Aliphatic copolyamide composition

Abstract

1. A polymer blend comprising: a) as component A) >50% to 99% by weight of at least one aliphatic copolyamide; b) as component B 1% to <50% by weight of at least one semicrystalline, semi-aromatic or aromatic polyamide, wherein the sum of the weight percentages of components A and B is 100% by weight; thermoplastic molding compositions comprising said polymer blend and at least one additional substance C), methods for producing said polymer blend and said thermoplastic molding composition, use of said polymer blend and said thermoplastic molding composition for producing molded and extruded articles, and molded and extruded articles produced from said polymer blend or said thermoplastic molding composition, wherein the sum of the weight percentages of components A and B is 100% by weight; thermoplastic molding compositions comprising said polymer blend and at least one additional substance C), methods for producing said polymer blend and said thermoplastic molding composition, use of said polymer blend and said thermoplastic molding composition for producing molded and extruded articles, and molded and extruded articles produced from said polymer blend or said thermoplastic molding composition.

Description

[Technical field]

[0001] The present invention relates to a polymer blend comprising at least one aliphatic copolyamide and at least one semicrystalline, semi-aromatic or aromatic polyamide, to a thermoplastic molding composition comprising said polymer blend and at least one additional substance, and to the use of said polymer blend or said thermoplastic molding composition for producing molded and extruded articles.

[0002] Aliphatic copolyamide PA6 / 6.36 can be obtained by copolymerization of caprolactam, HMD and aliphatic C36 dicarboxylic acid. PA6 / 6.36 is partially based on renewable resources, has reduced water absorption compared to standard polyamides such as PA6 or PA66, and shows good resistance to aqueous media, such as salt solutions. PA6 / 6.36 is used for film and sheet extrusion. However, the aliphatic copolyamide seems to be sticky, which can cause problems during injection molding and pipe extrusion processes. Furthermore, the aliphatic copolyamide seems to lose rigidity during conditioning in standard atmosphere.

[0003] The problem underlying the present invention is to provide a polyamide composition which has the advantageous properties of aliphatic copolyamides, in particular the copolyamide PA6 / 6.36, on the other hand an excellent performance profile, such as higher stiffness in the conditioned state, which composition is particularly suitable for molding processes, such as injection molding and pipe extrusion.

[0004] By providing a polymer blend comprising an aliphatic copolyamide and a semi-crystalline semi-aromatic or aromatic polyamide, a polyamide compound is obtained which has a superior performance profile compared to polyamide compounds based on polymer blends comprising a non-semi-crystalline semi-aromatic or aromatic polyamide and an aliphatic copolyamide, and which is highly suitable for injection molding and pipe extrusion processes.

[0005] Blends of aliphatic and aromatic polyamides are known.

[0006] Xanthos et al., Journal of Applied Polymer Science, Vol. 62, 1167-1177 (1996), describes blends of polyamide 6 (N6) with amorphous aromatic polyamide PA6I / 6T (Zytel-330 (2-330)) (AmArPA). Blends of various compositions have been extrusion compounded and injection molded with impact-modifying reactive elastomers. The relationship of blend morphology, blend components, structure and reactivity, and processing conditions to final properties is discussed.

[0007] Huang et al., Polymer 47 (2006) 624-638, studied the distribution of impact modifiers in blends of polyamide 6 (nylon 6) and the amorphous aromatic polyamide PA6I / 6T (Zytel 330) (AmArPA).

[0008] WO2007 / 041723 A1 describes a copolyamide composition for marine umbilicals, obtained by copolymerization of aromatic dicarboxylic acids, diamines and aliphatic dicarboxylic acids. A preferred copolyamide comprises repeat units (a) derived from terephthalic acid and hexamethylenediamine, and repeat units (b) derived from decanedioic acid and / or dodecanedioic acid and hexamethylenediamine.

[0009] WO 2019 / 057849 A1 relates to a heat-resistant polyamide composition comprising a copolyamide and an anhydride-functional polymer. The copolyamide comprises the reaction product of at least one lactam with a monomer mixture. The monomer mixture comprises at least one C 32 ~C 40 -dimer acid, and at least one C4-C 12 -Contains diamines.

[0010] US 2015 / 344686 relates to prepregs that can be used to obtain fiber-reinforced composite materials that are stable and exhibit excellent interlaminar fracture toughness and impact resistance under a wide range of molding conditions.

[0011] International Publication No. 2021 / 003047 (WO 2021 / 003047 A1) relates to prepregs that can be cured / molded to form aerospace composite parts.

[0012] None of WO 2019 / 057849, US 2015 / 344686 and WO 2021 / 003047 disclose blends that contain more than 50 wt. % of at least one aliphatic copolyamide plus at least 1 wt. % of at least one polyamide that is semi-crystalline and simultaneously semi-aromatic or aromatic.

[0013] However, the polymer blends of aliphatic polyamides and amorphous aromatic polyamides disclosed in the prior art do not sufficiently achieve the above-mentioned objectives.

[0014] The above problem is solved according to the present invention. a) from more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A); b) 1% by weight to less than 50% by weight of at least one semicrystalline, semiaromatic or aromatic polyamide as component B Including, wherein the sum of the weight percent of components A and B is 100 weight percent; This is achieved by polymer blending.

[0015] The invention also relates to a thermoplastic molding composition comprising said polymer blend and at least one additional substance C.

[0016] The invention also relates to a process for preparing said polymer blend by mixing components A and B.

[0017] The invention also relates to the use of these polymer blends or these thermoplastic molding compositions for producing all types of moldings, sheets, films, tubes and pipes.

[0018] The invention further relates to moulded articles, sheets, films, tubes or pipes made from these polymer blends or from these thermoplastic moulding compositions.

[0019] According to the invention, it has been found that the combination of an aliphatic copolyamide with a semi-crystalline semi-aromatic or aromatic polyamide achieves the above objectives.

[0020] The blends of the invention and the thermoplastic molding compositions of the invention are particularly characterized by one or more of the following properties: high stability against zinc chloride and AdBlue, high heat distortion temperature, high tensile modulus in dry and conditioned state, high stiffness in conditioned state, low water absorption, high barrier properties against fuels. The blends of the invention show improved processing properties in pipe and sheet extrusion and injection molding processes. Through this blending approach, the material can be easily removed from the injection molding machine and shows almost no tendency to stick to the nozzle compared to pure aliphatic copolyamides.

[0021] The blends according to the invention and the thermoplastic molding compositions according to the invention are useful in a wide range of applications, in particular in the field of engineering plastics in contact with fluids, such as coolants, brake and clutch fluids, chemicals (AdBlue), fuels and / or salts, in particular in the automotive industry, for example in extruded tubes (e.g. fluid pipes for fuels or coolants in cars), mandrels and injection molded articles, such as functional parts for sensors of engines (e.g. wheel speed sensors), pumps, connectors or injection molded or extruded parts for fuel cells.

[0022] blend The amount of component A) in the blends of the present invention is >50-99% by weight, preferably 55-97% by weight, more preferably 60-95% by weight.

[0023] The amount of component B) in the blends of the present invention is from 1 to <50% by weight, preferably from 3 to 45% by weight, more preferably from 5 to 40% by weight.

[0024] The sum of the weight percent of components A and B is 100 weight percent.

[0025] Preferably, component A) forms the continuous phase.

[0026] The weight ratio of component A) to component B) is preferably from 1.1:1 to 15:1, more preferably from 1.3:1 to 12:1, most preferably from 1.5:1 to 10:1, especially from 1.7:1 to 9:1.

[0027] Component B) Component B) is at least one semicrystalline semiaromatic or aromatic polyamide. Suitable semicrystalline semiaromatic or aromatic polyamides are known in the art. Preferably, the at least one semicrystalline polyamide of component B is semiaromatic and / or a copolyamide, more preferably, the at least one polyamide of component B is a semicrystalline semiaromatic copolyamide. Suitable semicrystalline semiaromatic copolyamides are disclosed, for example, in EP 0 299 222 A, EP 0 667 367 A and US 2012 / 0245283.

[0028] In general, the semicrystalline, semiaromatic copolyamides are copolymers prepared from the condensation of aliphatic amides, such as caprolactam and / or hexamethylenediamine, with aromatic dicarboxylic acids or aromatic dicarboxylic acid derivatives, such as terephthalic acid and / or isophthalic acid, i.e. these polyamides are partially aromatic polyamides.

[0029] More preferably, component B) is at least one semi-crystalline, semi-aromatic polyamide containing repeat units of hexamethylenediamine and terephthalic acid. Preferably, component B) contains 45-95% by weight, more preferably 60-80% by weight, most preferably 65-75% by weight of repeat units of hexamethylenediamine and terephthalic acid. The remainder may be aliphatic polyamide repeat units, such as caprolactam or hexamethylene adipamide, or semi-aromatic repeat units, such as polyamide 6I.

[0030] Preferably, component B) has a viscosity number VN of 60 to 200 ml / g, more preferably 70 to 140 ml / g.

[0031] In a further preferred embodiment, said at least one polyamide of component B has a melting point >250°C.

[0032] Most preferably, said at least one thermoplastic semi-aromatic semi-crystalline polyamide B) is selected from polyamide 6T / 6, polyamide 6T / 66, polyamide 6T / 6I and mixtures thereof.

[0033] Component A) Component A) is at least one aliphatic copolyamide. Suitable aliphatic copolyamides are known in the art.

[0034] Preferably, the aliphatic copolyamide of component A has a melting point of <220°C.

[0035] More preferably, said at least one copolyamide of component A) comprises the following components: A') 15% to 84% by weight of at least one lactam, B') The following ingredients B1') at least one type of C 32 ~C 40 Dimer acid and B2') At least one C4-C 12 Diamine Monomer mixture (M) containing 16% by weight to 85% by weight It is produced by polymerization of Here, the weight percentages of components A') and B') are based on the sum of the weight percentages of components A') and B'), respectively.

[0036] In the context of the present invention, the terms "component A')" and "at least one lactam" are used synonymously and therefore have the same meaning.

[0037] The same applies to the terms "component B')" and "monomer mixture (M)", which terms are likewise used synonymously in the context of the present invention and therefore have the same meaning.

[0038] According to the invention, the at least one copolyamide is prepared by polymerizing 15 to 84% by weight of component A') and 16 to 85% by weight of component B'), preferably by polymerizing 40 to 83% by weight of component A') and 17 to 60% by weight of component B'), and particularly preferably by polymerizing 60 to 80% by weight of component A') and 20 to 40% by weight of component B'), where the weight percentages of components A') and B'), respectively, are based on the sum of the weight percentages of components A') and B').

[0039] The sum of the weight percentages of components A') and B') is preferably 100% by weight.

[0040] It is understood that the weight percentages of components A') and B') refer to the weight percentages of components A') and B') prior to the polymerization, i.e., when components A') and B') have not yet reacted with one another. During the polymerization of components A') and B'), the weight ratio of components A') and B') may optionally vary.

[0041] The at least one copolyamide of component A) is produced by polymerization of components A') and B'). The polymerization of components A') and B') is known to those skilled in the art. The polymerization of components A') and B') is typically a condensation reaction. During the condensation reaction, component A') reacts with components B1') and B2') present in component B') and optionally with component B3'), which will be described below and may also be present in component B'). This results in amide bonds forming between the individual components. During the polymerization, component A') is typically at least partially in open-chain form, i.e. in the form of amino acids.

[0042] The polymerization of components A') and B') may be carried out in the presence of a catalyst. Suitable catalysts include any catalyst known to those skilled in the art that catalyzes the polymerization of components A') and B'). Such catalysts are known to those skilled in the art. Preferred catalysts are phosphorus compounds, such as sodium hypophosphite, phosphorous acid, triphenylphosphine or triphenylphosphite.

[0043] The polymerization of components A') and B') forms said at least one copolyamide, which therefore comprises units derived from component A') and units derived from component B'), the units derived from component B') comprising units derived from components B1') and B2') and optionally from component B3').

[0044] The polymerization of the components A') and B') forms the copolyamide as a copolymer. The copolymer may be a random copolymer. The copolymer may also be a block copolymer.

[0045] In a block copolymer, a block of units derived from component B') and a block of units derived from component A') are formed. These occur in an alternating order. In a random copolymer, the units derived from component A') alternate with those derived from component B'). The alternation is random. For example, two units derived from component B') may be followed by one unit derived from component A'), which in turn is followed by a unit derived from component B'), and then a unit comprising three units derived from component A').

[0046] The preparation of said at least one copolyamide preferably comprises the following steps: I) polymerizing said components A') and B') to obtain at least a first copolyamide; II) pelletizing the at least one first copolyamide obtained in step I) to obtain at least one pelletized copolyamide; III) extracting the at least one pelletized copolyamide obtained in step II) with water to obtain at least one extracted copolyamide; IV) drying the at least one extracted copolyamide obtained in step III) at a temperature (TT) to obtain said at least one copolyamide; IV) drying the at least one extracted copolyamide obtained in step III) at a temperature (TT) to obtain said at least one copolyamide.

[0047] The polymerization in step I) above may be carried out in any reactor known to those skilled in the art. Preference is given to stirred tank reactors. It is also possible to improve the reaction conditions by using auxiliaries known to those skilled in the art, such as antifoaming agents, for example polydimethylsiloxane (PDMS).

[0048] In step II), the at least one first copolyamide obtained in step I) may be pelletized by any method known to the person skilled in the art, for example by strand pelletization or underwater pelletization.

[0049] The extraction in step III) above may be carried out by any method known to those skilled in the art.

[0050] During the extraction in said step III), by-products typically formed during the polymerization of the components A') and B') in step I) are extracted from said at least one pelletized copolyamide.

[0051] In step IV) the at least one extracted copolyamide obtained in step III) is dried. Methods of drying are known to those skilled in the art. According to the invention, said at least one extracted copolyamide is dried at a temperature (T T ) is dried at the temperature (T T ) is preferably the glass transition temperature (T G(C) ) and the melting temperature (T M(C) ) below.

[0052] The drying in said step IV) is typically carried out for a period in the range of from 1 to 100 hours, preferably in the range of from 2 to 50 hours and particularly preferably in the range of from 3 to 40 hours.

[0053] It is believed that the drying in step IV) further increases the molecular weight of the at least one copolyamide.

[0054] The at least one copolyamide of component A) above - without the addition of component B) - typically has a glass transition temperature (T G(C) The glass transition temperature (T G(C) ) is determined according to ISO 11357-2:2014 and is, for example, in the range of 20°C to 50°C, preferably in the range of 23°C to 50°C and particularly preferably in the range of 25°C to 50°C.

[0055] In the context of the present invention, the glass transition temperature (T G(C)) is the glass transition temperature (T G(C) ) is the standard.

[0056] In the context of the present invention, "dry" should be understood to mean that the at least one copolyamide contains less than 1% by weight, preferably less than 0.5% by weight and especially preferably less than 0.1% by weight of water, based on the total weight of the at least one copolyamide. More preferably, "dry" should be understood to mean that the at least one copolyamide is free of water and most preferably that the at least one copolyamide is free of solvent.

[0057] Moreover, the at least one copolyamide typically has a melting temperature (T M(C) The at least one copolyamide has a melting temperature (T M(C) ) is, for example, in the range of 150 to 210°C, preferably in the range of 160 to 205°C and particularly preferably in the range of 160 to 200°C, as determined in accordance with ISO 11357-3:2014.

[0058] The at least one copolyamide generally has a viscosity number (VN) in the range of 150 to 300 ml / g, determined in a 0.5% by weight solution of the at least one copolyamide in a mixture of phenol / o-dichlorobenzene in a weight ratio of 1:1. (C) ).

[0059] The viscosity number (VN) of said at least one copolyamide (C) ), determined in a 0.5% by weight solution of said at least one copolyamide in a mixture of phenol / o-dichlorobenzene in a weight ratio of 1:1, is preferably in the range of 160 to 290 mL / g and particularly preferably in the range of 170 to 280 mL / g.

[0060] Component A') According to the invention, said component A') is at least one lactam.

[0061] In the context of the present invention, "at least one lactam" is understood to mean either exactly one lactam or a mixture of two or more lactams.

[0062] Lactams are known per se to those skilled in the art. Preferred according to the invention are lactams having 4 to 12 carbon atoms.

[0063] In the context of the present invention, "lactam" is to be understood as meaning a cyclic amide having preferably 4 to 12 carbon atoms, particularly preferably 5 to 8 carbon atoms, in the ring.

[0064] Suitable lactams are, for example, 3-aminopropanolactam (propio-3-lactam; β-lactam; β-propiolactam), 4-aminobutanolactam (butyro-4-lactam; γ-lactam; γ-butyrolactam), aminopentanolactam (2-piperidinone; δ-lactam; δ-valerolactam), 6-aminohexanolactam (hexano-6-lactam; ε-lactam; ε-caprolactam), 7-aminoheptanolactam (heptano-7-lactam; ζ-lactam; ζ-heptanolactam), 8-aminooctanolactam (octano-8-lactam; eta-lactam; eta-octanolactam), 9-aminononanolactam (nonano-9-lactam; θ-lactam; θ-nonanolactam), 10-aminodecanolactam (decano-10-lactam; ω-decanolactam), 11-aminoundecanolactam (undecano-11-lactam; ω-undecanolactam) and 12-aminododecanolactam (dodecano-12-lactam; ω-dodecanolactam).

[0065] Therefore, the present invention also provides a process, wherein the component A') is selected from the group consisting of 3-aminopropanolactam, 4-aminobutanolactam, 5-aminopentanolactam, 6-aminohexanolactam, 7-aminoheptanolactam, 8-aminooctanolactam, 9-aminononanolactam, 10-aminodecanolactam, 11-aminoundecanolactam and 12-aminododecanolactam.

[0066] The lactam may be unsubstituted or at least monosubstituted. When at least monosubstituted lactams are used, the nitrogen atom and / or ring carbon atoms may be C1-C 10 Alkyl, C5-C6 cycloalkyl, and C5-C 10 It may have one, two or more substituents independently selected from the group consisting of aryl.

[0067] Suitable C1~C 10 Examples of suitable C5-C6-cycloalkyl substituents are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. Examples of suitable C5-C6-cycloalkyl substituents are cyclohexyl. 10 The aryl substituent is phenyl or anthranyl.

[0068] It is preferred to use unsubstituted lactams, with γ-lactam (γ-butyrolactam), δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam) being preferred. Particularly preferred are δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam), with ε-caprolactam being especially preferred.

[0069] Monomer Mixture (M) According to the invention, the component B') is a monomer mixture (M). The monomer mixture (M) comprises the component B1'), i.e. at least one C 32 ~C 40 dimer acid, and B2'), i.e. at least one C4-C 12 Contains diamine.

[0070] In the context of the present invention, a monomer mixture (M) is to be understood as meaning a mixture of two or more monomers, where at least components B1') and B2') are present in the monomer mixture (M).

[0071] In the context of the present invention, the terms “component B1′)” and “at least one C 32 ~C 40 The terms "component B2')" and "at least one C4-C dimer acid" are used interchangeably and therefore have the same meaning. 12 The term "diamine" applies to the term "diamines". These terms are likewise used synonymously in the context of the present invention and therefore have the same meaning.

[0072] The monomer mixture (M) contains, for example, component B1') in the range of 45 to 55 mol % and component B2') in the range of 45 to 55 mol %, respectively, based on the sum of the molar percentages of components B1') and B2'), preferably based on the total amount of substance of the monomer mixture (M).

[0073] It is preferred if component B') comprises 47 to 53 mol % of component B1') and 47 to 53 mol % of component B2'), respectively, based on the sum of the molar percentages of components B1') and B2'), preferably based on the total amount of substance of component B').

[0074] It is particularly preferred if component B') comprises 49 to 51 mol % of component B1') and 49 to 51 mol % of component B2'), respectively, based on the sum of the molar percentages of components B1') and B2'), preferably based on the total amount of substance of component B').

[0075] The mole percentages of components B1') and B2') present in component B') typically add up to 100 mol %.

[0076] Component B') is a component B3'), i.e., at least one C4-C20 It may additionally contain a diacid.

[0077] In the context of the present invention, the terms “component B3′)” and “at least one C4-C 20 The terms "diacid" and "diacid" are used interchangeably and therefore have the same meaning.

[0078] When component B') additionally contains component B3'), it is preferred that component B') contains component B1') in a range of 25 to 54.9 mol %, component B2') in a range of 45 to 55 mol %, and component B3') in a range of 0.1 to 25 mol %, each based on the total amount of component B').

[0079] In this case, it is particularly preferable that component B') contains component B1') in the range of 13 to 52.9 mol%, component B2') in the range of 47 to 53 mol%, and component B3') in the range of 0.1 to 13 mol%, based on the total amount of component B').

[0080] It is most preferable that component B') contains component B1') in the range of 7 to 50.9 mol %, component B2') in the range of 49 to 51 mol %, and component B3') in the range of 0.1 to 7 mol %, each based on the total amount of component B').

[0081] When component B') additionally comprises component B3'), the mole percentages of components B1'), B2') and B3') typically total 100 mol %.

[0082] The monomer mixture (M) may further comprise water.

[0083] The components B1') and B2') and optionally B3') of component B') can react with each other to obtain amides. This reaction is known per se to the person skilled in the art. Therefore, component B') may contain components B1'), B2') and optionally B3') in fully reacted, partially reacted or unreacted form. It is preferred when component B') contains components B1'), B2') and optionally B3') in unreacted form.

[0084] In the context of the present invention, "in unreacted form" means that the component B1') is a carboxylic acid which ... 32 ~C 40 The component B2') exists as a dimer acid, and the component B2') is at least one of the C4-C 12 diamine and optionally the component B3') is at least one C4-C 20 It should be understood to mean that it exists as the diacid.

[0085] If the components B1') and B2') and optionally B3') have at least partially reacted, the components B1') and B2') and optionally B3') are at least partially in amide form.

[0086] component B1') According to the invention, component B1') is at least one C 32 ~C 40 It is a dimer acid.

[0087] In the context of the present invention, "at least one C 32 ~C 40 "Dimer acid" is exactly one type of C 32 ~C 40 Dimer acid or two or more types of C 32 ~C 40 It should be understood to mean any mixture of dimer acids.

[0088] Dimer acid is also called dimer fatty acid. 32 ~C 40Dimer acids are known per se to those skilled in the art and are typically prepared by dimerization of unsaturated fatty acids, which dimerization may be catalyzed, for example, by alumina.

[0089] At least one of the above C 32 ~C 40 Suitable unsaturated fatty acids for producing dimer acids are known to those skilled in the art and include, for example, unsaturated C 16 fatty acids, unsaturated C 18 Fatty acids and unsaturated C 20 It is a fatty acid.

[0090] Therefore, the component B1') is an unsaturated C 16 fatty acids, unsaturated C 18 Fatty acids and unsaturated C 20 It is preferred that the fatty acid is produced from an unsaturated fatty acid selected from the group consisting of fatty acids, wherein the unsaturated C 18 Fatty acids are particularly preferred.

[0091] Preferred unsaturated C 16 The fatty acid is, for example, palmitoleic acid ((9Z)-hexadec-9-enoic acid).

[0092] Preferred unsaturated C 18Fatty acids include, for example, petroselinic acid ((6Z)-octadec-6-enoic acid), oleic acid ((9Z)-octadec-9-enoic acid), elaidic acid ((9E)-octadec-9-enoic acid), vaccenic acid ((11E)-octadec-11-enoic acid), linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid), α-linolenic acid ((9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid), γ-linolenic acid ((6Z,9Z,12Z)- octadeca-6,9,12-trienoic acid), calendic acid ((8E,10E,12Z)-octadeca-8,10,12-trienoic acid), punicic acid ((9Z,11E,13Z)-octadeca-9,11,13-trienoic acid), alpha-eleostearic acid ((9Z,11E,13E)-octadeca-9,11,13-trienoic acid) and beta-eleostearic acid ((9E,11E,13E)-octadeca-9,11,13-trienoic acid). Particularly preferred are unsaturated C carboxylic acids selected from the group consisting of petroselinic acid ((6Z)-octadec-6-enoic acid), oleic acid ((9Z)-octadec-9-enoic acid), elaidic acid ((9E)-octadec-9-enoic acid), vaccenic acid ((11E)-octadec-11-enoic acid), and linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid). 18 It is a fatty acid.

[0093] Preferred unsaturated C 20 The fatty acid may, for example, be selected from the group consisting of gadoleic acid ((9Z)-eicosa-9-enoic acid), eicosenoic acid ((11Z)-eicosa-11-enoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid) and timnodonic acid ((5Z,8Z,11Z,14Z,17Z)-eicosa-5,8,11,14,17-pentaenoic acid).

[0094] Component B1') particularly preferably comprises at least one C 36 It is a dimer acid.

[0095] At least one of the above C 36 Dimer acids are unsaturated C 18It is preferably produced from a fatty acid. 36 The dimer acid is selected from the group consisting of petroselinic acid ((6Z)-octadec-6-enoic acid), oleic acid ((9Z)-octadec-9-enoic acid), elaidic acid ((9E)-octadec-9-enoic acid), vaccenic acid ((11E)-octadec-11-enoic acid) and linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid). 18 It is particularly preferred when it is produced from fatty acids.

[0096] The preparation of said component B1') from unsaturated fatty acids may result in the formation of trimer acids and may also leave residues of unreacted unsaturated fatty acids.

[0097] The formation of such trimer acids is known to those skilled in the art.

[0098] According to the invention, said component B1') preferably comprises at most 0.5% by weight of unreacted unsaturated fatty acids and at most 0.5% by weight of trimer acid, particularly preferably at most 0.2% by weight of unreacted unsaturated fatty acids and at most 0.2% by weight of trimer acid, respectively, based on the total weight of component B1').

[0099] Dimer acids (also known as dimerized fatty acids or dimer fatty acids) should generally, and in particular in the context of the present invention, be understood to mean mixtures produced by oligomerization of unsaturated fatty acids. They can be produced, for example, by catalytic dimerization of unsaturated fatty acids of vegetable origin, where the starting materials used are in particular unsaturated C 16 ~C 20The dimer fatty acid is a fatty acid. The coupling proceeds mainly by the Diels-Alder mechanism and results in a mixture of mainly dimer products having alicyclic, linear aliphatic, branched aliphatic, and C6 aromatic hydrocarbon groups between the carboxyl groups, depending on the number and position of the double bonds in the fatty acid used to prepare the dimer acid. Depending on the mechanism and / or any subsequent hydrogenation, the aliphatic groups may be saturated or unsaturated and the proportion of aromatic groups may vary. The groups between the carboxylic acid groups then contain, for example, 32 to 40 carbon atoms. The preparation preferably uses a fatty acid having 18 carbon atoms, so that the dimer product has 36 carbon atoms. The groups attached to the carboxyl groups of the dimer fatty acid preferably do not contain unsaturated bonds and do not contain aromatic hydrocarbon groups.

[0100] In the context of the present invention, the preparation is thus preferably 18 Fatty acids are used. It is particularly preferable to use linoleic acid, linoleic acid and / or oleic acid.

[0101] Depending on the reaction conditions, the oligomerization results in a mixture containing mainly dimer molecules, but also trimer molecules, as well as monomer molecules and other by-products. Purification by distillation is common. Commercially available dimer acids generally contain at least 80% by weight of dimer molecules, up to 19% by weight of trimer molecules, and at most 1% by weight of monomer molecules and other by-products.

[0102] It is preferable to use dimer acids which consist of dimer fatty acid molecules to the extent of at least 90% by weight, preferably to the extent of at least 95% by weight and very particularly preferably to the extent of at least 98% by weight.

[0103] The proportions of monomer, dimer and trimer molecules and other by-products in the dimer acid can be determined, for example, by gas chromatography (GC). The dimer acid is converted to the corresponding methyl esters by the boron trifluoride method (see DIN EN ISO 5509) prior to GC analysis and then analyzed by GC.

[0104] In the context of the present invention, the basic feature of "dimer acids" is that their preparation involves the oligomerization of unsaturated fatty acids. This oligomerization mainly forms dimer products, i.e. preferably to the extent of at least 80% by weight, particularly preferably at least 90% by weight, very particularly preferably at least 95% by weight and in particular at least 98% by weight. Thus, the fact that the oligomerization mainly forms dimer products that contain exactly two fatty acid molecules is the basis of this name and is in any case common. Therefore, an alternative expression of the related term "dimer acid" is "mixtures containing dimerized fatty acids".

[0105] The dimer acids that can be used can be obtained as commercial products. Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976, and Radiacid 0977 from Oleon NV, Pripol 1006, Pripol 1009, Pripol 1012, and Pripol 1013 from Croda, Empol 1008, Empol 1012, Empol 1061, and Empol 1062 from BASF SE, and Unidyme 10 and Unidyme Tl from Arizona Chemical.

[0106] The component B1') has an acid value, for example, in the range of 190 to 200 mg KOH / g.

[0107] component B2') According to the invention, the component B2') is at least one C4-C 12 It is a diamine.

[0108] In the present invention, "at least one C4-C 12 "Diamine" is exactly one type of C4-C 12 Diamine or two or more C4-C 12 It should be understood to mean any mixture of diamines.

[0109] In relation to the compound, "C4-C12 "Diamine" should be understood to mean an aliphatic and / or aromatic compound having 4 to 12 carbon atoms and two amino groups (-NH2 groups). The aliphatic and / or aromatic compounds may be unsubstituted or additionally at least monosubstituted. If the aliphatic and / or aromatic compounds are additionally at least monosubstituted, they may bear one, two or more substituents which do not participate in the polymerization of the components A') and B'). Such substituents are, for example, alkyl or cycloalkyl substituents. These are known per se to the person skilled in the art. Said at least one C4-C 12 The diamine is preferably unsubstituted.

[0110] Suitable components B2') are, for example, selected from the group consisting of 1,4-diaminobutane (butane-1,4-diamine; tetramethylenediamine; putrescine), 1,5-diaminopentane (pentamethylenediamine; pentane-1,5-diamine; cadaverine), 1,6-diaminohexane (hexamethylenediamine; hexane-1,6-diamine), 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane (decamethylenediamine), 1,11-diaminoundecane (undecamethylenediamine) and 1,12-diaminododecane (dodecamethylenediamine).

[0111] It is preferred if the component B2') is selected from the group consisting of tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine.

[0112] Component B3') According to the present invention, the component B3') optionally present in the component B') is at least one C4-C 20 It is a diacid.

[0113] In the present invention, "at least one C4-C 20 A diacid is exactly one C4-C 20 Diacid or two or more C4-C 20It should be understood to mean any mixture of diacids.

[0114] In relation to the present invention, "C4-C 20 "Diacids" should be understood to mean aliphatic and / or aromatic compounds having 2 to 18 carbon atoms and two carboxyl groups (-COOH groups). The aliphatic and / or aromatic compounds may be unsubstituted or additionally at least monosubstituted. If the aliphatic and / or aromatic compounds are additionally at least monosubstituted, they may bear one, two or more substituents which do not participate in the polymerization of components A') and B'). Such substituents are, for example, alkyl or cycloalkyl substituents. These are known to the skilled person. Preferably, said at least one C4-C 20 The diacid is unsubstituted.

[0115] Suitable components B3') are, for example, selected from the group consisting of butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid and hexadecanedioic acid.

[0116] It is preferred if the component B3') is selected from the group consisting of pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), decanedioic acid (sebacic acid) and dodecanedioic acid.

[0117] Most preferably, the at least one aliphatic polyamide of component A) comprises ε-caprolactam (as component A′), at least one C 36 It is derived from dimer acid (as component B1') and hexamethylenediamine (as component B2').

[0118] The component is preferably PA6 / 6.36, having a melting point of 190-210°C, in particular 195-200°C, especially 196-199°C, and / or a (polymerized) caprolactam content of 60-80% by weight, more preferably 65-75% by weight, especially 67-70% by weight, the remainder being hexamethylenediamine and C 36 Particularly preferred is the case where the PA6.36 units are derived from a diacid.

[0119] thermoplastic molding composition The invention further relates to a thermoplastic molding composition comprising the polymer blend according to the invention and at least one additional substance C).

[0120] The thermoplastic molding composition preferably comprises i) a) from more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A); b) as component B) 1% by weight to less than 50% by weight of at least one semicrystalline, semiaromatic or aromatic polyamide, wherein the sum of the weight percent of components A) and B) is 100 weight percent; Polymer blends 1 to 99.9% by weight; and ii) 0.1% to 99% by weight of at least one additional substance as component C) wherein the sum of the weight percent of the polymer blend and component C) is 100 weight percent.

[0121] Said at least one additional substance as component C) is selected from one or more of the following components: C1) at least one fibrous and / or particulate filler; C2) at least one impact modifier; C3) at least one thermoplastic polymer different from components A), B), C2) and C4); and C4) one or more further additives.

[0122] The invention therefore furthermore relates to a thermoplastic molding composition according to the invention which comprises as additional substance C) at least one fibrous and / or particulate filler as component C1).

[0123] The invention therefore furthermore relates to a thermoplastic molding composition according to the invention which comprises as additional substance C) at least one impact modifier as component C2).

[0124] The present invention therefore further relates to a thermoplastic molding composition according to the invention, which comprises as additional substance C) as component C3) at least one thermoplastic polymer which is different from components A), B), C2) and different from any further additives.

[0125] In one embodiment, the present invention provides i) a) from more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A); b) 1% by weight to less than 50% by weight of at least one semicrystalline, semiaromatic or aromatic polyamide as component B) wherein the sum of the weight percent of components A) and B) is 100 weight percent; Polymer blend 35-90% by weight, preferably 35-70% by weight, more preferably 40-60% by weight; iia) 10% to 65% by weight, preferably 30% to 65% by weight, more preferably 40% to 60% by weight, of at least one fibrous and / or particulate filler as component C1), and iib) 0 to 30% by weight, preferably 0 to 20% by weight, more preferably 0 to 10% by weight of at least one impact modifier as component C2) and / or one or more further additives as component C4). wherein the sum of the weight percents of the polymer blend, components C1), C2) and C4) is 100 weight percent.

[0126] If present, the amount of components C2) and / or C4) in the thermoplastic molding composition TM1 is from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight.

[0127] In a further embodiment, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: i) a) from more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A); b) 1% by weight to less than 50% by weight of at least one semicrystalline, semiaromatic or aromatic polyamide as component B) wherein the sum of the weight percent of components A) and B) is 100 weight percent; Polymer blend 35-90% by weight, preferably 35-70% by weight, more preferably 40-60% by weight; iia) 0% to 65% by weight, preferably 0 to 60% by weight, of at least one fibrous and / or particulate filler as component C1), and iib) 1 to 25% by weight, preferably 2 to 20% by weight, more preferably 3 to 15% by weight, of at least one impact modifier as component C2); and iic) one or more further additives as component C4) wherein the sum of the weight percent of the polymer blend, components C1), C2) and C4) is 100 weight percent.

[0128] When present, the amount of component C4) in the thermoplastic molding composition TM2 is from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight.

[0129] In a further embodiment, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: i) a) from more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A); b) 1% by weight to less than 50% by weight of at least one semicrystalline, semiaromatic or aromatic polyamide as component B) wherein the sum of the weight percent of components A) and B) is 100 weight percent; Polymer blend: 1-99.9% by weight, preferably 1.2-98% by weight, more preferably 1.5-90% by weight; iia) 0.1 to 99% by weight, preferably 2 to 98.8% by weight, more preferably 10 to 98.5% by weight of at least one thermoplastic polymer different from components A), B), C2) and C4) as component C3); iib) 0% to 65% by weight, preferably 0 to 60% by weight, of at least one fibrous and / or particulate filler as component C1), and iic) 0 to 30% by weight, preferably 0 to 20% by weight, more preferably 0 to 10% by weight of at least one impact modifier as component C2) and / or one or more further additives as component C4). wherein the sum of the weight percent of the polymer blend, components C1), C2) and C4) is 100 weight percent.

[0130] If present, the amount of components C2) and / or C4) in the thermoplastic molding composition TM3 is from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight.

[0131] By blending the inventive blend with at least one thermoplastic polymer different from components A), B), C2) and C4) as component C3), it is possible to achieve blending of the thermoplastic polymer C3), which generally has a melting point below that of component B), with component B) of the inventive blend. Direct blending of the thermoplastic polymer C3), which has a melting point below that of component B), with component B) will generally cause thermal decomposition.

[0132] For example, it is possible to blend a blend according to the invention (e.g. 30 wt. % ARLEN® C2000 (ArPA3) from Mitsui Chemicals Europe GmbH in 70 wt. % Ultramid® Flex F29 (AlCoPA1) from BASF SE) with polypropylene at 240° C. In contrast, direct blending of the individual polymers ArPA3, AlCoPA1 and polypropylene would cause thermal degradation of the polypropylene due to the high melting point of ArPA3 (310° C.).

[0133] Fibrous or particulate fillers C1) that may be mentioned are carbon fibres, glass fibres, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulphate and feldspar.

[0134] Preferred fibrous fillers that may be mentioned are carbon fibers, aramid fibers and potassium titanate fibers, and particularly preferred are glass fibers in the form of E-glass, which can be used in the commercially available form as rovings or as chopped glass.

[0135] The fibrous filler may be surface pretreated with a silane compound to improve compatibility with the thermoplastic.

[0136] Suitable silane compounds have the general formula: (X-(CH2) n ) k -Si-(OC m H 2m+1 ) 4-k wherein the substituents are defined as follows: X is [ka] and n is an integer of 2 to 10, preferably 3 to 4; m is an integer of 1 to 5, preferably 1 to 2; and k is an integer of 1 to 3, and preferably 1.

[0137] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and the corresponding silanes which contain a glycidyl group as the substituent X.

[0138] The amount of silane compound generally used for said surface coating is 0.01 to 2% by weight, preferably 0.025 to 1.0% by weight and in particular 0.05 to 0.5% by weight (based on C1).

[0139] Acicular mineral fillers are also suitable. For the purposes of the present invention, acicular mineral fillers are mineral fillers with strongly developed acicular characteristics. An example is acicular wollastonite. The mineral preferably has an L / D (length to diameter) ratio of 8:1 to 35:1, preferably 8:1 to 11:1. The mineral filler may be optionally pretreated with the above-mentioned silane compounds, but pretreatment is not essential.

[0140] Other fillers that may be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk, as well as lamellar or acicular nanofillers, the amount of which is preferably 0.1 to 10% (based on the thermoplastic molding composition). Preferred materials for this are boehmite, bentonite, montmorillonite, vermiculite, hectorite and laponite. The lamellar nanofillers are organically modified by prior art methods to give them good compatibility with organic binders. The addition of the lamellar or acicular nanofillers to the nanocomposites of the invention gives a further increase in mechanical strength.

[0141] The impact modifiers C2) (often also called elastomeric polymers, elastomers or rubbers) are quite generally copolymers preferably composed of at least two of the following monomers: ethylene, C3~18 Alpha-olefins such as propylene, butene, octene, decene or isobutene, butadiene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylates and / or methacrylates having 1 to 18 carbon atoms in the alcohol component, copolymers of which may be grafted, for example, with dicarboxylic acids or the corresponding anhydrides, such as maleic acid or maleic anhydride. Examples are ethylene and C grafted with maleic anhydride (as described above). 3~18 Copolymers of alpha olefins, such as ethylene / octene copolymers grafted with maleic anhydride and ethylene / propylene copolymers grafted with maleic anhydride.

[0142] Polymers of this type are described, for example, by Houben-Weyl, Methoden der organischen Chemie, vol. 14 / 1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), p. 392-406, and by C.B. Bucknall, monograph "Toughened Plastics" (Applied Science Publishers, London, UK, 1977).

[0143] Some preferred types of such elastomers are described below.

[0144] Preferred types of such elastomers are those known as ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.

[0145] EPM rubbers generally have virtually no residual double bonds, while EPDM rubbers can have 1 to 20 double bonds per 100 carbon atoms.

[0146] Examples of diene monomers for EPDM rubber that may be mentioned 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 alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes such as 3-methyltricyclo[5.2.1.0 2,6 ]-3,8-decadiene, and mixtures thereof. Preferred are 1,5-hexadiene, 5-ethylidenenorbornene and dicyclopentadiene. The diene content of the EPDM rubber is preferably 0.5 to 50% by weight, in particular 1 to 8% by weight, based on the total weight of the rubber.

[0147] The EPM and EPDM rubbers may preferably be grafted with reactive carboxylic acids or with their derivatives, examples of which are acrylic acid, methacrylic acid and their derivatives, such as glycidyl (meth)acrylate, and maleic anhydride.

[0148] Copolymers of ethylene with acrylic acid and / or methacrylic acid and / or esters of these acids are another group of preferred rubbers. The rubbers may 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 monomers containing epoxy groups preferably contain dicarboxylic acid groups and / or epoxy groups in the monomer mixture and are represented by the general formula I or II or III or IV. [ka] is incorporated into the rubber by adding a monomer having the formula: 1 ~R 9is 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.

[0149] base R 1 ~R 9 is preferably hydrogen, where m is 0 or 1 and g is 1. Corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

[0150] Preferred compounds of formulae I, II and IV are maleic acid, maleic anhydride and (meth)acrylates containing epoxy groups, 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 carboxy group, their behavior is close to that of their free acids, and therefore they are called monomers with latent carboxy groups.

[0151] The copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing anhydride groups, the remaining amounts being (meth)acrylates.

[0152] Particularly preferred are - 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 wherein the sum of the weight percent of the copolymer is 100 weight percent.

[0153] Other preferred (meth)acrylates are the methyl, ethyl, propyl, isobutyl and tert-butyl esters.

[0154] Comonomers which may be used together with these are vinyl esters and vinyl ethers.

[0155] The above ethylene copolymers can be prepared by processes known per se, preferably by random copolymerization at high pressure and elevated temperature. Suitable processes are well known.

[0156] Other preferred elastomers are emulsion polymers, the preparation of which is described, for example, in Blackley, monograph "Emulsion Polymerization."The emulsifiers and catalysts which can be used are known per se.

[0157] In principle, it is possible to use homogeneously structured elastomers, or else elastomers with a shell structure, the shell type structure being determined by the order of addition of the individual monomers, which also influences the morphology of the polymer.

[0158] Merely by way of example, monomers that may be mentioned here for the preparation of the rubber portion of the elastomer are acrylates, such as n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene, and mixtures thereof. These monomers 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.

[0159] The soft or rubbery phase of the elastomer (having a glass transition temperature below 0° C.) may be the core, the outer shell or an intermediate shell (in the case of elastomers with structures having more than two shells). Elastomers with more than one shell may have more than one shell composed of a rubbery phase.

[0160] If the structure of the elastomer contains, in addition to the rubber phase, one or more hard components (having a glass transition temperature above 20° C.), these are generally prepared by polymerizing, as main 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 also possible to use relatively small proportions of other comonomers.

[0161] In some cases, it has been found to be advantageous to use emulsion polymers having reactive groups on the surface. Examples of this type of group are epoxy, carboxy, latent carboxy, amino and amido groups, as well as groups of the general formula [ka] wherein the substituents may 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-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, which may be optionally substituted by an O-containing group or by an N-containing group, X is a chemical bond, C1-C 10-Alkylene group, or C6-C 12 - an arylene group, or [ka] and Y is OZ or NH-Z, and Z is C1~C 10 -Alkylene group or C6-C 12 -arylene group].

[0162] The grafting monomers described in EP-A 208 187 are also suitable for introducing reactive groups into the surface.

[0163] Other examples that may be mentioned are acrylamides, methacrylamides 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.

[0164] The particles of the rubber phase may be crosslinked. Examples of crosslinking monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, as well as the compounds described in EP-A 50 265.

[0165] It is also possible to use monomers known as graft-linking monomers, i.e. monomers with two or more polymerizable double bonds that react at different rates during the polymerization. Preference is given to the use of compounds of this type, in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive group (or groups) polymerize, for example, significantly slower. The different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. If another phase is then grafted onto this type of rubber, at least a portion of the double bonds present in the rubber react with the grafting monomer to form chemical bonds, i.e. the grafted phase is at least partially chemically bonded to the graft base.

[0166] Examples of this type of graft-linking monomer are monomers containing allyl groups, in particular the allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl itaconate, and the corresponding monoallyl compounds of these dicarboxylic acids.In addition to these, there is a wide variety of other suitable graft-linking monomers.For further details, reference can be made here to, for example, US Pat. No. 4,148,846.

[0167] The proportion of these crosslinking monomers in the impact-modified polymer is generally up to 5% by weight, preferably not more than 3% by weight, based on the impact-modified polymer.

[0168] Some preferred emulsion polymers are listed below. Firstly, mention may be made here of graft polymers having a core and at least one outer shell and having the following structure: [Table 1]

[0169] Instead of graft polymers with structures having more than one shell, 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 produced by the use of crosslinkable monomers or monomers with reactive groups.

[0170] Examples of preferred emulsion polymers are 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 shell composed of the above copolymers, and copolymers of ethylene and comonomers providing reactive groups.

[0171] The elastomers may also be prepared by other conventional methods, such as by suspension polymerization.

[0172] Preference is also given to silicone rubbers, such as those described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290.

[0173] It is, of course, also possible to use mixtures of the above-listed types of rubber.

[0174] Preferred thermoplastic polymers as component C3), different from components A), B), C2) and C4), are polymers having a melting point below 300°C, preferably below 280°C.

[0175] Examples of suitable thermoplastic polymers as component C3), which are different from components A), B), C2) and C4), are preferably - C2~C10 - monoolefins, such as ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and their C2-C6 10 -Alkyl esters, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, branched and unbranched C1-C 10 homopolymers or copolymers which comprise, in copolymerized form, at least one monomer selected from acrylates and methacrylates having an alcohol component of alcohols, vinyl aromatic compounds, such as styrene, acrylonitrile, methacrylonitrile, α,β-ethylenically unsaturated mono- and dicarboxylic acids, and maleic anhydride; - a polyamide different from components A and B, for example an amorphous polyamide; - homopolymers and copolymers of vinyl acetals; - polyvinyl ester; - Polycarbonate (PC); - polyesters, such as polyalkylene terephthalates, polyhydroxyalkanoates (PHAs), polybutylene succinates (PBSs), polybutylene succinate adipates (PBSA); - polyether; - Polyetherketone; - Thermoplastic polyurethane (TPU); - polysulfides; - polysulfone; - Polyethersulfone; - cellulose alkyl esters; and mixtures thereof is selected from.

[0176] Examples are polyolefins, acrylonitrile-butadiene-styrene copolymers (ABS), ethylene-propylene copolymers, ethylene-propylene-diene copolymers (EPDM), polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-styrene-acrylate (ASA), styrene-butadiene-methyl methacrylate copolymers (SBMMA), styrene-maleic anhydride copolymers, styrene-methacrylic acid copolymers (SMA), amorphous polyamides, C4-C8 alcohols, in particular butanol, hexanol, octanol and 2- Polyacrylates with the same or different alcohol groups from the group of ethylhexanol, polymethyl methacrylate (PMMA), methyl methacrylate-butyl acrylate copolymer, polyoxymethylene (POM), polyvinyl alcohol (PVAL), polyvinyl acetate (PVA), polyvinyl butyral (PVB), polycaprolactone (PCL), polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV), polylactic acid (PLA), ethyl cellulose (EC), cellulose acetate (CA), cellulose propionate (CP) or cellulose acetate butyrate (CAB).

[0177] Suitable further additives C4) are exemplified below as components C41) to C48).

[0178] The thermoplastic molding composition according to the invention can contain as component C41) from 0.05 to 3% by weight, preferably from 0.1 to 1.5% by weight and in particular from 0.1 to 1% by weight, of a lubricant, based on the thermoplastic molding composition.

[0179] 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 having 12 to 44 carbon atoms.

[0180] The metal ions are preferably the alkaline earth metals and Al, particularly preferably Ca or Mg.

[0181] Preferred metal salts are calcium stearate and calcium montanate, and aluminum stearate.

[0182] It is also possible to use mixtures of various salts in any desired mixing ratio.

[0183] The carboxylic acids may be monobasic or dibasic. Examples that may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and, particularly preferably, stearic acid, capric acid and montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms).

[0184] The fatty alcohols may be monohydric to tetrahydric. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, and preferred are glycerin and pentaerythritol.

[0185] The fatty amines may be monobasic to tribasic. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine, particularly preferred are ethylenediamine and hexamethylenediamine. Preferred esters or amides accordingly are glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.

[0186] It is also possible to use mixtures of various esters or amides, or combinations of esters and amides, in any desired mixing ratio.

[0187] The thermoplastic molding compositions according to the invention can contain as component C42) 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight and in particular 0.1 to 1% by weight, based on the thermoplastic molding composition, of Cu(I) salts, preferably Cu(I) halides, as stabilizer, in particular in a mixture with an alkali metal halide, preferably KI, in particular in a ratio of 1:4.

[0188] Preferred salts of monovalent copper used are copper(I) acetate, copper(I) chloride, copper(I) bromide and copper(I) iodide in amounts of 5 to 500 ppm, preferably 10 to 250 ppm, of copper, based on the polyamide (i.e. the polyamide blend according to the invention).

[0189] The advantageous properties are obtained especially when the copper is present in the polyamide in molecular distribution. This is achieved when a concentrate containing the polyamide, a salt of monovalent copper and an alkali metal halide in the form of a solid homogeneous solution is added to the molding composition. By way of example, a typical concentrate is composed of 79-95% by weight of polyamide and 21-5% by weight of copper iodide or a mixture composed of copper bromide and potassium iodide. The copper concentration in the solid homogeneous solution is preferably 0.3-3% by weight, in particular 0.5-2% by weight, based on the total weight of the solution, and the molar ratio of copper(I) iodide to potassium iodide is 1-11.5, preferably 1-5.

[0190] According to one embodiment of the invention, the molding composition is free of copper iodide and potassium iodide and in particular free of metal halides.

[0191] Suitable polyamides for the concentrate are homopolyamides and copolyamides, especially nylon 6 and nylon 6,6.

[0192] The thermoplastic molding compositions of the invention can contain, as component C43), oxidation retarders / antioxidants and / or heat stabilizers. Examples of oxidation retarders / antioxidants and heat stabilizers are sterically hindered phenols and / or phosphites and amines (e.g. TAD), hydroquinones, aromatic secondary amines such as diphenylamine, substituted varieties of these groups, and mixtures thereof, in concentrations of up to 3% by weight, more preferably up to 1.5% by weight, most preferably up to 1% by weight, based on the weight of the thermoplastic molding composition.

[0193] Suitable sterically hindered phenols are in principle all compounds which have a phenolic structure and which have at least one bulky group on the phenolic ring.

[0194] For example, the formula [ka] It is preferable to use a compound of the formula where: R 1 and R 2 is an alkyl group, a substituted alkyl group, or a substituted triazole group, and the group 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.

[0195] Antioxidants of the above type are described, by way of example, in DE-A 27 02 661 (US-A 4 360 617).

[0196] Another group of preferred sterically hindered phenols is provided by those derived from substituted benzene carboxylic acids, especially substituted benzene propionic acids.

[0197] Particularly preferred compounds from this class have the formula [ka] [In the formula, R 4 , R 5 , R 7 , and R 8 are, independently of one another, optionally substituted C1-C8 alkyl groups (at least one of which is a bulky group), and R 6 is a divalent aliphatic group having 1 to 10 carbon atoms and whose main chain may have a CO bond.

[0198] Preferred compounds corresponding to these formulas are [ka] It is.

[0199] All of the following are examples of sterically hindered phenols: 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], 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.

[0200] The compound which has proven to be particularly effective and is therefore preferably used is 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox (登録商標) 259), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamamide (Irganox (登録商標) 1098), and the above-mentioned product Irganox® from BASF SE (登録商標) 245, this product has particularly good suitability.

[0201] The antioxidants C43), which can be used individually or as a mixture, are present in an amount of 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight, in particular 0.1 to 1% by weight, based on the total weight of the molding composition.

[0202] In some cases, sterically hindered phenols having one or less sterically hindering groups ortho to the phenolic hydroxy group have been found to be particularly advantageous; especially when evaluating color fastness upon storage in diffuse light over extended periods of time.

[0203] As component C44), the thermoplastic molding materials can generally contain from 1.0 to 10.0% by weight, preferably from 2.0 to 6.0% by weight and in particular from 3.0 to 5.0% by weight, based on the weight of the thermoplastic molding composition, of at least one flame retardant (unless other amounts are explicitly stated).

[0204] The preferred flame retardants are phosphazenes.

[0205] "Phosphazene" is a compound represented by the general formula (IX) [ka] [In the formula, m is an integer of 3 to 25, and R 4 and R4' are the same or different, and C1 to C 20 -Alkyl, C6-C 30 -Aryl, C6-C 30 -arylalkyl or C6-C 30 -representing an alkyl-substituted aryl] or a cyclic phosphazene of the general formula (X) [ka] This should be understood to mean a linear phosphazene of the formula: [wherein n is 3 to 1000, X is -N=P(OPh)3 or -N=P(O)OPh, and Y is -P(OPh)4 or -P(O)(OPh)2].

[0206] The preparation of such phosphazenes is described in EP-A 0 945 478.

[0207] Particularly preferred is the compound of formula (XI) [ka] The formula is P3N3C 36 or a cyclic phenoxyphosphazene of formula (XII) [ka] It is a linear phenoxyphosphazene by

[0208] These phenyl groups may be optionally substituted. In the context of this specification, phosphazenes are described in Mark, JE, Allcock, HR, West, R., "Inorganic Polymers", Prentice Hall, 1992, p. 61-141.

[0209] Preferably used as component C44) 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, paragraph

[0041] . In one embodiment of the invention, the phenyl group in the cyclic phenoxyphosphazene is selected from the group consisting of C 1~4 -alkyl groups. Preference is given to the case where pure phenyl groups are concerned.

[0210] For further description of the cyclic phosphazenes, see Roempp Chemie Lexikon, 9th Edition, keyword "phosphazenes". Preparation is carried out via cyclophosphazenes, which can be obtained, for example, from PCl5 and NH4Cl, in which the chlorine groups in the cyclophosphazenes are replaced by phenoxy groups by reaction with phenol.

[0211] The cyclic phenoxyphosphazene compounds can be prepared, for example, as described in Allcock, HR, "Phosphorus-Nitrogen Compounds" (Academic Press, 1972) and Mark, JE, Allcock, HR, West, R., "Inorganic Polymers" (Prentice Hall, 1992).

[0212] Component C44) is preferably a mixture of cyclic phenoxyphosphazenes having 3 and 4 phenoxyphosphazene units. The weight ratio of rings containing 3 phenoxyphosphazene units to rings containing 4 phenoxyphosphazene units is preferably about 80:20. Larger rings of the phenoxyphosphazene units may be present as well, but in smaller amounts. A suitable cyclic phenoxyphosphazene is available from Fushimi Pharmaceutical Co., Ltd. under the name Rabitle. (登録商標) It can be obtained as FP-100. It is a pale yellow-white 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.

[0213] The thermoplastic molding material preferably comprises 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 as flame retardant, based on the amount of the thermoplastic molding composition.

[0214] For this reason, particularly solid, non-migratory phosphate esters having a melting point of 70° C. to 150° C. are preferred. This results in the product being easy to dose and exhibiting significantly less migration in the molding compound. A particularly preferred example is the commercially available phosphate ester Daihachi's PX-200. (登録商標) (CAS:139189-30-3), or Sol-DP from ICL-IP (登録商標) Additionally, phosphate esters in which the phenyl group is appropriately substituted are contemplated where this is possible to achieve the preferred melting range. The general structure is as follows, depending on the substitution pattern at the ortho or para positions on the aromatic ring: [ka] Where: R 1 =H, methyl, ethyl or isopropyl, but preferably H. n=0 to 7, preferably 0. R 2~6 =H, methyl, ethyl or isopropyl, but preferably methyl. 6 is preferably R 4 and R 5 is the same as: m=can be, but need not be, the same and is between 1, 2, 3, 4 and 5, but is preferably 2. R" may be H, methyl, ethyl or cyclopropyl, but is preferably methyl and H.

[0215] The PX-200 is shown as an example: [ka]

[0216] It is particularly preferred if at least one aromatic ester of polyphosphoric acid is used. Such aromatic polyphosphates can be obtained, for example, from Daihachi Chemical under the name PX-200.

[0217] As component C44), the thermoplastic molding composition according to the invention can comprise, based on the amount of the thermoplastic molding composition, 5.0 to 30.0% by weight, preferably 10.0 to 30.0% 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 phosphinic acid salt as described below as flame retardant.

[0218] Examples of preferred flame retardants of component C44) are metal phosphinates derived from hypophosphorous acid. For example, hypophosphorous acid and metal salts of Mg, Ca, Al or Zn as metals can be used. Particularly preferred here is Al hypophosphite.

[0219] Phosphinic acid salts of formula (I) and / or diphosphinic acid salts of formula (II) or polymers thereof are also suitable, [ka] Where: R 1 , R 2 are the same or different and represent hydrogen, linear or branched C1-C6-alkyl, and / or aryl; R 3 is linear or branched C1-C 10 -Alkylene, C6~C 10 -Arylene, C6~C 10 -Alkylarylene or C6-C 10 -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=1 to 4; n=1 to 4; x=1 to 4, preferably m=3 and x=3.

[0220] 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.

[0221] 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.

[0222] Particularly preferably, R 1 , R 2 is hydrogen, methyl or ethyl, and M is Al, with Al hypophosphite being particularly preferred.

[0223] The preparation of said phosphinate is preferably carried out by precipitation of the corresponding metal salt from aqueous solution.However, said phosphinate can also be precipitated in the presence of suitable inorganic metal oxide or sulfide as support material (white pigment, for example TiO2, SnO2, ZnO, ZnS, SiO2).Accordingly, this results in surface-modified pigment, which can be used as laser-markable flame retardant for thermoplastic polyester.

[0224] It is preferred when metal salts of substituted phosphinic acids are used in which, compared to hypophosphorous acid, one or two hydrogen atoms are replaced by phenyl, methyl, ethyl, propyl, isobutyl, isooctyl or the group R'-CH-OH is replaced by R'-hydrogen, phenyl, tolyl. The metals are preferably Mg, Ca, Al, Zn, Ti, Fe. Aluminum diethylphosphinate (DEPAL) is particularly preferred.

[0225] 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.

[0226] Further flame retardants are, for example, halogen-containing flame retardants.

[0227] Suitable halogen-containing flame retardants are preferably brominated compounds, such as brominated diphenyl ethers, brominated trimethylphenylindanes (DSB FR 1808), tetrabromobisphenol A and hexabromocyclododecane.

[0228] Suitable flame retardants are preferably brominated compounds, such as those having the structural formula: [ka] (Great Lakes BC 52 or BC 58).

[0229] formula: [ka] Polypentabromobenzyl acrylate having the formula: where n>4 (eg FR 1025 from ICL-IP) is particularly suitable.

[0230] Preferred brominated compounds further have the formula: [ka] and oligomeric reaction products (n>3) of tetrabromobisphenol A with epoxides (e.g., FR 2300 and 2400 from DSB).

[0231] 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 suitable as well. In a preferred embodiment of the invention, the brominated oligomeric styrene has formula I shown below, where R represents hydrogen or an aliphatic group, in particular an alkyl group, such as CH2 or C2H5, and n represents the number of repeating chain units. R 1 can be H, or else bromine, or else a fragment of a common free radical former: [ka]

[0232] The value n may be 1 to 88, preferably 3 to 58. The brominated oligostyrene contains 40.0 to 80.0% by weight of bromine, preferably 55.0 to 70.0% by weight. Preference is given to products consisting mainly of polydibromostyrene. The substances are meltable without decomposition and are soluble, for example, in tetrahydrofuran. They may be prepared either by cyclic bromination of - optionally aliphatically hydrogenated - styrene oligomers, such as are obtained, for example, by thermal polymerization of styrene (according to DE-OS 25 37 385), or by free-radical oligomerization of suitable brominated styrenes. The preparation of the flame retardant may also be carried out by ionic oligomerization of styrene and subsequent bromination. The amount of brominated oligostyrene required to give a polyamide with flame retardant properties depends on its bromine content. The bromine content in the thermoplastic molding composition according to the present invention is preferably 2.0 to 30.0% by weight, more preferably 5.0 to 12.0% by weight, based on the amount of the thermoplastic molding composition.

[0233] The brominated polystyrene according to the invention is typically obtained by the process described in EP-A 047 549: [ka]

[0234] The commercially available brominated polystyrenes obtainable by this process are mainly ring-substituted tribrominated products, n' (see III) generally having values ​​between 125 and 1500, which corresponds to molecular weights between 42500 and 235000, preferably between 130000 and 135000.

[0235] 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 and especially 65.0% by weight.

[0236] Commercially available powder products generally have a glass transition temperature between 160° C. and 200° C. and are available, for example, from Albemarle under the designation HP 7010 and from Ferro Corporation under the designation Pyrocheck (登録商標) Available in PB 68.

[0237] Mixtures of the brominated oligostyrenes and brominated polystyrenes may also be used in the molding compositions according to the invention, the mixing ratios of which can be freely selected.

[0238] Chlorine-containing flame retardants are also suitable, with Declorane plus from Oxychem being preferred.

[0239] Suitable halogen-containing flame retardants are preferably ring-brominated polystyrene, brominated polybenzyl acrylate, brominated bisphenol A epoxide oligomer or brominated bisphenol A polycarbonate.

[0240] In one embodiment of the invention, no halogen-containing flame retardants are used in the thermoplastic molding materials according to the invention.

[0241] Flame-retardant melamine compounds suitable as component C44) in the context of the present invention are those which, when added to glass-fiber-filled polyamide molding compositions, reduce the flammability and influence the combustion behavior in a flame-retardant manner, thus resulting in improved properties in the UL 94 test and in the glow-wire test.

[0242] 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.

[0243] Melamine cyanurates which are preferably suitable according to the invention are the reaction products of melamine (formula I) and cyanuric acid / isocyanuric acid (formulae Ia and Ib), preferably in equimolar amounts. [ka]

[0244] It is obtained, for example, by reaction of aqueous solutions of the starting compounds at 90°C to 100°C. Commercially available products have an average particle size d of 1.5 to 7 μm. 50 and d less than 50 μm 99 It is a white powder having a value of 0.01g / g.

[0245] Further suitable compounds (often also referred to as salts or adducts) are melamine sulfate, melamine, melamine borate, oxalate, primary phosphate, secondary phosphate and secondary pyrophosphate, melamine neopentyl glycol borate. According to the invention, the molding material is preferably free of polymeric melamine phosphate (CAS number 56386-64-2 or 218768-84-4).

[0246] This should be understood to mean melamine polyphosphate salts of 1,3,5-triazine compounds having an average condensation degree number n of 20 to 200 and a 1,3,5-triazine content of 1.1 to 2.0 mol of 1,3,5-triazine compounds per mole of phosphorus atom selected from the group consisting of melamine, melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine and diaminophenyltriazine. Preferably, the n-value of such salts is generally between 40 and 150 and the ratio of 1,3,5-triazine compounds per mole of phosphorus atom is preferably between 1.2 and 1.8. Furthermore, the pH of a 10% by weight aqueous slurry of the salts produced according to EP-B1 095 030 will generally be above 4.5 and preferably at least 5.0. The pH is typically determined by adding 25 g of the salt and 225 g of clean water to a 300 ml beaker at 25° C., stirring the resulting aqueous slurry for 30 minutes, and then measuring the pH. The n value above, the number-average condensation degree, may be determined by 31P solid-state NMR. JR van Wazer, CF Callis, J. Shoolery and R. Jones, J. Am. Chem. Soc., 78, 5715, 1956, disclose that the number of adjacent phosphate groups gives a unique chemical shift, which allows clear differentiation between orthophosphates, pyrophosphates, and polyphosphates.

[0247] Suitable guanidine salts are CAS Number Guanidine carbonate 593-85-1 Guanidine cyanurate, primary 70285-19-7 Guanidine phosphate, primary 5423-22-3 Guanidine phosphate, secondary 5423-23-4 Guanidine sulfate, primary 646-34-4 Guanidine sulfate, secondary 594-14-9 Guanidine pentaerythritol borate Not applicable Guanidine neopentyl glycol borate Not applicable and Urea Phosphate Green 4861-19-2 Urea cyanurate 57517-11-0 Ammelin 645-92-1 Ammelid 645-93-2 Merem 1502-47-2 Melon 32518-77-7 It is.

[0248] In the context of the present invention, "compound" should be understood to mean, for example, not only benzoguanamine itself and its adducts / salts, but also its nitrogen-substituted derivatives and its adducts / salts.

[0249] Also suitable is ammonium polyphosphate (NH4PO3) n [wherein n is about 200 to 1000, preferably 600 to 800], and Formula IV [ka] Tris(hydroxyethyl)isocyanurate (THEIC) or aromatic carboxylic acid Ar(COOH) m and m is 2, 3 or 4, which may optionally be present in mixture with one another, where Ar represents a mono-, bi- or tricyclic aromatic 6-membered ring system.

[0250] 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.

[0251] The preparation is carried out by the method in EP-A 584 567 by reacting the tris(hydroxyethyl)isocyanurate with the acid, its alkyl ester or its halide.

[0252] Such reaction products are mixtures of monomeric and oligomeric esters which may be crosslinked. The degree of oligomerization is typically from 2 to about 100, preferably from 2 to 20. Preferred are the mixtures of THEIC and / or reaction products thereof with phosphorus-containing nitrogen compounds, especially (NH4PO3) n Or use a mixture with melamine pyrophosphate or polymeric melamine phosphate. For example (NH4PO3) n The mixing ratio of THEIC is preferably 90.0-50.0:10.0-50.0, particularly 80.0-50.0:50.0-20.0, in terms of weight % based on the mixture of such compounds.

[0253] Also suitable flame retardants include those of formula V [ka]

[0033] In particular, the benzoguanidine compounds of the formula:

[0033] wherein R, R' represent a linear or branched alkyl group having 1 to 10 carbon atoms, preferably hydrogen, and in particular their adducts with phosphoric acid, boric acid and / or pyrophosphoric acid.

[0254] Also preferred is a compound of formula VI [ka] Allantoin compounds of the formula: [wherein R, R' are as defined in formula V] and their salts with phosphoric acid, boric acid and / or pyrophosphoric acid, and compounds of the formula: VII [ka] where R is as defined in formula V, or their salts with the above acids.

[0255] Suitable products are commercially available or can be obtained according to DE-A 196 14 424.

[0256] The cyanoguanidine (formula VIII) which can be used according to the invention can be obtained, for example, by reacting calcium cyanamide with carbonic acid and dimerizing the produced cyanamide at pH 9 to pH 10 to obtain cyanoguanidine. [ka]

[0257] The commercially available product is a white powder with a melting point of 209°C to 211°C.

[0258] Melamine cyanurate (e.g. Melapur from BASF SE) (登録商標) It is particularly preferred to use MC25).

[0259] In addition, other metal oxides can be used, such as antimony trioxide, antimony pentoxide, sodium antimonate and similar metal oxides. For a description of pentabromobenzyl acrylate and antimony trioxide or antimony pentoxide, reference can be made to EP-A 0 624 626.

[0260] It is also possible to use phosphorus as component C44), for example red phosphorus, which may be used, for example, in the form of a masterbatch.

[0261] formula [ka] Dicarboxylic acids of the formula: Where: R 1 ~R 4 are each independently halogen or hydrogen, provided that at least one group R 1 ~R4 represents a halogen, x=1 to 3, preferably 1 or 2 m=1 to 9, preferably 1 to 3, 6, 9, particularly 1 to 3 n=2~3 M = alkaline earth metals, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg.

[0262] Preferred dicarboxylates are those containing the group R 1 ~R 4 independently of one another Cl or bromine or hydrogen, particularly preferably all radicals R 1 ~R 4 is Cl or / and Br.

[0263] Be, Mg, Ca, Sr, Ba, Al, Zn, Fe are preferred as the metal M.

[0264] Such dicarboxylates are commercially available or can be prepared by the methods described in US Pat. No. 3,354,191.

[0265] Also functional polymers can be used as flame retardant component C44). These can be, for example, flame retardant polymers. Such polymers are, for example, described in US 8,314,202 and contain 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone repeat units. A further suitable functional polymer for increasing the amount of carbon residue is poly(2,6-dimethyl-1,4-phenylene oxide) (PPPO).

[0266] As component C45), the thermoplastic molding composition may contain 1 to 30% by weight, preferably 5 to 20% by weight, in particular 6 to 10% by weight, of at least one plasticizer.

[0267] In the context of the present invention, plasticizer is a compound that can reduce the glass transition temperature of the polyamide present in the thermoplastic molding composition.Suitable plasticizers are known by those skilled in the art.Examples are lactams, lactones, polyvinyl alcohols, sulfonamides such as N-(n-butyl)benzenesulfonamide and their derivatives, ethylene glycols such as tetraethylene glycol.

[0268] As component C46), the thermoplastic molding composition can contain UV stabilizers, generally in amounts of up to 2% by weight, based on the amount of the thermoplastic molding composition. Examples of suitable UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones.

[0269] As component C47), the thermoplastic molding composition can contain colorants. Materials which can be added as colorants are inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide and carbon black, as well as organic pigments, such as phthalocyanines, quinacridones, perylenes, and dyes, such as anthraquinones.

[0270] As component C48), the thermoplastic molding composition can contain a nucleating agent. Materials which can be used as nucleating agents are sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc.

[0271] The polymer blends of the invention can be prepared by methods known per se, usually by mixing. The invention therefore relates to a method for preparing the polymer blends according to the invention by mixing components A) and B).

[0272] The mixing of the starting components A) and B) can be carried out in a conventional mixing device known to those skilled in the art, such as a screw extruder, especially a twin-screw extruder, a Brabender mixer, or a Banbury mixer.The resulting product can then be extruded.After extrusion, the extrudate can be cooled and pelletized.

[0273] The thermoplastic molding compositions of the invention can also be prepared by methods known per se by those skilled in the art by mixing the starting components A), B) and C) in conventional mixing devices, such as screw extruders, in particular twin-screw extruders, Brabender mixers or Banbury mixers, and then extruding them. After extrusion, the extrudate can be cooled and pelletized.

[0274] It is also possible to premix the individual components, for example components A) and B), to form the polymer blend according to the invention, and then add the remaining starting materials C) individually and / or also in the form of a mixture.

[0275] The invention therefore furthermore relates to a process for the preparation of the thermoplastic molding composition according to the invention by mixing component A), B) or the polymer blend according to the invention with component C).

[0276] The mixing temperature is generally 230 to 320°C.

[0277] The inventive blends and the inventive thermoplastic molding compositions are particularly characterized by one or more of the following properties: high stability against zinc chloride and AdBlue, high heat distortion temperature, high tensile modulus in the dry and conditioned state, high stiffness in the conditioned state, low water absorption, high barrier properties against fuels. The inventive blends and the inventive thermoplastic molding compositions are highly suitable for injection molding and for sheet, film, tube and pipe extrusion processes and can be processed at mold temperatures that are typical for example for polyamide processing.

[0278] The polymer blends and thermoplastic molding compositions according to the invention are suitable for the production of all types of moldings, in particular for the production of injection-molded and blow-molded and extruded articles, in particular pipes and tubes.

[0279] The reinforced molding compositions comprising component C1) are particularly useful for injection molding. Particularly suitable for injection molding are therefore preferably the reinforced thermoplastic molding compositions TM1.

[0280] Unreinforced molding compositions free of component C1) are particularly useful for extrusion, more preferably for sheet, film, pipe or tube extrusion. Unreinforced thermoplastic molding compositions which are particularly suitable for extrusion are described above. Common applications for the blends and thermoplastic molding compositions of the present invention include automotive, aerospace, electrical, and industrial parts that must resist long-term exposure to harsh chemicals and / or extreme high temperatures.

[0281] Some specific examples are: in the field of engineering plastics in contact with working fluids, such as coolants, brake and clutch fluids, chemicals (AdBlue), fuels and / or salts, especially in the automotive industry, for example extruded tubes (e.g. fluid pipes for fuels or coolants in cars, coolants for batteries in electric vehicles), mandrels and injection molded articles, for example functional parts for sensors of engines (e.g. wheel speed sensors), pumps, connectors or injection molded or extruded articles for fuel cells.

[0282] In the electrical and electronic fields, the blends and thermoplastic molding compositions of the present invention 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.

[0283] Possible uses of the blends and thermoplastic molding compositions of the present invention in automotive and aerospace parts are for interior parts such as dashboards, steering column switches, seat parts, head rests, center consoles, gearbox parts, and door modules, exterior parts such as door handles, outside mirror parts, windshield wiper parts, windshield wiper protective housings, grilles, roof rails, sunroof frames, engine covers, cylinder head covers, intake pipes (especially intake manifolds), windshield wipers, and external body parts, and motor parts, fuel line connectors, coolant pumps, bushings, bearing pads in aircraft engines, charge air coolers, resonators, engine cover parts and heat shields, fuel cut-off and water heater manifold valves, connectors, high voltage bushings, motor housings, and headlight parts.

[0284] Possible uses of the blends and thermoplastic molding compositions of the present invention in the cooking and household sector are in the manufacture of parts for cooking appliances, such as fryers, irons, knobs, and also in the garden and leisure sector, such as parts for irrigation systems, or garden appliances, and door handles.

[0285] The invention therefore furthermore relates to the use of the polymer blends or thermoplastic molding compositions according to the invention for producing moldings, in particular for producing extrusions, injection moldings and blow moldings.

[0286] The present invention further relates to molded articles, such as injection molded and blow molded articles, and extruded articles, which are produced from the polymer blends or thermoplastic molding compositions according to the invention. Examples of molded and extruded articles are moldings, pipes, such as single- and multi-layer pipes, tubes, films and sheets.

[0287] Suitable and preferred uses and moulded and extruded articles are described above. [Brief description of the drawings]

[0288] [Figure 1] Storage in AdBlue [Diagram 2] Fuel permeation test results

[0289] Figure 1 shows the results of the storage test in AdBlue, in which the tensile breaking strengths of Examples 1-3 after 42 days of storage in AdBlue are compared with Comparative Examples 1 and 2. Curve 1 Comparative Example 1 Curve 2 Example 1 Curve 3 Example 2 Curve 4 Example 3 Curve 5 Comparative Example 2 On the abscissa the different times of the day are indicated. On the ordinate the retention [%] of the tensile breaking strength relative to the initial value is shown.

[0290] Figure 2 shows the results of the fuel permeation test. In Figure 2, the fuel barrier properties of the composition of the invention (Inventive Example 3) and the comparative compositions (Comparative Examples 1 and 2) at 40°C are shown. As reference / control, GF reinforced PA66 (Ultramid® A3WG6 bk564 from BASF SE) and GF reinforced PA6 (Ultramid® B3WG6 bk564 from BASF SE) were tested.

[0291] On the abscissa, various compositions and various solvents are listed: 1 Ultramid® A3WG6 bk564 2 Ultramid® B3WG6 bk564 3 Comparative Example 1 4. Example 3 5 Comparative Example 2 A EtOH B Hydrocarbons C total On the ordinate, the transmittance [g / m 2 ×d] is shown (where d means "day"). EXAMPLES

[0292] The following ingredients were used: Component A) AlCoPA1: PA6 / 6.36; Ultramid® Flex F29 from BASF SE; (64% caprolactam, 6.3% HMD, 29.7% C36 partial unsaturation); MT: 199°C; Relative viscosity: 2.8-3.0 AlCoPA2: PA6 / 6.36 from BASF SE; (64% Caprolactam, 6.3% HMD, 29.7% C36 Saturates; Ultramid® Flex F38 from BASF SE) MT: 199°C; Relative Viscosity: 3.7-3.9 AlCoPA3: PA6 / 6.36 from BASF SE; (51.5% Caprolactam, 8.5% HMD, 40.0% C36 Saturated; BASF SE) MT: 199°C; Relative Viscosity: 3.7-3.9 Component B) ArPA1: PA6 / 6T (30 / 70), having a viscosity number VN of 125 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; MT (melting point) 294° C. (Ultramid® T315 from BASF SE) ArPA2: PA6T / 6I (70:30); ARLEN® 3000 from Mitsui Chemicals Europe GmbH; having a viscosity number VN of 90 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, MT. 330° C., Tg: 125° C. ArPA3: PA6T / 66 (70:30): ARLEN® C2000 from Mitsui Chemicals Europe GmbH; has a viscosity number VN of 100 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, MT. 310° C., Tg: 125° C. AmArPA (comparison): amorphous PA6I / 6T; Zytel® HTN301 from DuPont International Operations Sarl Component C) GF (glass fiber): DS 1110 with a diameter of 10 μm (DS 1110-10N 4 mm in 3B-FIBREGLASS SPRL) CMB: Carbon black 30% by weight in LDPE L1: Lubricant, calcium stearate flakes; LIGASTAR® CA 600 G from Peter Greven GmbH & Co. KG L2: Lubricant, ACRAWAX® C beads S1: Stabilizer, Irganox® 1098 ED from BASF SE S2: Stabilizer, sodium hypophosphite monohydrate from OQEMA GmbH S3: Stabilizer, OKAFLEX® EM from OKA-Tec Vertriebs GmbH N1: Nucleating agent: Talc IT Extra AW from Elementis Minerals BV IM1: Impact modifier: EXXELOR® VA 1801 from EXXONMOBIL PETROLEUM & CHEMICAL BV IM2: Impact modifier: EXXELOR® VA 1803 from EXXONMOBIL PETROLEUM & CHEMICAL BV.

[0293] Granular manufacturing The polymers shown in Tables 1 and 3 were compounded in a twin-screw extruder ZSK25 in the amounts specified in Tables 1 and 3 and extruded through a round nozzle with a diameter of 4 mm to process the polymer composition into granules. The amounts shown in Table 1 are in weight %. The temperature profile of the extruder was adjusted to ensure that all polyamides were in the molten state. The temperatures are listed in Table 1, which refers to Scheme 1, which shows a schematic diagram of the extruder with the respective segments G1 to G11. The polyamides AlCoPA, ArPA, AmArPA and the additives S, CMB and L (see explanation below) were metered through the feed section. The glass fibers were metered in segment G5 through a side feeder.

[0294] The granules were processed into test specimens in a standard injection molding machine using the mold temperatures and melt resin temperatures listed in Table 1.

[0295] The tensile modulus, tensile stress at break and tensile strain at break are determined according to ISO 527. The Charpy (notched) impact resistance is determined according to ISO 179-2 / 1eU and ISO 179-2 / 1eAf, respectively. The melting point and crystallization temperature are determined according to ISO 11357. All standards mentioned above and below refer to the editions valid in January 2021.

[0296] Scheme 1: Schematic of an extruder [Table 2]

[0297] Table 1: Preparation and characterization of GF-reinforced compounds based on aliphatic copolyamide (AlCoPA) and aromatic polyamide (ArPA) [Table 3]

[0298] Table 2: Properties of GF reinforced blends [Table 4]

[0299] Stress Crack Resistance Test The test fluid is an aqueous zinc chloride solution with a concentration of 50% by weight. The tensile specimens are dry before testing (dry as molded). The tensile specimens are clamped on a bending mold with an end fiber elongation of 2%. The surface of the specimens is then wetted with zinc chloride solution during the test and images are recorded to determine the time to failure. The test is carried out until failure or terminated after 3 days if no failure occurs. As a reference / control, GF reinforced PA66 (Ultramid® A3EG5 sw564 (Ult. A3EG5 sw564) from BASF SE) and GF reinforced PA6 (Ultramid® B3EG6 sw564 (Ult. B3EG6 s4564) from BASF SE) with comparable tensile modulus were tested.

[0300] Table 2a: Zinc chloride stress crack resistance test results [Table 5]

[0301] Fuel permeation test (Fig. 2) Work procedure: injection moulding of test specimens (plates 150x150x1 mm). Accelerated conditioning at 40°C in the specified E10 fuel. Migration test at 40°C and GC analysis of the permeates (2 plates per sample). As reference / controls, GF reinforced PA66 (Ultramid® A3WG6 bk564 from BASF SE) and GF reinforced PA6 (Ultramid® B3WG6 bk564 from BASF SE) were tested.

[0302] 2) Preparation and characterization of blends of aliphatic copolyamide (AlCoPA) and aromatic polyamide (ArPA) Table 3: Blends of aliphatic copolyamide (AlCoPA) and aromatic polyamide (ArPA) [Table 6]

[0303] Table 4: Properties of blends of aliphatic copolyamide (AlCoPA) and aromatic polyamide (ArPA) [Table 7]

[0304] 3) Preparation and characterization of impact-modified compounds based on aliphatic copolyamide (AlCoPA) and aromatic polyamide (ArPA) Impact modifier IM1 in comparative example 4 and inventive example 6 was metered in via this feed together with the other components. In comparative examples 5 and 6 and inventive examples 7 to 12, impact modifier IM2 was metered in via a side feeder in segment G. In 7 to 12, impact modifier IM2 was metered in via a side feeder in segment G8.

[0305] [Table 8-1] [Table 8-2]

[0306] [Table 9]

[0307] Table 7: Pipe Extrusion The material was extruded through a nozzle with a 16.8 mm diameter and a 13.2 mm core into a 12 mm pipe. [Table 10]

[0308] Reinforced thermoplastic molding composition Table 1 describes the preparation of glass fiber reinforced compounds. The conditioned stiffness (tensile modulus and tensile strength) is significantly increased (Examples 1-3), whereas the stability against zinc chloride (stress crack resistance) remains high (see Table 3). Surprisingly, the compositions comprising a blend of an aliphatic copolyamide according to the invention with a semicrystalline semiaromatic polyamide show increased barrier properties against fuels, whereas the pure aliphatic copolyamide (Comparative Example 1) and the composition comprising a blend of an aliphatic copolyamide and an amorphous semiaromatic polyamide (Comparative Example 2) do not (see FIG. 2). Examples 1-3 and Comparative Example 2 have higher tensile breaking strength after 42 days of storage in AdBlue compared to Comparative Example 1 (FIG. 1). Furthermore, the blend of aliphatic copolyamide and polyamide 6T / 66 (Example 3) additionally shows increased heat distortion temperatures (HDTA and HDTB). When an amorphous semiaromatic polyamide is used (Comparative Example 2), the heat distortion temperature is further reduced (see Table 2). Although the melt temperatures of the semi-crystalline, semi-aromatic polyamides in Examples 2 and 3 were above 300°C, the resulting compounds could be processed in injection molding at a maximum melt temperature of 300°C.

[0309] In summary, reinforced thermoplastic compositions based on the blends of the present invention have been obtained that have high stability against zinc chloride and AdBlue, high heat distortion temperature, high stiffness in the conditioned state, low water absorption, high barrier properties against fuels, and can be processed in injection molding at melt temperatures below 300° C. This property profile provides a wide range of applications in the field of engineering plastics as described above.

[0310] In the first heating curve of the DSC curve of Example 3, the melting point of the aliphatic copolyamide (AlCoPA) at 195.4 ° C and the melting point of the semicrystalline, semiaromatic polyamide (ArPA3) at 308.77 ° C can be observed separately. Surprisingly, no significant transamination reaction occurred during compounding. In the second heating curve after the sample is kept in the molten state for 5 minutes, a new melting peak occurs at 174.95 ° C, which belongs to the transamidation reaction product from the aliphatic copolyamide (AlCoPA) and the semicrystalline, semiaromatic polyamide (ArPA3). Due to this observation, deliberate control of material properties can be carried out in the injection molding process.

[0311] Table 4 describes the preparation of the inventive polymer blends (Examples 4 and 5) of aliphatic copolyamide (AlCoPA) and semicrystalline, semiaromatic polyamide (ArPA). The blends were processed through injection molding and compared with Comparative Example 3, which does not contain the semicrystalline, semiaromatic polyamide. Comparative Example 3 was barely processable in injection molding, since the material stuck to the mold surface. As a result, it was necessary to work at very low mold temperatures (40°C). In contrast, inventive Examples 4 and 5 could be processed at higher mold temperatures (80°C), which are typical for polyamide processing. Inventive Examples 4 and 5 have a higher tensile modulus in the dry and conditioned state, and their heat distortion temperatures (HDTA and HDTB) are significantly increased compared to Comparative Example 3.

[0312] I. Impact-modified thermoplastic molding compositions Table 5 describes the preparation of impact-modified thermoplastic molding compositions in one compounding step. Comparative Examples 4 and 5 showed problems during the granulation process. The granules stuck together and it was almost impossible to cut them. Inventive Example 6 shows an increased tensile modulus in the conditioned state and an increased HDTB value compared to Comparative Example 5. Comparative Example 4 and Inventive Example 6 were extruded into 12 mm pipes. Inventive Example 6 could be extruded below the melt temperature of the semicrystalline, semiaromatic polyamide ArPA1 at 210°C. The pipe made from Inventive Example 6 had a smooth, opaque surface, whereas it was difficult to make a pipe from Comparative Example 4. The material stuck to the nozzle and it was impossible to make a pipe with a smooth surface. [Explanation of symbols]

[0313] Figure 1: 1 Comparative Example 1, 2 Example 1, 3 Example 2, 4 Example 3, 5 Comparative Example 2, abscissa time [days], ordinate retention of tensile breaking strength relative to the initial value [%] FIG. 2: 1 Ultramid® A3WG6 bk564, 2 Ultramid® B3WG6 bk564, 3 Comparative Example 1, 4 Example 3, 5 Comparative Example 2, A EtOH, B Hydrocarbons, C Total, ordinate Permeability [g / m 2 ×d]

Claims

1. 1. A polymer blend comprising: a) from >50% to 99% by weight of at least one aliphatic copolyamide as component A); b) 1% to less than 50% by weight of at least one semicrystalline, semiaromatic polyamide as component B Including; wherein the sum of the weight percent of components A and B is 100 weight percent; The polymer blend.

2. 10. The polymer blend of claim 1, wherein the polyamide of component B has a melting point greater than 250°C.

3. 3. The polymer blend of claim 1 or 2, wherein the polyamide of component B is a copolyamide.

4. 3. The polymer blend of claim 1 or 2, wherein the polyamide of component A has a melting point below 220°C.

5. The polyamide of component A is A') 15% to 84% by weight of at least one lactam; B') The following components B1') at least one C ３２ ~C ４０ Dimer acid and B2') at least one C ４ ~C １２ Diamine 16% by weight to 85% by weight of a monomer mixture (M) is a copolyamide preferably produced by polymerization of 3. The polymer blend of claim 1 or 2, wherein the weight percentages of components A') and B') are based on the sum of the weight percentages of components A') and B'), respectively.

6. 6. The polymer blend of claim 5, wherein the monomer mixture (M) comprises 45 mol% to 55 mol% of component B1') and 45 mol% to 55 mol% of component B2'), based on the sum of the mole percentages of components B1') and B2'), respectively.

7. A thermoplastic molding composition comprising the polymer blend of claim 1 and at least one additional substance C).

8. 8. The thermoplastic molding composition according to claim 7, comprising as additional substance C at least one fibrous and / or particulate filler as component C1).

9. 9. The thermoplastic molding composition according to claim 7, which comprises as additional substance C at least one impact modifier as component C2).

10. 9. The thermoplastic molding composition according to claim 7 or 8, comprising as additional substance C, as component C3), at least one thermoplastic polymer different from components A), B), C2) and different from any further additives.

11. A process for producing the polymer blend of claim 1 or 2 by mixing components A and B.

12. 8. A process for producing the thermoplastic molding composition according to claim 7 by mixing components A, B or the polymer blend according to claim 1 with at least one additional substance C.

13. 10. Use of the polymer blends according to claim 1 or the thermoplastic molding compositions according to claim 7 for the production of moldings and extrusions, in particular moldings, pipes, sheets, films and tubes.

14. 8. Moulded or extruded articles, preferably moulded bodies, pipes, sheets, films or tubes, made from the polymer blends according to claim 1 or the thermoplastic moulding compositions according to claim 7.

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