EP1456297A1

EP1456297A1 - Flameproof molding materials

Info

Publication number: EP1456297A1
Application number: EP02787790A
Authority: EP
Inventors: Matthias Bienmüller; Michael Wagner
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 2001-12-07
Filing date: 2002-11-25
Publication date: 2004-09-15
Also published as: HUP0402232A3; HUP0402232A2; WO2004041933A1; AU2002352117A1; DE10160138A1; JP2005525459A; CA2469597A1; CN1617907A; US20030149145A1; KR20040071710A

Abstract

The invention relates to thermoplastic molding materials, consisting of polyester melamine cyanurate, at least one phosphorous-containing flameproofing agent, at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids having 10 to 40 C atoms with aliphatic saturated alcohols or amines having 2 to 40 C atoms and processing auxiliary agents.

Description

INTEGRATED CIRCUIT PACKAGE 1NCLUDING MIN1ATURE ANTENNA

BACKGROUND OF THE INVENTION

The present invention relates generally to novel integrated circuit packages that include a new family of miniature antennas in the package. The present invention allows the integration of a fill wireless system into a single component.

There is a trend in the semiconductor industry towards the so-called System on Chip (SoC) and System on Package (SoP) concepts. This means integrating as many components of an electronic system as possible (processors, memories, logic gates, biasing circuitry, etc.) into a Single semiconductor chip (or "die") (SoC) or at least into a Single integrated circuit package ( SoP). The fill integration of Systems or Subsystems into a Single chip or package provides many advantages in terms of cost, size, weight, consumption, performance and product design complexity.

Several electronics components for consumer applications, such as handsets, wireless devices, personal digital assistants (PDA) or personal Computers are becoming more and more integrated into SoP / SoC products.

The concept of integrating a fill wireless system into a SoC / SoP device (FWSoC and FWSoP) is especially attractive owing to the tremendous growth and success of ceilular and wireless Systems. In particular, there is a new generation of short / medium ranks wireless applications such as Bluetooth ™, Hyperlan, IEEE802.11 and Ultra wide band (UWB) Systems where the progressive system integration into a Single, compact product is becoming a key success factor (see for instance S.Harris and H. Johnston, "Handset industry debate Bluetooth chip options",

WirlessEurope, May 2002). Recently, several vendors (for example www.infineon.com, www.st.com. Www.epson.com www.csr.com) are offering SoC or SoP products for applications that integrate everything into the chip or package, except for the antenna. The reason the antenna is excluded is that its integration into the SoC or SoP is a major engineering challenge in the product development, mainly due to the reduced size of the commercial SoP and SoC packages and the well-known constraints on the Performance of miniature antennas ,

There have been reported several attempts to integrate an antenna inside a semiconductor die or chip, which die or chip also includes an electronic system or Flame-carved molding compounds

The invention relates to thermoplastic molding compositions consisting of

A) 55 to 93.99% by weight of one or more polyesters

B) 3 to 15% by weight of melamine cyanurate

C) 3 to 15% by weight of at least one phosphorus-containing flame retardant, D) 0.01 to 5% by weight of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids having 10 to 40 C atoms with aliphatic saturated alcohols or amines 2 to 4Q C atoms, E) 0 to 10% by weight processing aids.

The invention further relates to the use of the molding compositions according to the invention for the production of fibers, films and moldings, and to the moldings of all types obtainable here.

There is increasing market interest for halogen-free flame-retardant polyesters. Essential requirements for the flame retardant include light intrinsic color, sufficient temperature stability for incorporation into thermoplastics, as well as its flame retardancy with good mechanical properties of the molding compounds.

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

Inorganic flame retardants, which have to be used in large quantities in order to be effective. Nitrogen-containing FR systems, such as melamine cyanurate, which show limited effectiveness in thermoplastics, for example polyamide. In reinforced polyamide, it is only effective in combination with shortened glass fibers. Melamine cyanurate is not effective in polyesters.

Phosphorus-containing FR systems that are generally not effective in polyesters.

Phosphorus / nitrogen-containing FR systems, such as Arnmom ^{'umpolyphosphate} or melamine phosphates, do not have sufficient thermal stability for thermoplastics which are processed at temperatures above 200 ° C.

JP-A 03/281 652 discloses polyalkylene terephthalates which contain melamine cyanurate and glass fibers, and a phosphorus-containing flame retardant. These molding compositions contain derivatives of phosphoric acid, such as phosphoric acid esters (valence level +5), which tend to "bloom" when subjected to thermal stress.

EP-A 0932643 also describes flame-retardant polyester film compositions which are flame-retardant with a combination of phosphorus-containing flame retardants and melamine cyanurate.

However, flow properties are negatively influenced by high contents of fillers (reinforcement, flame retardant additives). However, good flow properties are particularly important for thin-wall applications.

It is an object of the present invention to provide flame-retardant polyester molding compositions with an additivation which is tailored to the flame retardant and the mechanical properties and which are also suitable for thin-wall applications, with thin-wall applications meaning molded parts which can be produced from the molding compositions according to the invention and whose wall thicknesses (thicknesses) <1 , 6 mm, preferably <1.0 mm. Surprisingly, it was found that in unreinforced polyester molding compositions compared to corresponding reinforced molding compositions with significantly smaller amounts of at least one phosphorus-containing flame retardant in combination with melamine cyanurate and at least one ester or amide of saturated or unsaturated ahphatic carboxylic acids with 10 to 40 carbon atoms with aliphatic saturated alcohols or A with 2 to 40 C atoms can set a suitable requirement profile with regard to flame protection (e.g. at least UL94-V2, glow wire resistance GWFI 960 ° C) and mechanics (impact strength), and the molding compounds are also suitable for thin-wall applications.

The invention relates to thermoplastic molding compositions consisting of

A) 55 to 93.99% by weight of one or more polyesters

B) 3 to 15% by weight of melamine cyanurate C) 3 to 15% by weight of at least one phosphorus-containing flame retardant,

D) 0.01 to 5% by weight of at least one ester or amide of saturated or unsaturated ahphatic carboxylic acids with 10 to 40 C atoms with aliphatic saturated alcohols or amines with 2 to 40 C atoms,

E) 0 to 10% by weight of processing aids selected from the group

Stabilizers, antioxidants, agents against

Thermal decomposition and decomposition by ultraviolet

Light, lubricants and mold release agents, rubber-elastic polymers (also called impact modifiers), colorants, preferably dyes and pigments, nucleating agents, plasticizers,

the sum of the percentages by weight of components A) to E) being 100%.

Preferred embodiments can be found in the subclaims. The invention further relates to thermoplastic molding compositions according to the invention, containing at least one phosphine oxide of the general formula (I) as flame retardant C)

in which

R ¹ , R ² and R ^{3 are} identical or different alkyl, aryl, alkylaryl or cycloalkyl groups with 8 to 40 carbon atoms. ^"

Thermoplastic molding compositions according to claim 1, containing as flame retardant C at least one compound of the general formula

wherein

R ¹ to R ²⁰ independently of one another are hydrogen, a linear or branched alkyl group of up to 6 carbon atoms

n an average value of 0.5 to 50 and B each Ci-C 2 alkyl, preferably methyl, or halogen, preferably chlorine or bromine

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

X is a single bond, C = O, S, O, SO ₂ , C (CH ₃ ) ₂ , C -C ₅ alkylene, C ₂ -C ₅ alkylidene, C5-C cycloalkylidene, Cg-Ci ^ arylene, to which further aromatic rings optionally containing heteroatoms can be condensed, or a radical of the formula (II) or (III)

with Y carbon and

R21 and R22 can be selected individually for each Y, independently of one another hydrogen or C 1 -C 6 -alkyl, preferably hydrogen, methyl or ethyl,

m is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom Y R 1 and R 22 are simultaneously alkyl, mean. Preferred phosphorus compounds of the formula are those in which R 1 to R 20 independently of one another denote hydrogen or a methyl radical and in which q = 0. Particularly preferred are compounds in which X is SO ₂ , O, S, C = O, C2-C5-al ylidene, Cs-Cö-cycloalkylidene or Cg-C ^ -arylene. Compounds with X = C (CH) ₂ are very particularly preferred.

The invention furthermore relates to thermoplastic molding compositions in which component C) is composed of triphenylphosphine oxide, triphenylphosphine sulfide, triphenylphosphate, resorcinol bis (diphenylphosphate), triphenylphosphate or, very particularly preferably, bisphenol-A diphosphate or mixtures thereof.

The molding compositions 55 to 93, 99 preferably contain 65 to 93 and in particular 75 to 93% by weight of a thermoplastic polyester or mixtures of several thermoplastic polyesters as component (A).

Polyesters based on aromatic dicarabonic acids and an aliphatic or aromatic dihydroxy compound are generally used.

A first group of preferred polyesters are polyalkylene terephthalates with 2 to 10 carbon atoms in the alcohol part.

Such polyalkylene terephthalates are polyalkylene terephthalates with 2 to 10 carbon atoms in the alcohol part.

Such polyalkylene terephthalates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid. The aromatic ring can also be substituted, for example 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 in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds.

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.

The aliphatic dihydroxy compounds are diols with 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethylanol and neopentyl glycol or mixtures thereof are preferred.

Particularly preferred polyesters (A) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 carbon atoms. Of these, polyethylene terephthalate and polybutylene terephthalate or mixtures thereof are particularly preferred.

The viscosity number of the polyesters (A) is generally in the range from 70 to 220, preferably from 80 to 160 (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 up to 25 ° C).

Particularly preferred are 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 polyester. Such polyesters can be produced, for example, by the process of DE-A 44 01 055. The carboxyl end group content is usually determined by titration methods (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 in the mixture is preferably up to 50, in particular 10 to 30,% by weight, based on 100% by weight of A).

Such molding compositions according to the invention show very good flame retardant properties and better mechanical properties.

It is also advantageous to use PET recyclates (also called scrap PET) in a mixture with polyalkylene terephthalates such as PBT.

Recyclates are generally understood to mean:

1) so-called post industrial recyclate: this is production waste from polycondensation or processing e.g. Sprues at the

Injection molding, commodity for 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 by the end consumer after use. The most dominant item in terms of quantity are blow-molded PET bottles for mineral water, soft drinks and juices.

Both types of recyclate can either be in the form of regrind or in the form of granules! In the latter case, the pipe cycles after the separation and

Cleaning melted and granulated in an extruder. This usually facilitates handling, flowability and meterability for further processing steps. Recyclates, both granulated and in the form of regrind, can be used, the maximum edge length being 6 mm, preferably less than 5 mm.

Due to the hydrolytic cleavage of polyesters during processing (by

Traces of moisture) it is recommended to pre-dry the recyclate. 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 are derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.

Aromatic dicarboxylic acids are the compounds described for the polyalkylene terephthalates. Mixtures of 5 to 100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid, in particular mixtures of approximately 80% terephthalic acid with 20% isophthalic acid to approximately equivalent mixtures of these two acids, are used.

The aromatic dihydroxy compounds preferably have the general formula (I)

represents in time an alkylene or cycloalkylene group with up to 8 C atoms, an arylene group with up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in which m is from 0 to 2 has. The compounds (I) can bear on the phenylene groups from Cj-Cg-alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents. Examples of parent compounds of these compounds are dihydroxydiphenyl, di (hydroxyphenyl) alkane, di (hydroxyphenyl) cycloalkane,

Di- (hydroxyphenyl) sulfide, di- (hydroxypehnyl) ether, di- (hydroxyphenyl) ketone, di- (hydroxyphenyl sulfoxide, α, '-di (hydroxyphenyl) dialkylbenzene,

Di- (hydroxyphenyl) sulfone, di- (hydroxybenzoyl) benzene resorcinol and hydroquinone as well as their core alkylated or core halogenated derivatives.

Of these will be

4-DihydorxydiphenyI, 2,4-di- (4'-hydroxyphenyl) -2-methylbutane, α, α'-di (3'-methyl-4'-hydroxyphenyl) propane and 2,2-di- (3'chlor -4'-hydroxyphenyl) propane,

as well as in particular

2,2-di- (4'-hydroxyphenyl) propane 2,2-di (3 ', 5-dichlorodihydroxyphenyl) 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.

Mixtures of polyalkylene terephthalates and fully aromatic polyesters can of course also be used. These generally contain 20 to 98% by weight of the polyalkylene terephthalate and 2 to 80% by weight of the fully aromatic polyester.

Polyesters for the purposes of the present invention are also to be understood as meaning polycarbonates which are obtained by polymerizing aromatic dihydroxy compounds, in particular bis (4-hydroxyphenyl) 2,2-propane (bisphenol A) or its derivatives, e.g. are available with phosgene. Corresponding products are known per se and described in the literature and for the most part are also commercially available. The amount of the polycarbonates is up to 90% by weight, preferably up to 50% by weight, based on 100% by weight of component (A).

Of course, polyester block copolymers such as copolyether esters can also be used. Products of this type are known per se and are described in the literature, for example in US Pat. No. 3,651,014. Corresponding products are also commercially available, for example Hytrel ^® (DuPont).

As component B), the thermoplastic molding compositions according to the invention contain 3 to 15, preferably 3 to 10, and in particular 3 to 6% by weight of melamine cyanurate as flame retardant.

The melamine cyanurate used according to the invention (component B) is a reaction product of preferably equimolar amounts of melamine (formula (I)) and cyanuric acid or isocyanuric acid (formulas (Ha) and (Ilb))

(Ha) (Ilb)

Enolform keto form

It is obtained, for example, by reacting aqueous solutions of the starting compounds at 90 to 100 ° C. The commercially available product is a white powder with an average particle size d ₅₀ of 1.5 to 7 μ.

Suitable flame retardants C) are contained in the molding compositions according to the invention in amounts of 3 to 15, preferably 3 to 10 and particularly preferably 3 to 6% by weight, based on the total weight of components A) to E).

Component C) is an organic and / or inorganic phosphorus-containing compound in which the phosphorus has a valence level of -3 to +5. The value level should be understood to mean the term "oxidation level" as used in the textbook of inorganic chemistry by A.F. Hollemann and E. Wiberg, Walter des Gruyter and Co. (1964, 57th to 70th editions), pages 166 to 177. Phosphorus compounds of valence levels -3 to +5 are derived from phosphine (-3), diphosphine (-2), phosphine oxide (-l), elemental phosphorus (+0), hypophosphorous acid (+3), hypodiphosphoric acid (+4) and phosphoric acid (+5) from.

Only a few examples may be mentioned from the large number of compounds containing phosphorus. Examples of phosphorus compounds of the phosphine class which have the valence level -3 are aromatic phosphines, such as triphenylphosphine, tritolylphosphine, trionylphosphine, trinaphthylphosphine and others. Triphenylphosphine is particularly suitable.

Examples of phosphorus compounds of the diphosphine class which have the valence level -2 are tetraphenyldiphosphine, tetranaphthyldiphosphine and others. Tetranaphthyldiphosphine is particularly suitable. Phosphorus compounds of valence level -1 are derived from phosphine oxide.

Phosphine oxides of the general formula are suitable

in which

R ¹ , R ² and R ^{3 are} identical or different alkyl, aryl, alkylaryl or cycloalkyl groups with 8 to 40 carbon atoms.

Examples of phoxphin oxides are triphenylphosphine oxide, tritolylphospline oxide,

Trisnonylphenylphosphine oxide, tricyclohexylphosphine oxide, tris (n-butyl) phosphine oxide, tris (n-hexyl) phosphine oxide, tris (n-octyl) phosphine oxide, tris (cyanoethyl) phosphine oxide, benzylbis (cyclohexyl) phosphine oxide, Benzylbisphenylphosphine oxide, tricyclohexylphosphine oxide and tris (n-octyl) phosphine oxide.

Triphenylphosphine sulfide and its derivatives of the phosphine oxides as described above are also suitable. Phosphorus of grade +0 is the elementary phosphorus. Red and black phosphorus are possible. Red phosphorus is preferred.

Phosphorus compounds of the "oxidation level" +1 are e.g. Hypophosphites. They can have a salt character or be purely organic in nature. examples are

Calcium hypophosphite and magnesium hypophosphite, in addition also double hypophosphites or complex hypophosphites, or organic hypophosphites, such as cellulose hypophosphite esters, esters of hypophosphorous acids with diols, e.g. of 1,10-dodecyldiol. Substituted phosphinic acid and its anhydrides, e.g. Diphenylphosphinic acid can also be used

Question di-p-tolylphosphinic acid, di-cresylphosphinic anhydride. However, there are also compounds such as hydroquinone, ethylene glycol, propylene glycol bis (diphenylphosphinic acid) esters and others. in question. Aryl (alkyl) phosphinic amides, such as e.g. Diphenylphosphinic acid dimethylamide and sulfonamidoaryl (alkyl) phosphinic acid derivatives, e.g. p-Tolylsulfonamidodiphenylphosphinsäure. Hydroquinone and ethylene glycol bis (diphenylphosphinic acid) esters and the bisphenylphosphinate of hydroquinone are preferably used.

Phosphorus compounds of oxidation level +3 are derived from the phosphorous acid. Cyclic phosphonates derived from pentaerythritol, neopentyl glycol or pyrocatechol are suitable. In addition, phosphorus is of grade +3 in triaryl (alkyl) phosphites, e.g. Triphenyl phosphite, tris (4-decylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite or phenyldidecyl phosphite and others contain. There are also diphosphites, e.g. Propylene glycol-1, 2-bis- (diphosphite) or cyclic phosphites, which are derived from pentaerythritol, neopentyl glycol or catechol, into question.

Methyl neopentyl glycol phosphonate and phosphite and dimethyl pentaerythritol diphosphonate and phosphite are particularly preferred. Hypodiphosphates, such as, for example, tetraphenyl hypodiphosphate or bisneopentyl hypodiphosphate, are particularly suitable as phosphorus compounds of oxidation state +4.

Alkyl and aryl-substituted phosphates are particularly suitable as phosphorus compounds of oxidation level +5. Examples are phenylbisdodecyl phosphate, phenylethyl hydrogen phosphate, phenyl bis (3,5,5-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di (tolyl) phosphate, diphenyl hydrogen phosphate, bis (2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis (2-ethyl) -ethylhexyl) phenyl phosphate, di (nonyl) phenyl phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) -ρ-tolyl phosphate, p-tolyl-bis (2,5,5-trimethylhexyl) phosphate or 2-ethylhexyldiphenyl phosphate. Phosphorus compounds in which each radical is an aryloxy radical are particularly suitable.

The following are suitable Triphenyl phosphate and resorcinol bis (diphenyl phosphate) and its core-substituted derivatives of the general formula

in which the substituents have the following meaning:

R ⁴ , R ^{7 are} an aromatic radical with 6 to 20 C atoms, preferably a phenyl radical, which can be substituted with alkyl groups with 1 to 4 C atoms, preferably methyl,

R ^{8 is} a dihydric phenol, preferred

and n = 1 to 100, preferably 1 to 5.

Phosphorus compounds are particularly suitable in this context

formula

wherein

n an average value of 0.5 to 50 and

B each Cj-C 12 alkyl, preferably methyl, or halogen, preferably chlorine or bromine

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

X is a single bond, C = O, S, O, SO ₂ , C (CH ₃ ) ₂ , -CC ₅ alkylene, C ₂ -C ₅ alkylidene, C5-C6 cycloalkylidene, C6-Ci2- rylene the further aroma tables, optionally containing rings containing heteroatoms, or a radical of the formula (II) or (III)

with Y carbon and

R2I and R ****** individually selectable for each Y, independently of one another hydrogen or Ci-Cg-alkyl, preferably hydrogen, methyl or ethyl,

m is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom Y R ^ and R - * - * - are simultaneously alkyl,

mean.

Preferred phosphorus compounds of the formula (I) are those in which R ¹ to R ²⁰ independently of one another are hydrogen or a methyl radical and in which q = 0. Particularly preferred are compounds in which X is SO ₂ , O, S, C = 0, C2-C5-alkylidene, Cs-Cg-cycloalkylidene or Cg-Ci ^ -Arvlen. Compounds with X = C (CH ₃ ) ₂ are very particularly preferred. The degree of oligomerization n results as an average value from the manufacturing process of the listed phosphorus-containing compounds. The degree of oligomerization is usually n <10. Compounds with n of 0.5 to 5, particularly preferably 0.7 to 2.5, are preferred. Very particular preference is given to compounds which have a high proportion of molecules with n = 1 between 60% and 100%, preferably between 70 and 100%, particularly preferably between 79% and 100%. Due to the production process, the above compounds may also contain small amounts of triphenyl phosphate. The amounts of this substance are usually less than 5% by weight, compounds being preferred in the present context whose triphenyl phosphate content is in the range from 0 to 5%, preferably from 0 to 4%, particularly preferably from 0 to 2.5% based on the product used according to formula (I).

The phosphorus compounds of the formula (I) are known (cf., for example, EP-A 363 608, EP-A 640 655) or can be prepared in an analogous manner by known methods (for example Ullmann's Encyclopedia of Industrial Chemistry, vol. 18, p 301 ff.

1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).

The bisphenol A diphosphate (also referred to as bisphenol A bw diphenyl phosphate or tetraphenyl bisphenol A diphosphate, BDP), which is very particularly preferred in the context of the present invention, is commercially available commercially, among others. as Fyroflex BDP (Akzo Nobel Chemicals BV, Amersfoort, Holland), Ncendx P-30 (Albemarle, Baton Rouge, Louisiana, USA), Reofos BAPP (Great Lakes, West Lafayette, Indiana, USA) or CR 741 (Daihachi, Osaka, Japan).

Cyclic phosphates can also be used. Diphenylpentaerythritol diphosphate and phenylneopentyl phosphate are particularly suitable.

In addition to the low molecular weight phosphorus compounds listed above, oligomeric and polymeric phosphorus compounds are also suitable. Such polymeric, halogen-free organic phosphorus compounds with phosphorus in the polymer chain arise, for example, in the production of pentacyclic, unsaturated phosphine dihalides, as described, for example, in DE-A 20 36 173. The molecular weight, measured by vapor pressure osmometry in the dimethylformamide of the polyphospholine oxides, should be in the range from 500 to 7,000, preferably in the range from 700 to 2,000.

The phosphorus has the oxidation state -1.

Furthermore, inorganic coordination polymers of aryl (alkyl) phosphinic acids such as e.g. Poly-β-sodium (I) methylphenylphosphinate can be used. Their manufacture is specified in DE-A 31 40 520. The phosphorus has the oxidation number +1.

Furthermore, such halogen-free polymeric phosphorus compounds can be obtained through the

Reaction of a phosphonic acid chloride such as e.g. Phenyl, methyl, propyl, styryl and vinylphosphonic dichloride with bifunctional phenols, e.g. Hydroquinone, resorcinol, 2,3,5-trimethylhydroquinone, bisphenol-A, tetramethylbisphenol-A arise.

Further halogen-free polymeric phosphorus compounds which may be present in the molding compositions according to the invention are prepared by reacting phosphorus oxide trichloride or phosphoric acid ester dichlorides with a mixture of mono-, bi- and trifunctional phenols and other compounds bearing hydroxyl groups (cf. Houben-Weyl- Müller, Thieme-Verlag Stuttgart, Organic

Phosphorus Compounds Part II (1963)). Polymeric phosphonates can also be prepared by transesterification reactions of phosphonic acid esters with bifunctional phenols (cf. DE-A 29 25 208) or by reactions of phosphonic acid esters with diamines or diamides or hydrazides (cf. US-A 4 403 075). However, the inorganic poly (ammonium phosphate) is also suitable. It is also possible to use oligomeric pentaerythritol phosphites, phosphates and phosphonates according to EP-B 8 486, for example Mobil Antiblaze® 19 (registered trademark of Mobil Oil).

As component D), the molding compositions according to the invention contain 0.01 to 5, preferably 0.05 to 3 and in particular 0.1 to 2% by weight of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids with 10 to 40, preferably 16 to 22 C atoms with aliphatic saturated alcohols or amines with 2 to 40, preferably 2 to 6 C atoms.

The carboxylic acids can be 1- or 2-valent. Examples include 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 with 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, neopental glycol, pentaerythritol, 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, ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate. Glycerol monopalmitate, glycerol trilaurate, glycerol monobhenate and pentaerythritol tetrastearate.

Mixtures of different esters or amides or esters with amides can also be used in combination, the mixing ratio being arbitrary. As component E), the molding compositions according to the invention contain 0 to 10, in particular 0 to 5, very particularly preferably 0 to 3% by weight of conventional additives and customary processing aids, which are selected from the following group:

Stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, rubber-elastic polymers (also called impact modifiers), colorants, preferably dyes and pigments, nucleating agents, plasticizers.

E does not mean reinforcing materials in general, glass fibers,

Glass balls and other fibrous or particulate reinforcing fillers made of glass, carbon fibers, amorphous silica, asbestos, magnesium carbonate, wollastonite, kaolin, chalk, mica, barium sulfate and feldspar.

Typical additives E) are, for example, 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 with 1 to 18 C - Atoms in the alcohol component.

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

Publishers, London, 1977).

Some preferred types of such elastomers are presented below.

Preferred types of such elastomers are the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers. EPM rubbers generally have practically no more double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.

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

EPM or EPDM cartridges can preferably also be dripped with reactive carboxylic acids or their derivatives. Here are e.g. Acrylic acid, methacrylic acid and their derivatives, e.g. Glycidyl (meth) acrylate, as well as 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 also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Contain esters and anhydrides, and or monomers containing epoxy groups. These dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by adding monomers of the general formulas (I) or (II) or (III) or (IV) containing dicarboxylic acid or epoxy groups to the monomer mixture

R ¹ C (COOR ² ) = C (COOR ³ ) R ⁴ (I) R "

R \ / c

I (II)

CO, CO O

where R ¹ to R ^{9 represent} hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5.

The radicals R ¹ to R ^{9 are} preferably 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, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to that of the free acids and are therefore referred to as monomers with latent carboxyl groups.

The copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or monomers containing methacrylic acid and / or acid anhydride groups and the remaining amount of (meth) acrylic acid esters. Copolymers of are particularly preferred

50 to 98, in particular 55 to 95% by weight of ethylene,

0.1 to 40, in particular 0.3 to 20% by weight of glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and

I to 45, in particular 10 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.

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

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

The ethylene copolymers described above can be according to known

Processes are prepared, preferably by statistical copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.

Preferred elastomers are also emulsion polymers, the production of which e.g. at

Blackley is described in the monograph "Emulsion Polymerization". The emulsifiers and catalysts which can be used are known per se.

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

The monomers for the production of the rubber part of the elastomers are only representative of acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof. This Monomers can be copolymerized with other monomers such as, for example, styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate.

The soft or rubber phase (with a glass transition temperature below

0 ° C) of the elastomers can represent the core, the outer shell or a middle shell (in the case of elastomers with more than two layers); in the case of multi-layer elastomers, several shells can also consist of a rubber phase.

If, in addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 20 ° C) are involved in the construction of the elastomer, these are generally made by polymerizing styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylic acid esters and methacrylic - Acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate are produced as the main monomers. In addition, smaller shares in others can also be found here

Comonomers can be used.

In some cases it has proven advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are e.g. Epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups by the use of monomers of the general formula

can be introduced where the substituents can have the following meanings:

R ¹ ° is hydrogen or a C _j - to C4-alkyl group,

R ^{11 is} hydrogen, a C _} - to Cg-alkyl group or an aryl group, in particular

phenyl

R ^{12 is} hydrogen, a C 1-4 alkyl group, a Cg-C 1-4 aryl group or -OR13

R ^{13 is} a C _j to Cg alkyl or C ₆ to C ₁₂ aryl group which can optionally be substituted by O- or N-containing groups,

X is a chemical bond, a C ^ - to C- o-alkylene or Cg- to C - ^ - arylene

O group or N__ _γ

Y O-Z or NH-Z and

Z is a C ^ - to C- o-alkylene or Cg to C - ^ - arylene group.

The graft monomers described in P-A 208 187 are also suitable for introducing reactive groups on the surface.

Other examples include acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (Nt-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N-di- called ethylamino) ethyl acrylate.

The particles of the rubber phase can also be crosslinked. Monomers acting as crosslinkers are, for example, buta-l, 3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate and the compounds described in EP-A 50 265.

So-called graft-linking monomers can also be used, i.e. Monomers with two or more polymerizable double bonds that react at different rates during the polymerization. Compounds are preferably used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. polymerizes much slower (polymerize). The different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, i.e. the grafted phase is at least partially linked to the graft base via chemical bonds.

Examples of such graft-crosslinking monomers are monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids. In addition, there are a large number of other suitable graft-crosslinking monomers, for further details reference is made, for example, to US Pat. No. 4,148,846.

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

Some preferred emulsion polymers are listed below. First of all, there are graft polymers with a core and at least one outer shell that have the following structure:

These graft polymers, in particular ABS and / or ASA polymers in amounts of up to 40% by weight, are preferably used for impact modification of PBT, optionally in a mixture with up to 40% by weight of polyethylene terephthalate. Corresponding blend products are available under the trademark Ultradur®s (formerly Ultrablend®S from BASF AG). ABS / ASA blends with polycarbonates are commercially available under the trademark Terlbend® (BASF AG).

Instead of graft polymers with a multi-layer structure, it is also possible to use homogeneous, ie single-layer elastomers composed of buta- 1,3-diene, isoprene and n-butyl acrylate or their copolymers. These products can also be produced by using crosslinking monomers or monomers with reactive groups. Examples of preferred emulsion polymers are n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers with an inner core made of n-butyl acrylate or butane diene and an outer shell of the above copolymers and copolymers of ethylene with comonomers which provide reactive groups.

The elastomers described can also be made by other conventional methods, e.g. by suspension polymerization.

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 also preferred.

Mixtures of the rubber types listed above can of course also be used.

Examples of oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their

Mixtures in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.

UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding materials, are various substituted resorcinols,

Called salicylates, benzotriazoles and benzophenones.

Stabilizers also include stabilizing metal salts, metal compounds, metal oxides, sulfides and borates, in particular zinc oxide, zinc sulfide, zinc borate and oxides of lanthanides, being preferred. Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can also be added as colorants.

The nucleating agents used are <1% by weight, preferably <0.5% by weight, particularly preferably <0.3% by weight, based on the total molding composition, of conventional nucleating agents, sodium phenylphosphinate, aluminum oxide, silicon dioxide and, in particular, talc being preferred.

Lubricants and mold release agents, which are usually used in amounts of up to 1% by weight, are preferably long-chain fatty acids (for example stearic acid or behenic acid), their salts (for example Ca or Zn stearate) and amide derivatives (for example ethylene-bis -stearylamide) or montan waxes (mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms) as well as low molecular weight polyethylene or polypropylene waxes.

Examples of plasticizers are phthalic acid dioctyl ester, phthalic acid dibenzyl ester, phthalic acid butyl benzyl ester, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.

Examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers. These are e.g. by Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484 to 494 and by Wall in "Fluorpolymers" (Wiley

Interscience, 1972).

These fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have a particle size d5 _Q (number average) in the range from 0.05 to 10 μm, in particular from 0.1 to 5 μm. These small particle sizes can be particularly preferably used by using aqueous dispersions of achieve fluorine-containing ethylene polymers and their incorporation into a polyester melt.

The thermoplastic molding compositions according to the invention can be produced by processes known per se by mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruding them. After the extrusion, the extrudate can be cooled and crushed. Individual components can also be premixed and then the remaining starting materials added individually and / or likewise mixed. The mixing temperatures are usually included

230 to 290 ° C.

In a further procedure, components B) to D) and, if appropriate, customary additives E) can be mixed, made up and granulated with a polyester prepolymer. The granules obtained are then condensed in the solid phase under inert gas continuously or batchwise at a temperature below the melting point of component A) to the desired viscosity.

The thermoplastic molding compositions according to the invention are notable for good mechanical properties and good flame-retardant properties while passing the glow wire test. The processing takes place largely without changing the polymer matrix and the mold covering is greatly reduced. They are suitable for the production of fibers, foils and moldings, in particular for applications in the electrical and electronics sector.

Component A: PBT Pocan® B 1300 000000 (Bayer AG, Leverkusen,

Germany)

Component B: Melamine cyanurate (Melapur® MC 25, DSM-Melapur,

Heerlen, Holland) Component C / l: bisphenol A diphosphate (Reofos® BAPP, Great Lakes, West Lafayette, Indiana, USA)

Component C / 2: triphenyl phosphate (DisflamoU® TP, Bayer AG,

Leverkusen, Germany)

Component D: Montanglycol wax (E-wax, Hoechst, Frankfurt a.M.,

Germany)

Component E / l: stabilizer, 10% in PBT Pocan® B 1300 000000

Component E / 2: Nucleating agent

Component F (comparative test): chopped glass fiber (CS 7962, Bayer AG,

Leverkusen, Germany)

The composition of the recorder in percentages by weight

Claims

claims

1. Thermoplastic molding compositions consisting of

A) 55 to 93.99% by weight of one or more polyesters

B) 3 to 15% by weight of melamine cyanurate

C) 3 to 15% by weight of at least one phosphorus-containing flame retardant,

D) 0.01 to 5 wt .-% of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids with 10 to 40 carbon atoms with aliphatic. saturated alcohols or amines with 2 to 40 C atoms,

E) 0 to 10% by weight of processing aids, selected from the group of stabilizers, oxidation retarders,

Agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, rubber-elastic polymers (also called impact modifiers), colorants preferably dyes and pigments,

Nucleating agents, plasticizers,

the sum of the percentages by weight of components A) to E) being 100%.

2. Thermoplastic molding compositions according to Claim 1, containing as flame retardant C) at least one phosphine oxide of the general formula (I)

in which

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

3. Thermoplastic molding compositions according to Anspmch 1, containing as flame retardant C at least one compound of the general formula

wherein

R ¹ to R ²⁰ independently of one another are hydrogen, a linear or branched alkyl group of up to 6 carbon atoms,

n an average value of 0.5 to 50 and

B in each case C 1 -C 2 -alkyl, preferably methyl, or halogen, preferably chlorine or bromine, q each independently of one another 0, 1 or 2,

X is a single bond, CO, S, O, SO ₂ , C (CH ₃ ) ₂ , Ci-Cs-alkylene, C2-C5-alkylidene, Cs-Cg-cycloalkylidene, Cg-C ^ -arylene, to the further aromatic optionally Rings containing heteroatoms may be condensed, or a radical of the formula (II) or (III),

with Y carbon and

R ^ and R22 individually selectable for each Y, independently of one another hydrogen or C \ -Cg-alkyl, preferably hydrogen, methyl or ethyl,

m is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom Y R 1 and 1 2 are simultaneously alkyl,

mean.

4. Thermoplastic molding compositions according to one or more of the preceding claims, in which component C) from triphenylphosphate oxide, triphenylphosphine sulfide, triphenylphosphate, resorcinol bis (diphenylphosphate), triphenylphosphine or most preferably bisphenol A diphosphate or mixtures thereof.

5. Thermoplastic molding compositions according to one or more of the preceding claims, in which component D) is pentaerythritol tetrastearate or ethylene glycol bismontanoate.

6. Thermoplastic molding compositions according to one or more of the preceding claims, in which component A) consists of polybutylene terephthalate.

7. Thermoplastic molding compositions according to one or more of the preceding claims, in which component A) consists of a mixture of polyethylene terephthalate and polybutylene terephthalate.

8. Thermoplastic molding compositions according to one or more of the preceding claims, in which the proportion of polyethylene terephthalate in the mixture is 10 to 30 wt .-%.

9. Thermoplastic molding compositions according to one or more of the preceding claims, in which the polyethylene terephthalate consists of a recyclate with a residual moisture content of 0.01 to 0.7%.

10. Use of thermoplastic molding compositions according to one or more of the preceding claims for the production of fibers, films and moldings.

11. Moldings, fibers and films obtainable from the thermoplastic molding compositions according to one or more of the preceding claims.