can be obtained by partial or complete hydrolysis of ethylene-vinyl acetate copolymers.

[0057] Particularly suitable ethylene-vinyl alcohol copolymers have a number average molecular weight M of 10,000 to 30,000 g / mol, more preferably 12,500 to 22,500 g / mol, most preferably 15,000 to 20,000 g / mol. n Most preferably, it has a number average molecular weight M of 18000 g / mol. n , and a mass average molecular weight M of 50,000 g / mol W It has.

[0058] The polyhydric alcohol may contain additional functional groups other than hydroxyl groups. However, preferably, the polyhydric alcohol contains only hydroxyl groups as functional groups. The polyhydric alcohol may be linear, branched, or hyperbranched. Specifically, highly branched or hyperbranched structures partially composed of hydroxyl functional groups, as described, for example, in EP 2 227 507 B1 and DE 10 2004 051 241 A1, are also suitable for achieving the desired effect. For example, highly branched or hyperbranched polyetheramines having a hydroxyl value of 50 to 1,000 mg KOH / g, preferably 100 to 900 mg KOH / g, and more preferably 150 to 800 mg KOH / g, can be used.

[0059] As component C, 0.05 to 3% by mass, preferably 0.1 to 2% by mass, and particularly preferably 0.1 to 1% by mass, of at least one sterically hindered phenol antioxidant is used.

[0060] Component C preferably has a molecular weight of more than 500 g / mol, more preferably more than 1000 g / mol.

[0061] Thus, in one embodiment, the present invention provides a) as component A, 30 to 99.85% by weight of at least one thermoplastic polyamide; b) as component B, 0.1 to 10% by weight of a copolymer having more than 6 hydroxyl groups and a number average molecular weight M of more than 2000 g / mol n at least one polyhydric alcohol having the formula c) as component C, 0.05 to 3% by weight of at least one sterically hindered phenol antioxidant having a molecular weight of more than 1000 g / mol; d) as component D, 0 to 3% by weight of carboxylic acid and / or carboxylate groups having more than 3 groups and a number average molecular weight M of more than 300 g / mol n at least one polycarboxylic acid compound having the formula e) 0 to 50% by mass of at least one fibrous and / or particulate filler as component E; f) 0 to 25% by weight of further additives as component F a thermoplastic molding composition comprising Here, the total mass % of components A to F is 100 mass %.

[0062] Preferred components A, B, C, D, E and F are described herein.

[0063] Furthermore, component C preferably exhibits high thermal stability, e.g., a maximum mass loss of 5%, more preferably a maximum mass loss of 2%, measured in a TGA (thermogravimetric analysis) experiment (40°C to 120°C at 10°C / min, then 120°C to 600°C at 20°C / min, after 15 minutes at the latter temperature) at 300°C under nitrogen.

[0064] Component C has at least one branched C as a steric hindrance group. 3~12 Preferably, the phenolic group has at least one, more preferably at least two phenolic groups substituted with an alkyl group, and the substituted phenolic group is covalently bonded to the structure of component C.

[0065] Suitable sterically hindered phenols C are in principle all compounds which have a phenolic structure and which have at least one bulky group on the phenolic ring. The bulky group can be, for example, a branched C 3~12 - alkyl group, preferably branched C 3~6 -alkyl group, more preferably an isopropyl group or a tert.-butyl group.

[0066] For example, it is preferable to use compounds of the formula:

[0067] [ka] (In the formula, R 1 and R 2 is an alkyl group, a substituted alkyl group, or a substituted triazole group, and the radical R 1 and R 2 may be the same or different, and R 3 is an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group. The alkyl and alkoxy residues preferably have 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. The substituents are preferably C 1~12 -alkyl, more preferably C 1~6 -alkyl, most preferably C 1~4 -alkyl. Preferably, R 1 ~R 3 At least one of is a bulky group as defined above.

[0068] Antioxidants of the above mentioned type are described, for example, in DE-A 27 02 661 (US-A 4 360 617).

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

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

[0071] Particularly preferred compounds from this class are compounds of the formula:

[0072] [ka] (In the formula, R 4 , R 5 , R 7 and R 8 are, independently of one another, C1-C8 alkyl groups which themselves may have substituents (at least one of which is a bulky group), and R 6 is a divalent aliphatic radical having 1 to 10 carbon atoms and whose main chain may contain a C-O bond. 4 ~R 8 At least one of is a bulky group as defined above.

[0073] Preferred compounds corresponding to these formulas are:

[0074] [ka]

[0075] Examples of sterically hindered phenols include all of the following: 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox® 1010 from BASF SE), distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl-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.

[0076] Compounds which have proven particularly effective and are therefore preferably used are 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 259), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and also N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098), and the above-mentioned products Irganox® 245 and Irganox® 1010 from BASF SE, which have particularly good compatibility.

[0077] In some cases, sterically hindered phenols having one or less sterically hindering group in the ortho position relative to the phenolic hydroxy group have proven particularly advantageous, especially when assessing color fastness during storage in diffuse light over extended periods of time.

[0078] As component D, there are provided those having more than three carboxylic acid groups and / or carboxylate groups and a number average molecular weight M of more than 300 g / mol. n It is possible to use at least one polycarboxylic acid compound having the following formula: The amount of component D is 0 to 3 mass %, preferably 0 to 2 mass %, and more preferably 0 to 0.8 mass %.

[0079] When present, the amount of component D is 0.01 to 3 mass %, preferably 0.1 to 2 mass %, more preferably 0.2 to 0.8 mass %.

[0080] When component D is present, the maximum amount of component A is reduced by the minimum amount of component D. Thus, the maximum amount of component A is reduced by 0.01 wt %, preferably 0.1 wt %, more preferably 0.2 wt %.

[0081] The polyamide molding composition according to the invention does not need to contain component D. Thus, according to a first embodiment, the thermoplastic molding composition does not contain component D. However, the additional use of component D can further improve the heat aging resistance of the thermoplastic molding composition. Thus, according to a second embodiment of the invention, the thermoplastic molding composition contains 0.01 to 3% by weight, preferably 0.1 to 2% by weight, more preferably 0.2 to 0.8% by weight, of component D. Molding compositions containing component D in these amounts are particularly preferred according to the invention.

[0082] Component D preferably has a number average molecular weight (M) of more than 500 g / mol, more preferably more than 1000 g / mol, in particular more than 2000 g / mol, more in particular more than 3000 g / mol, and most in particular more than 2500 g / mol. n ) Most preferably, the polymer has a weight average molecular weight M W is in the range of 4000 to 80000 g / mol, more preferably 15000 to 45000 g / mol.

[0083] The essential feature of component D is the presence of more than three carboxylic acid groups and / or carboxylate groups in the polycarboxylic acid compound. The acid functions can be present as free acid groups or in the form of salts of free acids. It is important that acid or acid salt functionality is present in the polycarboxylic acid compound.

[0084] Component D preferably has more than 5 carboxylic acid and / or carboxylate groups, more preferably more than 8 carboxylic acid and / or carboxylate groups, and most preferably more than 12 carboxylic acid and / or carboxylate groups.

[0085] The carboxyl group is preferably a carboxylate salt group. Thus, the carboxylic acid group can be partially or completely neutralized, or partially or completely in the form of a salt. Ammonium salts, alkali metal salts, alkaline earth metal salts, iron salts, copper salts, or mixtures thereof are preferred. Most preferred are alkali metal salts of the carboxylic acid group. The polycarboxylic acid compound preferably has partially or completely neutralized carboxylic acid groups, more preferably neutralized with an alkali metal cation.

[0086] Component D can be selected from a variety of polycarboxylic acid compounds, provided that they meet the requirements of a minimum number of carboxylic acid and / or carboxylate groups and a minimum number-average molecular weight. Possible polycarboxylic acid compounds of component D are polyacrylic acid or polyacrylate, polymethacrylic acid and polymethacrylate, copolymers containing maleic acid groups, such as polyolefins containing maleic acid groups in the main chain or as grafts, such as neutralized ethylene-maleic anhydride copolymers, or polymers substituted with a sufficient number of acid or acid salt groups.

[0087] The polymer containing carboxylic acid and / or carboxylate groups can be linear, branched, or highly branched. It is also possible to use a polymer having a sufficient number of carboxylic acid and / or carboxylate end groups. For example, a branched, highly branched, or hyperbranched polyester having the required number of carboxylic acid and / or carboxylate end groups can be used.

[0088] In the following, polyacrylic acids and polyamines in which the N atoms are partially or polysubstituted with CH2CHOOH groups will be described in more detail.

[0089] Suitable polycarboxylic acid compounds are disclosed in the above-mentioned documents, such as US 2010 / 0028580 and WO 2012 / 106319 A2. An example is polyacrylic acid (CAS: 9004-01-04), including copolymers based on polyacrylic acid with suitable molecular weight and structure. A suitable product is Sokalan® NR 2500 from BASF SE.

[0090] Highly branched or hyperbranched structures are also suitable. Complexing agents based on amino acid structures containing at least two amino groups and at least four carboxylic acid groups are particularly suitable. In any case, it is preferable to apply component D as an acid salt due to its higher thermal stability.

[0091] Component D can also be a polymer chosen from polyamines whose N atoms are partially or fully substituted with CH2CHOOH groups and partially or fully neutralized with alkali metal cations.

[0092] The term "polyamine" in the context of component D refers to polymers and copolymers containing at least one amino group per repeat unit. The amino group may be selected from NH, NH, and preferably tertiary amino groups. In the polymers, the base polyamine is converted to a carboxymethyl derivative, and the N atoms are either fully substituted or preferably partially substituted, e.g., 50 to 95 mol %, preferably 70 to 90 mol %, with CHCHOOH groups, and partially or fully neutralized with alkali metal cations; therefore, tertiary amino groups are preferred. In the context of the present invention, such polymers in which more than 95 mol % to 100 mol % of the N atoms are substituted with CHCHOOH groups are considered fully substituted with CHCHOOH groups. For example, NH groups from polyvinylamine or polyalkyleneimine can be substituted with one or two CHCHOOH groups per N atom, preferably two CHCHOOH groups per N atom.

[0093] In the context of the present invention, the number of CHCHOOH groups in a polymer divided by the total potential number of CHCHOOH groups, assuming one CHCHOOH group per NH group and two CHCHOOH groups per NH group, is called the "degree of substitution."

[0094] The degree of substitution can be determined, preferably according to ASTM D2074-07, for example, by determining the amine number (amine value) of the polymer and its respective polyamine before conversion to a CH2CHOOH substituted polymer.

[0095] Examples of polyamines are polyvinylamines, polyalkylenepolyamines, especially polyalkyleneimines such as polypropyleneimine and polyethyleneimine.

[0096] In the context of the present invention, polyalkylene polyamines preferably contain at least 6 nitrogen atoms and at least 5 C2-C6 alkylene groups per molecule. 10 Polymers containing C2-C3-alkylene units, preferably C2-C3-alkylene units, such as pentaethylenehexamine, and in particular polyethyleneimine, which have 6 to 30 ethylene units per molecule. In the context of the present invention, polyalkylenepolyamines are understood to mean those polymeric materials obtained by homopolymerization or copolymerization of one or more cyclic imines or by grafting (co)polymers with at least one cyclic imine. Examples include polyvinylamines grafted with ethyleneimine and polyimideamines grafted with ethyleneimine.

[0097] Preferred polymers are polyalkyleneimines, such as polyethyleneimine and polypropyleneimine, with polyethyleneimine being preferred. Polyalkyleneimines, such as polyethyleneimine and polypropyleneimine, can be linear, essentially linear or branched.

[0098] In one embodiment of the present invention, the polyethyleneimine is selected from hyperbranched polyethyleneimines. Hyperbranched polyethyleneimines are characterized by their high degree of branching (DB). The degree of branching can be, for example, 13 It can be determined by C-NMR spectroscopy, preferably in DO, and is defined as follows: DB = D +T / D+T+L (wherein D (dendritic) corresponds to the proportion of tertiary amino groups, L (linear) corresponds to the proportion of secondary amino groups, and T (terminal) corresponds to the proportion of primary amino groups).

[0099] In the context of the present invention, a hyperbranched polyethyleneimine is a polyethyleneimine having a DB in the range of 0.25 to 0.90.

[0100] In one embodiment of the present invention, the polyethyleneimine has an average molecular weight M in the range of 600 to 75,000 g / mol, preferably in the range of 800 to 25,000 g / mol. W The polyethyleneimine is selected from hyperbranched polyethyleneimines (homopolymers) having the formula:

[0101] In another embodiment of the present invention, the polyethyleneimine is selected from copolymers of ethyleneimine, for example copolymers of ethyleneimine and at least one diamine other than ethyleneimine having two NH groups per molecule, such as propyleneimine, or copolymers of ethyleneimine and at least one compound having three NH groups per molecule, such as melamine.

[0102] In one embodiment of the invention, the polymer is partially or fully substituted with CHCHOOH groups and + The branched polyethyleneimine is selected from the group consisting of branched polyethyleneimines partially or fully neutralized with

[0103] In the context of the present invention, polymers are used in a covalently modified form, specifically in such a way that up to 100 mol % in total, preferably 50-98 mol % in total, of the nitrogen atoms of the primary and secondary amino groups of the polymer (percentages are based on the total N atoms of the primary and secondary amino groups in the polymer) have been reacted with at least one carboxylic acid, e.g., Cl-CHCOOH, or at least one equivalent of hydrocyanic acid (or its salt) and one equivalent of formaldehyde. In the context of this application, the reaction (modification) can therefore be, for example, alkylation. Most preferably, up to 100 mol %, preferably 50-99 mol % in total, of the nitrogen atoms of the primary and secondary amino groups of the polymer have been reacted with formaldehyde and hydrocyanic acid (or its salt), e.g., by the Strecker synthesis. The tertiary nitrogen atoms of polyalkyleneimines, which may form the basis (main chain) of the polymer, generally do not have CHCHOOH groups.

[0104] The polymer may, for example, have a number average molecular weight (M n Preferably, the number average molecular weight of the polymer is in the range of 500 to 1,000,000 g / mol, particularly preferably 800 to 50,000 g / mol, determined by determining the amine number (amine value) of each polyamine before and after alkylation according to, for example, ASTM D2074-07, and calculating the number of each CHCHOOH group. The molecular weight refers to the respective persodium salt.

[0105] Preferably, the CH2CHOOH groups of the polymer are partially or completely neutralized with an alkali metal cation. The unneutralized COOH groups may be, for example, free acids. Preferably, 90 to 100 mol % of the CH2CHOOH groups of the polymer are neutralized.

[0106] The CH2CHOOH groups of the polymer can be partially or completely replaced by any type of alkali metal cation, preferably K + and particularly preferably Na + It may be neutralized with

[0107] Most preferably, component D is based on polyethyleneimine N-substituted with acetic acid or acetate groups and their respective carboxylate salts, preferably alkali metal salts. The polyethyleneimine therefore has an amount of branching units in the polymer backbone of 20-50%, more preferably 25-35%. A suitable product is Trilon® P from BASF SE.

[0108] Thus, in one embodiment, the present invention provides a) as component A, 30 to 99.85% by weight of at least one thermoplastic polyamide; b) as component B, 0.1 to 10% by weight of a copolymer having more than 6 hydroxyl groups and a number average molecular weight M of more than 2000 g / mol n at least one polyhydric alcohol having the formula c) 0.05 to 3% by weight of at least one sterically hindered phenol antioxidant as component C; d) Component D is a copolymer having 0.01 to 3% by weight, preferably 0.1 to 2% by weight, more preferably 0.2 to 0.8% by weight of more than three carboxylic acid groups and / or carboxylate groups and a number average molecular weight M of more than 300 g / mol n wherein the polycarboxylic acid compound having more than three carboxylic acid and / or carboxylate groups is a polyethyleneimine N-substituted by acetic acid or acetate groups; e) 0 to 50% by mass of at least one fibrous and / or particulate filler as component E; f) 0 to 25% by weight of further additives as component F a thermoplastic molding composition comprising Here, the total mass % of components A to F is 100 mass %.

[0109] Preferred components A, B, C, D, E and F are described herein.

[0110] The thermoplastic molding composition contains, as component E, 0 to 50% by weight, preferably 0 to 45% by weight, more preferably 0 to 40% by weight of at least one fibrous and / or particulate filler.

[0111] Preferably, component E comprises glass fibers and is present in an amount of 10 to 50% by weight, more preferably 15 to 45% by weight, and most preferably 20 to 40% by weight.

[0112] When component E is present, the maximum amount of component A is reduced by the minimum amount of component E, so that the total amount of components A to F is still 100% by mass.

[0113] Examples of the fibrous or particulate filler E include carbon fiber, glass fiber, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, and feldspar.

[0114] Preferred fibrous fillers include carbon fibers, aramid fibers, and potassium titanate fibers, with glass fibers in the form of E-glass being particularly preferred, which can be used as rovings or in the form of commercially available chopped glass.

[0115] The fibrous filler may be surface pretreated with a silane compound to improve compatibility with thermoplastics.

[0116] Suitable silane compounds are those of the general formula (X-(CH2) n ) k -Si-(OC m H 2m+1 ) 4-k (wherein the substituents are defined as follows:

[0117] [ka]

[0118] n is an integer of 2 to 10, preferably 3 to 4, m is an integer of 1 to 5, preferably 1 to 2; k is an integer of 1 to 3, preferably 1. It has.

[0119] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and also the corresponding silanes containing a glycidyl group as substituent X.

[0120] Generally, the amount of silane compound used in the surface coating is 0.01 to 2% by weight, preferably 0.025 to 1.0% by weight, and especially 0.05 to 0.5% by weight (based on component E).

[0121] Acicular mineral fillers are also suitable.

[0122] For the purposes of the present invention, an acicular mineral filler is a mineral filler with strongly developed needle-like characteristics. An example is acicular wollastonite. The mineral preferably has an L / D (length / diameter) ratio of 8:1 to 35:1, preferably 8:1 to 11:1. The mineral filler may optionally be pretreated with the above-mentioned silane compounds, but pretreatment is not required.

[0123] Other fillers that may be mentioned are kaolin, calcined kaolin, wollastonite, talc, and chalk, as well as lamellar or acicular nanofillers, preferably in amounts of 0.1 to 10%. Preferred materials for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite, and laponite. The lamellar nanofillers are organically modified by prior art methods to provide good compatibility with organic binders. The addition of lamellar or acicular nanofillers to the nanocomposites of the present invention further improves the mechanical strength.

[0124] The molding composition of the present invention can contain, as component F, from 0 to 25% by weight, preferably from 0 to 20% by weight, more preferably from 0 to 15% by weight, of further additives.

[0125] If further additives are used, the minimum amount thereof is preferably 0.1 wt %, more preferably 0.25 wt %, most preferably 0.5 wt %.

[0126] The thermoplastic molding compositions of the invention can contain, as component F, conventional processing aids, as well as stabilizers, oxidation retardants, agents to counteract thermal and ultraviolet degradation, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.

[0127] The molding composition of the present invention may contain, as component F1, from 0.05 to 3% by weight, preferably from 0.1 to 1.5% by weight, in particular from 0.1 to 1% by weight, of a lubricant.

[0128] Preferred are salts of Al, alkali metals, or alkaline earth metals, or esters or amides of fatty acids having 10 to 44 carbon atoms, preferably 12 to 44 carbon atoms.

[0129] The metal ions are preferably alkaline earth metals and Al, particularly preferably Ca or Mg.

[0130] Preferred metal salts are calcium stearate and calcium montanate, and also aluminum stearate.

[0131] It is also possible to use mixtures of various salts in any desired mixing ratio.

[0132] The carboxylic acids can be monobasic or dibasic. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, particularly preferably stearic acid, capric acid, and also montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms).

[0133] The aliphatic alcohol may be monohydric to tetrahydric. Examples of the alcohol include n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, and pentaerythritol, with glycerol and pentaerythritol being preferred.

[0134] The fatty amines may be monobasic to tribasic. Examples thereof include stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and di(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides accordingly include glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.

[0135] It is also possible to use mixtures of various esters or amides, or mixtures of esters combined with amides, in any desired mixing ratio.

[0136] The molding composition of the invention can contain, as component F2, 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight, in particular 0.1 to 1% by weight, of a copper stabilizer, preferably a Cu(I) halide, in particular an alkali metal halide, preferably a mixture with KI (in particular in a ratio of 1:4), or a sterically hindered phenol, or a mixture thereof.

[0137] Preferred monovalent copper salts used are cuprous acetate, cuprous chloride, cuprous bromide, and cuprous iodide, which the material contains in an amount of 5 to 500 ppm, preferably 10 to 250 ppm, of copper based on the polyamide.

[0138] Particularly advantageous properties are obtained when copper is present in a molecular distribution in the polyamide. This is achieved by adding a concentrate containing polyamide, a monovalent copper salt, and an alkali metal halide in the form of a solid homogeneous solution to the molding composition. For example, a typical concentrate consists of 79-95% by weight of polyamide and 21-5% by weight of copper iodide or a mixture of copper bromide and potassium iodide. The copper concentration in the solid homogeneous solution is preferably 0.3-3% by weight, more preferably 0.5-2% by weight, based on the total weight of the solution. The molar ratio of cuprous iodide to potassium iodide is 1-11.5, preferably 1-5.

[0139] Suitable polyamides for the concentrate are homopolyamides and copolyamides, especially nylon-6.

[0140] 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 with alkali metal halides.

[0141] More preferably, the thermoplastic molding composition of the present invention is free of metal halides.With the trend towards increasing electro-mobility, electrification and connectivity in almost all industries, there is a great interest in metal halide-free systems, so-called electro-friendly systems.

[0142] Therefore, the thermoplastic molding composition is preferably free of metal halides, in particular free of Cu halides and alkali metal halides.

[0143] The molding composition of the present invention contains from 0.001 to 10% by weight, preferably from 0.05 to 5% by weight, in particular from 0.1 to 2.5% by weight of cellulose of a particle size (d 50 The powder may preferably be obtained by thermal decomposition of iron pentacarbonyl.

[0144] Iron exists in many allotropes: 1. α-Fe (ferrite) forms a space-centered cubic lattice, is magnetizable, dissolves small amounts of carbon, and occurs in pure iron at temperatures up to 928°C. At 770°C (the Curie temperature), it loses ferromagnetism and becomes paramagnetic. Iron at temperatures between 770 and 928°C is also called β-Fe. At room temperature and pressures of at least 13,000 MPa, α-Fe has a volume of about 0.20 cm 3 / mol decreases, resulting in the so-called ε-Fe, whose density (at 20000 MPa) increases from 7.85 to 9.1; 2. γ-Fe (austenite) forms a face-centered cubic lattice, is nonmagnetic, dissolves large amounts of carbon, and is only observed at temperatures in the range of 928-1398°C; 3. δ-Fe exists in the space center from 1398°C to its melting point of 1539°C.

[0145] Metallic iron is generally silvery white, has a density of 7.874 (heavy metal), a melting point of 1539°C, a boiling point of 2880°C, and a specific heat (18-100°C) of approximately 0.5g. -1 K -1 , tensile strength is 220~280N / mm 2 These values ​​apply to chemically pure iron.

[0146] The industrial production of iron uses smelting of iron ore, steel slag, calcined pyrite, or blast furnace dust, as well as re-smelting of scrap and alloys.

[0147] The iron powder of the present invention is produced by the thermal decomposition of iron pentacarbonyl, preferably at temperatures between 150° C. and 350° C. The particles thus obtained preferably have a spherical shape, and are therefore spherical or nearly spherical (another term used is spherolitic).

[0148] Preferred iron powders have the particle size distribution described below, as determined by laser scattering in very dilute aqueous suspension (e.g., using a Beckmann LS13320). The particle sizes (and distributions) described below can optionally be obtained by grinding and / or sieving.

[0149] where d XX means that XX% of the total volume of particles is smaller than the stated value.

[0150] d 50 Value: maximum 10 μm, preferably 1.6 to 8 μm, in particular 2.9 to 7.5 μm, very particularly 3.4 to 5.2 μm, d 10 Value: preferably 1 to 5 μm, in particular 1 to 3 μm, very particularly 1.4 to 2.7 μm, d 90 Value: preferably 3 to 35 μm, in particular 3 to 12 μm, very particularly 6.4 to 9.2 μm.

[0151] The iron powder preferably has an iron content of 97 to 99.8 g / 100 g, preferably 97.5 to 99.6 g / 100 g. The content of other metals is preferably less than 1000 ppm, in particular less than 100 ppm, very in particular less than 10 ppm.

[0152] The Fe content is usually determined by infrared spectroscopy.

[0153] The C content is preferably 0.01 to 1.2 g / 100 g, more preferably 0.05 to 1.1 g / 100 g, and in particular 0.4 to 1.1 g / 100 g. This C content in the preferred iron powder corresponds to the C content of a powder that is not reduced with hydrogen after the pyrolysis process.

[0154] Carbon content is usually determined by a method based on ASTM E1019, by burning the sample in a stream of oxygen and then detecting the resulting CO2 gas using IR (Juwe Leco CS230 or CS-mat 6250).

[0155] The nitrogen content is preferably up to 1.5 g / 100 g, preferably 0.01 to 1.2 g / 100 g.

[0156] The oxygen content is preferably up to 1.3 g / 100 g, preferably 0.3 to 0.65 g / 100 g.

[0157] N and O are determined by heating the sample to approximately 2100°C in a graphite furnace, where the oxygen obtained from the sample is converted to CO and measured by an IR detector. N liberated from N-containing compounds under reaction conditions is emitted with the carrier gas and detected and recorded by a TCD (thermal conductivity detector) (both methods based on ASTM E1019).

[0158] The tap density is preferably 2.5 to 5 g / cm 3 , especially 2.7 to 4.4 g / cm 3 This generally refers to the density when the powder is placed in a container and compressed by vibration. More preferably, the iron powder may be surface-coated with iron phosphate, iron phosphite, or SiO2.

[0159] The BET surface area according to DIN ISO 9277 is preferably between 0.1 and 10 m 2 / g, especially 0.1 to 5m 2 / g, preferably 0.2 to 1 m 2 / g, especially 0.4~1m 2 / g range.

[0160] To achieve particularly good dispersion of the iron particles, a masterbatch comprising a polymer may be used. Suitable polymers for this purpose are polyolefins, polyesters, or polyamides, where the masterbatch polymer is preferably the same as component A. The proportion by weight of iron in the polymer is generally 15 to 80% by weight, preferably 20 to 40% by weight.

[0161] If component D is used in the molding composition according to the invention, the elastomeric polymer is different from component D. Thus, if the composition contains component D, the polymer of component F, in particular the elastomeric polymer, is different from the polymer of component D.

[0162] Similarly, the polymer of component F is different from the polymer of component B.

[0163] An example of another conventional additive F is an elastomeric polymer (often also called impact modifier, elastomer, or rubber) in an amount of up to 25% by weight, preferably up to 20% by weight.

[0164] These are very generally copolymers preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile, and acrylates and / or methacrylates having 1 to 18 carbon atoms in the alcohol component.

[0165] Polymers of this type are described, for example, by Houben-Weyl, Methoden der organischen Chemie, vol. 14 / 1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), pp. 392-406, and by C.B. Bucknall in the monograph, Toughened Plastics (Applied Science Publishers, London, UK, 1977).

[0166] Some preferred types of such elastomers are described below.

[0167] Preferred types of such elastomers are those known as ethylene-propylene (EPM) rubber and ethylene-propylene-diene (EPDM) rubber.

[0168] EPM rubbers generally have substantially no residual double bonds, while EPDM rubbers may have from 1 to 20 double bonds per 100 carbon atoms.

[0169] Examples of diene monomers for EPDM rubber are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene, and also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclic dienes such as 3-methyltricyclo[2,3-dimethyl-1,5-hexadiene]. 2,6 ]-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 mass %, particularly 1 to 8 mass %, based on the total mass of the rubber.

[0170] The EPM and EPDM rubbers may preferably be grafted with reactive carboxylic acids or their derivatives, examples of which include acrylic acid, methacrylic acid, and their derivatives, such as glycidyl (meth)acrylate, and maleic anhydride.

[0171] Copolymers of ethylene with acrylic acid and / or methacrylic acid and / or esters of these acids are another group of preferred rubbers. The rubber may also contain dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids, such as esters and anhydrides, and / or monomers containing epoxy groups. These dicarboxylic acid derivatives or epoxy group-containing monomers are preferably incorporated into the rubber by adding to the monomer mixture a monomer containing a dicarboxylic acid group and / or an epoxy group and having the general formula I, II, III, or IV.

[0172] [ka]

[0173] (In the formula, R 1 ~R 9 is hydrogen or an alkyl group having 1 to 6 carbon atoms, m is an integer of 0 to 20, g is an integer of 0 to 10, and p is an integer of 0 to 5).

[0174] Preferably, the radical R 1 ~R 9 is 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.

[0175] Preferred compounds of formulas I, II and IV are maleic acid, maleic anhydride, and epoxy-containing (meth)acrylates, such as glycidyl acrylate and glycidyl methacrylate, and esters with tertiary alcohols, such as tert-butyl acrylate. Although the latter do not have a free carboxyl group, their behavior is similar to that of the free acid, and therefore they are called monomers with a latent carboxyl group.

[0176] 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, the remainder being (meth)acrylates.

[0177] Particularly preferred are copolymers composed of the following components: - 50 to 98% by weight, in particular 55 to 95% by weight, of ethylene, - 0.1 to 40% by weight, in particular 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, in particular 5 to 40% by weight, of n-butyl acrylate and / or 2-ethylhexyl acrylate.

[0178] Other preferred (meth)acrylates are the methyl, ethyl, propyl, isobutyl and tert-butyl esters.

[0179] Comonomers that can be used in conjunction with these are vinyl esters and vinyl ethers.

[0180] The above ethylene copolymers can be prepared by processes known per se, preferably by random copolymerization at high pressure and temperature. Suitable processes are well known.

[0181] Other preferred elastomers are emulsion polymers, the preparation of which is described, for example, in the monograph "Emulsion Polymerization" by Blackley. The emulsifiers and catalysts which can be used are known per se.

[0182] In principle, it is possible to use uniformly structured elastomers or elastomers with a shell structure. The shell structure is determined by the order of addition of the individual monomers. The morphology of the polymer is also influenced by this order of addition.

[0183] For example, to prepare the rubber fraction of the elastomer, monomers that may be mentioned here merely by way of example are acrylates, such as n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene, and mixtures thereof, which may be copolymerized with other monomers, such as styrene, acrylonitrile, vinyl ethers, and with other acrylates or methacrylates, such as methyl methacrylate, methyl acrylate, ethyl acrylate, or propyl acrylate.

[0184] The soft or rubbery phase of the elastomer (glass transition temperature below 0°C) may be the core, outer envelope, or intermediate shell (if the elastomer has more than two shells), and elastomers with more than two shells may have more than one shell composed of the rubbery phase.

[0185] If the structure of elastomers contains one or more hard elements (glass transition temperatures above 20°C) in addition to the rubber phase, they are generally prepared by polymerizing, as principal monomers, styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, or acrylates or methacrylates, such as methyl acrylate, ethyl acrylate, or methyl methacrylate. In addition to these, it is possible to use relatively small proportions of other comonomers.

[0186] In some cases, it has proven advantageous to use emulsion polymers that have reactive groups on their surface. Examples of this type of group include epoxy groups, carboxy groups, latent carboxy groups, amino groups and amide groups, as well as functional groups that can be introduced by combining monomers of the general formula:

[0187] [ka]

[0188] wherein the substituents can be defined as follows: R 10 is hydrogen or a C1-C4 alkyl group, R 11 is hydrogen, a C1-C8-alkyl group or an aryl group, in particular phenyl, R 12 is hydrogen, C1 to C 10 -Alkyl group, C6-C 12 -aryl group, or -OR 13 and R 13 is a C1-C8 alkyl group or a C6-C 12 -aryl group, X is a chemical bond, C1 to C 10 -Alkylene group, or C6-C 12 an arylene group, or

[0189] [ka] and Y is OZ or NH-Z, Z is C1 to C 10 -Alkylene group or C6-C 12 -arylene group).

[0190] The grafting monomers described in EP-A 208 187 are also suitable for introducing reactive groups into the surface.

[0191] Other examples include acrylamide, methacrylamide, and substituted acrylates or methacrylates such as (N-tert-butylamino)ethyl methacrylate, (N,N-dimethylamino)ethyl acrylate, (N,N-dimethylamino)methyl acrylate, and (N,N-diethylamino)ethyl acrylate.

[0192] The particles of the rubber phase may also be crosslinked. Examples of crosslinking monomers include 1,3-butadiene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, as well as the compounds described in EP-A 50 265.

[0193] It is also possible to use what are known as graft-linking monomers, i.e., monomers with two or more polymerizable double bonds that react at different rates during polymerization. The use of compounds of this type is preferred, in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive group(s) polymerize, for example, significantly slower. The different polymerization rates result in a constant proportion of unsaturated double bonds in the rubber. If another phase is then grafted onto this type of rubber, at least some of the double bonds present in the rubber will react with the grafting monomer to form chemical bonds, i.e., the grafted phase will have at least some chemical bonding to the graft base.

[0194] Examples of this type of graft-linking monomer include monomers containing allyl groups, particularly allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, and diaryl itaconate, and the corresponding monoallyl compounds of these dicarboxylic acids. In addition, there are a wide variety of other suitable graft-linking monomers. For further details, reference may be made to, for example, U.S. Pat. No. 4,148,846.

[0195] The proportion of these crosslinking monomers in the impact-modified polymer is generally not more than 5% by weight, preferably not more than 3% by weight, based on the impact-modified polymer.

[0196] Some preferred emulsion polymers are listed below: Here, we may first mention graft polymers having a core and at least one shell and having the following structure:

[0197] [Table 1]

[0198] Instead of graft polymers with multiple shell structures, it is also possible to use homogeneous, i.e., single-shell, elastomers composed of 1,3-butadiene, isoprene, and n-butyl acrylate, or copolymers thereof. These products can also be prepared by using crosslinking monomers or monomers with reactive groups.

[0199] Examples of preferred emulsion polymers include n-butyl acrylate-(meth)acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core composed of n-butyl acrylate or based on butadiene and an outer jacket composed of the above copolymers, and copolymers of ethylene and comonomers providing reactive groups.

[0200] The described elastomers can also be prepared by other conventional processes, such as suspension polymerization.

[0201] Silicone rubbers, as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290, are also preferred.

[0202] Of course, it is also possible to use mixtures of the above-mentioned types of rubber.

[0203] UV stabilizers that may be mentioned, generally in amounts up to 2% by weight based on the molding composition, are various substituted resorcinols, salicylates, benzotriazoles, and benzophenones.

[0204] Materials which can be added as colorants are inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide and carbon black, and also organic pigments, such as phthalocyanines, quinacridones, perylenes, and also dyes, such as anthraquinones.

[0205] Materials that can be used as nucleating agents are sodium phenylphosphinate, aluminum oxide, silicon dioxide, and also preferably talc.

[0206] The thermoplastic molding composition may further comprise, as component F, a flame retardant.

[0207] As component F, the thermoplastic molding material can contain 1.0 to 10.0% by weight, preferably 2.0 to 6.0% by weight, in particular 3.0 to 5.0% by weight, of at least one phosphazene of the general formula (IX) or (X) as flame retardant.

[0208] The minimum amount of component F is at least 1.0% by weight, preferably 2.0% by weight, especially 3.0% by weight.

[0209] The maximum amount of component F is 10.0% by weight, preferably 6.0% by weight, particularly preferably 5.0% by weight.

[0210] "Phosphazene" means a cyclic phosphazene of the general formula (IX):

[0211] [ka] (wherein m is an integer of 3 to 25, and R 4 and R 4’ are the same or different, C1 to C 20 -Alkyl-, C6-C 30 -Aryl-, C6-C 30 -arylalkyl- or C6-C 30 -alkyl-substituted aryl), or a linear phosphazene of general formula (X)

[0212] [ka] (In the formula, n represents 3 to 1000, X represents -N=P(OPh)3 or -N=P(O)OPh, and Y represents -P(OPh)4 or -P(O)(OPh)2.) is understood to mean

[0213] The preparation of such phosphazenes is described in EP-A 0 945 478.

[0214] Particularly preferred are compounds of the formula P3N3C 36 or a linear phenoxyphosphazene of formula (XII).

[0215] [ka]

[0216] The phenyl radical may be optionally substituted. Phosphazenes in the context of the present application are described in Mark, JE, Allcock, HR, West, R., Inorganic Polymers, Prentice Hall, 1992, pp. 61-141.

[0217] Preferably used as component F are cyclic phenoxyphosphazenes having at least three phenoxyphosphazene units. Corresponding phenoxyphosphazenes are described, for example, in US 2010 / 0261818, paragraphs

[0051] to

[0053] . Reference may be made in particular to formula (I) therein. Corresponding cyclic phenoxyphosphazenes are further described in EP-A-2 100 919, in particular in paragraphs

[0034] to

[0038] therein. The preparation can be carried out as described in EP-A-2 100 919, in particular in paragraph

[0041] . In one embodiment of the present invention, the phenyl group in the cyclic phenoxyphosphazene is C 1~4 - may be substituted with alkyl radicals. Preferred when pure phenyl radicals are involved.

[0218] For a further description of cyclic phosphazenes, reference can be made to the keyword "phosphazene" in Roempp Chemie Lexikon, 9th Edition. Preparation can be carried out, for example, from PCl5 and NH4Cl. This is done via the obtainable cyclophosphazene, in which the chlorine groups in the cyclophosphazene are replaced by phenoxy groups by reaction with phenol.

[0219] Cyclic phenoxyphosphazene compounds can be prepared, for example, as described in Allcock, H.R., Phosphorus-Nitrogen Compounds (Academic Press, 1972), and Mark, J.E., Allcock, H.R., West, R., Inorganic Polymers (Prentice Hall, 1992).

[0220] Preferably, component F is 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 also be present, but in smaller amounts. A suitable cyclic phenoxyphosphazene is available from Fushimi Pharmaceutical Co., Ltd. under the trade name Lavitol® FP-100. It is a matte white / yellow solid with a melting point of 110°C, a phosphorus content of 13.4%, and a nitrogen content of 6.0%. The proportion of rings containing three phenoxyphosphazene units is at least 80.0% by weight.

[0221] The thermoplastic molding composition preferably comprises as flame retardant 1.0 to 6.0% by weight, preferably 2.5 to 5.5% by weight, in particular 3.0 to 5.0% by weight, of at least one aliphatic or aromatic ester of phosphoric or polyphosphoric acid.

[0222] For this reason, solid non-migrating phosphate esters with melting points between 70°C and 150°C are particularly preferred. This results in products that are easy to measure and exhibit significantly less migration in molding materials. Particularly preferred examples are the phosphate ester PX-200 (CAS: 139189-30-3) available from Daihachi Chemical Industry Co., Ltd., or Sol-DP available from ICL-IP. Further phosphate esters with appropriate substitution of the phenyl group are contemplated if this allows the desired melting range to be achieved. Depending on the substitution pattern at the ortho- or para-position on the aromatic ring, the general structural formula is as follows:

[0223] [ka]

[0224] (In the formula, R 1 is H, methyl, ethyl or isopropyl, preferably H, n is 0 to 7, preferably 0; R2~6 is H, methyl, ethyl or isopropyl, preferably methyl, and preferably R 6 is R 4 and R 5 is the same as m may be, but need not be, the same and is 1, 2, 3, 4, and 5, preferably 2; R'' is H, methyl, ethyl or cyclopropyl, preferably methyl and H).

[0225] A specific example is the PX-200.

[0226] [ka]

[0227] It is particularly preferred to use at least one aromatic ester of polyphosphoric acid, such as that available from Daihachi Chemical Industry Co., Ltd. under the trade name PX-200.

[0228] As component F, the thermoplastic molding composition according to the invention can comprise 5.0 to 30.0% by weight, preferably 10.0 to 25.0% by weight, in particular 12.0 to 20.0% by weight, for example about 16.0% by weight, of at least one metal phosphinate or phosphinate salt, which are described below as flame retardants.

[0229] The minimum amount of component D is 5.0% by weight, preferably 10.0% by weight, in particular 12.0% by weight.

[0230] The maximum amount of component F is 30.0% by weight, preferably 25.0% by weight, particularly preferably 20.0% by weight.

[0231] Preferred examples of the flame retardant of component F include metal phosphinates derived from hypophosphorous acid. For example, metal salts of hypophosphorous acid containing Mg, Ca, Al, or Zn as the metal can be used. Aluminum hypophosphite is particularly preferred here.

[0232] Phosphinates of formula (I) or / and diphosphinates of formula (II), or polymers thereof, are also suitable:

[0233] [ka]

[0234] (In the formula, R 1 , R 2 are the same or different and represent hydrogen, C1-C6-alkyl, linear or branched, and / or aryl, R 3 is C1~C 10 -Alkylene, linear or branched, C6-C 10 -arylene, -alkylarylene or -arylalkylene; M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, and / or a protonated nitrogen base; m is 1 to 4, n is 1 to 4, and x is 1 to 4, preferably m is 3 and x is 3).

[0235] Preferably, R 1 , R 2 are the same or different and represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl, n-pentyl and / or phenyl.

[0236] Preferably, R 3 represents methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene, phenylene or naphthylene; methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene; phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.

[0237] Particularly preferably, R 1 , R2 is hydrogen, methyl, or ethyl, and M is Al, with Al hypophosphite being particularly preferred.

[0238] The preparation of phosphinates is preferably carried out by precipitation of the corresponding metal salt from an aqueous solution.However, phosphinates can also be precipitated in the presence of inorganic metal oxides or sulfides (white pigments, such as TiO2, SnO2, ZnO, ZnS, SiO2) suitable as carrier materials.Therefore, this can provide surface-modified pigments that can be used as laser-mark flame retardants for thermoplastic polyesters.

[0239] It is preferred to use metal salts of substituted phosphinic acids in which, compared to hypophosphorous acid, one or two hydrogen atoms are replaced by phenyl, methyl, ethyl, propyl, isobutyl, or isooctyl, or the radical R'-CH-OH is replaced by R'-hydrogen, phenyl, or tolyl. The metals are preferably Mg, Ca, Al, Zn, Ti, or Fe. Aluminum diethylphosphinate (DEPAL) is particularly preferred.

[0240] For a description of phosphinates or diphosphinates, reference can be made to DE-A 199 60 671, as well as DE-A 44 30 932 and DE-A 199 33 901.

[0241] Further flame retardants are, for example, halogen-containing flame retardants.

[0242] Suitable halogen-containing flame retardants are preferably brominated compounds, such as brominated diphenyl ether, brominated trimethylphenylindane (FR 1808 from DSB), tetrabromobisphenol A and hexabromocyclododecane.

[0243] Suitable flame retardants are preferably brominated compounds, such as brominated oligocarbonates having the following structural formula (Great Lakes BC 52 or BC 58):

[0244] [ka]

[0245] Particularly suitable are polypentabromobenzyl acrylates (eg FR 1025 from ICL-IP) having the following formula, where n is greater than 4:

[0246] [ka]

[0247] Preferred brominated compounds further include oligomeric reaction products of tetrabromobisphenol A with epoxides (n>3) (eg, FR 2300 and 2400 from DSB) having the formula:

[0248] [ka]

[0249] Brominated oligostyrenes 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 osmometry in toluene. Cyclic oligomers are also suitable. In a preferred embodiment of the present invention, the brominated oligomeric styrenes have the formula I shown below:

[0250] [ka]

[0251] where R represents hydrogen or an aliphatic radical, in particular an alkyl radical, such as CH or C H , n represents the number of repeating chain building blocks, and R 1 may be H, or bromine, or a fragment of a common free radical former).

[0252] The value n may be 1 to 88, preferably 3 to 58. The brominated oligostyrene contains 40.0 to 80.0% by weight, preferably 55.0 to 70.0% by weight, of bromine. Products based on polydibromostyrene are preferred. This material is meltable without decomposition and is soluble, for example, in tetrahydrofuran. They can be prepared by ring bromination (optionally aliphatic hydrogenation) of styrene oligomers, such as those obtained by thermal polymerization of styrene (according to DT-OS 25 37 385), or by free-radical oligomerization of suitable brominated styrenes. Flame retardants can also be prepared by ionic oligomerization of styrene followed by subsequent bromination. The amount of brominated oligostyrene required to impart flame retardancy to polyamides depends on the bromine content. The bromine content in the molding materials according to the present invention is 2.0 to 30.0% by weight, preferably 5.0 to 12.0% by weight.

[0253] The brominated polystyrene according to the invention is typically obtained by the process described in EP-A 047 549.

[0254] [ka]

[0255] The brominated polystyrene obtainable by this process, and commercially available brominated polystyrenes, are primarily ring-substituted tribrominated products, with n' (see III) generally having a value of 125 to 1500, corresponding to a molecular weight of 42,500 to 235,000, preferably 130,000 to 135,000.

[0256] The bromine content (based on the content of ring-substituted bromine) is generally at least 50.0% by weight, preferably at least 60.0% by weight, especially 65.0% by weight.

[0257] Commercially available powdered products generally have glass transition temperatures between 160°C and 200°C and are available, for example, from Albemarle under the tradename SAYTEX® HP-7010 and from Ferro Corporation under the tradename Pyrocheck® PB 68.

[0258] Mixtures of brominated oligostyrenes and brominated polystyrenes can also be used in the molding compositions according to the invention, the mixing ratios of which can be freely selected.

[0259] Chlorine-containing flame retardants are also suitable, with Declorane Plus® from OxyChem being preferred.

[0260] Preferably, suitable halogen-containing flame retardants are ring-brominated polystyrene, brominated polybenzyl acrylate, brominated bisphenol A epoxide oligomer or brominated bisphenol A polycarbonate.

[0261] In one embodiment of the invention, the thermoplastic molding compositions according to the invention are free of halogen-containing flame retardants.

[0262] Flame-retardant melamine compounds suitable as component F in the context of the present invention are melamine compounds which, when added to glass-fiber-filled polyamide molding compositions, reduce the flammability and influence the fire behavior in a flame-retardant manner, resulting in improved properties in the UL 94 test and the glow-wire test.

[0263] The melamine compound is, for example, selected from melamine borate, melamine phosphate, melamine sulfate, melamine pyrophosphate, melam, melem, melon or melamine cyanurate, or mixtures thereof.

[0264] Melamine cyanurates which are preferentially suitable according to the invention are reaction products of preferably equimolar amounts of melamine (formula I) and cyanuric acid / isocyanuric acid (formulas Ia and Ib).

[0265] [ka]

[0266] For example, it can be obtained by reacting an aqueous solution of the starting compounds at 90-100°C. Commercially available products have an average particle size d of 1.5-7 μm. 50 and d less than 50 μm 99 It is a white powder having a value of

[0267] Further suitable compounds (often also referred to as salts or adducts) are melamine sulfate, melamine, melamine borate, oxalate, phosphate primary, phosphate secondary and pyrophosphate secondary, melamine neopentyl glycol borate. According to the invention, the molding material preferably does not contain polymeric melamine phosphate (CAS No. 56386-64-2 or 218768-84-4).

[0268] This is understood to mean a melamine polyphosphate salt of a 1,3,5-triazine compound having an average condensation degree n of 20 to 200 and a 1,3,5-triazine content of 1,3,5-triazine compounds selected from the group consisting of melamine, melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, and diaminophenyltriazine per mole of phosphorus atom of 1.1 to 2.0 moles per mole of phosphorus atom. Preferably, the n value of such salts is generally 40 to 150, and the ratio of 1,3,5-triazine compounds per mole of phosphorus atom is preferably 1.2 to 1.8. Furthermore, the pH of a 10% by weight aqueous slurry of the salt prepared according to EP-B1 095 030 is generally above 4.5, preferably at least 5.0. The pH is typically determined by adding 25 g of salt and 225 g of purified 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, i.e., the number-average degree of condensation, can be determined by P solid-state NMR. J.R. van Wazer, C.F. Callis, J. Shoolery, and R. Jones, J. Am. Chem. Soc., 78, 5715, 1956, discloses that the number of adjacent phosphate groups gives unique chemical shifts that clearly distinguish between orthophosphate, pyrophosphate, and polyphosphate.

[0269] Suitable guanidine salts are: g carbonate (CAS number: 593-85-1), g Cyanurate prim. (CAS number: 70285-19-7), g phosphate prim. (CAS number: 5423-22-3), g phosphate sec. (CAS number: 5423-23-4), g sulfate prim. (CAS number: 646-34-4), g sulfate sec. (CAS number: 594-14-9), Guanidine pentaerythritol borate (no CAS number), Guanidine neopentyl glycol borate (no CAS number), and Urea phosphate green (CAS number: 4861-19-2), Urea cyanurate (CAS number: 57517-11-0), Ammeline (CAS number: 645-92-1), Ammelide (CAS number: 645-93-2), Melem (CAS number: 1502-47-2), Melon (CAS number: 32518-77-7).

[0270] In the context of the present invention, "compound" is understood to mean, for example, benzoguanamine itself and its adducts / salts, but also nitrogen-substituted derivatives and their adducts / salts.

[0271] Also, ammonium polyphosphate (NH4PO3) n wherein n is about 200 to 1000, preferably 600 to 800, and tris(hydroxyethyl)isocyanurate (THEIC) of formula IV,

[0272] [ka]

[0273] or aromatic carboxylic acids Ar(COOH), which may optionally be present in admixture with one another. m wherein Ar represents a monocyclic, bicyclic or tricyclic aromatic six-membered ring system and m is 2, 3 or 4, and reaction products thereof are also suitable.

[0274] Examples of suitable carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, mellophanic acid, prenitic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalenedicarboxylic acid, and anthracenecarboxylic acid.

[0275] The preparation is carried out according to the process of EP-A 584 567 by reaction of tris(hydroxyethyl)isocyanurate with an acid, its alkyl ester or its halide.

[0276] Such reaction products are mixtures of monomeric and oligomeric esters, which may be crosslinked. The degree of oligomerization is typically 2 to about 100, preferably 2 to 20. The THEIC and / or its reaction products are preferably mixed with phosphorus-containing nitrogen compounds, particularly (NH4PO3) n It is also preferred to use a mixture with melamine pyrophosphate or polymeric melamine phosphate, for example (NH4PO3) n and THEIC in a mixing ratio of 90.0-50.0:10.0-50.0, particularly 80.0-50.0:50.0-20.0, and the mass % is based on the mixture of such compounds.

[0277] Also suitable flame retardants are benzoguanidine compounds of formula V:

[0278] [ka]

[0279] where R, R' represent linear or branched alkyl radicals having 1 to 10 carbon atoms, preferably hydrogen, in particular adducts with phosphate, borate and / or pyrophosphate.

[0280] An allantoin compound of formula VI,

[0281] [ka]

[0282] where R, R' are as defined in formula V, and also their salts with phosphoric acid, boric acid and / or pyrophosphoric acid, and also glycolurils of formula VII, or their salts with the abovementioned acids, are preferred.

[0283] [ka]

[0284] where R is as defined in Formula V.

[0285] Suitable products are commercially available or can be obtained according to DE-A 196 14 424.

[0286] Cyanoguanidines (formula VIII) that can be used according to the invention can be obtained, for example, by reacting calcium cyanamide with carbonic acid, and the resulting cyanamide dimerizes at pH 9 to pH 10 to give cyanoguanidine.

[0287] [ka]

[0288] The commercially available product is a white powder with a melting point of 209°C to 211°C.

[0289] It is particularly preferred to use melamine cyanurate (for example Melapur® MC25 from BASF SE).

[0290] It is also possible to use separate metal oxides such as antimony trioxide, antimony pentoxide, sodium antimonate and similar metal oxides, however it is preferable to avoid using such metal oxides since they are already present in component F. For a description of pentabromobenzyl acrylate and antimony trioxide or antimony pentoxide, reference can be made to EP-A 0 624 626.

[0291] It is also possible to use phosphorus, for example red phosphorus, as a flame retardant, which can be used, for example, in the form of a masterbatch.

[0292] Dicarboxylic acids of the formula:

[0293] [ka]

[0294] (In the formula, R 1 ~R 4 represent, independently of one another, halogen or hydrogen, provided that at least one radical R 1 ~R 4 represents a halogen, x is 1 to 3, preferably 1 or 2; m is 1 to 9, preferably 1 to 3, 6, or 9, particularly 1 to 3; n is 2 to 3, M is an alkaline earth metal, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg).

[0295] Preferred dicarboxylates are those containing the radical R 1 ~R 4 are independently of one another Cl or bromine or hydrogen, particularly preferably all radicals R 1 ~R 4 Includes those where is Cl and / or Br.

[0296] The metal M is preferably Be, Mg, Ca, Sr, Ba, Al, Zn, or Fe.

[0297] Such dicarboxylates are commercially available or can be prepared according to the process described in US Pat. No. 3,354,191.

[0298] Functional polymers can also be used as component F. These may be, for example, flame-retardant polymers. Such polymers are described, for example, in US Pat. No. 8,314,202 and contain 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone repeating units. A further suitable functional polymer for increasing the amount of carbon residues is poly(2,6-dimethyl-1,4-phenylene oxide) (PPPO).

[0299] The thermoplastic molding compositions of the present invention can be produced by processes known per se, by mixing the starting components in conventional mixing equipment, such as a screw extruder, a Brabender mixer, or a Banbury mixer, and then extruding. After extrusion, the extrudate 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 between 230 and 320°C.

[0300] These materials are suitable for the production of any type of fiber, foil, and molded article, some examples include: cylinder head covers, motorcycle covers, intake manifolds, intercooler caps, plug connectors, gear wheels, cooling fan wheels, and cooling water tanks.

[0301] In the electrical and electronics fields, improved-flow polyamides 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 connections, terminal blocks, connector plugs, device connectors, cable harness components, circuit mounts, circuit mount components, three-dimensional injection molded circuit mounts, electrical connection elements, and mechatronic components.

[0302] Possible uses in automotive interiors are dashboards, steering column switches, seat components, headrests, center consoles, gearbox components, and door modules, and possible uses in automotive exteriors are 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 parts.

[0303] The combination of components B, C, and preferably D provides an efficient system for stabilizing polyamides above 180°C while maintaining a completely metal halide-free system.

[0304] In a preferred embodiment, the thermoplastic molding composition is completely halide-free and therefore also free of halogen-containing flame retardants.

[0305] In particular, the combination of a specific high-molecular-weight phenol-based radical scavenger and high-molecular-weight EVOH, optionally in combination with a high-molecular-weight polyacid, has proven to be an effective system for stabilizing polyamides. This additive does not come to the surface even when absorbing moisture or under electrical tension, thus preventing contamination and corrosion of electrical components. [Example]

[0306] The following ingredients were used: PA1: Polyamide-6 (Ultramid® B27 from BASF SE) having a viscosity number of 150 ml / g, measured in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25°C according to ISO 307, and a melting point of 220°C; PA2: Polyamide-66 (Ultramid® A27 from BASF SE) having a viscosity number of 150 ml / g, measured in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25°C according to ISO 307, and a melting point of 260°C. PA3: Polyamide 66 / 6 (Ultramid® C27 from BASF SE) having a viscosity number of 150 ml / g, measured in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25°C according to ISO 307, and a melting point of 195°C. GF: Standard E glass fiber, NEG E T249H, Lubricant: ethylene bisstearamide (EBS) from Lonza Cologne GmbH; Stabilizer 1a: Cuprous iodide (CAS: 7681-65-4) Stabilizer 1b: Potassium iodide (CAS: 7681-11-0) Stabilizer 2: EVOH (ethylene vinyl alcohol copolymer; CAS: 25067-34-9) with an ethylene content of 20% to 50%; Stabilizer 3: Irganox® 1010 from BASF SE; Stabilizer 4: Trilon® P from BASF SE; Stabilizer 5: DPE (dipentaerythritol, CAS: 126-58-9), Stabilizer 6: Iron powder (CAS: 7439-89-6), Colorant: Solvent Black 7 (CAS: 8005-02-5)

[0307] Preparation of granules Natural-colored polyamide granules were dried in a drying oven at 100°C for 4 hours to a humidity of less than 0.1%. Molding compositions were then prepared by melt-kneading. The components were mixed in a twin-screw extruder with a diameter of 25 mm and an L / D ratio of 36. Processing conditions were set at 16 kg / h and 260-330°C, employing a flat temperature profile depending on the base resin. The resulting extrudate was cooled and granulated.

[0308] The resulting granules were used for injection-molding tensile bars or plaques according to ISO 527-2 and Charpy sticks according to ISO 179-1. Molding temperatures, depending on the base resin, were 280-330°C melt temperature and 80-120°C mold temperature. The compositions and mechanical data of examples of the present invention (INV) and comparative examples (COMP) are shown in Tables 1 and 2 below.

[0309] The tensile modulus, tensile stress at break, and tensile strain at break were determined according to ISO 527. The Charpy (notched) impact strength was determined according to ISO 179-2 / 1eU and ISO 179-2 / 1eAf, respectively. The melting point and crystallization temperature were determined according to ISO 11357. All standards refer to the versions valid for 2020.

[0310] Heat aging experiments were performed using a standard laboratory oven at elevated temperatures and in air as shown in the table below. The retention of tensile strength and elongation at break after heat aging of the non-heat aged control specimens was considered to be 100% compared to the values ​​of unused specimens.

[0311] Example COMP2 is based on US 2010 / 0028580 A. For Example COMP2, migration of low molecular weight additives has been reported in the literature (EP 2 896 656 A1). For Examples COMP1, INV1, and INV2, no migration was observed under the test conditions. Additive migration or bleed-out was tested by injection molding 60 x 60 x 2 mm plaques at temperatures of 280°C / 80°C for PA6 and 290°C / 80°C for PA66. The resulting plaques were stored in an oven at 100°C and atmospheric pressure for 144 hours. Migration occurred, and in the case of low molecular weight additives such as DPE, a white powder was observed on the surface of the plaques.

[0312] After heat aging under the specified conditions, soot production was determined visually. As a more quantitative approach, the mass loss of molded plaques with dimensions of 60 × 60 × 2 mm and 60 × 60 × 1 mm was determined on a balance before and after accelerated heat aging at 200 °C for 1000 h.

[0313] [Table 2]

[0314] [Table 3]

[0315] The above examples show that by using Stabilizer 2 (a polyhydric alcohol derived from Component B) and Stabilizer 3 (a sterically hindered phenol antioxidant derived from Component C), it is possible to obtain a polyamide molding composition that exhibits high retention of tensile strength and elongation at break even after long-term heat treatment. Furthermore, by further using Stabilizer 4, which is a polycarboxylic acid compound of Component D, the heat aging resistance of the polyamide molding composition can be further improved (see Examples INV2, INV4, and INV5).

Claims

1. 1. A thermoplastic molding composition comprising: a) as component A, 30 to 99.84% by weight of at least one thermoplastic polyamide, b) as component B, 0.1 to 10% by weight of hydroxyl groups having more than 6 groups and a number average molecular weight M of more than 2000 g / mol ｎ at least one polyhydric alcohol having the formula c) as component C, 0.05 to 3% by weight of at least one sterically hindered phenol antioxidant; d) as component D, 0.01 to 3% by weight of polyethyleneimine having more than three carboxylic acid and / or carboxylate groups and N-substituted by acetic acid or acetate groups and having a number average molecular weight M of more than 500 g / mol ｎ at least one polycarboxylic acid compound having the formula e) as component E, 0 to 50% by weight of at least one fibrous and / or particulate filler, f) 0 to 25% by weight of further additives as component F Including, A thermoplastic molding composition, wherein the sum of the weight percent of components A to F is 100 weight percent.

2. 2. The thermoplastic molding composition of claim 1, wherein component B has more than 8 hydroxyl groups.

3. Component B has a number average molecular weight M of more than 3000 g / mol ｎ 3. The thermoplastic molding composition according to claim 1, wherein

4. 4. Thermoplastic molding composition according to claim 1, wherein component B is an ethylene-vinyl alcohol copolymer having an ethylene unit content of 10 to 60 mol %.

5. 5. The thermoplastic molding composition according to claim 1, wherein component C has a molecular weight of more than 500 g / mol.

6. Component D has a number average molecular weight M of more than 1000 g / mol ｎ 6. The thermoplastic molding composition according to claim 1, wherein 7. Thermoplastic molding composition according to any one of claims 1 to 5, wherein component D has a number average molecular weight M n of more than 2000 g / mol.

8. A thermoplastic molding composition according to any one of claims 1 to 7, wherein component D has more than 8 carboxylic acid groups and / or carboxylate groups.

9. Component C is at least one branched C ３～１２ 9. The thermoplastic molding composition according to claim 1, wherein the phenol group is substituted with at least one alkyl group.

10. 10. Thermoplastic molding composition according to any one of claims 1 to 9, wherein component D is present in an amount of 0.1 to 2% by weight.

11. 11. Thermoplastic molding composition according to any one of claims 1 to 10, wherein component E comprises glass fibres and is present in an amount of 10 to 50% by weight.

12. A method for preparing a thermoplastic molding composition according to any one of claims 1 to 11 by mixing components A to F.

13. 12. Use of the thermoplastic molding composition according to any one of claims 1 to 11 for producing any type of fibre, foil and moulded article.

14. 12. Fibers, foils or moldings made from the thermoplastic molding composition according to any one of claims 1 to 11.

15. b) as component B, 0.1 to 10 parts by weight of a copolymer having more than 6 hydroxyl groups and a number average molecular weight M of more than 2000 g / mol ｎ at least one polyhydric alcohol having the formula c) as component C, 0.05 to 3 parts by weight of at least one sterically hindered phenol antioxidant; d) as component D, 0.01 to 3 parts by weight of polyethyleneimine having more than three carboxylic acid and / or carboxylate groups and N-substituted by acetic acid or acetate groups and having a number average molecular weight M of more than 500 g / mol ｎ at least one polycarboxylic acid compound having the formula A mixture comprising or consisting of:

16. 16. The mixture of claim 15, wherein the amount of component D is 0.1 to 2 parts by weight.

17. 17. Use of a mixture according to claim 15 or 16 in a thermoplastic molding composition containing polyamide to improve its heat ageing resistance.

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