WO2019048309A1

WO2019048309A1 - Flame retardant polyester compositions and use thereof

Info

Publication number: WO2019048309A1
Application number: PCT/EP2018/073230
Authority: WO
Inventors: Harald Bauer; Sebastian HÖROLD; Martin Sicken
Original assignee: Clariant Plastics & Coatings Ltd
Priority date: 2017-09-07
Filing date: 2018-08-29
Publication date: 2019-03-14
Also published as: CN109467891B; DE102017215776A1; TW201920408A; EP3679091A1; CN109467891A

Abstract

The invention relates to flame retardant polyester compositions containing - thermoplastic polyester as component A, fillers and/or reinforcing materials as component B, phosphinic acid salt of formula (I) as component C, wherein R1 and R2 represent ethyl, M represents Al, Fe, TiOp or Zn, m is 2 to 3, and p = (4 - m) /2, a compound selected from the group consisting of Al-, Fe-, TiOp- or Zn salts of ethylbutyl phosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid and/or the dihexylphosphinic acid as component D, and phosphonic acid salt of formula (II) as component E, wherein R3 represents ethyl, Met represents Al, Fe, TiOq or Zn, n is 2 to 3, and q = (4 - n) /2, wherein the X-ray powder diffractogram of the compositions contain the following reflections: in the angle range 2θ from 9.099° to 9.442°, from 18.619° to 18.984° and from 26.268° to 26.679° and/or in the angle range 2θ from 5.112° to 5.312°, from 6.097° to 6.297°, from 10.082° to 10.282°, from 10.350° to 10.550° and from 12.308° to 12.508° and/or in the angle range 2θ from 9.117° to 9.317° and from 18.537° to 18.737° 5 and/or in the angle range 2θ from 8.300° to 8.500°. The polyester compositions can be used to produce fibres, films and moulded bodies, in particular for electrical and electronic applications.

Description

Description: The present invention relates to flame-retardant polyester compositions and molded articles made therefrom.

Flammable plastics generally have to be equipped with flame retardants in order to achieve the high flame retardance requirements demanded by plastics processors and in part by the legislature. Preference - also for ecological reasons - are non-halogenated

Flame retardant systems used that form little or no flue gases. Among these flame retardants, the salts of phosphinic acids (phosphinates) have proven to be particularly effective for thermoplastic polymers (DE 2 252 258 A and DE 2 447 727 A).

In addition, synergistic combinations of phosphinates with certain nitrogen-containing compounds are known which act more effectively in a whole series of polymers as flame retardants than the phosphinates alone (WO-2002/28953 A1 and DE 197 34 437 A1 and DE 197 37 727 A1).

From US Pat. No. 7,420,007 B2 it is known that dialkylphosphinates containing a small amount of selected telomers are suitable as flame retardants for polymers, the polymer only undergoing very little degradation upon incorporation of the flame retardant into the polymer matrix.

Flame retardants must often be added in high dosages in order to ensure a sufficient flame retardancy of the plastic according to international standards. Due to their chemical reactivity, which for the

Flame retardancy at high temperatures is required

Flame retardant, especially at higher dosages, the processing stability of plastics. It can lead to increased polymer degradation, crosslinking reactions, outgassing or discoloration.

From DE 10 2007 041 594 A1 flame-retardant polyester compounds are known, the thermoplastic polyester, polycarbonate, phosphinic acid salt and

optionally reaction products of melamine with phosphoric acid and / or condensed phosphoric acids or other nitrogen-containing flame retardants and optionally reinforcing agents and / or further additives. These are distinguished by a safe UL 94 V-0 classification, increased

Glow wire resistance, improved mechanics and reduced polymer degradation.

Further flame-retardant polyester compounds having this property profile are disclosed in DE 10 2010 049 968 A1. These compounds contain

thermoplastic polyester, phosphinic acid salt, phosphazene and

if appropriate, reaction products of the melamine with phosphoric acid and / or condensed phosphoric acids or other nitrogen-containing flame retardants and optionally reinforcing agents and / or further additives.

So far, however, it lacks flame-retardant phosphinate-containing

Polyester compositions that achieve all the required properties at the same time, in particular good electrical values and effective

Flame retardants.

It was therefore an object of the present invention, flame-retardant

To provide polyester compositions based on phosphinate-containing flame retardant systems which have all the aforementioned properties at the same time and which in particular have good electrical values (CTI, GWFI) and effective flame retardancy, characterized by shortest possible afterburning times (UL94).

The invention provides flame-retardant polyester compositions containing

thermoplastic polyester as component A, Fillers and / or reinforcing materials, preferably glass fibers, as component B,

Phosphinic acid salt of the formula (I) as component C.

wherein Ri and R2 are ethyl,

M is Al, Fe, TiOp or Zn,

m is 2 to 3, preferably 2 or 3, and

p = (4 - m) / 2

A compound selected from the group of the AI, Fe, TiOp or Zn salts of ethylbutylphosphinic acid, dibutylphosphinic acid,

Ethylhexylphosphinsäure, the Butylhexylphosphinsäure and / or the Dihexylphosphinsäure as component D, and

Phosphonic acid salt of the formula (II) as component E

wherein R 3 is ethyl,

Met is Al, Fe, TiOq or Zn,

n is 2 to 3, preferably 2 or 3, and

q = (4-n) / 2, the X-ray powder diffraction gramme being the

Compositions contains the following reflexes:

in the angular range 2Θ from 9.099 ° to 9.442 °, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 ° and / or

in the angular range 2Θ of 5.1 12 ° to 5.312 °, from 6.097 ° to 6.297 °, from 10,082 ° to 10,282 °, from 10,350 ° to 10,550 ° and from 12,308 ° to 12,508 ° and / or

in the angular range 2Θ from 9.1 17 ° to 9.317 ° and from 18.537 ° to 18.737 ° and / or in the angular range 2Θ from 8,300 ° to 8,500 °.

The X-ray spectra are taken with an X-ray powder diffractometer,

for example, with a device X ^' Pert MPD Fa. Phillips measured. The sample is irradiated with Cu-K-alpha radiation and the step time is 1 second.

Preferred polyester compositions according to the invention are those whose X-ray powder diffractogram contains the following reflections: in the angular range 2Θ of 9.099 ° to 9.442 °, of 18.619 ° to 18.984 ° and of 26.268 ° to 26.679 °.

In the polyester composition of the present invention, the proportion of component A is usually 25 to 95% by weight, preferably 25 to 75% by weight. In the polyester composition of the invention, the proportion of

Component B usually 1 to 45 wt .-%, preferably 20 to 40 wt .-%.

In the polyester composition of the present invention, the proportion of Component C is usually 1 to 35% by weight, preferably 5 to 20% by weight.

In the polyester composition of the present invention, the proportion of component D is usually 0.01 to 3% by weight, preferably 0.05 to

1, 5 wt .-%. In the polyester composition of the present invention, the proportion of component E is usually 0.001 to 1% by weight, preferably 0.01 to

0.6% by weight.

The percentages for the proportions of components A to E are based on the total amount of the polyester composition.

Preference is given to flame-retardant polyester compositions in which the proportion of component A is from 25 to 95% by weight, the proportion of component B is from 1 to 45% by weight,

the proportion of component C 1 to 35% by weight,

the proportion of component D 0.01 to 3 wt .-%, and

the proportion of component E is 0.001 to 1% by weight,

percentages are based on the total amount of

Refer to polyester composition.

Particularly preferred are flame retardant polyester compositions in which

the proportion of component A is from 25 to 75% by weight,

the proportion of component B is from 20 to 40% by weight,

the proportion of component C 5 to 20 wt .-%,

the proportion of component D 0.05 to 1, 5 wt .-%, and

the proportion of component E is from 0.01 to 0.6% by weight,

is.

Preferred salts of component C are those in which M ^{m +} Zn ²⁺ , Fe ³⁺ or in particular Al ³⁺ . Preferably used salts of component D are zinc, iron or

especially aluminum salts.

Preferably used salts of component E are those in which Met ^{n +} Zn ²⁺ , Fe ³⁺ or in particular Al ³⁺ .

Very particular preference is given to flame retardants

Polyester compositions in which M and Met are AI, m and n are 3 and in which the compounds of component D are present as aluminum salts. In a preferred embodiment, the above-described flame retardant polyester compositions contain inorganic phosphonate as further component F. The use of the inventively used as component F.

inorganic phosphonates or salts of phosphorous acid

(Phosphites) are known as flame retardants. So revealed

WO 2012/045414 A1 Flammschutzmittelkombinationen, in addition to

Phosphinic acid salts also salts of phosphorous acid (= phosphites) included.

The inorganic phosphonate (component F) preferably corresponds to the general formulas (IV) or (V)

[(HO) PO ₂ ] ² -p / 2 cat ^{P +} (IV)

[(HO) ₂ PO] - _p Kat ^{P +} (V) where Kat is a p-valent cation, in particular a cation of an alkali metal, alkaline earth metal, an ammonium cation and / or a cation of Fe, Zn or in particular of Al including the cations Al ( OH) or Al (OH) 2, and p is 1, 2, 3 or 4. The inorganic phosphonate (component F) is preferably aluminum phosphite [Al (H2PO3) 3], secondary aluminum phosphite [Al2 (HPO3) 3], basic aluminum phosphite [Al (OH) (H2PO3) 2 ^* 2aq], aluminum phosphite tetrahydrate [Al ₂ (HPO 3) 3 ^* 4aq], aluminum phosphonate, Al ₇ (HPO 3) 9 (OH) ₆ (1,6-hexanediamine) i, ₅ ^* 12H ₂ O, ΑΙ ₂ (ΗΡθ ³ ) ^{3 *} χΑΐ 2θ ³ ^* ηΗ ₂ Ο with x = 2.27 - 1 and / or

The inorganic phosphonate (component F) is preferably also aluminum phosphites of the formulas (VI), (VII) and / or (VIII)

Al 2 (HPO 3) 3 X (H ₂ O) q (VI) where q is 0 to 4

Al2, ooMz (HPO ₃₎ y (OH) vx (H ₂ O> lw (VII) wherein M is alkali metal cations, z is 0.01 to 1.5, and y is 2.63 to 3.5 and v is 0 to 2 and w is 0 to 4;

Al ₂ , oo (HPO 3) u (H ₂ PO 3) t x (H ₂ O) s (VI II), where u is 2 to 2.99 and 1 2 to 0.01 and s is 0 to 4,

and or

aluminum phosphite [Al (H2PO3) 3] to secondary aluminum phosphite

[Al ₂ (HPO 3) 3] to give basic aluminum phosphite [Al (OH) (H ₂ PO 3) 2 ^* 2aq]

Aluminum phosphite tetrahydrate [Al 2 (HPO 3) 3 ^* 4aq] to give aluminum phosphonate, Al ₇ (HPO ₃ ) 9 (OH) 6 (1,6-hexanediamine) i, 5 ^* 12H ₂ O, by ΑΙ ₂ (ΗΡθ ³ ) ³ * χΑΐ 2θ ³ ^* ηΗ ₂ Ο with x = 2,27 - 1 and / or AUHePieOis.

Preferred inorganic phosphonates (component F) are water-insoluble or sparingly soluble salts.

Particularly preferred inorganic phosphonates are aluminum, calcium and zinc salts.

Particularly preferably, component F is a

Reaction product of phosphorous acid and an aluminum compound.

Particularly preferred components F are aluminum phosphites with the

CAS numbers 15099-32-8, 1 19103-85-4, 220689-59-8, 56287-23-1,

156024-71 -4, 71449-76-8 and 15099-32-8.

The preparation of the preferably used aluminum phosphites is carried out by reacting an aluminum source with a phosphorus source and optionally a template in a solvent at 20-200 ° C for a period of up to 4 days. The aluminum source and the phosphorus source are mixed for 1 to 4 hours, heated under hydrothermal conditions or at reflux, filtered off, washed and z. B. at 1 10 ° C dried. Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum hydroxide (eg pseudoboehmite).

Preferred sources of phosphorus are phosphorous acid, (acidic)

Ammonium phosphite, alkali phosphites or alkaline earth phosphites.

Preferred Alkaliphosphite are disodium phosphite, dinat umphosphithydrat, trisodium phosphite, Kaliumhydrogenphosphit Preferred Dinatriumphosphithydrat is Brüggolen ^® H10 Fa. Brüggemann.

Preferred templates are 1, 6-hexanediamine, guanidine carbonate or ammonia.

Preferred alkaline earth metal phosphite is calcium phosphite.

The preferred ratio of aluminum to phosphorus to solvent is 1: 1: 3.7 to 1: 2.2: 100 mol. The ratio of aluminum to template is 1: 0 to 1: 17 mol. The preferred pH of the reaction solution is 3 to 9.

Preferred solvent is water.

Particularly preferably, the same salt of phosphinic acid as the phosphorous acid is used in the application, so z. For example, aluminum diethylphosphinate together with aluminum phosphite or Zinkdiethylphosphinat together with zinc phosphite.

In a preferred embodiment, the above-described flame retardant polyester compositions contain as component F

a compound of the formula (III)

in which Me is Fe, TiOr, Zn or in particular Al,

o is 2 to 3, preferably 2 or 3, and

r = (4-o) / 2. Preferred compounds of the formula (III) are those in which Me is ^{O 2} Zn ²⁺ , Fe ³⁺ or in particular Al ³⁺ .

Component F is preferably in an amount of 0.005 to 10 wt .-%, in particular in an amount of 0.02 to 5 wt .-%, based on the

Total amount of the polyester composition, before.

In a further preferred embodiment, the polyester composition according to the invention contains, as component H, a melamine polyphosphate having an average degree of condensation of from 2 to 200, preferably greater than or equal to 20.

The use of the present invention used as component H.

Polyphosphate derivatives of melamine with a degree of condensation greater than or equal to 20 as a flame retardant is known. Thus, DE 10 2005 016 195 A1 discloses a stabilized flame retardant containing 99 to 1% by weight.

Melaminpolyphosphat and 1 to 99 wt .-% additive with reserve alkalinity. This document also discloses that this flame retardant with a

Phosphinic acid and / or a phosphinic acid salt can be combined.

Preferred polyester compositions according to the invention contain as component H a melamine polyphosphate whose average

Condensation degree 20 to 200, in particular from 40 to 150, is.

In another preferred range, the average is

Condensation degree 2 to 100.

Further preferred polyester compositions according to the invention comprise, as component H, a melamine polyphosphate having a decomposition temperature of greater than or equal to 320 ° C, in particular greater than or equal to 360 ° C and most preferably greater than or equal to 400 ° C.

Melanin polyphosphates which are known from WO 2006/027340 A1 (corresponding to EP 1 789 475 B1) and WO 2000/002869 A1 (corresponding to EP 1 095 030 B1) are preferably used as components.

Melanninpolyphosphate are preferably used, the average degree of condensation between 20 and 200, in particular between 40 and 150, and the melamine content of 1, 1 to 2.0 mol, in particular 1, 2 to 1, 8 mol per mole of phosphorus atom.

Melanninpolyphosphate are also preferably used whose mean condensation ridge (number average) is> 20 whose decomposition temperature is greater than 320 ° C., whose molar ratio of 1,3,5-triazine compound to phosphorus is less than 1, 1, in particular 0.8 to 1, Is 0 and the pH of a 10% slurry in water at 25 ° C is 5 or higher, preferably 5.1 to 6.9.

In the polyester composition of the invention, the proportion of component H is usually 0 and 25 wt .-%, preferably 1 to 25 wt .-%, in particular 2 to 10 wt .-%, based on the total amount of

Polyester composition.

When using melamine polyphosphate as component H, the following are additionally present in the polyester compositions according to the invention

Reflexes (as X-ray powder diffraction gram) measured: In the angular range 2Θ from 14.765 ° to 15.076 °.

In a further preferred embodiment, the polyester composition according to the invention contains, as component I, melamine cyanurate. The melamine cyanurate used according to the invention as component I is known as a synergist in conjunction with diethyl phosphates in flame retardants for polymeric molding compositions, for example from WO 97/39053 A1). In the polyester composition according to the invention, the proportion of component I is usually 0 and 25 wt .-%, preferably 1 to 25 wt .-%, in particular 4 to 10 wt .-%, based on the total amount of

Polyester composition. When using melamine cyanurate as component I are in the

The following reflections (as X-ray powder diffractiongram) were additionally measured in the polyester compositions according to the invention: In the angular range 2Θ of 10.802 ° to 11004 ° and of 1 1775 to 11909 °. Preference is given to flame-retardant according to the invention

Polyester compositions having a Comparative Tracking Index, measured according to the International Electrotechnical Commission Standard IEC-601 12/3, of greater than or equal to 500 volts. Also preferred flame-retardant according to the invention

Polyester compositions achieve a rating of V0 to UL-94, especially measured on moldings of 3.2 mm to 0.4 mm thickness.

Further preferred flame-retardant according to the invention

Polyester compositions have a Glow Wire Flammability Index according to IEC-60695-2-12 of at least 960 ° C, in particular measured

Moldings of 0.75 - 3 mm thickness.

Further preferred flame-retardant according to the invention

Polyester compositions have a glow-wire resistance, expressed by glow-wire-ignition temperature (GWIT) according to IEC-60695-2-13 of at least 775 ° C, in particular measured on molded parts of 0.75 - 3 mm thickness. The flame retardant combinations used according to the invention stabilize the polyester (component A) very well against thermal degradation. This is reflected in the change in the specific viscosity of the polyester

Compounding and shaping of the invention

Polyester compositions. The thermal stress occurring there results in partial degradation of the polyester chains, which results in a reduction in the average molecular weight and, associated therewith, a reduction in the viscosity of a polyester solution. Typical values for the specific viscosity of polybutylene terephthalate, measured as 0.5% solution in

Phenol / dichlorobenzene (1: 1) at 25 ° C according to ISO 1628 with a

Capillary viscometers are 130 cm ³ / g. After compounding and shaping a polybutylene terephthalate composition according to the invention, typical values for the specific viscosity of the processed polybutylene terephthalate (determined as indicated above) range between 65 and 150 cm ³ / g, preferably between 100 and 129 cm ³ / g.

The polyester compositions according to the invention comprise as component A one or more thermoplastic polyesters.

The polyesters of component A are usually around

(cyclo) aliphatic or aromatic-aliphatic polyesters derived from (cyclo) aliphatic and / or aromatic dicarboxylic acids or their polyester-forming derivatives, such as their dialkyl esters or anhydrides, and from (cyclo) aliphatic and / or araliphatic diols or from (cyclo) aliphatic and / or aromatic hydroxycarboxylic acids or their polyester-forming derivatives, such as their alkyl esters or anhydrides derived. The term

"(Cyclo) aliphatic" includes cycloaliphatic and aliphatic compounds.

The thermoplastic polyesters of component A are preferably selected from the group of polyalkylene esters of aromatic and / or aliphatic dicarboxylic acids or their dialkyl esters. The thermoplastic polyesters used as component A can be prepared by known methods (Kunststoff-Handbuch, Vol. VIII, pages 695-710, Karl Hanser Verlag, Munich 1973). Preferably used components A are aromatic-aliphatic

thermoplastic polyesters and preferably thermoplastic polyesters derived by reacting aromatic dicarboxylic acids or their polyester-forming derivatives with aliphatic C 2 -C 10 -diols, in particular with C 2 -C 4 -diols.

According to preferably used components A are

Polyalkylene enterephthalates, and particularly preferably polyethylene terephthalates or polybutylene terephthalates. Polyalkylene terephthalates preferably contain at least 80 mol%, in particular 90 mol%, based on the dicarboxylic acid, units derived from terephthalic acid.

The inventively used as component A preferred

In addition to terephthalic acid radicals, polyalkylene terephthalates may contain up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or radicals of aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid,

4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic or azelaic acid, cyclohexanediacetic acid or cyclohexanedicarboxylic acid.

The inventively used as component A preferred

Polyalkylene terephthalates can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or tribasic or tetrabasic carboxylic acids, as described, for example, in US Pat. As described in DE-A-19 00 270 are branched. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol. Particularly preferred components A are polyalkylene terephthalates which are prepared solely from terephthalic acid and its reactive derivatives (eg

Dialkyl esters) and ethylene glycol and / or propanediol-1, 3 and / or butanediol-1, 4 are prepared (polyethylene and Polytrimethylen- and

Polybutylene terephthalate) and mixtures of these polyalkylene terephthalates.

Preferred polybutylene terephthalates contain at least 80 mol%,

preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80 mol%, preferably at least 90 mol%, based on the diol component butanediol-1, 4-radicals.

The preferred polybutylene terephthalates may further contain, in addition to 1,4-butanediol radicals, up to 20 mol% of other aliphatic diols having 2 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, e.g. B. residues of

Ethylene glycol; Propanediol-1, 3; 2-ethylpropanediol-1, 3; neopentyl glycol; Pentanediol-1, 5; Hexanediol-1, 6; Cyclohexanedimethanol-1, 4; 3-methyl pentanediol-2,4; 2-methyl-pentanediol-2,4; 2,2,4-trimethylpentanediol-1,3; 2-ethylhexanediol-1, 3; 2,2-diethyl-propanediol-1, 3; Hexanediol-2,5; 1,4-di - ([beta] -hydroxyethoxy) benzene; 2,2-bis (4-hydroxycyclohexyl) propane; 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane; 2,2-bis- (3- [beta] -hydroxyethoxyphenyl) -propane and 2,2-bis (4-hydroxypropoxyphenyl) propane.

Preferably used as component A according to the invention

Polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components and / or butanediol-1,4.

The thermoplastic component used as component A according to the invention

Polyesters may also be used in admixture with other polyesters and / or other polymers.

As component B fillers and / or preferably reinforcing materials are used, preferably glass fibers. It can also be mixtures of two or several different fillers and / or reinforcing materials used.

Preferred fillers are mineral particulate fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, nanoscale minerals, particularly preferably montmorillonites or nano-boehmites, magnesium carbonate, chalk, feldspar, glass beads and / or barium sulfate. Particular preference is given to mineral particulate fillers based on talc, wollastonite and / or kaolin.

Furthermore, needle-shaped mineral fillers are also particularly preferably used. Under needle-shaped mineral fillers is understood according to the invention a mineral filler with pronounced needle-like character. Preferred are needle-shaped wollastonites. Preferably, the mineral has a length to diameter ratio of 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, particularly preferably from 4: 1 to 12: 1. The average particle size of the acicular mineral fillers used according to the invention as component B is preferably less than 20 μm, more preferably less than 15 μm, particularly preferably less than 10 μm, determined using a CILAS granulometer.

The components B preferably used according to the invention are reinforcing materials. This may, for example, to

Reinforcement based on carbon fibers and / or glass fibers act.

The filler and / or reinforcing material may in a preferred

Be surface-modified embodiment, preferably with a

Adhesive or a primer system, particularly preferably on

Silane. In particular when glass fibers are used, in addition to silanes, polymer dispersions, film formers, branching agents and / or

Fiber processing aids are used. The glass fibers preferably used according to the invention as component B may be short glass fibers and / or long glass fibers. As short or long glass fibers, cut fibers can be used. Short glass fibers can also be used in the form of ground glass fibers.

In addition, glass fibers can also be used in the form of continuous fibers, for example in the form of rovings, monofilaments,

Filament yarns or twines or glass fibers can be used in the form of textile fabrics, for example as glass fabrics, as

Glass braid or as a glass mat.

Typical fiber lengths for short glass fibers prior to incorporation into the

Polyester matrix range from 0.05 to 10 mm, preferably from 0.1 to 5 mm. After incorporation into the polyester matrix, the length of the glass fibers has decreased. Typical fiber lengths for short glass fibers after the

Incorporation into the polyester matrix ranges from 0.01 to 2 mm, preferably from 0.02 to 1 mm.

The diameters of the individual fibers can vary within wide ranges. Typical diameters of the individual fibers range from 5 to 20 μm.

The glass fibers can have any cross-sectional shapes, for example round, elliptical, n-cornered or irregular cross-sections. Glass fibers with mono- or multilobal cross-sections can be used.

Glass fibers can be used as continuous fibers or as cut or ground glass fibers.

The glass fibers themselves, regardless of their cross-sectional area and their length, can be selected, for example, from the group of E-glass fibers, A-glass fibers, C-glass fibers, D-glass fibers, M-glass fibers, S-glass fibers,

R glass fibers and / or ECR glass fibers, wherein the E glass fibers, R glass fibers, S glass fibers and ECR glass fibers are particularly preferred. The glass fibers are preferably provided with a size, which preferably contains polyurethane as a film former and aminosilane as adhesion promoter.

Particularly preferably used E glass fibers have the following chemical composition: S1O2 50-56%; AI2O3 12-16%; CaO 16-25%; MgO <6%; B2O3 6-13%; F <0.7%; Na ₂ O 0.3-2%; K2O 0.2-0.5%; Fe ₂ Os 0.3%.

Particularly preferred R glass fibers have the following chemical composition: S1O2 50-65%; AI2O3 20-30%; CaO 6-16%; MgO 5-20%; Na ₂ O 0.3-0.5%; K2O 0.05-0.2%; Fe ₂ Os 0.2-0.4%, T1O2 0.1-0.3%.

Particularly preferably used ECR glass fibers have the following chemical composition: S1O2 57.5-58.5%; AI2O3 17.5-19.0%; CaO 11, 5-13.0%; MgO 9.5-1 1, 5.

The salts used according to the invention as component C of

Diethylphosphinic acid are known flame retardants for polymers

Molding compounds. Salts of diethylphosphinic acid with fractions of the phosphinic and phosphonic acid salts used according to the invention as components D and E are known flame retardants. The preparation of this combination of substances is z. B. in US 7,420,007 B2 described. The salts of diethylphosphinic acid used according to the invention

Component C may contain small amounts of salts of component D and salts of component E, for example up to 10 wt .-% of

Component D, preferably 0.01 to 6 wt .-%, and in particular 0.2 to 2.5 wt .-% thereof, and up to 10 wt .-% of component E, preferably 0.01 to 6 wt .-% , And in particular 0.2 to 2.5 wt .-% thereof based on the amount of components C, D and E. The salts of ethylphosphonic acid used according to the invention as component E are suitable as additives to diethyl phosphates in

Flame retardants for polymeric molding compositions also known, for example from DE 102007041594 A1.

In a further preferred embodiment, components C, D, E and optionally F, H and / or I are in particulate form, wherein the average

Particle size (dso) is 1 to 100 μιτι. The polyester compositions according to the invention may contain as component G further additives. Preferred components I for the purposes of the present invention are antioxidants, UV stabilizers,

Gamma ray stabilizers, hydrolysis stabilizers, co-stabilizers for antioxidants, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments and / or other flame retardants that differ from components C, D, E, F, H and I.

These include in particular phosphates, such as melamine poly (metal phosphates). Preferred metals for this purpose are the elements of FIG. 2.

Main group, the 3rd main group, the 2nd subgroup, the 4th subgroup and the subgroup Villa of the Periodic Table and cerium and / or lanthanum.

Melamine poly (metal phosphates) are preferably melamine poly (zinc phosphates), melamine poly (magnesium phosphates) and / or melamine poly (calcium phosphates).

Preference is given to (melamine) 2Mg (HPO4) 2, (melamine) 2Ca (HPO4) 2,

(Melamine) 2Zn (HPO4) 2, (melamine) 3AI (HPO4) 3, (melamine) 2Mg (P2O7),

(Melamine) 2Ca (P2O7), (melamine) 2Zn (P2O7), (melamine) 3AI (P2O7) 3/2.

Preferred are melamine poly (metal phosphates), which are known as

Hydrogen phosphato or pyrophosphato metallates with complex anions containing a have four- or sechsbindiges metal atom as a coordination center with bidentate hydrogen phosphate or pyrophosphate ligands.

Also preferred are melamine-intercalated aluminum, zinc or magnesium salts of condensed phosphates

Bis-melamine-zinc diphosphate and / or bis-melamine alumotriphosphate.

Preference is also given to salts of the elements of the 2nd main group, the

3rd main group, the 2nd subgroup, the 4th subgroup and the subgroup Villa of the Periodic Table and of cerium and / or lanthanum with anions of the oxo acids of the fifth main group (phosphates, pyrophosphates and

Polyphosphates).

Preference is given to aluminum phosphates, aluminum monophosphates; Aluminum orthophosphates (AIPO4), aluminum hydrogen phosphate (Al2 (HPO4) 3) and / or aluminum dihydrogen phosphate

Also preferred are calcium phosphate, zinc phosphate, titanium phosphate and / or iron phosphate

Preference is given to calcium hydrogenphosphate, calciumhydrogenphosphate dihydrate, magnesium hydrogenphosphate, titanium hydrogenphosphate (TIHC) and / or zinc hydrogenphosphate. Preference is given to aluminum dihydrogenphosphate, magnesium dihydrogenphosphate, calcium dihydrogenphosphate, zinc dihydrogenphosphate, zinc dihydrogenphosphate dihydrate and / or aluminum dihydrogenphosphate.

Particularly preferred are calcium pyrophosphate,

Calcium dihydrogen pyrophosphate, magnesium pyrophosphate zinc pyrophosphate and / or aluminum pyrophosphate. The foregoing and other related and phosphates, for example, by the JM Huber Corporation, USA, offered under Safire ^® Products, add about the types APP include Type II, AMPP, MPP, MPyP, PiPyP. PPaz, Safire ^® 400, Safire ^® 600, EDAP and others.

Other phosphates are disclosed, for example, in JP-A-2004204194, the

DE-A-102007036465 and EP-A-31331 12 and are expressly among the usable components I. The other additives are known per se as additives to polyester compositions and can be used alone or in admixture or in the form of masterbatches.

The abovementioned components A, B, C, D, E and optionally F, G, H and / or I can be processed in a wide variety of combinations with the flameproofed polyester composition according to the invention. It is thus possible to mix the components into the polyester melt at the beginning or at the end of the polycondensation or in a subsequent compounding process. Furthermore, there are processing processes in which individual components are added later. This is especially practiced when using pigment or additive masterbatches. In addition, there is the possibility, in particular powdered components on by the

Drying process possibly warm up warm polymer granules. Also, two or more of the components of the invention

Polyester compositions may be combined by mixing prior to incorporation into the polyester matrix. In this case, conventional mixing units can be used, in which the components in a suitable mixer, for. B. 0.01 to 10 hours at 0 to 300 ° C mixed.

From two or more of the components of the invention

Polyester compositions can also be prepared granules, which can then be introduced into the polyester matrix. For this purpose, two or more components of the invention

Polyester composition with granulation and / or binder in a suitable mixer or a granulating are processed into granules.

The initially formed crude product can be dried in a suitable dryer or tempered for further grain buildup.

The polyester composition of the present invention or two or more components thereof may be prepared by roll compaction in one embodiment.

The polyester composition according to the invention or two or more components thereof may in one embodiment be prepared by mixing, extruding, chopping (or breaking) the ingredients.

optionally broken and classified) and dried (and optionally coated).

The polyester composition of the present invention or two or more components thereof may be prepared by spray granulation in one embodiment.

The flame-retardant polymer molding composition according to the invention is preferably in granular form, for. B. as an extrudate or as a compound before. The granules preferably have a cylindrical shape with a circular, elliptical or irregular base, spherical shape, pillow shape, cube shape, cuboid shape, prism shape.

Typical length to diameter ratio of the granules are 1 to 50 to 50 to 1, preferably 1 to 5 to 5 to 1.

The granules preferably have a diameter of 0.5 to 15 mm, more preferably of 2 to 3 mm and preferably a length of 0.5 to 15 mm, particularly preferably 2 to 5 mm. The invention also relates to moldings produced from the flame-retardant polyester composition described above comprising the components A, B, C, D and E and optionally the components F and / or G.

The molded parts according to the invention may be any desired formations. Examples of these are fibers, films or moldings, obtainable from the novel flame-retardant polyester molding compositions by any desired molding process, in particular by injection molding or extrusion.

The preparation of the flame-retardant polyester moldings according to the invention can be carried out by any molding process. Examples include injection molding, pressing, foam injection, gas injection molding, blow molding,

Film casting, calendering, laminating or coating at higher temperatures with the flame-retardant polyester molding compound.

The molded parts are preferably injection-molded parts or extruded parts.

The flame-retardant polyester compositions according to the invention are suitable for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector. The invention preferably relates to the use of the flame-retardant polyester compositions according to the invention in or for connectors, current-carrying parts in power distributors (Fl protection), circuit boards, potting compounds, power connectors, circuit breakers, lamp housings, LED housings,

Capacitor housings, bobbins and fans, protective contacts, plugs, in / on boards, housings for plugs, cables, flexible printed circuit boards, charging cables for mobile phones, engine covers or textile coatings. The invention likewise preferably relates to the use of the flame-retardant polyester compositions according to the invention for the preparation of

Moldings in the form of components for the electrical / electronics sector,

in particular for parts of printed circuit boards, housings, foils, lines, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, regulators, memories and sensors, in the form of large-area components, in particular of housing parts for Switch cabinets and in the form of elaborately designed components with sophisticated geometry. The wall thickness of the shaped bodies according to the invention can typically be up to 10 mm. Particularly suitable are moldings with less than 1.5 mm wall thickness, more preferably less than 1 mm wall thickness and particularly preferably less than 0.5 mm wall thickness. The following examples illustrate the invention without limiting it.

1 . Used components

Commercially available polyesters (component A):

Polybutylene terephthalate (PBT): Ultradur ^® 4500 (BASF)

Polyethylene terephthalate (PET): Polyclear ^® 1100 (Invista)

Glass fibers (component B):

Glass fibers Vectrotex ^® EC 10 P 952 (Fa. Vectrotex, FR),

Flame retardant FM 1 (components C, D and E):

Aluminum salt of diethylphosphinic acid containing 0.9 mol% of aluminum ethyl butylphosphinate and 0.5 mol% of aluminum ethyl phosphonate prepared according to Example 3 of US Pat. No. 7,420,007 B2

Flame retardant FM 2 (components C, D and E):

Aluminum salt of diethylphosphinic acid containing 2.7 mol% of aluminum Ethyl butylphosphate and 0.8 mol% of aluminum ethylphosphonate prepared according to Example 4 of US Pat. No. 7,420,007 B2

Flame retardant FM 3 (components C, D and E):

Aluminum salt of diethylphosphinic acid containing 0.5 mol% of aluminum ethylbutylphospinate and 0.05 mol% of aluminum ethylphosphonate prepared by the process according to US Pat. No. 7,420,007 B2

Flame retardant FM 4 (components C, D and E):

Aluminum salt of diethylphosphinic acid containing 10 mol% of aluminum

Ethyl butylphosphate and 5 mol% of aluminum ethyl phosphonate prepared by the method according to US Pat. No. 7,420,007 B2

Flame retardant FM 5 (component C):

Aluminum salt of diethylphosphinic acid prepared in analogy to Example 1 of DE 196 07 635 A1

Flame retardant FM 6 (components C and E):

Aluminum salt of diethylphosphinic acid containing 8.8 mol% of aluminum ethylphosphonate prepared according to Example 2 of DE 10 2010 018 864 A1

Flame retardant FM 7 (component F):

Aluminum salt of phosphonic acid prepared according to Example 1 of

DE 10201 1 120218 A1

Flame retardant FM 8 (component H):

Melamine polyphosphate prepared according to the example of WO 2000/002869 A1

Flame retardant FM 9 (component I):

Melamincyanuarat, Melapur ^® MC (BASF) 2. Production, processing and testing of flame-retardant polyester molding compounds

The additives were blended with the polymer granules in the proportions shown in the Tables and loaded on a twin-screw extruder (Type

Leistritz ZSE 27 HP-44D) at temperatures of 240 to 280 ° C incorporated. The glass fibers were added via a side feeder. The homogenized polymer strand was stripped off, cooled in a water bath and then granulated.

After sufficient drying, the molding materials were on a

Injection molding machine (type Arburg 320 C / KT) processed to test specimens at melt temperatures of 260 to 280 ° C and tested for flame retardance and classified by the UL 94 test (Underwriter Laboratories). In addition to the

Classification was also given the afterburning time.

The Comparative Tracking Index of the molded parts was determined according to the International Electrotechnical Commission Standard IEC-601 12/3. The Glow Wire Flammability Index (GWFI Index) was standardized

IEC-60695-2-12 determined.

The X-ray spectra (X-ray powder diffractograms, "XRD values") of the

Polyamide compositions are measured using an X-ray powder diffractometer (XTert-MPD, Phillips). The sample was irradiated with Cu-K-alpha radiation and the step time was 1 second.

All tests of the respective series were carried out under similar conditions (such as temperature programs, screw geometries and injection molding parameters), unless otherwise stated. Examples 1 -5 and Comparative Examples V1 -V3 with PBT

The results of the experiments with PBT molding compositions are in the in the

listed in the following table. All amounts are expressed as weight percent and are based on the PBT molding compound including the flame retardants and reinforcing agents.

Table 1: PBT GF 30 test results (1 -5 according to the invention, V1 -V3 comparisons)

The polyester compositions according to the invention of Examples 1 to 5 are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm,

simultaneously have CTI 600 volts and GWFI 960 ° C. The addition of another component F in Example 5 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time.

The omission of components D and E in Comparative Example V1 resulted, in addition to a prolonged afterburning time, in a reduced CTI value compared to Examples 1-5.

The omission of component D in Comparative Example C2 resulted in a reduced CTI value in addition to an extension of the fire protection time compared to Example 2. In Comparative Example C3 was by increasing the concentration of

Although components C and D achieved a reduction in the afterburning time in comparison with example V2. However, this polyester composition still showed a longer afterburning time as compared to Example 2 and one

decreased CTI value.

Examples 6-10 and Comparative Examples V4-V6 with PET

The results of the experiments with PET molding compounds are in the in the

listed in the following table. All amounts are given as wt.% And refer to the polyester molding composition

including flame retardants and reinforcing agents. Table 2: PET GF 30 test results (6-10 according to the invention, V4-V6 comparisons)

The polyester compositions according to the invention of Examples 6 to 10 are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm and at the same time have CTI 600 volts and GWFI 960 ° C. The addition of another component F in Example 10 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time.

The omission of components D and E in Comparative Example C4 resulted, in addition to a prolonged afterburning time, in a reduced CTI value compared to Examples 6-10. The omission of component D in Comparative Example C5 resulted in a reduced CIT value in addition to an extended afterburn time compared to Example 7. In Comparative Example C6, an increase in the afterburning time was achieved by increasing the concentration of components C and E compared to Example V5. However, this polyester composition still showed a prolonged afterburn time compared to Example 7 and a reduced CTI value.

Claims

claims

1 . Flame-retardant polyester compositions containing

thermoplastic polyester as component A,

Fillers and / or reinforcing materials as component B,

Phosphinic acid salt of the formula (I) as component C o

[; ^IJ - °] M - «,

m

wherein Ri and R2 are ethyl,

M is Al, Fe, TiOp or Zn,

m means 2 to 3, and

p = (4 - m) / 2

Phosphonic acid salt of the formula (II) as component E

wherein R 3 is ethyl,

Met is Al, Fe, TiOq or Zn,

n 2 to 3 means, and

q = (4-n) / 2, where

the powder X-ray diffraction pattern of the compositions contains the following reflexes:

in the angular range 2Θ from 9.099 ° to 9.442 °, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 ° and / or in the angular range 2Θ of 5.1 12 ° to 5.312 °, from 6.097 ° to 6.297 °, from 10,082 ° to 10,282 °, from 10,350 ° to 10,550 ° and from 12,308 ° to 12,508 ° and / or

in the angular range 2Θ from 9.1 17 ° to 9.317 ° and from 18.537 ° to 18.737 ° and / or

in the angular range 2Θ from 8,300 ° to 8,500 °.

2. Flame-retardant polyamide compositions according to claim 1, characterized in that the X-ray powder diffraction gramme contains the following reflections: in the angular range 2Θ of 9.099 ° to 9.442 °, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 °.

3. Flame retardant polyester compositions according to at least one of claims 1 to 2, characterized in that M and Met are AI, m and n are 3 and that component D is an aluminum salt.

4. Flame retardant polyester compositions according to at least one of claims 1 to 3, characterized in that

the proportion of component A is from 25 to 95% by weight,

the proportion of component B is from 1 to 45% by weight,

the proportion of component C 1 to 35% by weight,

the proportion of component D 0.01 to 3 wt .-%, and

the proportion of component E is 0.001 to 1% by weight,

percentages are based on the total amount of

Refer to polyester composition.

5. Flame retardant polyester compositions according to claim 4, characterized in that

the proportion of component A is from 25 to 75% by weight,

the proportion of component B is from 20 to 40% by weight,

the proportion of component C 5 to 20 wt .-%,

the proportion of component D 0.05 to 1, 5 wt .-%, and

the proportion of component E is from 0.01 to 0.6% by weight, is.

6. Flame retardant polyester compositions according to at least one of claims 1 to 5, characterized in that they contain inorganic phosphonate as further component F.

7. Flame retardant polyester compositions according to claim 6, characterized in that the inorganic phosphonate is a compound of formula (III)

in which Me is Fe, TiOr, Zn or in particular Al,

o is 2 to 3, preferably 2 or 3, and

r = (4-o) / 2, and wherein the compound of formula (III) is present in an amount of from 0.005 to 10% by weight, based on the total amount of the polyester composition.

8. Flame-retardant polyester compositions according to at least one of claims 1 to 7, characterized in that they contain as component H a melamine polyphosphate having an average degree of condensation of 2 to 200, in particular greater than 20, preferably a melamine polyphosphate whose average degree of condensation is 20 to 200.

9. Flame retardant polyester compositions according to at least one of claims 1 to 8, characterized in that these as component I

Melamine cyanurate included.

10. Flame retardant polyester compositions according to at least one of claims 1 to 9, characterized in that it is a Comparative Tracking Index has measured according to the International Electrotechnical Commission Standard IEC-601 12/3 of greater than equal to 500 volts.

1 1. Flame retardant polyester compositions according to at least one of claims 1 to 10, characterized in that they reach a rating of V0 to UL-94 of 3.2 mm to 0.4 mm thickness.

12. Flame retardant polyester compositions according to any one of claims 1 to 1 1, characterized in that they have a Glow Wire Flammability Index according to IEC-60695-2-12 of at least 960 ° C at 0.75 - 3 mm thickness.

13. Flame retardant polyester compositions according to at least one of claims 1 to 12, characterized in that they have a Glow Wire IgnitionTemperature according to IEC 60695-2-13 of at least 775 ° C at

0.75 - 3 mm thick.

14. Flame retardant polyester compositions according to at least one of claims 1 to 13, characterized in that component A is one or more polyalkylene terephthalates.

Flame retardant polyester compositions according to claim 14, characterized in that component A is a

Polyethylene terephthalate is.

16. Flame retardant polyester compositions according to claim 14, characterized in that component A is a

Polybutylene terephthalate is.

17. Flame retardant polyester compositions according to at least one of claims 1 to 16, characterized in that as component B

Glass fibers are used.

18. Flame-retardant polyester compositions according to at least one of claims 1 to 17, characterized in that components C, D, E and optionally F, H and / or I are in particulate form, wherein the average particle size dso of these components is 1 to 100 μιτι.

19. Flame retardant polyester compositions according to at least one of claims 1 to 18, characterized in that it contains further additives as component G, wherein the further additives are selected from the group consisting of antioxidants, UV stabilizers,

Gamma ray stabilizers, hydrolysis stabilizers, co-stabilizers for antioxidants, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments and / or other flame retardants, which differ from components C, D, E, F, H and I.

20. Use of the polyester compositions according to any one of claims 1 to 19 for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector.