WO2016087324A1

WO2016087324A1 - Flame-retardant polyamides having sulfonic acid salts

Info

Publication number: WO2016087324A1
Application number: PCT/EP2015/077887
Authority: WO
Inventors: Michael Roth; Klaus Uske; Christoph Minges; Michaela HEUßLER; Martina BIEHL
Original assignee: Basf Se
Priority date: 2014-12-01
Filing date: 2015-11-27
Publication date: 2016-06-09

Abstract

The invention relates to thermoplastic molding masses, containing A) 10 to 98 wt% of a thermoplastic polyamide, B) 0.1 to 60 wt% of red phosphorus, C) 1 to 30 wt% of a thermoplastic polyester, D) 0 to 55 wt% of a fibrous filling material or a particulate filling material or mixtures thereof, E) 0.001 to 1 wt% of a fluorinated, aliphatic sulfonic acid salt, F) 0 to 10 wt% of a rubber-elastic polymerizate, G) 0 to 30 wt% of further additives, wherein the sum of the weight percentages A) to G) is 100%. The invention further relates to the use of such molding masses to produce fibers, film, and molded bodies and to the molding bodies, fibers, and film of any type that can be obtained in said use.

Description

Flame-retardant polyamides with sulfonic acid salts

Description The invention relates to thermoplastic molding compositions containing

A) 10 to 98% by weight of a thermoplastic polyamide,

B) 0.1 to 60% by weight of red phosphorus,

C) 1 to 30 wt .-% of a thermoplastic polyester

D) 0 to 55 wt .-% of a fibrous or particulate filler or mixtures thereof

E) 0.001 to 1% by weight of a fluorinated, aliphatic sulfonic acid salt,

F) 0 to 10 wt .-% of a rubber-elastic polymer

G) 0 to 30 wt .-% of other additives, wherein the sum of the weight percent A) to G) gives 100%.

Moreover, the present invention relates to the use of such molding compositions for the production of fibers, films and moldings and the moldings, fibers and films of any kind obtainable in this case.

It is known that the addition of red phosphorus to thermoplastics, especially to reinforced or filled polyamides, leads to effective fire protection (DE-A-1931387). Red phosphorus, however, tends to be affected under adverse conditions, e.g. elevated temperature, humidity, presence of alkali or oxygen, for the formation of decomposition products, such as hydrogen phosphide and acids of the monohydric to pentavalent phosphorus. In thermoplastics, e.g. Although polyamides, incorporated red phosphorus is largely protected due to the embedding in the polymer against thermal oxidation, but it can also come here in the longer term to the formation of decomposition products. This is disadvantageous in that improper processing of granules in the injection molding process, the forming phosphine can lead to odor nuisance and is also toxic. The simultaneously occurring acids of phosphorus can precipitate on the surface of moldings, whereby especially the creep resistance of the moldings is reduced.

There has therefore been no lack of attempts to improve the stability of the flame retardant used for plastics fe red phosphorus. Thus, a stabilizing effect can be achieved by adding oxides or hydroxides of zinc, magnesium or copper. According to DE-A-2625691, in addition to this stabilization by metal oxides, the phosphor particles are coated with a polymer. However, this coating or encapsulation process is quite expensive and, in addition, the stabilizing effect of the system is not satisfactory in all cases. An additional stabilization can be achieved by microencapsulation of the phosphor, see EP-A 837 100, which is technically complicated and the compounds of the encapsulation trigger problems in the processing with other constituents of the molding composition. Other flame-retardant polyamide / polyester blends are described in WO 2010/146143 and WO 2013/030024, whose P stability is in need of improvement.

It is an object of the present invention to provide thermoplastic molding compositions containing an effectively stabilized red phosphorus as a flame retardant, i. have a lower phosphorus and phosphinic acid. In addition, a good resistance during processing and a particularly homogeneous dispersibility in the plastic melt should be achieved. In addition, the vertical fire test to be improved as well as the annealing resistance. Accordingly, the molding compositions defined above were found. Preferred embodiments can be taken from the subclaims.

As component A), the molding compositions according to the invention contain 10 to 98, preferably 20 to 90 and in particular 20 to 70 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 1 10 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 U.S. Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210 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.

Suitable dicarboxylic acids are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids. 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 proportionality nis 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, Polyhexamethylensebacin- acid amide 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 aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by so-called direct polymerization in the presence of water, as for example in DE-A 10313681, EP-A 1 198491 and EP 922065.

In addition, mention should also be made of polyamides which are e.g. are obtainable by condensation of 1, 4-diaminobutane with adipic acid at elevated temperature (polyamide 4.6). Manufacturing processes for polyamides of this structure are known e.g. in 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). Further high-temperature-resistant polyamides are known from EP-A 19 94 075 (PA 6T / 6I / MXD6). The production of the preferred partly aromatic copolyamides with a low triamine content can be carried out by the processes described in EP-A 129 195 and 129 196.

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-aminopelargonic acid

PA 1 1 1 1 -aminoundecanoic acid

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

AA / BB-polymers

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 61 and PA 6T)

PA PACM 12 diaminodicyclohexylmethane, laurolactam

PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane

PA 12 / MACMI laurolactam, dimethyldiaminodicyclohexylmethane, isophthalic acid

PA 12 / MACMT laurolactam, dimethyldiaminodicyclohexylmethane, terephthalic acid

PA PDA-T phenylenediamine, terephthalic acid

Preferred flame retardant B) is elemental red phosphorus, in particular in combination with glass fiber-reinforced molding compositions, which can be used in untreated form. However, particularly suitable are preparations in which the phosphorus is superficially with low molecular weight liquid substances such as silicone oil, paraffin oil or esters of phthalic acid (especially dioctyl phthalate, see EP 176 836) or adipic acid or with polymeric or oligomeric compounds, e.g. is coated with phenolic resins or aminoplasts and polyurethanes (see 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 of red phosphorus, for example in a polyamide or elastomers are suitable as flame retardants. In particular, polyolefin homo- and copolymers are useful as concentrate polymers. However, the proportion of the concentrate polymer-if no polyamide is used as a thermoplastic-should not be more than 35% by weight, based on the weight of the components A) and B), in the molding compositions according to the invention. Preferred concentrate compositions are

Bi) 30 to 90 wt .-%, preferably from 45 to 70 wt .-% of a polyamide or

elastomers,

B2) 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 (dso) 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.

The content of component B) in the molding compositions according to the invention is 0.1 to 60, preferably 0.5 to 40 and in particular 1 to 15 wt .-%, based on the sum of components A) to G).

As component C), the molding compositions according to the invention contain 1 to 30, preferably 5 to 28 and in particular 15 to 25 wt .-% of at least one thermoplastic polyester.

Generally, polyesters C) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used.

A first group of preferred polyesters are polyalkylene terephthalates, in particular those having 2 to 10 carbon atoms in the alcohol part.

Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, e.g. by halogen such as chlorine and bromine or by C 1 -C 4 -alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.

These polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds in a manner known per se.

Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids. Of the aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1 , 4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof.

Particularly preferred polyesters C) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 C atoms. Of these, in particular, polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof are preferred. Also preferred are PET and / or PBT, which contain up to 1 wt .-%, preferably up to 0.75 wt .-% 1, 6-hexanediol and / or 2-methyl-1, 5-pentanediol as further monomer units.

The viscosity number of the polyesters C) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (wt : 1 at 25 ° C) according to ISO 1628.

Particular preference is given to polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg of polyester. Such polyesters can be prepared, for example, by the process of DE-A 44 01 055. The carboxyl end group content is usually determined by titration methods (e.g., potentiometry).

Particularly preferred molding compositions contain as component C) a mixture of polyesters whose main constituent is polyethylene terephthalate (PET). The proportion of polyethylene terephthalate in the mixture is preferably 50 to 100, in particular 75 to 100% by weight, based on 100 wt .-% C).

Furthermore, it is advantageous to use PET recyclates (also termed scrap PET), optionally mixed with polyalkylene terephthalates such as PBT. Recyclates are generally understood as:

1) so-called Post Industrial Recyclate: these are production waste in polycondensation or in processing, e.g. Sprues in injection molding processing, start-up goods in injection molding or extrusion or edge sections of extruded sheets or foils.

2) Post Consumer Recyclate: These are plastic items that are collected and processed after use by the end user. By far the dominating items in terms of volume are blow-molded PET bottles for mineral water, soft drinks and juices. Both types of recycled material can be present either as regrind or in the form of granules. In the latter case, the slag cyclates after separation and purification are melted in an extruder and granulated. This usually facilitates the handling, the flowability and the metering for further processing steps.

Both granulated and as regrind present recyclates can be used, the maximum edge length should be 10 mm, preferably less than 8 mm.

Due to the hydrolytic cleavage of polyesters during processing (due to traces of moisture) it is advisable to pre-dry the recyclate. The residual moisture content after drying is preferably <0.2%, in particular <0.05%.

Another group to be mentioned are fully aromatic polyesters derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.

Suitable aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to using mixtures of 5 to 100 mol% of isophthalic acid and 0 to 95 mol% of terephthalic acid, in particular mixtures of about 80% of terephthalic acid with 20% of isophthalic acid to approximately equivalent mixtures of these two acids.

The aromatic dihydroxy compounds preferably have the general formula

in which Z represents an alkylene or cycloalkylene group having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m is the value 0 to 2 has. The compounds may also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.

As a parent of these compounds his example

dihydroxydiphenyl,

Di (hydroxyphenyl) alkane,

Di (hydroxyphenyl) cycloalkane,

Di (hydroxyphenyl) sulfide,

Di (hydroxyphenyl) ether,

ketone di- (hydroxyphenyl),

di- (hydroxyphenyl) sulfoxide,

a, a'-di- (hydroxyphenyl) -dialkylbenzol,

Di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene

Resorcinol and hydroquinone and their nuclear alkylated or ring-halogenated derivatives called. Of these will be

4,4'-dihydroxydiphenyl,

2,4-di- (4'-hydroxyphenyl) -2-methylbutane

a, a'-di- (4-hydroxyphenyl) -p-diisopropylbenzene,

2,2-di- (3'-methyl-4'-hydroxyphenyl) propane and

2,2-di- (3'-chloro-4'-hydroxyphenyl) propane, and in particular

2,2-di- (4'-hydroxyphenyl) propane

2,2-di- (3 ', 5-dichlordihydroxyphenyl) propane,

1: 1 - di- (4'-hydroxyphenyl) cyclohexane,

3,4'-dihydroxybenzophenone,

4,4'-dihydroxydiphenylsulfone and

2.2- Di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane or mixtures thereof is preferred.

Of course, it is also possible to use mixtures of polyalkylene terephthalates and wholly aromatic polyesters. These generally contain from 20 to 98% by weight of the polyalkylene terephthalate and from 2 to 80% by weight of the wholly aromatic polyester. Of course, polyester block copolymers such as copolyetheresters may also be used. Such products are known per se and are known in the literature, e.g. in the

US-A 3,651,014. Also in the trade, corresponding products are available, e.g. Hytrel® (DuPont). As fibrous or particulate fillers D) are carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar called in amounts of 0 to 55 or 50, preferably from 5 to 50 wt .-%, in particular 10 to 40 wt .-% can be used.

Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or cut glass in the commercial forms. The fibrous fillers can be surface-pretreated for better compatibility with the thermoplastics with a silane compound. Suitable silane compounds are those of the general formula

(X- (CH 2) n) kS i- (O-C _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.

Also suitable are acicular mineral fillers.

In the context of the invention, the term "needle-shaped mineral fillers" is understood to mean a mineral filler with a pronounced, needle-like character. An example is needle-shaped wollastonite. Preferably, the mineral has an L / D (length: diameter ratio of 8: 1 to 35: 1, preferably 8: 1 to 1: 1: 1) The mineral filler may optionally be pretreated with the silane compounds mentioned above, the pretreatment However, it is not absolutely necessary to use further fillers such as kaolin, calcined kaolin, wollastonite, talc and chalk, as well as platelet-shaped or needle-shaped nanofillers, preferably in quantities of between 0.1 and 10%, boehmite, bentonite, montmorillonite, vermicullite and the like being preferred In order to obtain a good compatibility of the platelet-shaped nanofillers with the organic binder, the platelet-shaped nanofillers according to the prior art are organically modified The addition of the platelet-shaped or needle-shaped nanofillers to the nanocomposites according to the invention leads to a further increase in the mechanical properties

Strength.

As component E), the inventive 0.001 to 1, preferably 0.001 to 0.5 and in particular 0.01 to 0.1 wt .-% of a fluorinated aliphatic sulfonic acid salt. Suitable sulfonic acid salts E) have the general formula

R - SOs ⁰ 1 / y M ^{Y +} where

R is a straight-chain or branched Al kylrest having 1 to 18 carbon atoms, with the proviso that at least one hydrogen of the alkyl radical is substituted by fluorine, y is 1 or 2

M alkali or alkaline earth metal mean. Preferred radicals R are linear or branched alkyl radicals having 1 to 10 C atoms, the methyl, ethyl, propryl, butyl, pentyl or hexyl radical being particularly preferred.

In particular, R of the above general formula means an alkyl radical as defined above, which is perfluorinated, i. all hydrogen atoms have been replaced by fluorine.

Preferred salts are alkali metal salts, with sodium or potassium being particularly preferred. Accordingly, y in the above formula means 1.

Preferred salts E) are Na trifluoromethanesulfonate,

Potassium 1, 1, 2,2,3,3,4,4,4 nonafluorobutane-1-sulfonate or

Potassium 1, 1, 2,2,3,3,4,4,5,5,6,6,6 tridecafluorohexane-1-sulfonate

or mixtures thereof.

Such salts are commercially available e.g. available as RM65 from the company Miteni SpA.

As component F), the molding compositions can contain from 0 to 10, preferably from 0.5 to 10, in particular from 1 to 8,% by weight of rubber-elastic 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 carbon atoms in the alcohol component. Such polymers are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg-Thieme-Verlag, Stuttgart, 1961), pages 392 to 406 and in the monograph by CB Bucknall "Toughened Plastics" (Applied Science Publishers , London, 1977). In the following some preferred types of such elastomers are presented:

Preferred component F) are impact modifiers based on ethylene copolymers which are composed of:

Fi) 40 to 98 wt .-%, preferably 50 to 94.5 wt .-% of ethylene

F ₂ ) 2 to 40 wt .-%, preferably 5 to 40 wt .-% of a (meth) acrylate having 1 to 18 carbon atoms, or / and

F3) 0 to 20 wt .-%, preferably 0.05 to 10 wt .-% of functional monomers selected from the group of ethylenically unsaturated mono- or dicarboxylic acids

or the carboxylic acid anhydrides or epoxide groups or mixtures thereof, the sum of the percentages by weight Fi) to F3) being 100%,

or an ethylene (meth) acrylic acid copolymer which is up to 72% neutralized with zinc.

Particularly preferred are ethylene copolymers composed of: Fi) 50 to 69.9% by weight of ethylene

F ₂ ) 30 to 40 wt .-% of a (meth) acrylate having 1 to 18 carbon atoms

F3) 0.1 to 10 wt .-% of functional monomers according to claim 1, wherein the sum of the weight percent Fi) to F3) gives 100%.

The proportion of the functional groups F3) is 0.05 to 5, preferably 0.2 to 4 and in particular 0.3 to 3.5 wt .-%, based on 100 wt .-% F).

Particularly preferred components F3) 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 6 -alkyl esters of acrylic acid or methacrylic acid D 2 are suitable, but preference is given to esters having 1 to 12 C atoms, in particular 2 to 10 C atoms.

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. 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. Other examples of monomers F3) are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular butyl acrylate and dicarboxylic acids such as maleic acid and fumaric acid or anhydrides of these acids and their monoesters. 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 of these 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 preparation of the ethylene copolymers described above can be carried out by processes known per se, preferably by random copolymerization under high pressure and elevated temperature.

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 copolymers is between 10,000 and 500,000 g / mol, preferably between 15,000 and 400,000 g / mol (Mn, determined by GPC in 1, 2,4-trichlorobenzene with PS calibration).

Commercial products preferably used are Fusabond ^® A 560, A Lucalen ^® 2910, Lucalen ^® A 31 10 Nucrel 3990 Nucrel 925, Lotader Ax 9800, 3 getabond FS 7 M.

.

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. Blackley is described in the monograph "Emulsion Polymerization." The emulsifiers and catalysts which can be used are known per se, particular preference is given to copolymers which contain no units F2) but which have neutralized the acid component F3) with Zn. acrylic acid copolymers which have been neutralized with zinc up to 72% (commercially available as Suryn® 9520 from Dupont).

Of course, it is also possible to use mixtures of the rubber types listed above. Further additives G) may be present in amounts of up to 30, preferably up to 20 wt .-%.

As component G), the molding compositions according to the invention may contain 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a lubricant.

Preferred are Al, alkali, alkaline earth or ester or amides of fatty acids having 10 to 44 carbon atoms, preferably having 12 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 1 - to 3-valent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are corresponding to glyceryl distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol 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 component G), the molding compositions of the invention 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a Cu stabilizer, preferably a Cu (l) - halide, in particular Mixture with an alkali halide, preferably KJ, in particular in the ratio 1: 4, included. Suitable salts of monovalent copper are preferably Cu (I) complexes with PPh 3, copper (I) acetate, copper (I) chloride, bromide and iodide. These are contained in amounts of 5 to 500 ppm of copper, preferably 10 to 250 ppm, based on polyamide. The advantageous properties are obtained in particular when the copper is present in molecular distribution in the polyamide. This is achieved by adding to the molding compound a concentrate containing polyamide, a salt of monovalent copper and an alkali halide in the form of a solid, homogeneous solution. A typical concentrate consists, for example, of 79 to 95% by weight of polyamide and 21 to 5% by weight of a mixture of copper iodide or bromide and potassium iodide. The concentration of the solid homogeneous solution of copper is preferably between 0.3 and 3, in particular between 0.5 and 2 wt .-%, based on the total weight of the solution and the molar ratio of copper (I) iodide to potassium iodide is between 1 and 1 1, 5, preferably between 1 and 5. Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular polyamide 6 and polyamide 6.6.

Suitable hindered phenols G) are in principle all compounds having a phenolic structure which have at least one sterically demanding group on the phenolic ring.

Preferably, e.g. Compounds of the formula

into consideration, in which mean:

R ¹ and R ^{2 are} an alkyl group, a substituted alkyl group or a substituted triazole group, wherein the radicals R ¹ and R ^{2 may be the} same or different and R ^{3 is} an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group. Antioxidants of the type mentioned are described, for example, in DE-A 27 02 661 (US Pat. No. 4,360,617).

Another group of preferred sterically hindered phenols are derived from substituted benzenecarboxylic acids, especially substituted benzenepropionic acids.

Particularly preferred compounds of this class are compounds of the formula HO-W // -CH, - CH, - COROC-CH, - CH,

where R ⁴ , R ⁵ , R ⁷ and R ⁸ independently of one another are C 1 -C ⁸ -alkyl groups which in turn may be substituted (at least one of which is a sterically demanding group) and R ^{6 is} a bivalent aliphatic radical having 1 to 10 C atoms means that may also have CO bonds in the main chain.

Preferred compounds corresponding to this formula are

(Irganox® 245 from BASF SE)

(Irganox® 259 from BASF SE)

By way of example, a total of sterically hindered phenols may be mentioned: 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 1,6-hexanediol bis [3- (3,5-di-tert. -butyl-4-hydroxyphenyl) -propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], distearyl-3,5-di-tert. butyl-4-hydroxybenzylphosphonate, 2,6,7-trioxa-1-phosphabicyclo [2.2.2] oct-4-ylmethyl-3,5-di-tert-butyl-4-hydroxyhydro-cinnamate , 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearyl-thiotriazylamine, 2- (2'-hydroxy-3'-hydroxy-3 ', 5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1, 3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-) hydroxybenzyl) benzene, 4,4'-methylenebis (2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyl-dimethylamine.

Have been found to be particularly effective and therefore preferably be used 2,2'-methylene-bis (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-hydroxyphenyl) -propionate] and N, N'-hexamethylene-bis-3,5- di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098) and the Irganox® 245 from BASF SE described above, which is particularly well suited.

The antioxidants G), which can be used individually or as mixtures, are in an amount of from 0.05 to 3% by weight, preferably from 0.1 to 1.5% by weight, in particular from 0.1 to 1 Wt .-%, based on the total weight of the molding compositions A) to G). In some cases, sterically hindered phenols having no more than one sterically hindered group ortho to the phenolic hydroxy group have been found to be particularly advantageous; especially when assessing color stability when stored in diffused light for extended periods of time. As component G), the molding compositions according to the invention may contain 0.05 to 5, preferably 0.1 to 2 and in particular 0.25 to 1, 5 wt .-% of a nigrosine.

Nigrosines are generally understood to mean a group of black or gray indulene-related phenazine dyes (azine dyes) in various forms (water-soluble, fat-soluble, spray-soluble) which are useful in wool dyeing and printing, in the blackening of silks, for dyeing leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscope dyes.

Technically, nigrosine is obtained by heating nitrobenzene, aniline, and aniline with anhydrous metal. Iron and FeC (name of Latin niger = black).

Component G) can be used as free base or else as salt (for example hydrochloride). Further details on nigrosines can be found, for example, in the electronic lexicon Rompp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword "nigrosine".

As component G), the thermoplastic molding compositions of the invention may contain conventional processing aids such as stabilizers, antioxidants, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.

Examples of antioxidants and heat stabilizers are sterically hindered phenols and / or phosphites and amines (eg TAD), hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations up to 1 wt .-%, based on the Called weight of the thermoplastic molding compositions. As UV stabilizers, which are generally used in amounts of up to 2 wt .-%, based on the molding composition, various substituted resorcinols, salicylates, Benzotriazo- le and benzophenones may be mentioned.

It is possible to add inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as anthraquinones as colorants. As nucleating agents, sodium phenylphosphinate, alumina, silica and preferably talc may be used.

The thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which the starting components are mixed in customary mixing devices, such as screw extruders, Brabender mills or Banbury mills, and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed. The mixing temperatures are usually 230 to 320 ° C.

According to a further preferred procedure, the components B) to G) can be mixed with a prepolymer, formulated and granulated. The granules obtained are then condensed in the solid phase under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity.

The thermoplastic molding compositions according to the invention are distinguished by good flame retardance and excellent glow-wire resistance and phosphorus stability. These are therefore suitable for the production of fibers, films and moldings of any kind.

Here are some examples: connectors, plugs, connector parts, harness components, circuit boards, circuit board components, three-dimensional injection-molded circuit strength, electrical connectors and mechatronic components. The moldings or semifinished products to be produced according to the invention from the thermoplastic molding compositions can be used, for example, in the motor vehicle, electrical, electronics, telecommunications, information technology, entertainment, computer industry, in vehicles and other means of transportation, in ships, spaceships, in the household, in office equipment, sports, in medicine and in general in objects and building parts which require increased fire protection. For the kitchen and household sector, the use of flow-improved polyamides for the production of components for Küchengerate, such as fryers, irons, buttons, and applications in the garden and leisure sector possible. Examples

The following components were used:

Component A:

Polyamide 66 with a viscosity number VZ of 150 ml / g, measured as a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. according to ISO 307 (Ultramid® A27 from BASF SE was used).

Component B:

50% concentrate of red phosphorus of average particle size (dso) of 10 to 30 μηη in nylon 6.

Component C:

Polyethylene terephthalate with VZ 80-100 ml / g according to DIN 53728-3.

Component D:

Standard chopped glass fiber for polyamides, length = 4.5 mm, diameter = 10μιτι.

Component E:

Potassium - 1, 1, 2,2,3,3,4,4,4 - nonafluorobutane-1-sulfonate

Component F / 1:

Ethylene-methyl acrylate-glycidyl methacrylate copolymer 67: 25: 8 (Lotader ^® AX 8900, Arkema GmbH)

Component F / 2:

Ethylene-n-butyl acrylate-acrylic acid copolymer (88: 8: 4)

(Lucalen ^® A31 10, Basell DE GmbH) component G / 1

Irganox ^® 1098 from BASF SE (N, N'-hexane-1, 6-diyl bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl propionamide])

Component G / 2

Ethylene bis stearamide Component G / 3

Commercially available zinc oxide

To demonstrate the inventions described improvements of Flammschutzeigen- shafts corresponding plastic molding compounds were prepared by compounding. The individual components were mixed for this purpose in a twin-screw extruder ZSK 26 (Berstorff) at a throughput of 20 kg / h and about 270 ° C at a flat temperature profile, discharged as a strand, cooled to Granulierfähigkeit and granulated. The specimens for the examination listed in Table 1 were sprayed on an Arburg 420C injection molding machine at a melt temperature of about 270 ° C. and a mold temperature of about 80 ° C.

The test specimens for the tension tests were produced according to ISO 527-2: / 1993 and the test specimens for the impact measurements according to ISO 179-2 / 1 eA.

The MVR measurements were carried out according to ISO 1 133.

The flame retardance of the molding compositions was determined, on the one hand, by the method UL94-V (Underwrite's Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", p. 14 to p. 18 Northbrook 1998) ,

The glow-wire resistance GWFI (Glow Wire Flammability Index) on boards was performed according to IEC 60695-2-12. The GWFI is a general suitability test for plastics in contact with live parts. The highest temperature is determined in which one of the following conditions is fulfilled in 3 consecutive tests: a) no ignition of the sample or b) afterburning time or afterglow time <30 s after the end of the contact time of the filament and no ignition of the substrate. The compositions of the molding compositions and the results of the measurements are shown in the table:

table

Component [% by weight] Comparative Comparison Comparison Example Example 1 Example 2 Example 3

A 43.29 43.3 43.3 43.3

B 8.0 8.0 8.0 -

C 20.0 20.0 20.0 20.0

D 26.0 26.0 26.0 26.0

E 0.01 - - 0.01

F / 1 1 .5 1 .5 - 1 .5

F / 2 - - 1 .5 -

G / 1 + G / 2 + G / 3 1 .2 (0.3 + 0.3 + 0.6) 1 .2 1 .2 1 .2

Viscosity number / [ml / g] 154 150 152 -

Modulus of elasticity / [MPa] 9250 9210 9280 -

Breaking stress / [MPa] 147 149 151 -

Elongation at break / [%] 2.6 2.8 2.7 -

Charpy Notch6.6 7.0 6.6 - ability / [kJ / m2]

MVR 275 ° C / 5kg / [ml / 10 22 23 29 - min]

UL94 / 0.4mm V-0 V-2 n.b. n.d.

UL94 / 0.8mm V-0 V-0 V-2 n.b.

GWFImax / 1 .0mm / [° C] 960 960 960 -

GWITmax / 1 .0mm / [° C] 775 750 725 -

Claims

claims

Thermoplastic molding compositions containing

A) 10 to 98% by weight of a thermoplastic polyamide,

B) 0.1 to 60% by weight of red phosphorus,

C) 1 to 30 wt .-% of a thermoplastic polyester

D) 0 to 55 wt .-% of a fibrous or particulate filler or mixtures thereof

E) 0.001 to 1% by weight of a fluorinated, aliphatic sulfonic acid salt,

F) 0 to 10 wt .-% of a rubber-elastic polymer

G) 0 to 30 wt .-% of other additives, wherein the sum of the weight percent A) to G) gives 100%. Thermoplastic molding compositions according to claim 1, comprising

A) 20 to 90% by weight

B) 0.5 to 40% by weight

C) 5 to 28% by weight

D) 0 to 50% by weight

E) 0.001 to 0.5% by weight

F) 0.5 to 10% by weight

G) 0 to 20% by weight

Thermoplastic molding compositions according to claims 1 or 2, in which component F) is composed of an ethylene copolymer containing from 0.1 to 20% by weight of functional monomers.

Thermoplastic molding compositions according to claims 1 to 3, containing as component C) a polyalkylene terephthalate.

Thermoplastic molding compositions according to claims 1 to 4, in which the sulfonic acid salt E) has the general formula.

R - S0 ₃ V _y M y ⁺ where

R is a straight-chain or branched alkyl radical having 1 to 18 C atoms, with the proviso that at least one hydrogen of the alkyl radical is substituted by fluorine, y 1 or 2

M alkali or alkaline earth metal means.

Thermoplastic molding compositions according to claims 1 to 5, in which R of the general formula according to claim 5 is perfluorinated.

Thermoplastic molding compositions according to claims 1 to 6, wherein M is the general formula according to claim 5 sodium or potassium and y is 1.

Thermoplastic molding compositions according to claims 1 to 7, in which the sulfonic acid salt E) is prepared from Na trifluoromethanesulfonate

Potassium 1, 1, 2,2,3,3,4,4,4 nonafluorobutane-1-sulfonate or

Potassium 1, 1, 2,2,3,3,4,4,5,5,6,6,6 tridecafluorohexane-1-sulfonate

or mixtures thereof is constructed.

Use of the thermoplastic molding compositions according to claims 1 to 8 for the production of fibers, films and moldings.

10. fibers, films and moldings obtainable from the thermoplastic molding compositions according to claims 1 to 8.