Impact modifier mixtures in flame retardant polyamides compositions

Abstract

Thermoplastic molding composition comprising at least one thermoplastic polyamide, red phosphorus, a first olefin copolymer, based on of ethylene and at least one (meth)acrylate having from 1 to 18 carbon atoms, a second olefin copolymer, based on ethylene and at least one alpha-olefin having from 3 to 10 carbon atoms, optionally at least one fibrous and / or particulate filler, and optionally at least one further additive; a process for producing the thermoplastic moulding composition, the use of the thermoplastic molding composition for producing fibers, foils or moldings, fibers, foils or moldings comprising the thermoplastic molding composition, and the use of a mixture of a first olefin copolymer, based on ethylene and at least one (meth)acrylate having from 1 to 18 carbon atoms and a second olefin copolymer, based on ethylene and least one alpha-olefin having from 3 to 10 carbon atoms as impact modifier in a thermoplastic molding composition comprising at least one thermoplastic polyamide and red phosphorus.

Description

[0001] Impact modifier mixtures in flame retardant polyamides compositions

[0002] Description

[0003] The present invention relates to a thermoplastic molding composition comprising at least one thermoplastic polyamide, red phosphorus, a first olefin copolymer, based on of ethylene and at least one (meth)acrylate having from 1 to 18 carbon atoms, a second olefin copolymer, based on ethylene and at least one alpha-olefin having from 3 to 10 carbon atoms, optionally at least one fibrous and / or particulate filler, and optionally at least one further additive; a process for producing the thermoplastic moulding composition, the use of the thermoplastic molding composition for producing fibers, foils or moldings, fibers, foils or moldings comprising the thermoplastic molding composition, and the use of a mixture of a first olefin copolymer, based on ethylene and at least one (meth)acrylate having from 1 to 18 carbon atoms and a second olefin copolymer, based on ethylene and least one alpha-olefin having from 3 to 10 carbon atoms as impact modifier in a thermoplastic molding composition comprising at least one thermoplastic polyamide and red phosphorus.

[0004] Red phosphorus has been known for a long time as an extremely effective flame retardant specifically for glass- fiber-reinforced polyamides and for many other plastics. However, many applications require that plastics compositions are not only provided with high flame retardancy. In high-specification applications in the electrical and electronics sector constantly increasing importance is placed on the fine-tuning of properties of materials to give a balanced product profile involving high flame retardancy values together with very good values for mechanical and electrical properties.

[0005] A decisive factor specifically in the case of thin- walled components which by way of example have highly stressed snap connections is that the materials used in particular have good tensile strain values while also having high toughness.

[0006] Glassfiber-reinforced compounded polyamide materials comprising halogen-free flame-retard- ancy systems generally have poorer mechanical properties than similar compositions without any flame-retardancy system, specifically in relation to tensile strain at break and impact resistance. However, addition of impact modifiers based on olefin (co)polymers often leads to severely impaired flame-retardancy properties.

[0007] W02014170148 A1 relates to the use of thermoplastic molding compositions comprising A) from 10 to 97% by weight of a thermoplastic polyamide, B) from 1 to 10% by weight of red phosphorus, C) from 0.15 to 6% by weight of a dialkylphosphinic salt, where the ratio of B) to C) is from 6:1 to 6:4, D) from 1 to 10% by weight of an ethylene copolymer as impact modifier comprising as component D) a copolymer of D1) from 40 to 98% by weight of ethylene D2) from 2 to 40% by weight of a (meth)acrylate having from 1 to 18 carbon atoms, or / and D3) from 0 to 20% by weight of functional monomers selected from the group of the ethylenically unsaturated mono- or dicarboxylic acids or of the carboxylic anhydrides or epoxide groups, or a mixture of these, or an ethylene-(meth)acrylic acid copolymer neutralized with zinc up to an extent of 72%,

[0008] E) from 0 to 5% by weight of talc powder with a median particle size (d50 value) below 7.5 pm,

[0009] F) from 0 to 60% by weight of further additional substances, where the sum of the percentages by weight of components A) to F) is 100%, for the production of flame-retardant, glow- wire-resistant moldings.

[0010] EP0384232 A1 relates to flameproofed thermoplastic molding compositions containing (A) 10- 99% by weight of a thermoplastic polyamide or polyester or polyphenylene ether or a mixture thereof, (B) 1-50% by weight of red phosphorus having a particle size of up to 2 mm which contains, per 100 parts by weight, from 0.05 to 5 parts by weight of a polyurethane or polyester-pol- yurethane as phlegmatizer, (C) 0-60% by weight of a fibrous or particulate filler or a mixture thereof and (D) 0-20% by weight of an elastomeric polymer. Component (D) may be an olefin polymer formed from (d1 ) 40-100% by weight of at least one a-olefin of from 2 to 8 carbon atoms, d2) 0-50% by weight of a diene, d3) 0-45% by weight of a primary or secondary C1-C12- alkyl ester of acrylic or methacrylic acid or a mixture thereof, d4) 0-40% by weight of an acidfunctional or latently acid-functional monomer of an ethylenically unsaturated monomer dicarboxylic acid, d5) 0-40% by weight of an epoxy-containing monomer and d6) 0-5% by weight of another free radical polymerizable monomer.

[0011] EP0303031 A1 relates to flameproofed thermoplastic molding compositions containing (A) 5- 92% by weight of a polyamide, (B) 5-60% by weight of a reinforcing filler and as flame retardant combination (C) 2-15% by weight of red phosphorus and (D) 1-30% by weight of an olefin polymer formed from d1 ) 40-100% by weight of at least one a-olefin of from 2 to 8 carbon atoms, d2) 0-50% by weight of a diene, d3) 0-45% by weight of a primary or secondary C1-C12-alkyl ester of acrylic or methacrylic acid or a mixture thereof, d4) 0-40% by weight of an acid-functional or latently acid-functional monomer of an ethylenically unsaturated monomer dicarboxylic acid, d5) 0-40% by weight of an epoxy-containing monomer, wherein component (D) is not an olefin homopolymer and the molding compositions do not comprise titanium dioxide.

[0012] It is therefore an object of the present invention to provide impact-modified polyamides which have a halogen-free flame-retardancy system and comprising specific impact modifiers, having the required properties in terms of toughness and at the same time having good fire-protection properties, and in particular have glow-wire resistance.

[0013] The object is achieved by a thermoplastic molding composition comprising a) from 10 to 97.9% by weight of at least one thermoplastic polyamide, as component A), b) from 0.1 to 20% by weight of red phosphorus, as component B), c) from 1 to 20% by weight of a first olefin copolymer, based on: c1 ) from 40 to 98% by weight, preferably from 50 to 94.5% by weight, of ethylene, as component C1); c2) from 2 to 40% by weight, preferably from 5 to 40% by weight, of at least one (meth)acry- late having from 1 to 18 carbon atoms, as component C2); c3) from 0 to 20% by weight, preferably from 0.05 to 10% by weight, of at least one ethylenically unsaturated mono- or dicarboxylic acid, at least one ethylenically unsaturated oxirane, or a mixture of these, as component C3); c4) from 0 to 5% by weight, preferably from 0.05 to 2% by weight, of at least one ethylenically unsaturated dicarboxylic anhydride; preferably maleic anhydride, as component C4); where the sum of the percentages by weight C1), C2), C3) and C4) is 100%, as component C); d) from 1 to 20% by weight of a second olefin copolymer, based on: d1 ) from 35 to 98% by weight, preferably from 45 to 80% by weight, of ethylene, as component D1 ); d2) from 2 to 65% by weight, preferably from 20 to 55% by weight, of at least one alpha-olefin having from 3 to 10 carbon atoms, as component D2); d3) from 0 to 5% by weight, preferably from 0.05 to 2% by weight, of at least one ethylenically unsaturated dicarboxylic anhydride; preferably maleic anhydride, as component D3); where the sum of the percentages by weight D1 ), D2) and D3) is 100%, as component D), e) from 0 to 60% by weight of at least one fibrous and / or particulate filler, as component E), and f) from 0 to 60% by weight of at least one further additive, as component F), where the total of the percentages by weight of components A) to F) is 100% by weight, wherein the at least one thermoplastic polyamide of component A) consists of PA6, PA66 and mixtures thereof.

[0014] The thermoplastic molding composition of the invention in general has a UL94 V-0 or V-1 rating at 0.8 mm.

[0015] The object is further achieved by a process for producing the inventive thermoplastic molding composition having a UL94 V-0 or V-1 rating at 0.8 mm comprising the step of mixing the components A), B), C), D) and optionally E) and optionally F); and the use of the inventive thermoplastic molding composition having a UL94 V-0 or V-1 rating at 0.8 mm or the thermoplastic molding composition obtained by the inventive process for producing fibers, foils or moldings, preferably connectors and conjunction boxes; and fibers, foils or moldings, preferably connectors and conjunction boxes comprising the inventive thermoplastic molding composition or the thermoplastic molding composition obtained by the inventive process for producing fibers, foils or moldings, especially connectors and conjunction boxes.

[0016] Further, the object is achieved by the use of a mixture comprising a first olefin copolymer, based on: c1 ) from 40 to 98% by weight, preferably from 50 to 94.5% by weight, of ethylene, as component C1 ); c2) from 2 to 40% by weight, preferably from 5 to 40% by weight, of at least one (meth)acry- late having from 1 to 18 carbon atoms, as component C2); c3) from 0 to 20% by weight, preferably from 0.05 to 10% by weight, of at least one ethylenically unsaturated mono- or dicarboxylic acid, at least one ethylenically unsaturated oxirane, or a mixture of these, as component C3); c4) from 0 to 5% by weight, preferably from 0.05 to 2% by weight, of at least one ethylenically unsaturated dicarboxylic anhydride; preferably maleic anhydride, as component C4); where the sum of the percentages by weight C1), C2), C3) and C4) is 100%, as component C); and a second olefin copolymer, based on: d1 ) from 35 to 98% by weight, preferably from 45 to 80% by weight, of ethylene, as component D1 ); d2) from 2 to 65% by weight, preferably from 20 to 55% by weight, of at least one alpha-olefin having from 3 to 10 carbon atoms, as component D2); d3) from 0 to 5% by weight, preferably from 0.05 to 2% by weight, of at least one ethylenically unsaturated dicarboxylic anhydride; preferably maleic anhydride, as component D3); where the sum of the percentages by weight D1), D2) and D3) is 100%, as component D), as impact modifier for producing a thermoplastic molding composition having a UL94 V-0 or V-1 rating at 0.8 mm and comprising at least one thermoplastic polyamide, selected from the group consisting of PA6, PA66 and mixtures thereof, as component A) and red phosphorus, as component B).

[0017] It has been found by the inventors of the present invention that an impact-modifier combination comprising components C) and D) fulfills the required properties in terms of toughness and fireprotection properties in polyamide molding compositions comprising red phosphorus.

[0018] In the context of the present invention, the term “copolymer” encompasses polymers formed from two or more, for example 3 or 4, different monomers.

[0019] The polyamides are designated in the context of the invention using abbreviations, some of which are customary in the art, which consist of the letters PA followed by numbers and letters. Some of these abbreviations are standardized in DIN EN ISO 1043-1 . Polyamides which can be derived from aminocarboxylic acids of the H2N — (CH2)x — COOH type or the corresponding lactams are identified as PAZ where Z denotes the number of carbon atoms in the monomer. For example, PA6 represents the polymer of 6-caprolactam or of uj-aminocaproic acid. Polyamides derivable from diamines and dicarboxylic acids of the H2N — (CFhX — NH2 and HOOC-(CH2)y- COOH types are identified as PAZ1Z2 where Z1 denotes the number of carbon atoms in the diamine and Z2 the number of carbon atoms in the dicarboxylic acid. Copolyamides are designated by listing the components in the sequence of their proportions, separated by slashes. For example, PA 66 / 610 is the copolyamide of hexamethylenediamine, adipic acid and sebacic acid. For monomers having an aromatic or cycloaliphatic group, the following letter abbreviations are used: T=terephthalic acid, l=isophthalic acid, MXDA=m-xylylenediamine, IPDA=iso- phoronediamine, PACM=4,4'-methylenebis(cyclohexylamine), MACM=2,2'-dimethyl-4, 4'-meth- ylenebis(cyclohexylamine). The expression “amorphous polyamide” encompasses (co)polyamides which do not exhibit any change in phase and have only one glass transition temperature (Tg).

[0020] The expression “semicrystalline polyamide” encompasses (co)polyamides which have both a glass transition temperature (Tg) and a melting temperature (Tm).

[0021] Glass transition temperatures (Tg) and melting temperatures (Tm) can be determined by means of differential scanning calorimetry (DSC). The determination can be effected in a manner known per se (DIN EN ISO 11357, Parts 1 to 3).

[0022] Hereinafter, some compounds which can derive from acrylic acid and methacrylic acid are abbreviated by insertion of the syllable “(meth)” into the compound derived from acrylic acid.

[0023] The inventive molding compositions comprise, as component A), from 10 to 97.9% by weight, preferably from 20 to 96% by weight, and in particular from 30 to 87% by weight, of at least one polyamide. The polyamides of the molding compositions of the invention generally have an intrinsic viscosity of from 90 to 350 ml / g, preferably from 110 to 240 ml / g, determined in a 0.5% by weight solution in 96% by weight sulfuric acid at 25° C to ISO 307.

[0024] Component A) is selected from PA 6 and PA 66 and mixtures thereof.

[0025] As component B) 0.1 to 20 % by weight, preferably 1 to 10 % by weight, more preferably 3 to 8 % by weight of red phosphorus (P) are present in the inventive molding compositions, based on the entirety of components A) to F).

[0026] The amount of component B) is in each case calculated on P.

[0027] Generally, elemental red phosphorus can be employed as component B) in the inventive molding compositions, in particular in combination with glassfiber-reinforced molding compositions, it can be used in untreated form.

[0028] However, particularly suitable preparations are those in which the phosphorus has been surface-coated with low-molecular-weight liquid substances, such as silicone oil, paraffin oil, or esters of phthalic acid (in particular dioctyl phthalate, see EP 176 836) or adipic acid, or with polymeric or oligomeric compounds, e.g. with phenolic resins or amino plastics, or else with polyurethanes (see EP-A 384 232, DE-A 19648 503). The amounts comprised of these “phlegmatizing agents” are generally from 0.05 to 5% by weight, based on 100% by weight of B).

[0029] Concentrates of red phosphorus, e.g. in a polyamide or elastomer, are moreover suitable as component B). In particular, polyolefin homo- and copolymers are suitable as concentrate polymers.

[0030] Preferred concentrate compositions are

[0031] Bi) from 30 to 90% by weight, preferably from 45 to 70% by weight, of a polyamide A) or a first olefin copolymer C), or a second olefin copolymer D), and

[0032] B2) from 10 to 70% by weight, preferably from 30 to 55% by weight, of red phosphorus. The polyamide used for the masterbatch can differ from A) or preferably can be the same as A), in order to avoid any incompatibility or melting point difference having an adverse effect on the molding composition.

[0033] The median particle size (dso) of the phosphorus particles dispersed in the molding compositions is preferably in the range from 0.0001 to 0.5 mm; in particular from 0.001 to 0.2 mm.

[0034] The molding compositions of the invention comprise, as component C), 1 to 20% by weight, preferably 1.5 to 15% by weight, more preferably 2 to 10% by weight, of a first olefin copolymer.

[0035] The first olefin copolymer is based on: c1 ) from 40 to 98% by weight, preferably from 50 to 94.5% by weight, more preferably from 55 to 80% by weight of ethylene, as component C1 ); c2) from 2 to 40% by weight, preferably from 5 to 40% by weight, more preferably from 10 to 38% by weight of at least one alkyl (meth)acrylate having from 1 to 18 carbon atoms, as component C2); c3) from 0 to 20% by weight, preferably from 0.05 to 10% by weight, more preferably from 1 to 8% by weight of at least one ethylenically unsaturated mono- or dicarboxylic acid, at least one ethylenically unsaturated oxirane, or a mixture of these, as component C3); c4) from 0 to 5% by weight, preferably from 0.05 to 2% by weight, more preferably from 0.5 to 1 .5% by weight of at least one ethylenically unsaturated dicarboxylic anhydride; preferably maleic anhydride, as component C4); where the sum of the percentages by weight C1), C2), C3) and C4) is 100%, as component C).

[0036] Component C2) is at least one alkyl (meth)acrylate having from 1 to 18 carbon atoms in its alkyl part.

[0037] Suitable components C2) are therefore the alkyl esters of (meth)acrylic acid with alcohols of the formula (II)

[0038] R4-OH (II) in which

[0039] R4is Ci-Cis-alkyl, preferably Ci-Cio-alkyL

[0040] Examples of these are methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, 2- ethylhexyl (meth)acrylate and 2-(n-propyl)heptyl(meth)acrylate.

[0041] More preferably, component C2) is at least one alkyl (meth)acrylate having from 1 to 4 carbon atoms in its alkyl part, for example methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acry- late. Most preferably, component C2) is n-butylacrylate. Component C3) is at least one ethylenically unsaturated mono- or dicarboxylic acid, at least one ethylenically unsaturated oxirane, or a mixture of these.

[0042] Suitable ethylenically unsaturated monocarboxylic acids are preferably monoethylenically unsaturated C3-C23 monocarboxylic acids. Suitable monoethylenically unsaturated C3-C23 monocarboxylic acids are monocarboxylic acids having a linear or branched alkenyl radical having 2 to 22 carbon atoms.

[0043] Among the monoethylenically unsaturated C3-C23 monocarboxylic acids having a linear or branched alkenyl radical having 2 to 22 carbon atoms, preference is given to C3-C23 monoethylenically unsaturated monocarboxylic acids of the formula (V) in which

[0044] R10 is selected from hydrogen and

[0045] C1-C10-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-bu- tyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimeth- ylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, n-decyl;

[0046] R11 is selected from hydrogen and

[0047] C1-C10-alkyl, for example methyl, ethyl, n-pro- pyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertbutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, n-decyl.

[0048] In a preferred embodiment, R10 is hydrogen or C1-C4-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, especially methyl or ethyl, very particularly hydrogen or methyl.

[0049] In another preferred embodiment, R11 is hydrogen or C1-C4-alkyl such as methyl, ethyl, n-pro- pyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, especially hydrogen or methyl and very particularly hydrogen.

[0050] Among these, particular preference is given to monoethylenically unsaturated C3-C6 monocarboxylic acids. Examples of these are acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid and isocrotonic acid. Very particularly preferred monoethylenically unsaturated C3-C6 monocarboxylic acids are acrylic acid and methacrylic acid.

[0051] Additionally suitable are monoethylenically unsaturated monocarboxylic acids having a cycloaliphatic radical, where the carboxyl group is bonded to a ring carbon atom of the cycloaliphatic radical. Useful cycloaliphatic radicals include monocyclic and bicyclic radicals. The cycloaliphatic radical comprises a total of 5 to 22 carbon atoms. The cycloaliphatic radical may be substituted by further aliphatic groups, especially alkyl groups, more preferably 1 , 2 or 3 C1-C4-al- kyl groups. More particularly, the cycloaliphatic radical is C5-C12-cycloalkenyl which is unsubstituted or bears 1 , 2 or 3 C1-C4-alkyl groups. Suitable ethylenically unsaturated dicarboxylic acids are monoethylenically unsaturated C4-C20 dicarboxylic acids.

[0052] Useful monoethylenically unsaturated C4-C20 dicarboxylic acids are dicarboxylic acids having a linear or branched alkenyl radical having 2 to 18 carbon atoms. Among these, preference is given to monoethylenically unsaturated C4-C20 dicarboxylic acids of the formula (VII) in which

[0053] R14 and R15 are each independently selected from hydrogen and C1-C8-alkyl, preferably selected from hydrogen and C1-C6-alkyL

[0054] Preferred compounds of the formula (VII) are maleic acid and fumaric acid, especially maleic acid.

[0055] Examples of monoethylenically unsaturated C4-C20 dicarboxylic acids are additionally monoethylenically unsaturated dicarboxylic acids having a cycloaliphatic radical, where both carboxyl groups are bonded to ring carbon atoms of the cycloaliphatic radical. The cycloaliphatic radical has a total of 5 to 22 carbon atoms. The cycloaliphatic radical is preferably a monocyclic or bicyclic radical. The cycloaliphatic radical may be substituted by further aliphatic groups, especially alkyl groups, more preferably 1 , 2 or 3 C1-C4-alkyl groups. More particularly, the cycloaliphatic radical is C5-C12-cycloalkenyl which is unsubstituted or bears 1 , 2 or 3 C1-C4-alkyl groups. The cycloaliphatic radical is more preferably a bicyclo[2.2.1]hept-2-en-yl group or a 2- methylbicyclo[2.2.1]hept-2-en-yl group. Examples of cycloaliphatic, monoethylenically unsaturated dicarboxylic acids are bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid and 5-methylbicy- clo[2.2.1]hept-5-ene-2,3-di- carboxylic acid.

[0056] Suitable ethylenically unsaturated oxiranes are preferably ethylenically unsaturated oxiranes of the formula (IV)

[0057] O

[0058] CH2= CR9— C — O — (CH2)O— CH — CHR8o

[0059] (IV) in which

[0060] R8 and R9 are each independently selected from hydrogen and C1-C6-alkyl; and o is an integer from 0 to 5. Preferred compounds of the formula (IV) are ethylenically unsaturated glycidyl ester, such as glycidyl acrylate and glycidyl methacrylate.

[0061] Preferably, component C3) is at least one ethylenically unsaturated monocarboxylic acid, at least one ethylenically unsaturated monoglycidyl ester, or a mixture of these; preferably (meth)acrylic acid and / or glycidyl(meth)acrylate, more preferably (meth)acrylic acid, most preferably acrylic acid.

[0062] Component C4) is at least one ethylenically unsaturated dicarboxylic anhydride, preferably at least one monoethylenically unsaturated C4-C20 dicarboxylic anhydride. Useful dicarboxylic anhydrides are, for example, the anhydrides of the aforementioned (se C3)) ethylenically unsaturated C4-C20 dicarboxylic acids in which the carboxyl groups are arranged in such a way that they can form an intramolecular anhydride.

[0063] Suitable monoethylenically unsaturated C4-C20 dicarboxylic anhydrides are preferably those of the formula

[0064] (VIII) in which

[0065] R16 and R17 are each independently selected from hydrogen and C1-C8-alkyl, preferably selected from hydrogen and C1-C6-alkyL

[0066] A very particularly preferred component C4) is maleic anhydride.

[0067] Suitable monoethylenically unsaturated C4-C20 dicarboxylic anhydrides are additionally monoethylenically unsaturated dicarboxylic anhydrides having a cycloaliphatic radical.

[0068] The cycloaliphatic radical is generally a monocyclic or bicyclic radical and has a total of 5 to 18 carbon atoms. The cycloaliphatic radical may be substituted by further aliphatic groups, especially alkyl groups, more preferably 1 , 2 or 3 C1-C4-alkyl groups. Examples of monoethylenically unsaturated dicarboxylic anhydrides having a cycloaliphatic group are bicyclo[2.2.1]hept-5-ene- 2,3-dicarboxylic anhydride and 5-methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride.

[0069] A preferred component C) is an olefin copolymer based on ethylene as component C1 ), ethyl acrylate or n-butyl acrylate as component C2), and acrylic acid as component C3) and / or maleic anhydride as component C4). More preferably, component C) is an olefin polymer based on from 55 to 80% by weight of ethylene as component C1 ), from 10 to 38% by weight ethyl acrylate or n-butyl acrylate as component C2), and from 1 to 8% by weight acrylic acid as component C3) and / or from 0.5 to 1.5% by weight maleic anhydride as component C4), where the sum of the percentages by weight C1), C2), C3) and C4) is 100%.

[0070] Corresponding products are for example available from BASF SE under the trade name Lu- polen© KR 1270.

[0071] The molding compositions of the invention comprise, as component D), 1 to 20% by weight, preferably 2 to 18% by weight, more preferably 3 to 15% by weight, of a second olefin copolymer.

[0072] The second olefin copolymer is based on: d1 ) from 35 to 98% by weight, preferably from 45 to 80% by weight, more preferably from 50 to 80% by weight of ethylene, as component D1 ); d2) from 2 to 65% by weight, preferably from 20 to 55% by weight, more preferably from 30 to 50% by weight of at least one alpha-olefin having from 3 to 10 carbon atoms, as component D2); d3) from 0 to 5% by weight, preferably from 0.05 to 2% by weight, more preferably from 0.3 to 1 .5% by weight of at least one ethylenically unsaturated dicarboxylic anhydride; preferably maleic anhydride, as component D3); where the sum of the percentages by weight D1), D2) and D3) is 100%, as component D).

[0073] Component D2) is at least one alpha-olefin having from 3 to 10 carbon atoms. Preferably, component D2) is at least one alpha-olefin having from 3 to 8 carbon atoms.

[0074] In the context of the present invention, alpha-olefins are understood to mean those olefins which have an olefinic double bond at one end (i.e. in the a,p position) of the longest carbon chain of the molecule. alpha-Olefins are also called terminal alkenes, a-olefins, or 1 -alkenes. The alpha-olefins are branched and linear.

[0075] C3 -C10-a-Olefins are therefore linear or branched alkenes having from 3 to 10 carbon atoms and a C — C double bond at one end (i.e. in the a,p position) of the longest carbon chain of the molecule. C3 -C8-a-Olefins are linear or branched alkenes having from 3 to 8 carbon atoms and a C — C double bond at one end (i.e. in the a,p position) of the longest carbon chain of the molecule.

[0076] Examples for linear alpha-olefins are 1 -octene, propene, 1 -butene, and 1 -decene. An example for a branched alpha-olefin is isobutylene.

[0077] Preferably, component D2) is 1 -octene. Component D3) is at least one ethylenically unsaturated dicarboxylic anhydride, preferably at least one monoethylenically unsaturated C4-C20 dicarboxylic anhydride. Useful dicarboxylic anhydrides are, for example, the anhydrides of the aforementioned (se C3)) ethylenically unsaturated C4-C20 dicarboxylic acids in which the carboxyl groups are arranged in such a way that they can form an intramolecular anhydride.

[0078] Suitable and preferred ethylenically unsaturated dicarboxylic anhydrides are the same as mentioned as component C4) above.

[0079] Component D3) is most preferably maleic anhydride.

[0080] Preferably, components D1 ) and D2) form a copolymer which is grafted with suitable monomers D3) for introducing functional groups. More preferred components D) are ethylene / 1 -octene copolymers grafted with suitable monomers D3) for introducing functional groups.

[0081] A preferred component D) is an olefin copolymer based on ethylene as component D1 ), 1 -octene as component D2), and maleic anhydride as component D3).

[0082] More preferably, component D) is an olefin polymer based on from 50 to 80% by weight of ethylene as component D1 ), from 30 to 50% by weight of 1 -octene as component D2), and from 0.3 to 1 .5% by weight of maleic anhydride as component D3), where the sum of the percentages by weight D1 ), D2) and D3) is 100%.

[0083] Corresponding products are for example available under the trade name

[0084] Fusabond© N493 available from Dow and Scona TSPOE 1002CMB1-2© available from BYK.

[0085] The thermoplastic molding composition according to any one of claims 1 to 3, wherein the weight ratio of component C) to component D) is from 0.3 : 1 to 2 : 1 , preferably 0.5 : 1 to 1 .5 : 1.

[0086] The molding compositions of the invention can comprise, as component E), 0 to 60% by weight, preferably 1 to 50% by weight, more preferably 5 to 40% by weight, of at least one fibrous and / or particulate filler.

[0087] Preferably, component E) is selected from the group consisting of glass fibers, carbon fibers, glass beads, e.g. solid or hollow glass beads, ground glass, amorphous quartz glass, aluminum borosilicate glass having an alkali content of about 1 %, amorphous silica, quartz flour, alkaline earth metal silicate, especially calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or milled quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite, boehmite, bentonite, vermiculite, hectorite, laponite, pseudoboehmite of formula AIO(OH), magnesium carbonate, talc, aramid fibers, potassium titanate fibers, barium carbonate, alkaline earth metal oxide, metallic fibers, ceramic fibers, titanium dioxide, aluminum oxide, plaster, zirconium oxide, antimony oxide, clay, silica-alumina, sericite, diatomite, silica stone, glassy hollow microspheres, red oxide, lamellar or acicular nanofillers and mixtures thereof.

[0088] Preferred fillers that may be mentioned are glass fibers, especially in the form of E glass. These can be used in the form of e.g. rovings or chopped glass, generally in all forms available commercially.

[0089] The glass fibers preferably have a diameter of 3 to 15 pm, more preferably 4 to 12 pm.

[0090] In case of chopped glass fibers, the length is preferably 3 to 10 mm, preferably 3.5 to 8 mm.

[0091] An example are standard chopped glass fibers (i.e. E glass fibers) for polyamides, length=4.5 mm, diameter=10 pm.

[0092] In order to improve compatibility with the thermoplastics, the fillers, especially the glass fibers, can be surface-pretreated with a silane compound.

[0093] Suitable silane compounds are those of the general formula in which the definitions of the substituents are as follows: n is an integer from 2 to 10, preferably from 3 to 4, m is an integer from 1 to 5, preferably from 1 to 2, k is an integer from 1 to 3, preferably 1 .

[0094] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, and also the corresponding silanes which comprise a glycidyl group as substituent X.

[0095] The amounts of the silane compounds generally used for surface treatment are from 0.01 to 2% by weight, preferably from 0.025 to 1 .0% by weight, and in particular from 0.05 to 0.5% by weight (based on the total weight of the fibrous filler).

[0096] Acicular mineral fillers are also suitable.

[0097] For the purposes of the invention, acicular mineral fillers are mineral fillers with strongly developed acicular character. An example is acicular wollastonite. The mineral preferably has an L / D (length to diameter) ratio of from 8:1 to 35:1 , preferably from 8:1 to 11 :1 . The mineral filler may, if appropriate, have been pretreated with the abovementioned silane compounds, but the pretreatment is not essential.

[0098] Other fillers which may be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk, and also lamellar or acicular nanofillers. Materials preferred for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite, and laponite. The lamellar nanofillers are organically modified by prior-art methods, to give them good compatibility with the polyamide. Addition of the lamellar or acicular nanofillers to the inventive molding compositions gives a further increase in mechanical strength.

[0099] The molding compositions of the invention comprise 0 to 60% by weight, preferably 0.1 to 10 % by weight, more preferably 0.3 to 5% by weight, of at least one further additive as component F), based on the total weight of the molding compositions. The amount refers to the total weight% of component F) in the inventive molding compositions.

[0100] Further additives are for example acid scavengers for the red phosphorus, a dialkylphosphinic salt, and / or conventional processing aids, such as lubricants, antioxidants, a nigrosine, stabilizers, oxidation retarders, agents to counteract decomposition due to heat and decomposition due to ultraviolet light, lubricants and mold-release agents, colorants, such as dyes and pigments, nucleating agents, plasticizers, etc.

[0101] The molding compositions of the invention can comprise a dialkylphosphinic salt, as component F). If the a dialkylphosphinic salt is present, it is generally present in an amount from 0.15 to 6% by weight, preferably from 0.5 to 5% by weight, and in particular from 1 to 3% by weight, based on the total weight of the molding composition.

[0102] It is preferable that the dialkylphosphinic salt is composed of where R1and R2are mutually independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, phenyl,

[0103] M=Mg, Ca, Al, Ti, Zn, Fe, Li, Na, K, or a protonated nitrogen base, x=from 1 to 4, n=from 1 to 4.

[0104] Particular preference is given to R1and R2=methyl or ethyl and M=AI or Zn, and particular preference is given here to Al diethylphosphinate or Zn diethylphosphinate. The phosphinates are preferably produced via precipitation of the corresponding metal salts from aqueous solutions. However, the phosphinates can also be precipitated in the presence of, as support material, a suitable inorganic metal oxide or metal sulfide (white pigments, for example TiC>2 SnC>2 ZnO, ZnS, SiC>2). The products are therefore surface-modified pigments.

[0105] The molding compositions of the invention can comprise acid scavengers for the red phosphorus, as component F). If the acid scavengers for the red phosphorus are present, they are generally present in an amount from 0.01 to 2% by weight, preferably from 0.1 to 1 .5% by weight, and in particular from 0.1 to 1 % by weight, based on the total weight of the molding composition.

[0106] Suitable acid scavengers are ZnO, Zn borate, Zn stannate, MgO, Mg(OH)2j ZnCOs, MgCOs, CaCOs Mg Ca carbonates, and AIOOH, particular preference being given here to ZnO, basic ZnCOs, Mg(OH)2; CaCOs and CuO / ZnO / AI2O3 mixed oxides CaCOs, ZnO.

[0107] Examples for suitable conventional processing aids are mentioned in the following in more detail:

[0108] The inventive molding compositions may comprise at least one lubricant. If the lubricant is present, it is generally present in an amount 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.

[0109] Preference is given to the salts of Al, of alkali metals, or of alkaline earth metals, or esters or amides of fatty acids having from 10 to 44 carbon atoms, preferably having from 12 to 44 carbon atoms.

[0110] The metal ions are preferably alkaline earth metal, Zn and Al, particular preference being given to Ca or Mg. Preferred metal salts are Ca stearate and Ca montanate, and also Al stearate. It is also possible to use a mixture of various salts, in any desired mixing ratio.

[0111] The carboxylic acids can be monobasic or dibasic. Examples which may be mentioned are pelaigonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, and particularly preferably stearic acid, capric acid, and also montanic acid (a mixture of fatty acids having from 30 to 40 carbon atoms).

[0112] The aliphatic alcohols can be monohydric to tetrahydric. Examples of alcohols are n-butanol, n- octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, preference being given to glycerol and pentaerythritol.

[0113] The aliphatic amines can be mono- to tribasic. Examples of these are stearylamine, ethylenediamine, propy- lenediamine, hexamethylenediamine, di(6-aminohexyl) amine, particular preference being given to ethylenediamine and hexamethylenediamine. Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tet- rastearate. It is also possible to use a mixture of various esters or amides, or of esters with amides in combination, in any desired mixing ratio. The molding compositions of the invention can comprise at least one antioxidant, as component F). If the antioxidant is present, it is generally present in an amount from 0.05 to 3% by weight, preferably from 0.01 to 1.5% by weight, and in particular from 0.1 to 1 % by weight, based on the total weight of the molding compositions.

[0114] Suitable antioxidants are sterically hindered phenols which are in principle all of the compounds which have a phenolic structure and which have at least one bulky group on the phenolic ring. Examples of compounds that can be used with preference are those of the formula where:

[0115] R1and R2are an alkyl group, a substituted alkyl group, or a substituted triazole group, and where the radicals R1and R2may be identical or different, and R3is an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group.

[0116] Antioxidants of the abovementioned type are described by way of example inDE-A 27 02 661 U.S. Pat. No. 4 360 617).

[0117] Another group of preferred sterically hindered phenols is provided by those derived from substituted benzenecarboxylic acids, in particular from substituted benzenepropionic acids. Particularly preferred compounds from this class are compounds of the formula where R4, R5, R7, and R8, independently of one another, are C1-C8-alkyl groups which themselves may have substitution (at least one of these substituents being a bulky group), and R6is a divalent aliphatic radical which has from 1 to 10 carbon atoms and whose main chain may also have C — O bonds. Preferred compounds corresponding to this formula are (Irganox® 1098 from BASF SE)

[0118] (Irganox® 259 from BASF SE)

[0119] All of the following should be mentioned as examples of sterically hindered phenols: 2,2'-methylenebis(4-methyl-6-tert-butylphenol),1 ,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxy- phenyl) propionate], pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate], distearyl 3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, 2,6,7-trioxa-l-phosphabicyclo[2.

[0120] 2.2]oct-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhy drocinnamate, 3,5 -di -tert-butyl -4 -hydrox- yphenyl-3,5-distearylthiotriazylamine, 2-(2'-hydroxy-3'-hydroxy-3',5'-di-tert-butylphenyl)-5- chlorobenzo triazole, 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 -hydroxybenzy Idimethy lamine.

[0121] Compounds which have proven particularly effective and which are therefore used with preference are 2,2'- methylenebis(4-methyl-6-tert-butylphenyl), 1 ,6-hexanediol bis(3,5-di-tert-butyl-4- hydroxyphenyl] propionate (Irganox® 259), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxy- phenyl)propionate, and also N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098), and Irganox® 245 from BASF SE, which has particularly good suitability.

[0122] In some instances, sterically hindered phenols having not more than one sterically hindered group in ortho position with respect to the phenolic hydroxy group have proven particularly advantageous, in particular when assessing colorfastness on storage in diffuse light over prolonged periods.

[0123] Materials known as copper stabilizers provide another group of preferred antioxidants.

[0124] If present, the copper stabilizers are present in amounts of from 0 to 1% by weight, preferably from 0.05 to 0.5% by weight, based on the total weight of the molding composition.

[0125] These copper stabilizers are generally composed of two components, namely of a mixture of copper compounds and of specific halide salts. The usual copper compounds are the copper(l) halides, and also copper salts such as copper acetate, copper sulfate, or copper stearate, and the copper complexes, for example copper acetylacetonate. In order that these compounds are effective as antioxidants, halogen compounds must be added in large excess. Those used here are in particular potassium iodide, and also potassium bromide. The amount used here is usually selected in such a way that the molar ratio copper:halogen is 1 : from 5 to 15. The recommended amount added is generally from 30 to 200 ppm of copper. Preference is moreover given to copper complexes with the following complex ligands: triphenylphosphines, mercaptobenzimidazoles, acetylacetonates, and glycine. Particular preference is given to triphenylphosphines and mercaptobenzimidazoles .

[0126] Preferred copper complexes used are usually formed via reaction of copper(l) ions with the phosphine compounds or mercaptobenzimidazole compounds. By way of example, said complexes can be obtained via reaction of triphenylphosphine with a copper(l) halide suspended in chloroform (G. Kosta, E. ReisenhoferandL. Stafani, J. Inorg. Nucl. Chem. 27 (1965) 2581). However, it is also possible to carry out a reductive reaction of copper(ll) compounds with triphenylphosphine and thus obtain the copper(l) adducts (F. U. Jardine, L. Rule, A. G. Vohrei, J. Chem. Soc. (A) 238-241 (1970)).

[0127] Examples of suitable complexes can be represented by the following formulae:

[0128] [Cii(PPli3)3X], [Cu^PPh^], [Cu(PPh3)X]4and

[0129] [Cu(PPh3)2)X]. where X is selected from Cl?Br,

[0130] I, CM, SCN, or 2-MBI.

[0131] The molding compositions of the invention can comprise, as component F), a nigrosin.

[0132] If a nigrosine is present, it is generally present in an amount from 0 to 5% by weight, preferably from 0.1 to 2% by weight, and in particular from 0.25 to 1 .5% by weight, based on the total weight of the molding composition.

[0133] Nigrosins are generally a group of black or gray phenazine dyes (azine dyes) related to the in- dulines and taking various forms (water-soluble, liposoluble, spirit-soluble), used in wool dyeing and wool printing, in black dyeing of silks, and in the coloring of leather, of shoe creams, of varnishes, of plastics, of stoving lacquers, of inks, and the like, and also as microscopy dyes. Nigrosins are obtained industrially via heating of nitrobenzene, aniline, and aniline hydrochloride with metallic iron and FeCh (the name being derived from the Latin niger = black).

[0134] The nigrosin can be used in the form of free base or else in the form of salt (e.g. hydrochloride). Further details concerning nigrosins can be found by way of example in the electronic encyclopedia Rompp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword “Nigrosin”.

[0135] Examples of oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, and amines (e.g. TAD), hydroquinones, aromatic secondary amines, such as diphenylamines, various substituted members of these groups, and mixtures of these, at concentrations of up to 1 % by weight, based on the weight of the thermoplastic molding compositions.

[0136] UV stabilizers that may be mentioned, the amounts of which used are generally - if present - up to 2% by weight, based on the molding composition, are various substituted resorcinols, salicylates, benzotriazoles, benzophenones and hydroxyphenyltriazines.

[0137] Materials that can be added as colorants are inorganic pigments, such as titanium dioxide, ultra- marine blue, iron oxide, and carbon black, and also organic pigments, such as phthalocyanines, quinacridones, perylenes, and also dyes, such as anthraquinones.

[0138] Materials that can be used as nucleating agents are sodium phenylphosphinate, talc powder, aluminum oxide, silicon dioxide.

[0139] The thermoplastic molding compositions of the invention can be produced by processes known per se, by mixing the starting components A), B), D), and C), and also optionally F) and optionally E). Suitable mixing apparatus are conventional mixing apparatus, such as screw-based extruders, Brabender mixers, or Banbury mixers, and then extruding the same. The extrudate can be cooled and pelletized. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise in the form of a mixture. The mixing temperatures are generally from 230 to 320° C.

[0140] In another preferred method of operation, it is possible to mix components B), D), and C), and also optionally F) and optionally E) with a prepolymer, and to compound and pelletize the material. The resultant pellets are then solid-phase condensed under inert gas continuously or batch- wise at a temperature below the melting point of component A) until the desired viscosity is reached.

[0141] The inventive thermoplastic molding compositions feature good toughness and at the same time good flame retardancy and excellent phosphorus stability.

[0142] These materials are suitable for the production of moldings which pass the GWFI (glow wire flammability index) test in accordance with DIN EN 60 695-2-12 at 825°C.

[0143] Some examples for suitable applications will now be mentioned: plug connectors, plugs, plug parts, cable harness components, circuit mounts, circuit-mount components, three-dimension- ally injection-molded circuit mounts, electrical connectors, and mechatronic components.

[0144] The moldings or semifinished products to be produced from the inventive thermoplastic molding compositions can be used by way of example in the motor vehicle industry, electrical industry, electronics industry, telecommunications industry, information technology industry, consumer electronics industry, or computer industry, in vehicles and other means of conveyance, in ships, in spacecraft, in the household, in office equipment, in sports, in medicine, and also generally in articles and parts of buildings which require increased fire protection.

[0145] Possible uses of improved-flow polyamides in the kitchen and household sector are for the production of components for kitchen devices, e.g. fryers, smoothing irons, knobs, and also applications in the garden and leisure sector.

[0146] EXAMPLES

[0147] The following components were used:

[0148] Component a:

[0149] Nylon-6, 6 with intrinsic viscosity IV 150 mL / g, measured in 0.5% by weight solution in 96% by weight sulfuric acid at 25° C. to ISO 307 (using Ultramid® A27 from BASF SE).

[0150] Component b: red phosphorus of an average particle size (d50) from 15 to 25 pm and max. 40% of particles < 10 pm.

[0151] Component c: an olefin polymer made of: 59.8% by weight of ethylene, 35% by weight of n-bu- tyl acrylate, 4.5% by weight of acrylic acid, and 0.7% by weight of maleic anhydride with melt index MFI (190 / 2.16) 10 g / 10 min (Lupolen® KR1270). The copolymer was produced via copolymerization of the monomers at elevated temperature and elevated pressure.

[0152] Component d / 1 : an olefin polymer made of: 53.3% by weight of ethylene, 46.7% by weight of 1- octene, and 0.4 to 0.6% by weight of maleic anhydride with melt index MFI (190 / 2.16) 1.4 g / 10 min. (Fusabond® N493).

[0153] Component d / 2: an olefin polymer made of: 55.7% by weight of ethylene, 44.3% by weight of 1- octene, and >0.45% by weight of maleic anhydride with melt index MFI (190 / 2.16) 13 g / 10 min. (Scona TSPOE® 1002CMB1-2).

[0154] Component e / 1 :

[0155] Standard chopped glass fiber for polyamides, length=4.5 mm, diameter=10 pm.

[0156] Component e / 2:

[0157] N,N'-Hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098, CAS: 23128-74-7)

[0158] Component e / 3: commercially available fatty acids, C14-18, C 14-18-al kyl esters (CAS: 85566- 24-1 ) (lubricants) Component e / 4: commercially available zinc oxide (CAS: 1314-13-2) (acid scavenger)

[0159] Component e / 5: 30% concentrate of carbon black in PA6 (Ultramid® B27) (colorant)

[0160] In order to provide evidence of the improvements described in the invention, appropriate plastics molding compositions were manufactured via compounding. To this end, the individual components were mixed in a ZSK 26 (Berstorff) twin-screw extruder with throughput 20 kg / h and a flat temperature profile at about 290° C., extruded in the form of strand, cooled until pelletizable, and pelletized.

[0161] The test specimens for the study set out in Table 1 were injection-molded in an Arburg 420°C injection-molding machine at a melt temperature of about 290°C and mold temperature of about 80°C.

[0162] The test specimens for the stress tests were produced in accordance with ISO 527-271993, and the test specimens for the impact resistance tests were produced in accordance with ISO 179- 2 / 1 eA.

[0163] The MVR tests were carried out in accordance with ISO1133.

[0164] The flame retardancy of the molding compositions was determined firstly by the UL 94 V method (Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances”, p. 14 to p. 18 Northbrook 1998)

[0165] Glow - wire resistance GWFI (glow - wire flammability index) was tested in accordance with DIN EN 60695-2-12 on plaques. The GWFI test is a general suitability test for plastics in contact with parts that carry an electrical potential. The temperature determined is the highest at which one of the following conditions is met in three successive tests: (a) no ignition of the specimen or (b) afterflame time or afterglow time 30 s after end of exposure to the glow wire, and no ignition of the underlay.

[0166] The table gives the constitutions of the molding compositions and the results of the measurements. Table 1

[0167] 1) not classified, i.e. UL94 test failed

[0168] Based on the data in table 1 it is obvious that the use of a modifier mixture leads to improved flaming properties at low wall thickness (UL94 V-0 resp. V-1 rating at 0,8mm) and improved GWFI performance.

Claims

Claims1 . A thermoplastic molding composition comprising a) from 10 to 97.9% by weight of at least one thermoplastic polyamide, as component A), b) from 0.1 to 20% by weight of red phosphorus, as component B), c) from 1 to 20% by weight of a first olefin copolymer, based on: c1 ) from 40 to 98% by weight, preferably from 50 to 94.5% by weight, of ethylene, as component C1 ); c2) from 2 to 40% by weight, preferably from 5 to 40% by weight, of at least one (meth)acrylate having from 1 to 18 carbon atoms, as component C2); c3) from 0 to 20% by weight, preferably from 0.05 to 10% by weight, of at least one ethylenically unsaturated mono- or dicarboxylic acid, at least one ethylenically unsaturated oxirane, or a mixture of these, as component C3); c4) from 0 to 5% by weight, preferably from 0.05 to 2% by weight, of at least one ethylenically unsaturated dicarboxylic anhydride; preferably maleic anhydride, as component C4); where the sum of the percentages by weight C1 ), C2), C3) and C4) is 100%, as component C); d) from 1 to 20% by weight of a second olefin copolymer, based on: d1 ) from 35 to 98% by weight, preferably from 45 to 80% by weight, of ethylene, as component D1 ); d2) from 2 to 65% by weight, preferably from 20 to 55% by weight, of at least one alpha-olefin having from 3 to 10 carbon atoms, as component D2); d3) from 0 to 5% by weight, preferably from 0.05 to 2% by weight, of at least one ethylenically unsaturated dicarboxylic anhydride; preferably maleic anhydride, as component D3); where the sum of the percentages by weight D1 ), D2) and D3) is 100%, as component D), e) from 0 to 60% by weight of at least one fibrous and / or particulate filler, as component E), and f) from 0 to 60% by weight of at least one further additive, as component F), where the total of the percentages by weight of components A) to F) is 100% by weight, wherein the at least one thermoplastic polyamide of component A) consists of PA6, PA66 and mixtures thereof.

2. The thermoplastic molding composition according to according to claim 1 , wherein the thermoplastic molding composition has a UL94 V-0 or V-1 rating at 0.8 mm.

3. The thermoplastic molding composition according to claim 1 or 2, wherein the amount of component B) is from 0.5 to 15% by weight, preferably from 1 to 10% by weight.

4. The thermoplastic molding composition according to any one of claims 1 to 3, wherein the weight ratio of component C) to component D) is from 0.3 : 1 to 2 : 1.

5. The thermoplastic molding composition according to any one of claims 1 to 4, wherein component C2) is at least one alkyl (meth)acrylate having from 1 to 4 carbon atoms in its alkyl part.

6. The thermoplastic molding composition according to any one of claims 1 to 5, wherein component C3) is at least one ethylenically unsaturated monocarboxylic acid, at least one ethylenically unsaturated monoglycidyl ester, or a mixture of these; preferably (meth)acrylic acid and / or glycidyl(meth)acrylate, more preferably (meth)acrylic acid, most preferably acrylic acid.

7. The thermoplastic molding composition according to any one of claims 1 to 6, wherein component C4) is at least one ethylenically unsaturated dicarboxylic anhydride, preferably maleic anhydride.

8. The thermoplastic molding composition according to any one of claims 1 to 7, wherein component D2) is at least one alpha-olefin having from 3 to 8 carbon atoms, preferably 1- octene.

9. The thermoplastic molding composition according to any one of claims 1 to 7, wherein component D3) is maleic anhydride.

10. The thermoplastic molding composition according to any one of claims 1 to 9, wherein component E) is selected from the group consisting of glass fibers, carbon fibers, glass beads, e.g. solid or hollow glass beads, ground glass, amorphous quartz glass, aluminum borosilicate glass having an alkali content of about 1 %, amorphous silica, quartz flour, alkaline earth metal silicate, especially calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or milled quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite, boehmite, bentonite, vermiculite, hectorite, laponite, pseudoboehmite of formula AIO(OH), magnesium carbonate, talc, aramid fibers, potassium titanate fibers, barium carbonate, alkaline earth metal oxide, metallic fibers, ceramic fibers, titanium dioxide, aluminum oxide, plaster, zirconium oxide, antimony oxide, clay, silica-alumina, sericite, diatomite, silica stone, glassy hollow microspheres, red oxide, and mixtures thereof.

11. A process for producing the thermoplastic molding composition according to any one of claims 1 to 10 comprising the step of mixing the components A), B), C), D) and optionally E) and optionally F).

12. The use of the thermoplastic molding composition according to any one of claims 1 to 10 or obtained by the process according to claim 11 for producing fibers, foils or moldings, preferably connectors and conjunction boxes.

13. Fibers, foils or moldings, preferably connectors and conjunction boxes comprising the thermoplastic molding composition according to any one of claims 1 to 10 or obtained by the process according to claim 11.

14. Use of a mixture comprising a first olefin copolymer, based on: c1 ) from 40 to 98% by weight, preferably from 50 to 94.5% by weight, of ethylene, as component C1); c2) from 2 to 40% by weight, preferably from 5 to 40% by weight, of at least one (meth)acrylate having from 1 to 18 carbon atoms, as component C2); c3) from 0 to 20% by weight, preferably from 0.05 to 10% by weight, of at least one ethylenically unsaturated mono- or dicarboxylic acid, at least one ethylenically unsaturated oxirane, or a mixture of these, as component C3); c4) from 0 to 5% by weight, preferably from 0.05 to 2% by weight, of at least one ethylenically unsaturated dicarboxylic anhydride; preferably maleic anhydride, as component C4); where the sum of the percentages by weight C1), C2), C3) and C4) is 100%, as component C); and a second olefin copolymer, based on: d1 ) from 35 to 98% by weight, preferably from 45 to 80% by weight, of ethylene, as component D1); d2) from 2 to 65% by weight, preferably from 20 to 55% by weight, of at least one alphaolefin having from 3 to 10 carbon atoms, as component D2); d3) from 0 to 5% by weight, preferably from 0.05 to 2% by weight, of at least one ethylenically unsaturated dicarboxylic anhydride; preferably maleic anhydride, as component D3); where the sum of the percentages by weight D1), D2) and D3) is 100%, as component D), as impact modifier for producing a thermoplastic molding composition having a UL94 V-0 or V-1 rating at 0.8 mm and comprising at least one thermoplastic polyamide selected from the group consisting of PA6, PA66 and mixtures thereof, as component A) and red phosphorus as component B), for producing fibers, foils or moldings.