EP1144508A3

EP1144508A3 - Flameproof extrudates and flameproof moulded bodies produced by means of pressing methods

Info

Publication number: EP1144508A3
Application number: EP99964521A
Authority: EP
Inventors: Herbert Magerstedt; Hans-Leo Weber; Rolf Spatz; Kurt-Rainer Stahlke
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1998-12-16
Filing date: 1999-12-03
Publication date: 2002-09-11
Also published as: CN1357027A; HK1047758A1; IL143222A0; KR20010101238A; AU3035500A; CA2355274A1; WO2000036013A3; ID28970A; WO2000036013A2; JP2003500489A; BR9916193A; EP1144508A2; DE19857965A1

Abstract

The invention relates to flameproof extrudates, especially films, sheets and cable sheaths, with a polyalkylene terephthalate and pentabrombenzyl polyacrylate (PBBPA) base. The inventive extrudates have an improved breaking stress and elongation at break, improved electrical properties and an improved surface finish.

Description

Flame-retardant extrudates and flame-retardant molded articles manufactured using the press process

The invention relates to flame-retardant extrudates, in particular films, sheets and

Cable sheaths based on polyalkylene terephthalate and pentabromobenzyl polyacrylate (PBBPA) with improved tensile strength and elongation (breaking stress and elongation), electrical properties and surface properties.

As is known, for example, from the literature on plastics 80 (1990), pages 3 and 4, plastics, such as thermosets, elastomers, polyamide, polycarbonate, etc., can be made flame-retardant by using halogenated hydrocarbons.

From the references listed above it can be seen that plastic parts which contain halogenated hydrocarbons are indeed good flame retardants

Have effect, but due to the halogen-containing flame retardant additives used so far have a poor surface quality, so that the production of flame-retardant films or very thin-walled molded parts made of PBT is not possible.

Pentabromobenzyl mono- and polyacrylate and their use as flame retardants in thermoplastic resins is described in EP-A 344 700. Extrudates, such as films and sheets, which have the desired properties are not described therein.

The object of the present invention is to provide flame-retardant extrudates such as films, sheets and cable sheaths based on polyalkylene terephthalate and a commercially available, inexpensive and therefore economical flame retardant, which have a high surface quality, improved electrical properties and improved tensile strength and elongation (breaking stress and elongation ) on- point and can be easily produced from the thermoplastic molding materials by conventional techniques, such as extrusion, blow molding, pressing.

It has been found that extrudates (foils, sheets and cable sheathing) and molded articles based on polyalkylene terephthalate, which are equipped with a pentabromobenzyl polyacrylate (PBBPA), have an unexpected excellent surface and good flow behavior combined with very good flame-retardant behavior with high tensile strength and elongation (breaking stress and elongation) and high electrical and good other properties without damaging the thermoplastic matrix. Another advantage of the invention is that the thermoplastic molding compositions based on polyalkylene terephthalate and PBBPA are excellent for extrudates (foils, sheets and cable jackets), e.g. by extrusion, blow molding, cable harnessing and processing in molded parts by pressing. The extrudates according to the invention (foils, plates and cable sheathing) and in

Shaped articles produced by pressing processes can then be produced using conventional techniques, e.g. Thermoforming, further processing, printing and / or laser marking.

The present invention relates to molded articles and extrudates produced in the pressing process, in particular films, sheets and cable sheaths based on thermoplastic molding compositions

A) 55 to 97.7, preferably 60 to 95.5, in particular 70 to 95 parts by weight of polyalkylene terephthalate,

B) 2 to 30, preferably 3 to 25, in particular 4 to 20 parts by weight of pentabromobenzyl polyacrylate,

C) 0.3 to 12, preferably 0.5 to 10, in particular 1 to 8 parts by weight

Antimony compound (s) and D) 0 to 90 parts by weight of polycarbonate and / or polyester carbonate

the sum of A) + B) + C) + D) is 100 and up to 10 parts by weight of polyalkylene terephthalate can be replaced by polyolefins.

The extrudates (foils, sheets and cable sheathing) and molded articles produced by the pressing process are available from thermoplastic molding compositions containing the above-mentioned components A) to D). The thermoplastic molding compositions are distinguished by good flame-retardant behavior without damaging the thermoplastic matrix in conjunction with a high surface quality, improved electrical properties and, because of their good flow behavior, are particularly suitable for the production of films and plates.

The invention further relates to the use of thermoplastic molding compositions containing the abovementioned components for the production of flame-retardant extrudates (films, sheets and cable sheathing) and flame-retardant molded articles produced in the compression molding process with improved properties in terms of elongation at break, stress at break and surface properties.

Foils are usually materials that can be wound, while plates are generally stiff and therefore cannot be wound.

Films in the sense of the invention generally have a thickness of <1200 μm, preferably 25 to 1000 μm, in particular 50 to 850 μm.

Panels in the sense of the invention generally have a thickness of 1.2 mm to several cm, preferably 1.2 mm to 4 cm, in particular 1.2 mm to 2.5 cm. Component A

Polyalkylene terephthalates (component A) in the sense of the invention are reaction products of aromatic dicarboxylic acid or reactive derivatives thereof (for example dimethyl esters or anhydrides) and aliphatic, cyclo ^'aliphatic or araliphatic diols and mixtures of these reaction products.

Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Vol.

VIII, p. 695 FF, Karl-Hanser-Verlag, Munich 1973).

Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol component, ethylene glycol and / or butanediol-1,4-residues or their mixture with 1,4 cyclohexanediol.

In addition to terephthalic acid residues, the preferred polyalkylene terephthalates can contain up to 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as residues of

Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic acid, azelaic acid, cyclohexanediacetic acid.

The preferred polyalkylene terephthalates can contain up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, e.g. Residues of propanediol-1,3,2-ethylpropanediol-1,3, neopentylglycol, pentanediol-1,5, hexanediol-1,6,1,4-cyclohexanediol, cyclohexane-dimethanol-1,4,3-methylpentanediol-2 , 4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1, 3 and -l, 6,2-ethylhexanediol-1, 3, 2,2-diethylpropanediol-1, 3, hexanediol-2, 5, 1,4-di- (β-hydroxyethoxy) benzene, 2,2-

B is- (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis (3-ß-hydroxyethoxyphenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-OS 24 07 674, 24 07 776, 27 15 932).

The polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acid, e.g. in the DE-OS

19 00 270 and U.S. Patent 3,692,744 are described. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol.

It is advisable to use no more than 1 mole% of the branching agent, based on the

Acid component to use.

Particularly preferred are polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (for example its dialkyl esters), diols selected from ethylene glycol, 1,4-butanediol and 1,4-cyclohexanediol or mixtures thereof (polyethylene and polybutylene terephthalate), and Mixtures of these polyalkylene terephthalates.

Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components, particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) terephthalates.

The polyalkylene terephthalates preferably used as component A generally have an intrisic viscosity of about 0.4 to 1.5 dl / g, preferably 0.5 to

1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. Component B

Pentabromobenzyl polyacrylate is generally known and is described, for example, in EP-A 344 700. It is commercially available (Dead Sea Bromine Group, Beer Sheva, Israel).

PBBPA can also be prepared in situ by adding pentabromobenzyl monoacrylate in thermoplastic molding compositions (EP-A 344 700).

Component C

Preferred antimony compounds are antimony trioxide and / or antimony pentoxide, which are generally known compounds.

Component D

Polycarbonates are preferably used in an amount of 0 to 75 parts by weight, based on the total molding composition.

Polycarbonates can very particularly preferably be used in an amount of 20 to 70% by weight.

Parts, based on the total molding compound, are added.

Aromatic polycarbonates and / or aromatic polyester carbonates according to component D which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for the production of aromatic polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964, and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the production of aromatic polyester carbonates, for example DE-OS 3 077 934 ). Aromatic polycarbonates are prepared, for example, by reacting diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface method, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols.

Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)

in which

A ^{1 is} a single bond, -C-C5-alkylene, C2-C5-alkylidene, C -Cg-cycloalkylene, -O-, -SO-, -CO-, -S-, -SO2-, Cg-Ci ^ - Arylene, which may be condensed with further aromatic rings optionally containing heteroatoms, or a radical of the formula

or a radical of the formula (III)

B independently of one another Ci-Cg-alkyl, preferably C _] -C -alkyl, especially methyl, halogen, preferably chlorine and / or bromine, Cg-Ci o-aryl, preferably phenyl, Cγ-C ^ aralkyl, phenyl-Cι- C alkyl, preferably benzyl,

x each independently of one another 0, 1 or 2,

p are 1 or 0, and

R6 and R ^ can be selected individually for each Z, independently of one another, hydrogen or Ci-Cg-alkyl, preferably hydrogen, methyl and / or ethyl,

Z carbon and

m is an integer from 4 to 7, preferably 4 or 5,

with the proviso that on at least one atom Z

R6 and R? are alkyl at the same time.

Preferred diphenols are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis- (hydroxyphenyl) -Cι-C5-alkane, bis- (hydroxyphenyl) -C5-Cg-cycloalkane, bis- (hydroxyphenyl) ether, bis- (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, Bis (hydroxyphenyl) sulfones and α, α-bis (hydroxyphenyl) diisopropyl benzenes such as their core-brominated and / or core-chlorinated derivatives.

Particularly preferred diphenols are 4,4'-diphenylphenol, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis -

(4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis- (3-chloro-4 -hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

2,2-bis (4-hydroxyphenyl) propane (bisphenol-A) is particularly preferred.

The diphenols can be used individually or as any mixtures.

The diphenols are known from the literature or can be obtained by processes known from the literature.

Suitable chain terminators for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or

2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) phenol according to DE-OS 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) phenol and 4- (3rd , 5-dimethylheptyl) phenol. The amount of chain terminators to be used is generally between 0.5 mol% and 10 mol%, based on the molar sum of the diphenols used in each case.

The thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M _w , measured, for example, by means of an ultracentrifuge or scattered light measurement) of 10,000 to 200,000, preferably 20,000 to 80,000. The thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of> three-functional compounds, for example those with > three phenolic groups.

Both homopolycarbonates and copolycarbonates are suitable. To produce copolycarbonates according to the invention as component A, 1 to 25% by weight, preferably 2.5 to 25% by weight (based on the total amount of diphenols to be used), polydiorganosiloxanes with hydroxy-aryloxy end groups can also be used. These are known (see, for example, from US Pat. No. 3,419,634) or can be produced by processes known from the literature. The production of polydiorganosiloxane-containing copolycarbonates is e.g. in DE-OS 3 334 782.

In addition to the bisphenol A homopolycarbonates, preferred polycarbonates are

Copolycarbonates of bisphenol-A with up to 15 mol%, based on the molar sum of diphenols, of diphenols other than those mentioned as preferred or particularly preferred, in particular of 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane .

Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.

Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20: 1 are particularly preferred.

A carbonic acid halide, preferably phosgene, is additionally used as a bifunctional acid derivative in the production of polyester carbonates.

As chain terminators for the production of the aromatic polyester carbonates, besides the monophenols already mentioned, there are also their chlorocarbonic acid esters as well as the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by C 1 -C 22 -alkyl groups or by halogen atoms, and aliphatic C2-C22-monocarboxylic acid chlorides.

The amount of chain terminators is 0.1 to 10 mol% in each case, based on moles of diphenols in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichlorides in the case of monocarboxylic acid chloride chain terminators.

The aromatic polyester carbonates can also contain aromatic hydroxycarboxylic acids.

The aromatic polyester carbonates can be linear or branched in a known manner (see also DE-OS 2 940 024 and DE-OS 3 007 934).

For example, 3- or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-4,4'-benzophenonetetracarboxylic acid tetrachloride, 1, 4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, can be used as branching agents in amounts of 0.01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or 3- or polyfunctional phenols, such as phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2, 4,4-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane, 1,3,5-tri- (4-hydroxyphenyl) benzene, 1,1,1-tri- (4-hydroxyphenyl ) -ethane, tri- (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenyl-isopropyl) - phenol, tetra- (4-hydroxyphenyl) methane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4 -dihydroxyphenyl) propane, tetra- (4- [4-hydroxyphenyl-isopropyl] phenoxy) methane, 1,4-bis- [4,4'-dihydroxytriphenyl) methylj-benzene, in amounts of 0.01 to 1.0 mol%, based on the diphenols used. Phenolic branching agents can be introduced with the diphenols, acid chloride branching agents can be introduced together with the

Acid dichlorides are entered. The proportion of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired.

The proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the

Sum of ester groups and carbonate groups.

Both the ester and the carbonate content of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate.

The relative solution viscosity (η _re ι) of the aromatic polyester carbonates is in the range 1.18 to 1.4, preferably 1.22 to 1.3 (measured on solutions of 0.5 g polyester carbonate in 100 ml methylene chloride solution at 25 ° C. ).

The thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture with one another.

The aromatic polycarbonates can be prepared by known methods, e.g. by melt transesterification of a corresponding bisphenol with diphenyl carbonate and in solution from bisphenols and phosgene. The solution can be homogeneous (pyridine method) or heterogeneous (two-phase interface method) (cf. H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, S 33ff, Intersciencs Publ. 1964).

The aromatic polycarbonates generally have average molecular weights

M _w from approximately 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration).

For the purposes of the invention, copolycarbonates are, in particular, Poydiorganosiloxane-polycarbonate block copolymers with an average molecular weight M _w of approximately 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration) and with a content of aromatic carbonate structural units of approximately 75 to 97.5% by weight, preferably 85 to 97% by weight and a content of polydiorganosiloxane structural units of approximately 25 to 2.5% by weight, preferably 15 to 3% by weight, the block copolymers being prepared starting from polydiorganosiloxanes containing α, ω-bis-hydroxyaryloxy end groups and having a degree of polymerization P _n of 5 to 100, preferably 20 to 80.

The polydiorganosiloxane-polycarbonate block polymers can also be a mixture of polydiorganosiloxane-polycarbonate block copolymers with conventional polysiloxane-free, thermoplastic polycarbonates, the total content of polydiorganosiloxane structural units in this mixture being approximately 2.5 to 25% by weight.

Such polydiorganosiloxane-polycarbonate block copolymers are characterized in that they contain, on the one hand, aromatic carbonate structural units (1) and, on the other hand, polydiorganosiloxanes (2) containing aryloxy end groups in the polymer chain,

II

-O-Ar-O-C-O-Ar-O- (1),

RR ¹

- O-Ar-O - (- S Ii-O-) _a - (- S Ii-O-) _b - (- S Ii-O-) - Ar-O- (2),

RR ¹ R ¹

wherein

Ar are identical or different aryl residues from diphenols and R and R are identical or different and represent linear alkyl, branched alkyl, alkenyl, halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated aryl, but preferably methyl,

and

the number of diorganosiloxy units is n = a + b + c = 5 to 100, preferably 20 to 80.

Alkyl in the above formula (2) is, for example, C} -C20-alkyl, alkenyl in the above formula (2) is, for example, C2-C6-alkenyl; Aryl in the above formula (2) is Cg-C ^ aryl. Halogenated in the above formula means partially or completely chlorinated, brominated or fluorinated.

Examples of alkyls, alkenyls, aryls, halogenated alkyls and halogenated aryls are methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, chloromethyl, perfluorobutyl, perfluorooctyl and chlorophenyl.

Such polydiorganosiloxane-polycarbonate block copolymers are e.g. known from U.S. Patent 3,189,662, U.S. Patent 3,821,325 and U.S. Patent 3,832,419.

Preferred polydiorganosiloxane-polycarbonate block copolymers are produced by combining α, ω-bishydroxyaryloxy end group-containing polydiorganosiloxanes together with other diphenols, optionally with the use of branching agents in the usual amounts, e.g. according to the two-phase interface method (see

H. Schnell, Chemistry and Physics of Polycarbonates Polymer Rev. Vol. IX, page 27 ff, Interscience Publishers New York 1964), the ratio of the bifunctional phenolic reactants being chosen so that the content of aromatic carbonate structural units according to the invention is derived therefrom and diorganosiloxy units results. Such polydiorganosiloxanes containing α, ω-bishydroxyaryloxy end groups are known, for example, from US Pat. No. 3,419,634.

The thermoplastic molding composition can contain up to 10, in particular 1 to 8 parts by weight (based on 100 parts by weight of total weight) of polyolefms. suitable

Polyolefms are polymers of aliphatic unsaturated hydrocarbons, such as ethylene, propylene, butylene or isobutylene, which, for. B. radical polymerization can be obtained and average weight average molecular weights M _w (measured by gel chromatography methods) between 3,000 and 3,000,000. Both high pressure and low pressure polyolefin can be used. Polyethylenes and polypropylenes are preferred.

The molding compositions can contain nucleating agents such as microtalk. The molding compositions may also contain conventional additives such as lubricants, mold release agents, processing stabilizers and anti-dripping agents (e.g. polytetrafluoroethylene) as well as dyes and pigments.

The sheets produced in the extrusion or pressing process can be components from the electrical sector, for which good electrical properties combined with good flame-retardant behavior and good flowability and high

Surface quality without damaging the thermoplastic matrix are desired.

So come e.g. Housing parts, connector strips and lamp bases as well as parts from the motor vehicle sector are used.

Films made from the molding compositions can also be for the electrical sector, for which good flame-retardant behavior and good electrical properties without damage to the thermoplastic matrix are desired.

Cable sheaths can be used, for example, for the electrical sector as well as in automobile construction, for which good flame-retardant behavior, high electrical Properties and chemical resistance as well as thermal stability without damaging the thermoplastic matrix are desired.

For the preparation of films, sheets and cable sheathings the compo- nents are mixed and compounded usually at temperatures of about ^'260 ° C to 320 ° C by an extruder.

Examples

Description of the test methods for testing molded articles

Flame test according to UL 94 (IEC 707)

Bending test according to ISO 178

Melt volume rate (volume flow index) according to ISO 1133

Table 1

The electrical properties are measured as follows:

The components specified in the examples are mixed and by means of a

Extruders compounded under normal conditions and then in one Injection molding machine processed under normal PBT processing conditions (melt temperature approx. 260 ° C) to test specimens.

The properties of these test specimens are checked.

As pentabromobenzyl polyacrylate (PBB-PA) Eurobrom FR 1025, Eurobrom B.V. (NL) Rijswijk Netherlands.

Example 1 according to the invention 79.0% by weight of polybutylene terephthalate (PBT),

(Relative solution viscosity 1.707-1.153, measured at T = 25 ° C. in a 0.5% solution of phenol and o-dichlorobenzene, mixing ratio 1: 1 parts by weight) 15.0% by weight of PBB-PA 5.2%. -% antimony trioxide

0.8% by weight additives

Example 2 according to the invention

79.0% by weight of polybutylene terephthalate (PBT), (relative solution viscosity 1.834-1.875, measured at T = 25 ° C. in a 0.5% strength solution of phenol and o-dichlorobenzene, mixing ratio 1: 1 parts by weight) 15.0 % By weight PBB-PA 5.2% by weight antimony trioxide 0.8% by weight additives Comparative Example 3

79.2% by weight of polybutylene terephthalate (PBT)

(Relative solution viscosity 1.707-1.153, measured at T = 25 ° C. in a 0.5% solution of phenol and o-dichlorobenzene, mixing ratio 1: 1 parts by weight) 15.0% by weight of epoxidized tetrabromobisphenol A 5.0%. % Antimony trioxide 0.8% by weight additives

Comparative Example 4

80.7% by weight polybutylene terephthalate (PBT)

(relative solution viscosity 1.643-1.705, measured at T = 25 ° C in a 0.5% solution of phenol and o-dichlorobenzene, mixing ratio 1: 1 parts by weight)

13.5% by weight ethylene bis-tetrabromophthalimide 5.0% by weight antimony trioxide 0.8% by weight additives

Example 5 according to the invention

91.4% by weight of polybutylene terephthalate (PBT)

(Relative solution viscosity 1.707-1.153, measured at T = 25 ° C. in a 0.5% solution of phenol and o-dichlorobenzene, mixing ratio 1: 1 parts by weight) 6.0% by weight PBB-PA

1.8% by weight of antimony trioxide 0.8% by weight of additives Table 2 (results)

Comparative Example 3 is a comparison to Examples 1 and 5 The table shows that the test specimens which were produced from the molding compositions according to the invention have a significantly better tracking resistance, a comparable or better flowability (MVR) and a better mechanical level than the comparative test specimens. The molding compositions according to the invention can also be processed into test specimens with thin walls, so that particularly good fire behavior is achieved here. Comparative examples 3 and 4 cannot be processed into test specimens with a thickness of 0.4 mm in accordance with the flame test description.

Furthermore, the specified components can be mixed and processed into films in a film extrusion machine under customary PBT processing conditions (melt temperature approx. 250 ° C.).

Description of the test methods for testing on foils

Flame test according to UL 94 (IEC 707)

The test according to UL 94V and UL 94 VTM can be used for foils. Sections 8.1 and 11.1 of UL 94 specify the criteria for selecting the test method. Tensile test according to ISO 1184.

Films according to the invention are produced in the thickness range from 0.1 mm to 0.8 mm and tested in a flame test in accordance with UL 94.

Example 1 according to the invention processed into film:

With a film thickness of 0.6 mm, a V-0 resulted in the test according to UL 94V. With a film thickness of 0.1 mm, the test is carried out according to UL 94 VTM and results in VTM-0. Example 2 According to the Invention:

Films according to the invention are produced in the thickness range from 0.125 mm to 0.75 mm and tested in a flame test in accordance with UL 94.

Table 3 Results of the flame test (example 2)

The tensile strength and elongation and the modulus of elasticity are determined on these films in a tensile test in accordance with ISO 1884.

Table 4 Results of mechanical properties (example 2)

Comparative example 3

The product could not be processed into foils (demolition, heavily disturbed surfaces).

Comparative example 4

In contrast to the comparative tests, the molding compositions according to the invention can be processed to give films which have a high surface quality, in particular with regard to gloss and uniformity. At the same time, excellent fire behavior is achieved with a high level of mechanical properties.

Claims

claims

1. Containing extrudates and moldings produced in the pressing process based on thermoplastic molding compositions

A) 55 to 97.7 parts by weight of polyalkylene terephthalate,

B) 2 to 30 parts by weight of pentabromobenzyl polyacrylate,

C) 0.3 to 12 parts by weight of antimony compound (s) and

D) 0 to 90 parts by weight of polycarbonate and / or polyester carbonate

where the sum of A) + B) + C) + D) is 100 and up to 10 parts by weight of polyalkylene terephthalate can be replaced by polyolefins.

2. Extrudates and molded articles produced according to claim 1 based on thermoplastic molding compositions

A) 60 to 95.5 parts by weight of polyalkylene terephthalate,

B) 3 to 25 parts by weight of pentabromobenzyl polyacrylate,

C) 0.5 to 10 parts by weight of antimony compound (s),

D) 0 to 75 parts by weight of polycarbonate and / or polyester carbonate.

3. extrudates and molded articles produced in the pressing process according to claim 1 based on thermoplastic molding compositions

A) 70 to 95 parts by weight of polyalkylene terephthalate, B) 4 to 20 parts by weight of pentabromobenzyl polyacrylate,

C) 1 to 8 parts by weight of antimony compound (s) and

D) 0 to 75 parts by weight of polycarbonate and / or polyester carbonate.

4. extrudates and molded articles produced on the basis of thermoplastic molding compositions according to the preceding claims, wherein the thermoplastic molding compositions contain customary additives.

5. extrudates and molded articles based on thermoplastic molding compositions according to claim 5, wherein the additives are selected from at least one additive from the group consisting of nucleating agents, lubricants, mold release agents, processing stabilizers, dyes, pigments and anti-dripping agents.

6. foils, plates and cable sheathing according to the preceding claims.

7. Use of thermoplastic molding compositions according to claim 1 to 5 for the production of extrudates and molded articles produced in the pressing process with improved properties in terms of elongation at break and stress and surface quality.

8. Use according to claim 7 for the production of foils, plates and cable sheathing.