DE19827845A1 - Fire-resistant polyester moulding material, useful for the production of fibres, film and moulded products, especially electrical components - Google Patents

Abstract

Thermoplastic polyester moulding materials containing a combination of a nitrogen compound, an inorganic phosphorus compound and an organic phosphorus compound. Thermoplastic moulding materials containing: (A) 5-96 wt% polyester, (B) 1-30 wt% nitrogen compound, (C) 1-30 wt% inorganic phosphorus compound, (D) 1-30 wt% organic phosphorus compound, (E) 0-5 wt% ester(s) or amide(s) of 10-40C optionally unsaturated aliphatic carboxylic acids with 2-40C saturated aliphatic alcohols or amines and (F) 0-60 wt% other additives. An Independent claim is also included for moulded products obtained from these materials.

Description

The invention relates to thermoplastic molding compositions comprising

• A) 5 to 96 wt .-% of a polyester
• B) 1 to 30 wt .-% of a nitrogen compound
• C) 1 to 30 wt .-% of an inorganic phosphorus compound
• D) 1 to 30 wt .-% of an organic phosphorus compound
• E) 0 to 5 wt .-% of at least one ester or amide ge saturated or unsaturated aliphati shear carboxylic acids with 10 to 40 C-Ato with aliphatic saturated Alko get or amines with 2 to 40 carbon atoms
• F) 0 to 60 wt .-% of other additives, wherein the sum the weight percent of components A) to F) is 100%.

Furthermore, the invention relates to the use of the invention according to the molding compositions for the production of fibers, films and mold bodies as well as the moldings of any kind available here.

There is an increasing market interest for halogen-free flame protected polyester. Essential requirements for the flame Protective agents are: light inherent color, adequate temperature stability for incorporation into thermoplastics, as well as its Efficacy in reinforced and unreinforced polymer (so-called wick effect with glass fibers).

In this case, the fire test for unreinforced polyester according to UL 94 to be passed with V-O. For reinforced polyester should be at least the classification V2 and / or the glow wire test passed become.

In addition to the halogen-containing systems, four halogen-free FR systems are in principle used in thermoplastics:

• - Inorganic flame retardants that show efficacy must be used in high amounts.  
• Nitrogen-containing FR systems, such as melamine cyanurate, which has a limited effectiveness in thermoplastics z. B. polyamide shows. In reinforced polyamide, it is only in conjunction with shortened glass fibers effectively. In polyesters is melamine cyanurate alone is not effective.
• - Phosphorus-containing FR systems, which are generally not in polyesters are very effective.
• - Phosphorus / nitrogen-containing FR systems, such. For example ammonium polyphosphates or melamine phosphates used for thermoplastics, which are processed at temperatures above 200 ° C, none have sufficient thermal stability.

From JP-A 03/281 652 polyalkylene terephthalates are known, which contain melamine cyanurate (MC) and glass fibers as well as a phosphorus-containing flame retardant. Contain these molding compounds Derivatives of phosphoric acid such as phosphoric acid ester (valence stage +5), which under thermal stress to "bloom" tend.

These disadvantages are also evident for the combination of melamine cyanurate with resorcinol bis (diphenyl phosphate), which from the JP-A 05/070 671 is known. Furthermore, these molding compounds high phenol values during processing and insufficient me chanical characteristics.

From JP-A 09/157 503 polyester molding compounds with MC, Phos Phorverbindungen and lubricants known which less than Contain 10% reinforcing agent. Flame retardant and mechanical Properties of such molding compounds need to be improved as well as migration and phenol formation during processing.

From EP-A 699 708 and BE-A 875 530 are phosphinic salts as Flame retardant for polyester known.

In WO 97/05705 combinations of MC with phosphorhalti compounds and lubricants for polyester disclosed.

The present invention therefore an object of the invention, flame to provide solid polyester molding compositions, which according to Ul 94 achieve a sufficient classification and the annealing wire test exist. The mold covering should be minimized and the flowability during processing can be improved.  

Furthermore, the thermal stability during processing and the long-term thermal stability, especially at elevated Ge Use temperature, can be improved.

Accordingly, the initially defined thermoplastic form found masses. Preferred embodiments are the sub to extract claims.

As component (A), the molding compositions according to the invention contain 5 to 96, preferably 10 to 70 and in particular 10 to 60 wt .-% a thermoplastic polyester.

Generally, polyesters based on aromatic dicarbon acids and an aliphatic or aromatic dihydroxy connection used.

A first group of preferred polyesters are polyalkylene tereph thalates with 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, for. B. halogens 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-Butylgrup pen.

These polyalkylene terephthalates can be prepared by the reaction of aroma dicarboxylic acids, their esters or other ester-forming Derivatives with aliphatic dihydroxy compounds in themselves be be known manner.

Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, Terephthalic acid and isophthalic acid or mixtures thereof NEN. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cyclo aliphatic dicarboxylic acids such as adipic acid, azelaic acid, Sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids be set.

Of the aliphatic dihydroxy compounds diols with 2 to 6 carbon atoms, especially 1,2-ethanediol, 1,3-propane diol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclo hexanediol, 1,4-cyclohexanedimethylanol and neopentyl glycol or their mixtures are preferred.  

Particularly preferred polyesters (A) are polyalkylene tereph thalates derived from alkanediols containing 2 to 6 carbon atoms, to call. Of these, in particular, polyethylene terephthalate lat, polypropylene terephthalate and polybutylene terephthalate or their mixtures are preferred. Further preferred are PET and / or PBT containing up to 1% by weight, preferably up to 0.75% by weight 1,6-hexanediol and / or 5-methyl-1,5-pentanediol as further mono contain units.

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

Particularly preferred are polyesters whose carboxyl end groups content up to 100 meq / kg, preferably up to 50 meq / kg and ins special is up to 40 meq / kg polyester. Such poly For example, esters can be prepared by the process of DE-A 44 01 055 getting produced. The carboxyl end group content becomes more common determined by titration method (eg potentiometry).

Particularly preferred molding compositions contain as component A) a mixture of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). The proportion of polyethylene terephthalate be preferably carries in the mixture up to 50, in particular 10 to 30 wt .-%, based on 100 wt .-% A).

Such molding compositions of the invention show very good flame protective properties and better mechanical properties.

Furthermore, it is advantageous PET recyclate (also scrap PET ge called) in admixture with polyalkylene terephthalates such as PBT put.

Recyclates are generally understood as:

• 1. so-called Post Industrial Recyclate: this is about Production waste in polycondensation or Ver working z. B. sprues in the injection molding, starting in injection molding or extrusion or edge sections of extruded sheets or foils.
• 2nd Post Consumer Recyclate: this is art fabric after use by the end user collected and processed. The quantity by far  dominating articles are blow-molded PET bottles for mine water, soft drinks and juices.

Both types of recyclate can be either as regrind or in shape of granules present. In the latter case, the tubes are recycled after separation and purification in an extruder molten zen and granulated. This is usually the handling, the Rie selectivity and dosing for further processing steps made easier.

Both granulated and as regrind present recyclates can be used, whereby the maximum edge length 6 mm, should preferably be less than 5 mm.

Due to the hydrolytic cleavage of polyesters in the Ver working (by traces of moisture) it is recommended that the Re to pre-dry cyclically. The residual moisture content after drying is preferably 0.01 to 0.7, in particular 0.2 to 0.6%.

Another group to be mentioned are fully aromatic polyesters which of aromatic dicarboxylic acids and aromatic dihydroxy Derive connections.

As aromatic dicarboxylic acids are already in the Polyalkylene terephthalates described compounds. Prefers are mixtures of 5 to 100 mol% of isophthalic acid and 0 to 95 mol% terephthalic acid, in particular mixtures of about 80% Terephthalic acid with 20% isophthalic acid to about equivalent Mixtures of these two acids used.

The aromatic dihydroxy compounds preferably have the general formula

in which Z represents an alkylene or cycloalkylene group having up to 8 carbon atoms, an arylene group having up to 12 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m the value 0 until 2 has. The compounds I can 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,
α, α'-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
α, α'-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 are preferred.

Of course, you can also mixtures of polyalkylene use terephthalates and wholly aromatic polyesters. These generally contain from 20 to 98% by weight of the polyalkylene tereph thalates and 2 to 80 wt .-% of wholly aromatic polyester.

Among polyesters in the context of the present invention are also intended Polycarbonates obtained by polymerization of aromatic dihydroxy compounds, especially bis (4-hydroxy phenyl) 2,2-propane (bisphenol A) or its derivatives, e.g. B. with Phosgene are available. Corresponding products are in themselves be Known and described in the literature and mostly in the Trade available. The amount of polycarbonates is up to  90% by weight, preferably up to 50% by weight, based on 100% by weight the component (A).

Of course, polyester block copolymers such as Copolyetherester can be used. Such products are on known and in the literature, for. In US-A 3,651,014, described. Also in the trade are obtained corresponding products Lich, z. Hytrel® (DuPont).

As component B) thermoplasti invention contain rule molding compositions 1 to 30, preferably 1 to 20, and in particular 5 to 15% by weight of a nitrogen compound.

The melamine cyanourate which is preferably suitable according to the invention (component B) is a reaction product of preferably equimolar amounts of melamine (formula V) and cyanuric acid or isocyanuric acid (formulas Va and Vb)

You get it z. B. by reaction of aqueous solutions of the starting compounds at 90 to 100 W. The commercially available Pro product is a white powder with a mean particle size d ₅₀ of 1.5-7 microns.

Other suitable compounds (often as salts or adducts are melamine, melamine borate, oxalate, phosphate prim., sec. and pyrophosphate sec., neopentyl glycol boric acid lamin as well as polymeric melamine phosphate (CAS No. 56386-64-2).  

Suitable guanidine salts are

CAS-No. G-carbonate 593-85-1 G-cyanurate prim. 70285-19-7 G-phosphate prim. 5423-22-3 G-phosphate sec. 5423-23-4 G-sulfate prim. 646-34-4 G-sulfate sec. 594-14-9 Pentaerythritborsäureguanidin N / A. Neopentylglycolborsäureguanidin N / A. and urea phosphate green 4861-19-2 urea cyanurate 57517-11-0 ammeline 645-92-1 ammelide 645-93-2 melem 1502-47-2 Melon 32518-77-7

For the purposes of the present invention, compounds are intended to be so probably z. B. benzoguanamine itself and its adducts or salts as also the nitrogen-substituted derivatives and its adducts or salts are understood.

Also suitable are ammonium polyphosphate (NH ₄ PO ₃ ) _n with n about 200 to 1000, preferably 600 to 800, and tris (hydroxyethyl) isocyanate (THEIC) of the formula VI

or its reaction products with aromatic carboxylic acids Ar (COOH) _m , which may optionally be present in admixture with each other, wherein Ar is a mono-, di- or trinuclear aromatic six-membered system and m is 2, 3 or 4.

Suitable carboxylic acids are, for example, phthalic acid, isoph thalian acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, mellophanic acid, Prehnic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalene dicar carboxylic acids and anthracene carboxylic acids.  

The preparation is carried out by reacting the tris (hydroxy ethyl) isocyanurates with the acids, their alkyl esters or theirs Halides according to the methods of EP-A 584 567.

Such reaction products are a mixture of monomeric and oligomeric esters, which may also be crosslinked. The degree of oligomerization is usually 2 to about 100, preferably 2 to 20. Preferably, mixtures of THEIC and / or its reaction products with phosphorus-containing nitrogen compounds, in particular (NH ₄ PO ₃ ) _n or melamine pyrophosphate or polymeric melamine phosphate used. The mixing ratio z. B. from (NH ₄ PO ₃ ) _n to THEIC is preferably 90 to 50 to 10 to 50, especially 80 to 50 to 50 to 20 wt .-%, based on the mixture of such components B).

Also suitable are benzoguanamine compounds of the formula VII

in the R, R 'straight-chain or branched alkyl radicals having 1 to 10 C atoms, preferably hydrogen, and in particular their Adducts with phosphoric acid, boric acid and / or pyrophosphoric acid.

Also preferred are allantoin compounds of the formula VIII

where R, R 'have the meaning given in formula VII and their salts with phosphoric acid, boric acid and / or pyrophosphoric acid and glycolurils of the formula IX or its salts with the abovementioned acids

in which R has the meaning given in formula VII.

Suitable products are commercially or according to DE-A 196 14 424 he hältlich.

The usable according to the invention cyanoguanidine (formula X) he holds z. B. by reaction of calcium cyanamide (calcium cyanamide) with carbon dioxide, wherein the resulting cyanamide dimerized at pH 9 to 10 to cyanoguanidine.

The commercially available product is a white powder with a Melting point from 209 ° C to 211 ° C.

As component C), the molding compositions according to the invention contain 1 to 30, preferably 1 to 20 and in particular 1 to 10 wt .-% of an inorganic phosphorus compound. Preference is given to phosphine acid salts of the formula (I) and / or diphosphinic salts of formula (II) and / or their polymers

where the substituents have the following meanings:
R ¹ , R ^{2 is} hydrogen, C ₁ - to C ₆ -alkyl, preferably C ₁ - to C ₄ -alkyl, linear or branched, z. Methyl, ethyl, n -propyl, iso -propyl, n -butyl, tert -butyl, n -pentyl; phenyl; wherein preferably at least one radical R ¹ or R ² , in particular R ¹ and R ^{2 is} hydrogen;

R ^{3 is} C ₁ to C ₁₀ alkylene, linear or branched, e.g. B. Methyl len, ethylene, n-propylene, iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene;
Arylene, e.g. Phenylene, naphthylene;
Alkylarylene, e.g. Methyl-phenylene, ethyl-phenylene, tert-butyl-phenylene, methyl-naphthylene, ethyl-naphthylene, tert-butyl-naphthylene;
Arylalkylene, z. Phenyl-methylene, phenyl-ethylene, phenyl-propylene, phenyl-butylene;
M is an alkaline earth, alkali metal, Al, Zn, Fe, boron;
m is an integer of 1 to 3;
n is an integer of 1 and 3 and
x 1 or 2.

Particular preference is given to compounds of the formula II in which R ¹ and R ^{2 are} hydrogen, where M is preferably Zn or Al and calcium phosphinate is very particularly preferred.

Such products are commercially available for. B. as calcium phosphinate he hältlich.

Suitable salts of the formula I or II in which only one radical R ¹ or R ^{2 is} hydrogen are, for. As salts of phenylphosphinic acid, with their Na and / or Ca salts are preferred.

Suitable organic phosphorus-containing flame retardants D) are in the molding compositions according to the invention contain in amounts of 1 to 30, preferably 1 to 25 and in particular 5 to 20 wt .-% based on the total weight of components A) to E).

In the component D) is organic phosphor ent holding compounds in which the phosphorus is the valence state -3 to +5. Under the valency level is the term "Oxidation state" are understood, as in the textbook of Anor ganic chemistry by A. F. Hollemann and E. Wiberg, Walter des  Gruyter and Co. (1964, 57th to 70th Edition), pages 166 to 177, is reproduced. Phosphorus compounds of valence states -3 to +5 are derived from phosphine (-3), diphosphine (-2), phosphino xid (-1), elemental phosphorus (+0), hypophosphorous acid (+1), phosphorous acid (+3), hypodiphosphoric acid (+4) and phosphorus acid (+5).

From the large number of phosphorus-containing compounds are only some examples mentioned.

Examples of phosphorus compounds of the phosphine class, which are the Valence state -3 are aromatic phosphines, such as Triphenylphosphine, tritolylphosphine, trinonylphosphine, trinaph thylphosphine u. a. Particularly suitable is triphenylphosphine.

Examples of phosphorus compounds of diphosphine class, which the Valence level -2 are tetraphenyl diphosphine, tetra naphthyl diphosphine and the like a. Particularly suitable is tetranaphthyldi phosphine.

Phosphorus compounds of valence state -1 are derived from Phosphine oxide from.

Suitable phosphine oxides of the general formula III

wherein R ¹ , R ² and R ^{3 are the} same or different alkyl, aryl, alkylaryl or cycloalkyl groups having 8 to 40 carbon atoms.

Examples of phosphine oxides are triphenylphosphine oxide, tritolyl phosphine oxide, trisnonylphenylphosphine oxide, tricyclohexylphosphine oxide, tris (n-butyl) phosphine oxide, tris (n-hexyl) phosphine oxide, Tris (n-octyl) phosphine oxide, tris (cyanoethyl) phosphine oxide, Benzyl bis (cyclohexyl) phosphine oxide, benzyl bisphenyl phosphine oxide, Phenylbis- (n-hexyl) phosphine oxide. Also preferred are oxi diert reaction products of phosphine with aldehydes, esp other of t-butylphosphine with glyoxal. Particularly preferred be set Triphenylphosphinoxid, Tricyclohexlyphosphinoxid and tris (n-oetyl) phosphine oxide.

Also suitable is triphenylphosphine sulfide and its as above described derivatives of phosphine oxides and triphenyl phosphate.  

Phosphorus of the valence state +0 is the elemental phosphorus. In Question come red and black phosphorus. Preference is red Phosphorus.

Phosphorus compounds of the "oxidation state" +1 are z. B. Hypo phosphite. Examples are organic hypophosphites, such as Cellulo sehypophosphitester, esters of hypophosphorous acids with Dio len, such as B. of 1,10-dodecyldiol. Also substituted phosphine acids and their anhydrides, such as. Diphenylphosphinic acid, be used. Further suitable are di-p-tolyl phosphinic acid, di-cresylphosphinic anhydride. But it comes also compounds such as hydroquinone, ethylene glycol, propylene glycol col-bis (diphenylphosphinic) ester u. a. in question. Further are suitable aryl (alkyl) phosphinic acid amides, such as. B. diphenyl phosphinic acid dimethylamide and sulfonamidoaryl (alkyl) phosphinic acid rederivate, such as B. p-tolylsulfonamidodiphenylphosphinic acid. Hydroquinone and ethylene glycol are preferably used bis (diphenylphosphinic) ester and the bis-diphenylphosphinate of hydroquinone.

Phosphorus compounds of the oxidation state +3 are derived from the phosphorous acid. Suitable cyclic phosphonates derived from pentaerythritol, neopentyl glycol or pyrocatechol such as. B.

where R is a C ₁ - to C ₄ -alkyl radical, preferably methyl radical, X = 0 or 1 (Amgard® P45 from Albright & Wilson). Furthermore, phosphorus of the valence state +3 in triaryl (al kyl) phosphites, such as. As triphenyl phosphite, tris (4-decylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite or phenyl didecyl phosphite, inter alia. But there are also diphosphites, such as. As propylene glycol-1,2-bis (diphosphite) or cyclic Phosp hite derived from pentaerythritol, neopentyl glycol or Brenzkate chin, in question.

Particularly preferred are methyl neopentyl glycol phosphonate and phosphite and dimethylpentaerythritol diphosphonate and phosphite.  

The most important phosphorus compounds of the +4 oxidation state are Hypodiphosphates, such as. For example, tetraphenyl hypodiphosphate or bisneo pentyl hypodiphosphate into consideration.

Suitable phosphorus compounds of the oxidation state +5 are, in particular, alkyl- and aryl-substituted phosphates. Examples are phenylbisdodecylphosphate, phenylethylhydrogenphosphate, phenylbis (3,5,5-trimethylhexyl) phosphate, ethyldiphenylphosphate, 2-ethylhexyldi (tolyl) phosphate, diphenylhydrogenphosphate, bis (2-ethylhexyl) -p-tolylphosphate, tritolylphosphate, bis (2-ethylhexyl) ethylhexyl) phenylphosphate, di (nonyl) phenylphosphate, phenylmethylhydrogenphosphate, di (dodecyl) -p-tolylphosphate, p-tolylbis (2,5,5-trimethylhexyl) phosphate or 2-ethylhexyldiphenylphosphine. Particularly suitable are phosphorus compounds in which each of the radicals is an aryloxy radical. Especially suitable is tri phenyl phosphate and resorcinol bis (diphenyl phosphate) (RDP) and its ring-substituted derivatives of the general formula IV

in which the substituents have the following meanings:
R ⁴ -R ^{7 is} an aromatic radical having 6 to 20 C atoms, preferably a phenyl radical which may be substituted by alkyl groups having 1 to 4 C atoms, preferably methyl,
R ^{8 is} a divalent phenol radical, preferred

and n an average value between 0.1 and 100, preferably 0.5 to 50, in particular 0.8 to 10 and especially 1 to 5.

The commercially available RDP products under the trademarks Fyroflex® RDP (Akzo Nobel) and CR 733-S (Daihachi) are conditional by the manufacturing process mixtures of approx. 85% RDP with approx. 2.5% triphenyl phosphate and about 12.5% oligomeric proportions, in where the degree of oligomerization is usually less than 10.  

Furthermore, cyclic phosphates can also be used. Particularly suitable here is diphenylpentaerythritol diphosphate and phenylneopentyl phosphate.

Except the above-mentioned low molecular weight phosphorus compounds are still oligomeric and polymeric phosphorus compounds in question.

Such polymeric, halogen-free organic phosphorus compounds with phosphorus in the polymer chain arise, for example, in the Preparation of Pentacyclic, Unsaturated Phosphine Dihalogens Niden, as described for example in DE-A 20 36 173 is. The molecular weight measured by vapor pressure osmometry in Dimethylformamide, the Polyphospholinoxide should in the range of 500 to 7,000, preferably in the range of 700 to 2,000.

The phosphorus here has the oxidation state -1.

Furthermore, inorganic coordination polymers of aryl (Al- kyl) -phosphinic acids such. For example, poly-β-sodium (I) -methylphenylphosphine phinate are used. Their preparation is described in DE-A 31 40 520 specified. The phosphorus has the oxidation number +1.

Furthermore, such halogen-free polymeric phosphorus compound tions by the reaction of a phosphonic acid chloride, such as. B. Phenyl, methyl, propyl, styryl and vinylphosphonic dichloro with bifunctional phenols, such as. Hydroquinone, resorcinol, 2,3,5-trimethylhydroquinone, bisphenol-A, tetramethylbisphenol-A arise.

Other non-halogenated polymeric phosphorus compounds used in the may be contained by molding compositions Reaction of phosphorus oxychloride or phosphoric acid ester loriden with a mixture of mono-, bi- and trifunctional Phenols and other hydroxyl-bearing compounds forth (see Houben-Weyl-Muller, Thieme Verlag Stuttgart, Orga nische phosphorus compounds Part II (1963)). Furthermore, poly mere phosphonates by transesterification reactions of phosphonic acids star with bifunctional phenols (see DE-A 29 25 208) or by reactions of phosphonic acid esters with diamines or diami or hydrazides (see U.S. Patent 4,403,075). In Another question is the inorganic poly (ammonium phosphate).

There may also be oligomeric pentaerythritol phosphites, phosphates and phosphonates according to EP-B 8 486, z. B. Mobil Antiblaze® 19 (eing trademark of Mobil Oil).  

As component E), the molding compositions 0 to 5, preferably 0.05 to 3 and in particular 0.1 to 2 wt .-% min at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids having 10 to 40, preferably 16 to 22 C Atoms with aliphatic saturated alcohols or amines with 2 to 40, preferably 2 to 6 carbon atoms.

The carboxylic acids can be 1- or 2-valent. As examples are Pelargonic acid, palmitic acid, lauric acid, margaric acid, Do decanedioic acid, behenic acid and most preferably stearic acid, Capric acid and montanic acid (mixture of fatty acids with 30 bis 40 C-atoms).

The aliphatic alcohols can be 1 to 4 valent. Examples for alcohols, n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, wherein Glycerol and pentaerythritol are preferred.

The aliphatic amines can be monohydric to trihydric. Examples these are stearylamine, ethylenediamine, propylenediamine, hexame thylenediamine, di (6-aminohexyl) amine, wherein ethylenediamine and hexa methylenediamine are particularly preferred. Preferred esters or Amides are correspondingly glycerol distearate, glycerol tristearate, Ethylene diamine distearate, glycerol monopalmitate, glycerol trilaurate, Glycerol monobehenate and pentaerythritol tetrastearate.

It is also possible to use mixtures of different esters or amides or Ester can be used in combination with amides, the Mi ratio is arbitrary.

As component F), the molding compositions 0 to 60, in particular up to 50 wt .-% of other additives enthal th.

Usual additives F) are available, for example, in amounts of up to 40, preferably up to 30% by weight of elastomeric polymers (often also as Schlagzähmodifier, elastomers or rubbers be draws).

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 z. B. in Houben-Weyl, methods of orga nische Chemie, 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) described.

The following are some preferred types of such elastomers presented.

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

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

As diene monomers for EPDM rubbers are konju greedy dienes such as isoprene and butadiene, non-conjugated dienes with 5 to 25 carbon atoms, such as penta-1,4-diene, hexa-1,4-diene, hexane xa-1,5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cycli dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and Dicyclopentadiene and alkenylnorbornenes such as 5-ethylidene-2-nor bornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-iso propenyl-5-norbornene and tricyclodienes such as 3-methyl-tri - cyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof. Preference is given to hexa-1,5-diene, 5-ethylidenenorbornene and dicyclo pentadiene. The diene content of the EPDM rubbers is vorzugswei 0.5 to 50, in particular 1 to 8 wt .-%, based on the Ge total weight of the rubber.

EPM or EPDM rubbers may preferably also be reactive Carboxylic acids or derivatives thereof may be grafted. Here are z. B. Acrylic acid, methacrylic acid and their derivatives, e.g. B. Glyci dyl (meth) acrylate, and called maleic anhydride.

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 can still di carboxylic acids such as maleic acid and fumaric acid or derivatives of these 1 acids, eg. As esters and anhydrides, and / or epoxy groups contained tend tend monomers. These dicarboxylic acid derivatives or epoxy-containing monomers are preferably incorporated by addition of dicarboxylic acid or epoxy groups containing monomers of all general formulas I or II or III or IV to the monomer mixture in the rubber

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.

Preferably, the radicals R ¹ to R 9 are 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 the 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, glycine dylmethacrylate and the esters with tertiary alcohols, such as t-Bu tylacrylat. Although the latter have no free carboxyl groups but in their behavior they approach the free acids and are therefore termed monomers with latent carboxyl groups net.

Advantageously, the copolymers consist of 50 to 98 wt .-% Ethy len, 0.1 to 20 wt .-% of epoxy-containing monomers and / or Methacrylic acid and / or acid anhydride groups containing Monomers and the remaining amount of (meth) acrylic acid esters.

Particularly preferred are copolymers of
50 to 98, in particular 55 to 95 wt .-% ethylene,
0.1 to 40, in particular 0.3 to 20 wt .-% glycidyl acrylate and / or the glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and
1 to 45, in particular 10 to 40 wt .-% 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 may also be used as comonomers be set.

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

Preferred elastomers are also emulsion polymers whose Her position z. As in Blackley in the monograph "Emulsion Polymeri The usable emulsifiers and kata Lystoren are known per se.

Basically, homogeneously constructed elastomers or sol be used with a shell structure. The cup-like Construction is determined by the order of addition of the individual monomers certainly; Also, the morphology of the polymers is from this train order of succession.

Only representative are here as monomers for the production the rubber part of the elastomers acrylates such. For example, n-butylacry lat and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof. These monomers can Kings nen with other monomers such. As styrene, acrylonitrile, vinyls and other acrylates or methacrylates such as methyl metha crylate, methyl acrylate, ethyl acrylate and propyl acrylate copolymeri be siert.

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 with more than two) structure); in multi-shell elastomers can also consist of several shells of a rubber phase.

Are in addition to the rubber phase still one or more Hartkompo nents (with glass transition temperatures of more than 20 ° C) on the structure involved in the elastomer, they are generally by  Polymerization of styrene, acrylonitrile, methacrylonitrile, α-Me ethylstyrene, p-methylstyrene, acrylic acid esters and methacrylic acid star such as methyl acrylate, ethyl acrylate and methyl methacrylate as Main monomers produced. In addition, here can lower Shares of other comonomers are used.

In some cases it has proven to be advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are for. For example, epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups by the 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, the graft monomers described in EP-A 208 187 are suitable for the introduction of reactive groups on the surface.

Other examples are acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (N-t- Butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate,  (N, N-dimethylamino) -methyl acrylate and (N, N-diethylamino) ethyl called crylate.

Furthermore, the particles of the rubber phase can also be crosslinked his. Crosslinking monomers are, for example, Bu ta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclo pentadienyl acrylate and those described in EP-A 50 265 Links.

Furthermore, so-called graft-crosslinking monomers (graft linking monomers), d. H. Monomers with two or more polymerizable double bonds in the polymerisati react on different speeds. Vorzugswei Such compounds are used in which at least one reactive group at about the same speed as the rest Monomers polymerized while the other reactive group (or reactive groups) e.g. B. polymerized much slower (Polymerize). The different rates of polymerization contribute a certain proportion of unsaturated doping pelbindungen in rubber with it. Will then be on a grafted another phase so react such rubber the double bonds present in the rubber at least partially with the grafting monomers to form chemical bonds gen, d. H. the grafted phase is at least partially over linked chemical bonds with the graft.

Examples of such graft-linking monomers are allyl groups containing monomers, in particular allyl esters of ethylenically un saturated carboxylic acids such as allyl acrylate, allyl methacrylate, Diallyl maleate, diallyl fumarate, diallyl itaconate or the like ing monoallyl compounds of these dicarboxylic acids. There are also there are a variety of other suitable graft-linking monomials rer; for more details, see, for example, the US PS 4 148 846.

In general, the proportion of these crosslinking monomers on the toughening modifying polymer up to 5% by weight preferably not more than 3 wt .-%, based on the impact mod discriminating polymers.

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:

These graft polymers, in particular ABS and / or ASA polymers in amounts up to 40% by weight, are preferably to the impact strength modification of PBT, optionally mixed with up to 40 wt .-% polyethylene terephthalate used. Appropriate Blend products are under the trademark Ultradur®S (formerly Ultrablend®S from BASF AG). ABS / ASA blends with Polycarbonates are under the trademark Terblend® (BASF AG) in Trade available.

Instead of graft polymers having a multi-shell structure can also be homogeneous, d. H. single-shell elastomers from Bu ta-1,3-diene, isoprene and n-butyl acrylate or their copolymers be used. These products can also be used by others of crosslinking monomers or monomers having reactive groups getting produced.

Examples of preferred emulsion polymers are n-butyl acrylate lat / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers with an inner core of n-butyl acrylate or on buta dienbasis and an outer shell of the above Copolymers and copolymers of ethylene with comonomers, the reak deliver effective groups.  

The elastomers described may also be other customary Method, for. B. by suspension polymerization, who made the.

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

Of course, mixtures of the above can be added led rubber types are used.

As fibrous or particulate fillers are coals fabric fibers, glass fibers, glass beads, amorphous silica, asbestos, Calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, Chalk, powdered quartz, mica, barium sulfate and feldspar ge called in amounts up to 50 wt .-%, in particular 1 to 40%, in particular 20 to 35 wt .-% are used.

Preferred fibrous fillers are carbon fibers, Aramid fibers and potassium titanate fibers called glass fibers are particularly preferred as E-glass. These can be called rovings or cut glass in the commercial forms.

The fibrous fillers can for better compatibility with the thermoplastic with a silane compound superficially pretreated.

Suitable silane compounds are those of the general formula

(X- (CH ₂ ) _n ) _k -Si (OC _m H _{2m + 1} ) _2-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, aminobutyl triethoxysilane and the corresponding silanes, which as Substituent X contain a glycidyl group.  

The silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1 wt .-% (based on D) used for surface coating.

Also suitable are acicular mineral fillers.

Under acicular mineral fillers is in the sense of Invention a mineral filler with pronounced acicular character understood. As an example, be needle-shaped ger called wollastonite. Preferably, the mineral is one L / D (length diameter) ratio of 8: 1 to 35: 1 before given from 8: 1 to 11: 1. The mineral filler can optionally with the abovementioned silane compounds pretreated; however, the pretreatment is not necessarily required.

As further fillers are kaolin, calcined kaolin, Wollastonite, called talc and chalk.

As component F), the inventive thermoplastic Molding conventional processing aids such as stabilizers, Oxidation retardants, anti-heat decomposition and decomposition agents by ultraviolet light, lubricants and mold release agents, dyeing such as dyes and pigments, nucleating agents, Weichma cher etc.

As examples of oxidation inhibitors and heat stabilizers are sterically hindered phenols and / or phosphites, hydrochi none, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures in Concentrations up to 1 wt .-%, based on the weight of called thermoplastic molding compositions.

As UV stabilizers, generally in amounts up to 2 wt .-%, based on the molding composition, are ver various substituted resorcinols, salicylates, benzotriazoles and Called benzophenones.

Inorganic pigments, such as titanium dioxide, ultramarine blue, Iron oxide and carbon black, and organic pigments such as phthalo cyanines, quinacridones, perylenes, and dyes such as nigrosine and Anthrachinone be added as colorant.

As nucleating agents, sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc are used.  

Lubricants and mold release agents which are different from E) and are usually used in amounts up to 1 wt .-%, are preferably long-chain fatty acids (eg stearic acid or bees acid), their salts (eg Ca or Zn stearate) or montan waxes (Mixtures of straight-chain, saturated carboxylic acids with Ket ten lengths of 28 to 32 carbon atoms) and low molecular weight poly ethylene or polypropylene waxes.

Examples of plasticizers are dioctyl phthalate, Dibenzyl phthalate, butyl benzyl phthalate, carbon hydrogenated oils, called N- (n-butyl) benzenesulfonamide.

The molding compositions according to the invention may still contain 0 to 2% by weight containing fluorine-containing ethylene polymers. This is it to polymers of ethylene having a fluorine content of 55 to 76 wt .-%, preferably 70 to 76 wt .-%.

Examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene ethylene-hexafluoropropylene copolymers or tetrafluoroethylene copo lymerisates with smaller proportions (usually up to 50% by weight) copolymerizable ethylenically unsaturated monomer. These be z. By Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484 to 494 and by Wall in "Fluoropoly mers "(Wiley Interscience, 1972).

These fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have a particle size d ₅₀ (number average) in the range of 0.05 to 10 .mu.m, in particular from 0.1 to 5 .mu.m. These small particle sizes can be achieved particularly preferably by using aqueous dispersions of fluorine-containing ethylene polymers and incorporating them into a polyester melt.

The thermoplastic molding compositions according to the invention can according to known processes are prepared in which the off gang components in conventional mixing devices such as screws extruders, Brabender mills or Banbury mills and mixes then extruded. After extrusion, the extrudate can abge cooled and crushed. It can also be individual components are premixed and then the remaining starting materials individually and / or also mixed. The mixing tempe Temperatures are usually 230 to 290 ° C.

In a preferred procedure, components B) to D) and optionally conventional additives E) with a poly ester prepolymers are mixed, formulated and granulated. The resulting granules are then submerged in solid phase  Inert gas continuously or discontinuously at a Temperature below the melting point of component A) to the desired viscosity condensed.

The novel thermoplastic molding compositions are characterized due to good mechanical properties and good flame protection at the same time passing the glow wire test. The Ver Work is done largely without changing the polymer matrix and improved flowability and the mold surface becomes greatly reduced. Furthermore, the combination according to the invention shows a synergistic effect on the long-term thermal stability, especially at high service temperatures. They are suitable for the production of fibers, films and molds bodies, in particular for applications in the electrical and electronic industries Area. These applications are especially lamp parts like Lam pen holders and holders, plugs and sockets, spu body, housing for capacitors or contactors and Si fuse switch, relay housing and reflectors.

Examples

Component A / 1: Polybutylene terephthalate having a viscosity number of 130 ml / g and a carboxyl end group content of 34 meq / kg (Ultradur® B 4520 from BASF AG) (VZ measured in 0.5 wt .-% solution of phenol / o-dichlorobenzene , 1: 1 mixture at 25 ° C according to ISO 1628), containing based on 100 wt .-% A / 1 0.67 wt .-% Pentae rythrittetrastearat (component E)
Component A / 2; Polyethylene terephthalate (PET) with a VZ of 76 ml / g
Component B / 1: melamine cyanurate
Component B / 2: polymeric melamine phosphate (CAS No. 56386-64-2)
Component B / 3: ammonium polyphosphate N ≈ 1000
Component B / 4: oligomeric terephthalic acid ester of tris (2-hydroxyethyl) isocyanurate according to Example 3 of EP-A 584 567
Component C / 1: Calcium Phosphinate [Ca ₂ (H ₂ PO ₂ ) ₂ ]
Component C / 2: Al (CH ₃ C ₂ H ₅ PO ₂ ) ₃ according to EP-A 584 567
Component D: resorcinol bis (diphenyl phosphate) (CR 733-S from Daihachi)
Component F: chopped glass fiber with a thickness of 10 μm (epoxisilanized size).

Components A) to F) were on a twin-screw extruder mixed at 250 to 260 ° C and extruded in a water bath. To Granulation and drying were done on an injection molding machine Test specimen sprayed and tested.

For the fire test rods were hosed and according to usual Kon tioning in accordance with UL 94. The glow wire test he followed on plates 60/60 mm with 1 and 3 mm thickness. Checked was at 960 ° C wire temperature.

To investigate the migration, test bars were tested according to ISO 179 (Impact bar) and annealed at 150 ° C for 3 days. because After the weight loss was measured.

The stability was determined by examining the VZ of moldings after storage at 150 ° C (5, 10 and 15 days). In addition, the impact strength was measured after storage for 20 days, furthermore the modulus of elasticity in MPa according to ISO 527, tensile strength in MPa according to ISO 527, impact strength in kJ / m ² according to ISO 179 / 1eU, VZ according to ISO 1628 in ml / g.

The flowability was in a flow spiral (d = 1.5 mm) at an injection pressure of 37 bar and a melt temperature of 260 W. certainly.

The summary of the molding compositions and the results of the measurements are shown in the table.

Claims (10)

1. Thermoplastic molding compositions containing

• A) 5 to 96 wt .-% of a polyester
• B) 1 to 30 wt .-% of a nitrogen compound
• C) 1 to 30 wt .-% of an inorganic phosphorus compound
• D) 1 to 30 wt .-% of an organic phosphorus compound
• E) 0 to 5 wt .-% of at least one ester or amide ge saturated or unsaturated aliphati shear carboxylic acids with 10 to 40 C-Ato get with aliphatic saturated Alko or amines having 2 to 40 carbon atoms
• F) 0 to 60 wt .-% of other additives, wherein the sum of the weight percent of components A) to F) gives 100%.

2. Thermoplastic molding compositions according to claim 1, comprising as component C) a phosphinic acid salt of the formula I and / or a diphosphinic acid salt of the formula II and / or polymers thereof
where the substituents have the following meanings:
R ¹ , R ^{2 is} a linear or branched C ₁ - to C ₆ -alkyl radical, phenyl radical, hydrogen,
R ^{3 is} a linear or branched C ₁ - to C ₁₀ -alkylene radical, arylene, alkylaryl or arylalkylene radical,
M alkaline earth, alkali metal, Zn, Al, Fe, boron,
m is an integer from 1 to 3,
n is an integer of 1 and 3,
x 1 or 2; 3. Thermoplastic molding compositions according to claims 1 or 2, comprising as flame retardant D) at least one phosphine oxide of the general formula III
where R ¹ , R ² and R ^{3 are the} same or different alkyl, aryl, alkylaryl or cycloalkyl groups having 8 to 40 C-atoms be interpreted. 4. Thermoplastic molding compositions according to claims 1 to 3, in which the component D) is composed of triphenylphosphine oxide, triphenyl phosphine sulfide, triphenyl phosphate, or triphenylphosphine or a phosphorus compound of the formula IV or mixtures thereof:
in which the substituents have the following meanings:
R ⁴ -R ^{7 is} an aromatic radical having 6 to 20 C atoms, preferably a phenyl radical which may be substituted by alkyl groups having 1 to 4 C atoms, preferably methyl,
R ^{8 is} a dihydric phenol, preferred
and n means an average of between 0.1 to 100. 5. Thermoplastic molding compositions according to claims 1 to 4, ent holding 1 to 40 wt .-% of a fibrous filler as Component F). 6. Thermoplastic molding compositions according to claims 1 to 5, in where component E) is pentaerythritol tetrastearate. 7. Thermoplastic molding compositions according to claims 1 to 6, in those component A) from a mixture of polyethylene terephthalate and polybutylene terephthalate. 8. Thermoplastic molding compositions according to claims 6 or 7, in the polyethylene terephthalate from a recycled material with a residual moisture content of 0.01 to 0.7%. 9. Use of the thermoplastic molding compositions according Ansprü Chen 1 to 8, for the production of fibers films and mold bodies. 10. Moldings obtainable from the thermoplastic molding compositions according to claims 1 to 8.