DE102014215370A1 - Long fiber-reinforced flame-retardant polyamides - Google Patents

Abstract

The invention relates to thermoplastic molding compositions comprising A) from 10 to 93% by weight of a thermoplastic polyamide B) from 1 to 15% by weight of red phosphorus C) from 0 to 20% by weight of an impact modifier D) from 5 to 50% by weight a long-fiber-shaped reinforcing material with a fiber length of 2 to 25 mm and an L / D ratio of 500 to 3500 E) 0 to 30 wt .-% of other additives, wherein the sum of the weight percent of components A) to E) gives 100%.

Description

• A) 10 bis 93 Gew.-% eines thermoplastischen Polyamides
• B) 1 bis 15 Gew.-% roter Phosphor
• C) 0 bis 20 Gew.-% eines Schlagzähmodifiers
• D) 5 bis 50 Gew.-% eines langfaserförmigen Verstärkungsstoffes mit einer Faserlänge von 2 bis 25 mm und einem L/D Verhältnis von 500 bis 3500
• E) 0 bis 30 Gew.-% weiterer Zusatzstoffe,

wobei die Summe der Gewichtsprozente der Komponenten A) bis E) 100% ergibt.The invention relates to thermoplastic molding compositions comprising

• A) 10 to 93 wt .-% of a thermoplastic polyamide
• B) 1 to 15 wt .-% red phosphorus
• C) 0 to 20 wt .-% of an impact modifier
• D) 5 to 50 wt .-% of a long-fiber-reinforced reinforcing material with a fiber length of 2 to 25 mm and an L / D ratio of 500 to 3500
• E) 0 to 30% by weight of further additives,

where the sum of the weight percent of components A) to E) is 100%.

Furthermore, the invention relates to the use of the thermoplastic molding compositions for the production of long-fiber-reinforced granules and the granules obtainable in this case. In addition, the invention relates to the use of such granules for the production of impact-resistant flame-retardant moldings of any kind and the moldings obtainable in this case.

Process for the preparation of long-fiber-reinforced molding compositions and granules are, for example, from EP-A 1788027 and 1788028 such as 1788029 known.

In particular, the so-called pultrusion or pultrusion method has proven itself for the production of long-fiber-reinforced thermoplastics (LFT). Here, the endless fiber strand (roving) is completely pushed through with the polymer melt and then cooled and cut. The long-fiber-reinforced rod granules produced in this way can be processed into shaped parts using the usual processing methods.

Thermoplastic polyamides have long been used as materials. In addition to their mechanical, thermal, electrical and chemical properties, properties such as flame retardance and high filament resistance are becoming increasingly important. Examples include household appliances (e.g., plugs) and electronics (such as circuit breaker covers).

In addition, there is an increasing market interest in halogen-free flame-retardant thermoplastic polyamides with optimized processing behavior. Here are the essential requirements for the flame retardant good temperature stability during polymer processing to prevent tool coatings, as well as a reduced migration of the finished molding.

The effectiveness of halogen-free flame retardant additive mixtures consisting of phosphinates and nitrogen-containing synergists or reaction products of melamine with phosphoric acid (melamine polyphosphate) is essentially defined by fire tests according to UL94-V. For certain applications of flame-retardant polyamide molding compounds in the household appliance sector, however, the glow-wire test is after IEC 60695-2-13 Of importance, of many halogen-free flame retardant polyamide molding compounds - such as in DE-A-199 33 901 described - is not fulfilled.

The object of the present invention was therefore to provide halogen-free flame-retardant polyamide molding compounds with high glow-wire resistance and improved processability (reduced outgassing and tool coverings).

Accordingly, the molding compositions defined above were found. Preferred embodiments are given in the dependent claims.

Surprisingly, it has now been found that long glass fiber reinforced, halogen-free flame-retardant polyamide molding compositions based on red phosphorus of a specific particle size distribution, the required properties meet outstanding.

As component A), the molding compositions of the invention contain 10 to 94, preferably 20 to 90 and in particular 30 to 85 wt .-% of at least one polyamide.

The polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307 ,

Semicrystalline or amorphous resins having a weight average molecular weight of at least 5,000, such as those in the US Pat. No. 2,071,250 . 2 071 251 . 2 130 523 . 2,130,948 . 2 241 322 . 2 312 966 . 2 512 606 and 3 393 210 are described are preferred.

Examples include polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam and polyamides obtained by reacting dicarboxylic acids with diamines.

As dicarboxylic acids alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used. Here only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be mentioned as acids.

Suitable diamines are particularly alkanediamines having 6 to 12, especially 6 to 8 carbon atoms and m-xylylenediamine are suitable (for example Ultramid ^® X17 from BASF SE, a 1: 1 molar ratio of MXDA with adipic acid), di- (4-aminophenyl) methane, Di- (4-amino-cyclohexyl) -methane, 2,2-di (4-aminophenyl) -propane, 2,2-di- (4-aminocyclohexyl) -propane or 1,5-diamino-2-methylpentane.

Preferred polyamides are Polyhexamethylenadipinsäureamid, Polyhexamethylensebacinsäureamid and polycaprolactam and Copolyamides 6/66, in particular with a share of 5 to 95 wt .-% of caprolactam units (eg Ultramid ^® C31 BASF SE).

Further suitable polyamides are obtainable from ω-aminoalkyl nitriles such as, for example, aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by so-called direct polymerization in the presence of water, for example in US Pat DE-A 10313681 . EP-A 1198491 and EP 922065 described.

In addition, polyamides may also be mentioned which are obtainable, for example, by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (polyamide 4,6). Production processes for polyamides of this structure are described, for example, in US Pat EP-A 38 094 . EP-A 38 582 and EP-A 39 524 described.

Furthermore, polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers or mixtures of a plurality of polyamides are suitable, the mixing ratio being arbitrary. Particular preference is given to mixtures of polyamide 66 with other polyamides, in particular copolyamides 6/66.

Furthermore, such partially aromatic copolyamides as PA 6 / 6T and PA 66 / 6T have proven to be particularly advantageous, the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444). Other high temperature resistant polyamides are from EP-A 19 94 075 known (PA 6T / 6I / MXD6).

The production of the preferred partially aromatic copolyamides having a low triamine content can be carried out according to the methods described in US Pat EP-A 129 195 and 129 196 described method.

The following non-exhaustive list contains the mentioned, as well as other polyamides A) in the context of the invention and the monomers contained. AB-polymers: PA 4 pyrrolidone PA 6 ε-caprolactam PA 7 Ethanolactam PA 8 capryllactam PA 9 9-amine Opel argon acid PA 11 11-aminoundecanoic PA 12 laurolactam AA / BB-polymers PA 46 Tetramethylenediamine, adipic acid PA 66 Hexamethylenediamine, adipic acid PA 69 Hexamethylenediamine, azelaic acid PA 610 Hexamethylenediamine, sebacic acid PA 612 Hexamethylenediamine, decanedicarboxylic acid PA 613 Hexamethylenediamine, undecanedicarboxylic acid PA 1212 1,12-dodecanediamine, decanedicarboxylic acid PA 1313 1,13-diaminotridecane, undecanedicarboxylic acid PA 6T Hexamethylenediamine, terephthalic acid PA 9T 1,9-nonanediamine, terephthalic acid PA MXD6 m-xylylenediamine, adipic acid PA 6I Hexamethylenediamine, isophthalic acid PA 6-3-T Trimethylhexamethylenediamine, terephthalic acid PA 6 / 6T (see PA 6 and PA 6T) PA 6/66 (see PA 6 and PA 66) PA 6/12 (see PA 6 and PA 12) PA 66/6/610 (see PA 66, PA 6 and PA 610) PA 6I / 6T (see PA 6I and PA 6T) PA PACM 12 Diaminodicyclohexylmethane, laurolactam PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane PA 12 / MACMI Laurinlactam, dimethyldiaminodicyclohexylmethane, isophthalic acid PA 12 / MACMT Laurinlactam, dimethyl-diaminodicyclohexylmethane, terephthalic acid PA PDA-T Phenylenediamine, terephthalic acid

Preferred flame retardant B) is elemental red phosphorus, which can be used in untreated form.

However, preparations are particularly suitable in which the phosphorus on the surface with low molecular weight liquid substances such as silicone oil, paraffin oil or esters of phthalic acid (in particular dioctyl phthalate, s. EP 176 836 ) or adipic acid or with polymeric or oligomeric compounds, for example with phenolic resins or aminoplasts and polyurethanes are coated (s. EP-A 384 232 . DE-A 196 48 503 ). Such so-called phlegmatizers are generally contained in amounts of 0.05 to 5 wt .-%, based on 100 wt .-% B).

In addition, concentrates (so-called batch) of red phosphorus, e.g. in a polyamide or elastomers (component C) as a flame retardant suitable. In particular, polyolefin homopolymers and copolymers are also suitable as concentrate polymers. However, the proportion of the concentrate polymer - if no polyamide is used as a thermoplastic - not more than 35 wt .-% based on the weight of components A) and B) in the molding compositions according to the invention.

• B₁) 30 bis 90 Gew.-%, vorzugsweise von 45 bis 70 Gew.-% eines Polyamids oder eines von Polyamiden verschiedenen Konzentratpolymers
• B₂) 10 bis 70 Gew.-%, vorzugsweise von 30 bis 55 Gew.-% roter Phosphor.

Preferred concentrate compositions are

• B ₁ ) from 30 to 90% by weight, preferably from 45 to 70% by weight, of a polyamide or of a concentrate polymer other than polyamides
• B ₂ ) 10 to 70 wt .-%, preferably from 30 to 55 wt .-% red phosphorus.

The polyamide used for the batch can be different from A) or preferably equal to A), so that incompatibilities or melting point differences have no negative effect on the molding composition.

The average particle size (d ₅₀ ) of the phosphor particles distributed 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 (≜ 1 μm to 200 μm), in particular from 5 to 35 μm, measured according to DIN 53195 ,

The content of component B) in the molding compositions according to the invention is 1 to 15, preferably 1 to 10 and in particular 2 to 10 wt .-%, based on the sum of components A) to E).

As component C), the molding compositions can contain from 0 to 20, preferably from 1 to 20, in particular from 2 to 20,% by weight of elastomeric polymers (often also referred to as impact modifiers, elastomers or rubbers).

In general, these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters having 1 to 18 C atoms in the alcohol component.

Such polymers are e.g. in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg Thieme Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph by C.B. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977).

In the following some preferred types of such elastomers are presented.

Preferred types of such elastomers are the so-called ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers generally have practically no double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.

As diene monomers for EPDM rubbers, for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1,4-diene, hexa-1,5 -diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadienes and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene 2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof. Preference is given to hexa-1,5-diene, 5-ethylidenenorbornene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.

EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives. Here are e.g. Acrylic acid, methacrylic acid and its derivatives, e.g. Glycidyl (meth) acrylate, and called maleic anhydride.

wobei R¹ bis R⁹ Wasserstoff oder Alkylgruppen mit 1 bis 6 C-Atomen darstellen und m eine ganze Zahl von 0 bis 20, g eine ganze Zahl von 0 bis 10 und p eine ganze Zahl von 0 bis 5 ist.Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids. In addition, the rubbers may also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, for example esters and anhydrides, and / or monomers containing epoxy groups. These dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by addition of monomers containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture

wherein R ¹ to R ^{9 represent} hydrogen or alkyl groups having 1 to 6 carbon atoms and 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.

The radicals R ¹ to R ⁹ preferably denote hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

Preferred compounds of formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to the free acids and are therefore termed monomers with latent carboxyl groups. Advantageously, the copolymers consist of 50 to 98 wt .-% of ethylene, 0.1 to 20 wt .-% of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.

Particularly preferred are copolymers of 50 to 98, in particular 55 to 95% by weight of ethylene, 0.1 to 40, in particular from 0.3 to 20% by weight of glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and 1 to 45, in particular 5 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.

Further preferred esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.

In addition, vinyl esters and vinyl ethers can also be used as comonomers.

The ethylene copolymers described above can be prepared by methods known per se, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are generally known.

Preferred elastomers are also emulsion polymers, their preparation e.g. at Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts which can be used are known per se.

Basically, homogeneously constructed elastomers or those with a shell structure can be used. The shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.

Representatives which may be mentioned here as monomers for the preparation of the rubber part of the elastomers are acrylates such as, for example, n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene, and mixtures thereof. These monomers can be copolymerized with other monomers such as styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate.

The soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers may be the core, the outer shell, or a middle shell (for elastomers having more than two shell construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase. If, in addition to the rubber phase, one or more hard components (having glass transition temperatures of more than 20 ° C.) are involved in the construction of the elastomer, these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylic esters and methacrylates such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as main monomers. In addition, smaller proportions of other comonomers can also be used here.

eingeführt werden können,
wobei die Substituenten folgende Bedeutung haben können:
R¹⁰ Wasserstoff oder eine C₁- bis C₄-Alkylgruppe,
R¹¹ Wasserstoff, eine C₁- bis C₈-Alkylgruppe oder eine Arylgruppe, insbesondere Phenyl,
R¹² Wasserstoff, eine C₁- bis C₁₀-Alkyl-, eine C₆- bis C₁₂-Arylgruppe oder -OR¹³
R¹³ eine C₁- bis C₈-Alkyl- oder C₆- bis C₁₂-Arylgruppe, die gegebenenfalls mit O- oder N-haltigen Gruppen substituiert sein können,
X eine chemische Bindung, eine C₁- bis C₁₀-Alkylen- oder C₆-C₁₂-Arylengruppe oder

Y O-Z oder NH-Z und
Z eine C₁- bis C₁₀-Alkylen- oder C₆- bis C₁₂-Arylengruppe.In some cases it has proven to be advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups obtained by concomitant use of monomers of the general formula

can be introduced
where the substituents may have the following meanings:
R ^{10 is} hydrogen or a C ₁ - to C ₄ -alkyl group,
R ^{11 is} hydrogen, a C ₁ - to C ₈ -alkyl group or an aryl group, in particular phenyl,
R ^{12 is} hydrogen, a C ₁ - to C ₁₀ -alkyl, a C ₆ - to C ₁₂ -aryl group or -OR ¹³
R ^{13 is} a C ₁ - to C ₈ -alkyl or C ₆ - to C ₁₂ -aryl group which may optionally be substituted by O- or N-containing groups,
X is a chemical bond, a C ₁ - to C ₁₀ -alkylene or C ₆ -C ₁₂ -arylene group or

Y OZ or NH-Z and
Z is a C ₁ - to C ₁₀ -alkylene or C ₆ - to C ₁₂ -arylene group.

Also in the EP-A 208 187 grafting monomers described are suitable for introducing reactive groups on the surface. Other examples which may be mentioned are acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and (N, N-diethylamino) called ethyl acrylate.

Furthermore, the particles of the rubber phase can also be crosslinked. Examples of monomers acting as crosslinking agents are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate and those described in US Pat EP-A 50 265 described compounds.

Furthermore, it is also possible to use so-called graft-linking monomers, ie monomers having two or more polymerizable double bonds which react at different rates during the polymerization. Preference is given to using those compounds in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups), for example, polymerizes (polymerizes) much more slowly. The different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. Is then on such a rubber a grafted on further phase, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, ie, the grafted phase is at least partially linked via chemical bonds with the graft base.

Examples of such graft-crosslinking monomers are allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids. In addition, there are a variety of other suitable graft-linking monomers; for more details, for example, on the U.S. Patent 4,148,846 directed.

In general, the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.

In the following, some preferred emulsion polymers are listed. First, graft polymers having a core and at least one outer shell, which have the following structure: Type Monomers for the core Monomers for the shell I Buta-1,3-diene, isoprene, n-butyl acrylate, ethylhexyl acrylate or mixtures thereof Styrene, acrylonitrile, methylmethacrylate II like I but with the co-use of networkers like I III like I or II n-butyl acrylate, ethyl acrylate, methyl acrylate, buta-1,3-diene, isoprene, ethylhexyl acrylate IV like I or II as I or III but with the concomitant use of monomers having reactive groups as described herein V Styrene, acrylonitrile, methyl methacrylate or mixtures thereof first shell of monomers as described under I and II for the core second shell as described under I or IV for the shell

Instead of graft polymers with a multi-shell structure can also homogeneous, d. H. single-shell elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or copolymers thereof are used. These products can also be prepared by concomitant use of crosslinking monomers or monomers having reactive groups.

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 of n-butyl acrylate or butadiene-based and an outer shell of the above copolymers and copolymers of ethylene with comonomers which provide reactive groups.

The described elastomers may also be prepared by other conventional methods, e.g. by suspension polymerization.

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

Particularly preferred rubbers C) are ethylene copolymers, as described above, which contain functional monomers, the functional monomers being selected from the group of the carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, carboxylic acid amide, carboximide, amino, hydroxyl, epoxide , Urethane or oxazoline groups or mixtures thereof.

The proportion of the functional groups is 0.1 to 20, preferably 0.2 to 10 and in particular 0.3 to 7 wt .-%, based on 100 wt .-% C).

Particularly preferred monomers are composed of an ethylenically unsaturated mono- or dicarboxylic acid or a functional derivative of such an acid.

In principle, all primary, secondary and tertiary C ₁ -C ₁₈ -alkyl esters of acrylic acid or methacrylic acid, but esters with 1-12C atoms, in particular with 2-10C atoms are preferred.

Examples thereof are methyl, ethyl, propyl, n-, i-butyl and t-butyl, 2-ethylhexyl, octyl and decyl acrylates or the corresponding esters of methacrylic acid. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.

Instead of or in addition to the esters, acid-functional and / or latent acid-functional monomers of ethylenically unsaturated mono- or dicarboxylic acids or monomers containing epoxy groups may also be present in the olefin polymers.

Acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert-butyl acrylate and dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids and their monoesters may be mentioned as further examples of monomers.

Suitable latent acid-functional monomers are those compounds which form free acid groups under the polymerization conditions or during the incorporation of the olefin polymers into the molding compositions. Examples which may be mentioned are anhydrides of dicarboxylic acids having up to 20 carbon atoms, in particular maleic anhydride and tertiary C ₁ -C ₁₂ -alkyl esters of the abovementioned acids, in particular tert-butyl acrylate and tert-butyl methacrylate.

The acid-functional or latent acid-functional monomers and the monomers containing the epoxy groups are preferably incorporated into the olefin polymers by adding compounds of the general formulas I-IV to the monomer mixture.

The melt index of the ethylene copolymers is generally in the range of 1 to 80 g / 10 min (measured at 190 ° C and 2.16 kg load).

The molecular weight of these ethylene-α-olefin copolymers is between 10,000 and 500,000 g / mol, preferably between 15,000 and 400,000 g / mol (Mn as determined by GPC in 1,2,4-trichlorobenzene with PS calibration).

In a particular embodiment, ethylene-α-olefin copolymers produced by so-called "single site catalysts" are used. More details can the US 5,272,236 be removed. In this case, the ethylene-α-olefin copolymers have a polyolefin narrow molecular weight distribution less than 4, preferably less than 3.5.

Commercial products preferably used are B Exxelor ^® VA 1801 or 1803 Kraton ^® G 1901 or FX Fusabond ^® N NM493 D or Fusabond ^® A560 Exxon, and Kraton ^® DuPont and Tafmer MH 7010 from Mitsui companies.

Of course, it is also possible to use mixtures of the rubber types listed above.

The long-fiber-form fillers D) are used in amounts of from 5 to 50% by weight, in particular from 5 to 40% by weight, which have a fiber length of from 2 to 25 mm, preferably from 3 to 15 mm, and an L / D ( Length / diameter) ratio of 500 to 3500, in particular 550 to 1500 and especially 600 to 900.

Preferred fibrous fillers are carbon fibers, aramid fibers, glass fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These are used as rovings in the commercial forms.

n eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4
m eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 2
k eine ganze Zahl von 1 bis 3, bevorzugt 1The glass fibers used according to the invention as rovings have a diameter of 6 to 20 μm, preferably of 10 to 18 μm, the cross section of the glass fibers being round, oval or angular. In particular, E-glass fibers are used according to the invention. But it can also all other types of glass fiber, such as A, C, D, M, S, R glass fibers or any mixtures thereof or mixtures with E-glass fibers be used. The fibrous fillers can be surface-pretreated for better compatibility with the thermoplastic with a silane compound. Suitable silane compounds are those of the general formula (X- (CH ₂ ) _n ) _k -Si- (OC _m H _{2m + 1} ) _4-k in which the substituents have the following meanings:

n is an integer from 2 to 10, preferably 3 to 4
m is an integer from 1 to 5, preferably 1 to 2
k is an integer from 1 to 3, preferably 1

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

The silane compounds are generally used in amounts of 0.01 to 2, preferably 0.025 to 1.0 and in particular 0.05 to 0.5 wt .-% (based on D) for surface coating.

Other suitable coating agents (also called sizing agents) are based on isocyanates, phenolic resins or acrylic acid derivatives.

In addition, the thermoplastic molding compositions according to the invention may contain, as component E), further additives which are different from A) to D).

As component E), the molding compositions of the invention may contain a total of 0 to 30, in particular up to 30 wt .-% of other additives and processing aids based on the total amount (100 wt .-%) of the components A) to E).

The thermoplastic molding compositions advantageously contain a lubricant. As component E), the molding compositions of the invention may be from 0 to 3, preferably from 0.05 to 3, preferably from 0.1 to 1.5 and in particular from 0.1 to 1 wt .-% of a lubricant based on the total amount of the components A) to E) included. Preference is given to Al, alkali metal, alkaline earth metal salts or ester or amides of fatty acids having 10 to 44 carbon atoms, preferably having 14 to 44 carbon atoms. The metal ions are preferably alkaline earth and Al, with Ca or Mg being particularly preferred. Preferred metal salts are Ca-stearate and Ca-montanate as well as Al-stearate. It is also possible to use mixtures of different salts, the mixing ratio being arbitrary.

The carboxylic acids can be 1- or 2-valent. Examples which 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 (mixture of fatty acids having 30 to 40 carbon atoms). The aliphatic alcohols can be 1 to 4 valent. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.

The aliphatic amines can be monohydric to trihydric. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Accordingly, preferred esters or amides are glycerin distearate, glycerol tristearate, ethylenediamine distearate, glycerin monopalmitate, glycerol trilaurate, glycerin monobehenate and pentaerythritol tetrastearate.

It is also possible to use mixtures of different esters or amides or esters with amides in combination, the mixing ratio being arbitrary.

As further component E), the thermoplastic molding compositions according to the invention can contain customary processing auxiliaries, such as stabilizers, antioxidants, further agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants, such as dyes and pigments, Nucleating agents, plasticizers and rubbers, etc. included. Examples of oxidation inhibitors and heat stabilizers are phosphites, sterically hindered phenols and further amines (eg TAD), hydroquinones, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions called.

As UV stabilizers, which are generally used in amounts of up to 2 wt .-%, based on the molding composition, various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned.

It is possible to add inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black and / or graphite, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and anthraquinones as colorants. As nucleating agents, sodium phenylphosphinate, alumina, silica and preferably talc may be used. As component E), the thermoplastic molding compositions according to the invention 0.01 to 2 wt .-%, preferably 0.05 to 1.5 wt .-%, particularly preferably 0.1 to 1.5 wt .-% of at least one heat stabilizer, respectively based on the total weight of components A) to E).

The polyester molding compositions according to the invention can be prepared by the known processes for the production of long fiber reinforced rod granules, in particular by pultrusion processes in which the endless preheated fiber strand (roving) is drawn through the polymer melt at a constant rate while being completely impregnated with the polymer melt and subsequently cooled and cut. The long-fiber-reinforced rod granules obtained in this way, which preferably have a granule length of 2 to 25 mm, in particular of 5 to 14 mm, can be further processed to shaped parts by the usual processing methods (such as injection molding, pressing).

The preferred L / D ratio of the granules after pultrusion is 2 to 8, in particular 3 to 4.5.

The polymer strand prepared from molding compositions according to the invention can be processed with all known granulation to granules, such as. B. by strand granulation, in which the strand is cooled in a water bath and then cut.

Particularly good properties can be achieved in the molded part with gentle processing methods. In this context, gentle means above all that an excessive fiber breakage and the associated strong reduction of the fiber length is largely avoided. In injection molding, this means that screws with a large diameter and low compression ratio, in particular smaller than 2, and generously dimensioned nozzles and sprue channels are preferably used. In addition, it must be ensured that the rod granules melt rapidly with the help of high cylinder temperatures (contact heating) and that the fibers are not excessively crushed by excessive shear stress. Taking into account these measures moldings are obtained according to the invention, which have on average a higher fiber length than comparable molded parts made of short fiber reinforced molding compositions. This achieves an additional improvement in the properties, in particular in the tensile, modulus, tear resistance and notched impact strength.

After molding processing e.g. by injection molding, the fiber length is usually 0.05 to 10 mm, in particular 0.35 to 1.5 mm.

The moldings produced from the molding compositions according to the invention are used for the production of interior and exterior parts, preferably with supporting or mechanical function in the field of electrical, furniture, sports, mechanical engineering, sanitation and hygiene, medicine, energy and drive technology, automobile and other means of transport or housing material Equipment and apparatus for telecommunications, consumer electronics, household appliances, mechanical engineering, heating systems, or fasteners for installations or for containers and ventilation parts of all kinds.

The impact strength, in particular the notch impact strength of the molded parts according to the invention is significantly higher, at the same time an effective flame retardancy and glow wire resistance are given.

processing methods

• – CoBi-lnjektion oder Montagespritzguss für Hybridteile, bei denen die erfindungsgemäße Polyesterformmasse mit anderen kompatiblen oder inkompatiblen Werkstoffen, wie z.B. Thermoplasten, Duroplasten oder Elastomeren kombiniert wird.
• – Insertteile, wie z.B. Lagerstellen oder Gewindeeinsätze aus der erfindungsgemäßen Polyesterformmasse, umspritzt mit anderen kompatiblen oder inkompatiblen Werkstoffen, wie z.B. Thermoplasten, Duroplasten oder Elastomeren.
• – Outsertteile, wie Rahmen, Gehäuse oder Stützen aus der erfindungsgemäßen Polyesterformmasse, in welche Funktionselemente aus anderen kompatiblen oderinkompatiblen Werkstoffen, wie z.B. Thermoplasten, Duroplasten oder Elastomeren eingespritzt werden.
• – Hybridteile (Elemente aus der erfindungsgemäßen Polyesterformmasse kombiniert mit anderen kompatiblen oder inkompatiblen Werkstoffen, wie z.B. Thermoplasten, Duroplasten oder Elastomeren) hergestellt durch Verbundspritzguss, Spritzschweißen. Montagespritzguss, Ultraschall, Reib- oder Laserschweißen, Kleben, Börteln oder Nieten.
• – Halbzeuge und Profile (z.B. hergestellt durch Extrusion, Pultrusion, Schichtung oder Lamination).
• – Oberflächenbeschichtung, Kaschierungen, chemisches- oder physikalisches Metallisieren, Beflockung, wobei die erfindungsgemäße Polyesterformmasse das Substrat selbst oder der Substratträger oder bei Hybrid/Bi-lnjektionsteilen ein definierter Substratbereich sein kann, welcher auch durch nachträgliche chemische (z.B. Ätzen) oder physikalische Behandlung (z.B. spanabhebend oder LASER-Abtrag) zur Oberfläche gebracht werden kann.
• – Bedrucken, Transferdruck, 3-D Druck, Laserbeschriften.

In addition to the usual processing methods, such as extrusion or injection molding, the following processing methods are also suitable:

• CoBi injection or assembly injection molding for hybrid parts, in which the polyester molding composition according to the invention is combined with other compatible or incompatible materials, such as, for example, thermoplastics, thermosets or elastomers.
• - Insert parts, such as bearings or threaded inserts of the polyester molding composition according to the invention, encapsulated with other compatible or incompatible materials, such as thermoplastics, thermosets or elastomers.
• - Outsertteile, such as frames, housings or supports of the polyester molding composition according to the invention, in which functional elements of other compatible or incompatible materials, such as thermoplastics, thermosets or elastomers are injected.
• - Hybrid parts (elements of the polyester molding composition according to the invention combined with other compatible or incompatible materials, such as thermoplastics, thermosets or elastomers) produced by composite injection molding, spray welding. Assembly injection molding, ultrasonic, friction or laser welding, gluing, mortar or riveting.
• - Semi-finished products and profiles (eg produced by extrusion, pultrusion, layering or lamination).
• Surface coating, laminating, chemical or physical metallization, flocking, wherein the polyester molding composition of the invention may be the substrate itself or the substrate carrier or hybrid / Bi injection parts a defined substrate area, which also by subsequent chemical (eg etching) or physical treatment (eg machining or LASER removal) can be brought to the surface.
• - Printing, transfer printing, 3-D printing, laser marking.

Examples

The following components were used:

Component A:

• Polyamide 66 with a viscosity number VZ of 125 ml / g, measured as 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C after ISO 307 (It was Ultramid ^® A24 from BASF SE used).

Component B / 1:

• 50% concentrate of red phosphorus of average particle size (d ₅₀ ) of 10 to 30 microns in polyamide 6 (Masteret 20450 ex Italmatch Chemicals).

Component B / V:

• A commercial mixture of aluminum diethylphosphinate, melamine polyphosphate, and zinc borate (Exolit OP1312 ^® of the company. Clariant).

Component D:

• Glass fiber roving with 2400 Tex (company 3B) and a diameter of 17 μm (Tex = g / km glass fiber).

Component E / 1:

• IRGANOX ^® 1098 (commercially available BASF SE) N, N'-hexamethylene-bis-3,5-di-ter.-butyl-4-hydroxhydrocinnamid

Component E / 2:

• calcium stearate

Component E / 3:

• aluminum stearate

Component E / 4:

• zinc oxide

Component E / 5:

30% concentrate from a carbon black having a BET specific surface area (measured after DIN 66131 ) of 180 m ² / g in polyamide 6.

The molding compositions and test specimens were prepared as follows:
Long fiber reinforced granules by pultrusion and injection molding

The individual components (components A, B, D and processing aids) were mixed in a side-mounted twin-screw extruder at 280 ° C and filled with a mass flow of 28 kg / h via a transition to the 285 ° C hot impregnation chamber. The rovings, which had been preheated to 210 ° C., were prestressed so that the individual glass fibers would not touch each other and be drawn through the polymer melt at a constant speed of 9 to 12 m / min, thereby becoming completely saturated with the polymer melt and then cooled to about room temperature and Cut into 12 mm long rods. The long fiber reinforced rod granules obtained in this way had an L / D ratio of about 4.

The specimens for the tests listed in Table 1 were sprayed on an Arburg 420C injection molding machine at a melt temperature of about 290-300 ° C. and a mold temperature of about 100 ° C.

The test specimens for the tension tests were after ISO 527-2: / 1993 and the test specimens for the impact measurements ISO 179-2 / 1 eA produced. The tool coating was visually assessed on the mold.

The flame retardancy of the molding compositions was firstly determined by the method UL94V ( 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 ) certainly.

Glow wire resistance was detected by glow wire ignition test GWIT (Glow Wire Ignition Temperature) DIN EN 60695-2-13 certainly. In the GWIT test, the maximum temperature is determined on 3 test specimens (for example on 60 × 60 × 1.5 mm geometry plates) with the aid of a glowing wire at temperatures between 550 and 960 ° C., and in 3 consecutive tests during the exposure time of the filament does not lead to ignition. The specified glow wire ignition temperature is 25K above the maximum determined temperature. The criterion of ignition is a flame with firing times> 5 sec. Table: Compositions of the molding compositions and measurement results Components [% by weight] Comparative example Inventive example A 47.78 37.27 B / 1 - 8th B / V 18 - D 33 50 E / 1 12:35 12:35 E / 2 - 12:35 E / 3 12:20 - E / 4 - 0.70 E / 5 0.67 3:33 Tensile modulus [MPa] 11000 18500 Breaking stress [MPa] 170 230 Elongation at break [%] 2.2 1.7 Notched impact strength [kJ / m2] 19.3 23.5 UL94 (1.6mm) V-0 V-0 GWIT 775 ° C / 1.5mm Fulfills Fulfills GWFI 960 ° C / 1.5mm Fulfills Fulfills Tool coating on the plate tool after 300 shots Strong white coating on entire plate surface Almost no surface.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 1788027 A [0003]
• EP 1788028 A [0003]
• EP 1788029 A [0003]
• DE 19933901 [0007]
• US 2071250 [0013]
• US 2071251 [0013]
• US 2130523 [0013]
• US 2130948 [0013]
• US 2241322 [0013]
• US 2312966 [0013]
• US 2512606 [0013]
• US 3393210 [0013]
• DE 10313681 A [0018]
• EP 1198491A [0018]
• EP 922065 [0018]
• EP 38094A [0019]
• EP 38582A [0019]
• EP 39524A [0019]
• EP 1994075A [0021]
• EP 129195 [0022]
• EP 129196A [0022]
• EP 176836 [0025]
• EP 384232 A [0025]
• DE 19648503 A [0025]
• EP 208187 A [0051]
• EP 50265A [0052]
• US 4148846 [0054]
• DE 3725576A [0060]
• EP 235690A [0060]
• DE 3800603A [0060]
• EP 319290A [0060]
• US 5272236 [0072]

Cited non-patent literature

• IEC 60695-2-13 [0007]
• ISO 307 [0012]
• DIN 53195 [0029]
• ISO 307 [0098]
• DIN 66131 [0099]
• ISO 527-2: / 1993 [0103]
• ISO 179-2 / 1 eA [0103]
• 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 [0104]
• DIN EN 60695-2-13 [0105]

Claims (9)

1) Thermoplastic molding compositions containing A) 10 to 93 wt .-% of a thermoplastic polyamide B) 1 to 15 wt .-% red phosphorus C) 0 to 20 wt .-% of an impact modifier D) 5 to 50 wt .-% of a long fiber-shaped reinforcing fabric with a fiber length of 2 to 25 mm and an L / D ratio of 500 to 3500 E) 0 to 30% by weight of further additives, where the sum of the weight percent of components A) to E) is 100%. Thermoplastic molding compositions according to claim 1, containing as component A). Polyamide 66 or blends of polyamide 66 with other polyamides. Thermoplastic molding compositions according to claims 1 or 2, in which the red phosphorus B) has an average particle size d ₅₀ value) of 5 to 35 μm. Thermoplastic molding compositions according to claims 1 to 3, in which component D) has a fiber length of 3 to 15 mm and an L / D ratio of 550 to 1500. Use of the thermoplastic molding compositions according to claims 1 to 4 for the production of long-fiber-reinforced granules. Use according to claim 5, wherein the production of long-fiber-reinforced granules takes place via pultrusion. Long fiber-reinforced granules obtainable from the thermoplastic molding compositions according to claims 1 to 4. Use of the granules according to claim 7 for the production of flame-retardant, impact-resistant, glow-wire-resistant shaped bodies of any kind. Moldings of any kind obtainable from the granules according to claim 7.