DE102017215776A1 - Flame retardant polyester compositions and their use - Google Patents

Abstract

The invention relates to flame retardant polyester compositions comprising - thermoplastic polyester as component A, - fillers and / or reinforcing agents as component B, - phosphinic acid salt of formula (I) as component Cworin Rund REthyl, M is Al, Fe, TiO or Zn, m is 2 to 3 and p = (4-m) / 2-is selected from the group of the Al, Fe, TiO or Zn salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid and / or dihexylphosphinic acid as component D. and phosphonic acid salt of formula (II) as component Eworin REthyl, Met is Al, Fe, TiO or Zn, n is 2 to 3, and q = (4 - n) / 2, the X-ray powder diffraction gram of the compositions containing the following reflexes: in the angular range 2θ of 9.099 ° to 9.442 °, of 18.619 ° to 18.984 ° and of 26.268 ° to 26.679 ° and / or in the angular range 2θ of 5.125 ° to 5.312 °, of 6.097 ° to 6.297 °, of 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 9.117 to 9.317 ° and from 18.537 ° to 18.737 ° and / or in the angular range 2θ from 8.300 ° to 8.500 ° .The polyester compositions can be used for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector.

Description

The present invention relates to flame retardant polyester compositions and moldings produced 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. Preferably - also for ecological reasons - non-halogenated flame retardant systems are used, which 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 nitrogenous compounds are known to be more effective than flame retardants in a variety of polymers as the flame retardant phosphinates ( WO-2002/28953 A1 such as DE 197 34 437 A1 and DE 197 37 727 A1 ).

From the US 7,420,007 B2 It is known that dialkylphosphinates containing a small amount of selected telomers are suitable as flame retardants for polymers, wherein the polymer undergoes only a rather low degradation during 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 is required for flame retardancy at high temperatures, flame retardants, especially at higher dosages, can affect the processing stability of plastics. It can lead to increased polymer degradation, crosslinking reactions, outgassing or discoloration.

From the DE 10 2007 041 594 A1 flame-retardant polyester compounds are known which contain 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 other additives. These are characterized by a safe UL 94 V-0 classification, increased glow wire strength, improved mechanics and reduced polymer degradation.

Other flame retardant polyester compounds with this property profile are used in the DE 10 2010 049 968 A1 disclosed. These compounds contain thermoplastic polyester, phosphinic acid salt, phosphazene 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 other additives.

However, flame-retardant phosphinate-containing polyester compositions have so far failed to achieve all the required properties at the same time, in particular good electrical values and effective flame retardancy.

It is an object of the present invention, therefore, to provide flame-retardant 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). exhibit.

• - thermoplastischen Polyester als Komponente A,
• - Füllstoffe und/oder Verstärkungsstoffe, vorzugsweise Glasfasern, als Komponente B,
• - Phosphinsäuresalz der Formel (I) als Komponente C
  
  • worin R₁ und R₂ Ethyl bedeuten,
  • M Al, Fe, TiO_p oder Zn ist,
  • m 2 bis 3, vorzugsweise 2 oder 3, bedeutet, und
  • p = (4-m)/2 ist
• - Verbindung ausgewählt aus der Gruppe der Al-, Fe-, TiO_p- oder Zn-Salze der Ethylbutylphosphinsäure, der Dibutylphosphinsäure, der Ethylhexylphosphinsäure, der Butylhexylphosphinsäure und/oder der Dihexylphosphinsäure als Komponente D, und
• - Phosphonsäuresalz der Formel (II) als Komponente E
  
  • worin R₃ Ethyl bedeutet ist,
  • Met Al, Fe, TiO_q oder Zn ist,
  • n 2 bis 3, vorzugsweise 2 oder 3, bedeutet, und
  • q = (4 - n) / 2 ist, wobei das Röntgenpulverdiffraktrogramm der Zusammensetzungen folgende Reflexe enthält:
    • im Winkelbereich 2θ von 9,099° bis 9,442°, von 18,619° bis 18,984° und von 26,268° bis 26,679° und/oder
    • im Winkelbereich 2θ von 5,112° bis 5,312°, von 6,097° bis 6,297°, von 10,082° bis 10,282°, von 10,350° bis 10,550° und von 12,308° bis 12,508° und/oder
    • im Winkelbereich 2θ von 9,117° bis 9,317° und von 18,537° bis 18,737° und/oder
    • im Winkelbereich 2θ von 8,300° bis 8,500°.

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 R ₁ and R _{2 are} ethyl,
  • M is Al, Fe, TiO _p or Zn,
  • m is 2 to 3, preferably 2 or 3, and
  • p = (4-m) / 2
• - A compound selected from the group of Al, Fe, TiO _p - or Zn-salts of Ethylbutylphosphinsäure, the dibutylphosphinic, the 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, TiO is _q or Zn,
  • n is 2 to 3, preferably 2 or 3, and
  • q = (4-n) / 2, wherein 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 5.125 ° to 5.312 °, of 6.097 ° to 6.297 °, of 10.082 ° to 10.282 °, of 10,350 ° to 10,550 ° and of 12,308 ° to 12,508 ° and / or
    • in the angular range 2θ of 9.117 ° to 9.317 ° and 18.537 ° to 18.737 ° and / or
    • in the angular range 2θ of 8,300 ° to 8,500 °.

The X-ray spectra are measured with an X-ray powder diffractometer, for example with an X'Pert-MPD device from Phillips. 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 angle 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 present invention, the proportion of Component B is usually 1 to 45% by weight, preferably 20 to 40% by weight.

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% by weight.

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.

• - der Anteil von Komponente A 25 bis 95 Gew.-%,
• - der Anteil von Komponente B 1 bis 45 Gew.-%,
• - der Anteil von Komponente C 1 bis 35 Gew.-%,
• - der Anteil von Komponente D 0,01 bis 3 Gew.-%, und
• - der Anteil von Komponente E 0,001 bis 1 Gew.-%,

beträgt, wobei die Prozentangaben sich auf die Gesamtmenge der Polyesterzusammensetzung beziehen. 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 is from 0.01 to 3% by weight, and
• the proportion of component E is 0.001 to 1% by weight,

is, wherein the percentages are based on the total amount of the polyester composition.

• - der Anteil von Komponente A 25 bis 75 Gew.-%,
• - der Anteil von Komponente B 20 bis 40 Gew.-%,
• - der Anteil von Komponente C 5 bis 20 Gew.-%,
• - der Anteil von Komponente D 0,05 bis 1,5 Gew.-%, und
• - der Anteil von Komponente E 0,01 bis 0,6 Gew.-%,

beträgt.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 is from 5 to 20% by weight,
• the proportion of component D is 0.05 to 1.5% by weight, 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⁺ .

Preferred salts of component D are zinc, iron or in particular 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-retardant polyester compositions in which M and Met are Al, 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, which in addition to phosphinic salts also salts of phosphorous acid (= phosphites).

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 cat ^{p +} (V)
wherein 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 Al including the cations Al (OH) or Al (OH) ₂ , and p 1, 2, 3 or 4 means.

Preferably, the inorganic phosphonate (component F) is aluminum phosphite [Al (H ₂ PO ₃ ) ₃ ], secondary aluminum phosphite [Al ₂ (HPO ₃ ) ₃ ], basic aluminum phosphite [Al (OH) (H ₂ PO ₃ ) ₂ * 2aq], aluminum phosphite tetra hydrate [Al ₂ (HPO ₃ ) ₃ * 4aq], aluminum phosphonate, Al ₇ (HPO ₃ ) ₉ (OH) ₆ (1,6-hexanediamine) _1.5 * 12H ₂ O, Al ₂ (HPO ₃ ) ³ * xAl ₂ O ₃ * nH ₂ O with x = 2.27-1 and / or Al ₄ H ₆ P ₁₆ O ₁₈ .

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, Al _2,00 M _z (HPO ₃ ) _y (OH) _v x (H ₂ O) _w (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 _2,00 (HPO ₃ ) _u (H ₂ PO ₃ ) _t x (H ₂ O) _s (VIII),
where u is 2 to 2.99 and t is 2 to 0.01 and s is 0 to 4,
and or
aluminum phosphite [Al (H2P0 ₃ ) ₃ ] to give secondary aluminum phosphite [Al ₂ (HPO ₃ ) ₃ ], basic aluminum phosphite [Al (OH) (H ₂ PO ₃ ) ₂ * 2aq], aluminum phosphite tetrahydrate [Al ₂ (HPO ₃ ) ₃ * 4aq] to give aluminum phosphonate to give Al ₇ (HPO ₃ ) ₉ (OH) ₆ (1,6-hexanediamine) _1.5 * 12H ₂ O, Al ₂ (HPO ₃ ) ³ * xAl ₂ O ₃ * nH ₂ O with x = 2,27 - 1 and / or Al ₄ H ₆ P ₁₆ O ₁₈ .

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

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

Component F is particularly preferably a reaction product of phosphorous acid and an aluminum compound.

Particularly preferred components F are aluminum phosphites having the CAS numbers 15099-32-8, 119103-85-4, 220689-59-8, 56287-23-1, 156024-71-4, 71449-76-8 and 15099-32 -8th.

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. dried at 110 ° C.

Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum hydroxide (eg pseudoboehmite).

Preferred phosphorous sources are phosphorous acid, (acidic) ammonium phosphite, alkali phosphites or alkaline earth phosphites.

Preferred alkali metal phosphites are disodium phosphite, disodium phosphite hydrate, trisodium phosphite, potassium hydrogen phosphite

Preferred Dinatriumphosphithydrat is Brüggolen ^® H10 of the company. 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.

• worin Me Fe, TiO_r, Zn oder insbesondere Al ist,
• o 2 bis 3, vorzugsweise 2 oder 3, bedeutet, und
• r = (4 - o) / 2 ist.

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, TiO _r , 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 ^{o +} Zn ²⁺ , Fe ³⁺ or in particular Al ³⁺ .

Component F is preferably present in an amount of from 0.005 to 10% by weight, more preferably in an amount of from 0.02 to 5% by weight, based on the total amount of the polyester composition.

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 greater than or equal to 20.

The use of the polyphosphate derivatives of melamine used according to the invention as component H with a degree of condensation of greater than or equal to 20 as flame retardants is known. So revealed the DE 10 2005 016 195 A1 a stabilized flame retardant containing 99 to 1 wt .-% melamine polyphosphate and 1 to 99 wt .-% additive with reserve alkalinity. It is also disclosed in this document that this flame retardant can be combined with a phosphinic acid and / or a phosphinic acid salt.

Preferred polyester compositions according to the invention contain, as component H, a melamine polyphosphate whose average degree of condensation is from 20 to 200, in particular from 40 to 150.

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

As component H, preference is given to using melamine polyphosphates which consist of WO 2006/027340 A1 (corresponding EP 1 789 475 B1 ) and WO 2000/002869 A1 (corresponding EP 1 095 030 B1 ) are known.

Preference is given to using melamine polyphosphates whose average degree of condensation is between 20 and 200, in particular between 40 and 150, and whose melamine content is 1.1 to 2.0 mol, in particular 1.2 to 1.8 mol, per mole of phosphorus atom.

Likewise preferred melamine polyphosphates are 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 according to the invention, the proportion of component H is usually 0 and 25% by weight, preferably 1 to 25% by weight, in particular 2 to 10% by weight, based on the total amount of the polyester composition.

When using melamine polyphosphate as component H, the following reflexes (as X-ray powder diffractiongram) are additionally measured in the polyester compositions according to the invention: in the angular range 2θ of 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 the polyester composition.

When using melamine cyanurate as component I, the following reflections (as X-ray powder diffractiongram) are additionally measured in the polyester compositions according to the invention: in the angular range 2θ of 10.802 ° to 11.004 ° and of 11.775 to 11.990 °.

Preference is given to flame retardant polyester compositions according to the invention which have a Comparative Tracking Index, measured in accordance with International Electrotechnical Commission Standard IEC-60112/3, of greater than or equal to 500 volts.

Likewise preferred flame retardant polyester compositions according to the invention achieve a rating of V0 according to UL-94, in particular measured on moldings of 3.2 mm to 0.4 mm thickness.

Further preferred flame retardant polyester compositions according to the invention have a Glow Wire Flammability Index according to IEC 60695-2-12 of at least 960 ° C., in particular measured on shaped parts of 0.75-3 mm thickness.

Other preferred flame-retardant polyester compositions of the present invention have a glow-wire resistance, expressed by Glow-Ignition-Temperature (GWIT), of at least 775 ° C. according to IEC-60695-2-13, in particular measured on moldings 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 in compounding and shaping the polyester compositions according to the invention. The thermal stress which results therefrom results in a partial degradation of the polyester chains, which results in a reduction in the average molecular weight and, associated therewith, in a reduction in the viscosity of a polyester solution. Typical values for the specific viscosity of polybutylene terephthalate, measured as a 0.5% strength solution in phenol / dichlorobenzene (1: 1) at 25 ° C. according to ISO 1628 with a capillary viscometer, 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 generally (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 of (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.

Components A preferably used according to the invention are polyalkylene terephthalates, and of these 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 polyalkylene terephthalates which are preferably used according to the invention as component A may contain, in addition to terephthalic acid radicals, 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 polyalkylene terephthalates which are preferably used according to the invention as component A can be prepared by incorporating relatively small amounts of trihydric or trihydric alcohols or difunctional or tricarboxylic carboxylic acids, as described, for example, in US Pat. B. in the DE-A-19 00 270 are described to be 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 (for example their dialkyl esters) and ethylene glycol and / or 1,3-propanediol and / or 1,4-butanediol (polyethylene and polytrimethylene 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 1,4-butanediol 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; 1,3-propanediol; 2-ethyl-1,3-; neopentyl glycol; 1,5-pentanediol; 1,6-hexanediol; Cyclohexane-1,4; 3-methyl pentanediol-2,4; 2-methyl-pentanediol-2,4; 2,2,4-trimethyl pentanediol-1,3; 2-ethylhexanediol-1,3; 2,2-diethyl-1,3-propanediol; 2,5-hexanediol; 1,4-Di - ([beta] -hydroxyethoxy) benzene; 2,2-bis (4-hydroxycyclohexyl) -propane; 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane; 2,2-bis- (3- [beta] -hydroxyethoxyphenyl) -propane and 2,2-bis (4-hydroxypropoxyphenyl) -propane.

Polyalkylene terephthalates preferably used as component A according to the invention 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 1,4-butanediol.

The thermoplastic polyesters used as component A according to the invention can also be used in a mixture with other polyesters and / or further polymers.

As component B fillers and / or preferably reinforcing materials are used, preferably glass fibers. It is also possible to use mixtures of two or more different fillers and / or reinforcing materials.

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 used with particular preference. Under acicular mineral fillers according to the invention is a mineral filler with strong pronounced needle-like character understood. Needlelike wollastonites are preferred. 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 mean particle size of the needle-shaped 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. These may be, for example, reinforcing materials based on carbon fibers and / or glass fibers.

In a preferred embodiment, the filler and / or reinforcing agent may be surface-modified, preferably with a primer or an adhesion promoter system, particularly preferably based on silane. In particular, when using glass fibers, polymer dispersions, film formers, branching agents and / or glass fiber processing aids may be used in addition to silanes.

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 fabric, as glass braid or as 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 incorporation into the polyester matrix range 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, the E glass fibers, R glass fibers, S glass fibers and ECR glass fibers being particularly preferred. The glass fibers are preferably provided with a size which preferably contains polyurethane as film former and aminosilane as adhesion promoter.

Particularly preferably used E glass fibers have the following chemical composition: SiO ₂ 50-56%; Al ₂ O ₃ 12-16%; CaO 16-25%; MgO ≤ 6%; B ₂ O ₃ 6-13%; F ≤ 0.7%; Na ₂ O 0.3-2%; K ₂ O 0.2-0.5%; Fe ₂ O ₃ 0.3%.

Particularly preferably used R glass fibers have the following chemical composition: SiO ₂ 50-65%; Al ₂ O ₃ 20-30%; CaO 6-16%; MgO 5-20%; Na ₂ O 0.3-0.5%; K ₂ O 0.05-0.2%; Fe ₂ O ₃ 0.2-0.4%, TiO ₂ 0.1-0.3%.

Particularly preferably used ECR glass fibers have the following chemical composition: SiO ₂ 57.5-58.5%; Al ₂ O ₃ 17.5-19.0%; CaO 11.5-13.0%; MgO 9.5-11.5.

The salts of diethylphosphinic acid used according to the invention as component C are known flameproofing agents for polymeric molding compositions.

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. In US 7,420,007 B2 described.

The salts of diethylphosphinic acid of component C used according to the invention may contain small amounts of salts of component D and of salts of component E, for example up to 10% by weight of component D, preferably 0.01 to 6% by weight, and in particular 0 , 2 to 2.5% by weight thereof, and up to 10% by weight of Component E, preferably 0.01 to 6% by weight, and more preferably 0.2 to 2.5% by weight thereof on the amount of components C, D and E.

The salts of ethylphosphonic acid used according to the invention as component E are likewise known, for example from, as additives to diethyl phosphates in flame retardants for polymeric molding compositions DE 10 2007 041 594 A1 ,

In a further preferred embodiment, components C, D, E and optionally F, H and / or I are in particulate form, the average particle size (d ₅₀ ) being 1 to 100 μm.

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 derived from components C, D, E, F, H and I differ.

The further additives are known per se as additives to polyester compositions and can be used alone or mixed 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, it is possible, in particular pulverulent components aufzutrommeln on the possibly by the drying process warm polymer granules.

Also, two or more of the components of the polyester compositions of the present invention may be combined by blending 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 polyester compositions according to the invention it is also possible to prepare granules which can subsequently be introduced into the polyester matrix.

For this purpose, two or more components of the polyester composition according to the invention with granulation aids and / or binders can be processed into granules in a suitable mixer or a granulating disc.

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 optionally breaking and classifying) the ingredients and drying (and optionally coating).

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 above-described flame-retardant polyester composition containing 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 molding, internal gas pressure injection molding, blow molding, film casting, calendering, laminating or coating at higher temperatures with the flameproofed 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 (RCD), circuit boards, potting compounds, power connectors, circuit breakers, lamp housings, LED housings, capacitor housings, bobbins and fans, protective contacts, plugs, in / on circuit 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 production of shaped articles 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, controllers, memories and sensors, in the form of large-area components, in particular of housing parts for control cabinets and in the form of agile 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.

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 butyl phosphinate and 0.5 mol% of aluminum ethyl phosphonate prepared according to Example 3 of US 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 butyl phosphinate and 0.8 mol% of aluminum ethyl phosphonate prepared according to Example 4 of US 7,420,007 B2

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

Aluminum salt of diethylphosphinic acid containing 0.5 mol% of aluminum ethyl butylphosphate and 0.05 mol% of aluminum ethyl phosphonate prepared by the process according to US 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 ethylphosphonate prepared by the process according to US 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 ethyl phosphonate 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 10 2011 120 218 A1

Flame retardant FM 8 (component H)

Melaminpolyphosphat prepared according to the example of WO 2000/002869 A1

Flame retardant FM 9 (component I):

Melamincyanuarat, Melapur ^® MC (BASF)

Production, processing and testing of flame-retardant polyester molding compounds

The additives were mixed with the polymer granules in the proportions shown in the tables and incorporated on a twin-screw extruder (Leistritz ZSE 27 HP-44D type) at temperatures of 240 to 280 ° C. 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 processed on an injection molding machine (type Arburg 320 C / KT) at mass temperatures of 260 to 280 ° C to test specimens and tested and classified by the UL 94 test (Underwriter Laboratories) on flame retardancy and classified. In addition to the classification, the afterburning time was also indicated.

The Comparative Tracking Index of the molded parts was determined according to the International Electrotechnical Commission Standard IEC-60112/3.

The Glow Wire Flammability Index (GWFI Index) was determined according to the IEC-60695-2-12 standard.

The X-ray spectra (X-ray powder diffractograms, "XRD values") of the polyamide compositions are measured using an X-ray powder diffractometer (X'Pert-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 listed in the examples listed in the table below. 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) Example no. 1 1a 1b 1c 2 3 4 5 V1 V2 V3 A: PBT 50 50 50 50 50 50 50 50 50 50 42 B: glass fibers EC10 30 30 30 30 30 30 30 30 30 30 30 C + D + E: FM 1 20 15 15 15 - - - - - - - C + D + E: FM 2 - - - - 20 - - 18 - - - C + D + E: FM 3 - - - - - 20 - - - - - C + D + E: FM 4 - - - - - - 20 - - - - C: FM 5 - - - - - - - - 20 - - C + E: FM 6 - - - - - - - - - 20 28 Q: FM 7 - - - - - - - 2 - - - H: FM 8 - 5 - 2 - - - - - - - I: FM 9 - - 5 3 - - - - - - - UL 94 0.4mm / [sec.] V-0/28 V-0/30 V-0/32 V-0/29 V-0/23 V-0/43 V-0/22 V-0/12 V-0/49 V-0/47 V-0/35 GWFI [° C] 960 960 960 960 960 960 960 960 960 960 960 CTI [Volt] 600 600 600 600 600 600 600 600 500 500 550 XRD 2θ [°] all samples showed reflections in the range of 9.099 ° to 9.442 °, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 °

The polyester compositions of Examples 1 to 5 according to the invention are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm, while having 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, a reduction in the afterburning time was achieved by increasing the concentration of components C and D compared to Example V2. However, this polyester composition still showed a longer afterburn time compared to Example 2 and a reduced CTI value.

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

The results of the tests with PET molding compounds are listed in the examples listed in the table below. All amounts are expressed as weight percent and are based on the polyester molding composition including the flame retardants and reinforcing agents. Table 2: PET GF 30 test results (6-10 according to the invention, V4-V6 comparisons) Example no. 6 7 8th 9 10 V4 V5 V6 A: PET 58 58 58 58 58 58 58 52 B: glass fibers EC10 30 30 30 30 30 30 30 30 C + D + E: FM 1 12 - - - - - - - C + D + E: FM 2 - 12 - - 10 - - - C + D + E: FM 3 - - 12 - - - - - C + D + E: FM 4 - - - 12 - - - - C: FM 5 - - - - - 12 - - C + E: FM 6 - - - - - - 12 18 Q: FM 7 - - - - 2 - - - UL 94 0.4mm / [sec.] V-0/26 V-0/21 V-0/40 V-0/20 V-0/11 V-0/46 V-0/44 V-0/32 GWFI [° C] 960 960 960 960 960 960 960 960 CTI [Volt] 600 600 600 600 600 500 500 550 XRD 2θ [°] all samples showed reflections in the range of 9.099 ° to 9.442 °, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 °

The polyester compositions of Examples 6 to 10 according to the invention are molding compositions which reach the UL 94 V-0 fire rating 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.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 2252258 A [0003]
• DE 2447727 A [0003]
• WO 2002/28953 A1 [0004]
• DE 19734437 A1 [0004]
• DE 19737727 A1 [0004]
• US Pat. No. 7420007 B2 [0005, 0093, 0119, 0120, 0121, 0122]
• DE 102007041594 A1 [0007, 0095]
• DE 102010049968 A1 [0008]
• WO 2012/045414 A1 [0027]
• DE 102005016195 A1 [0048]
• WO 2006/027340 A1 [0051]
• EP 1789475 B1 [0051]
• WO 2000/002869 A1 [0051, 0126]
• EP 1095030 B1 [0051]
• WO 9739053 A1 [0057]
• DE 1900270 A [0072]
• DE 19607635 A1 [0123]
• DE 102010018864 A1 [0124]
• DE 102011120218 A1 [0125]

Claims (20)

Flame retardant polyester compositions comprising - thermoplastic polyester as component A, - fillers and / or reinforcing agents as component B, - phosphinic acid salt of the formula (I) as component C.

wherein R ₁ and R _{2 are} ethyl, M is Al, Fe, TiO _p or Zn, m is 2 to 3, and p = (4 - m) / 2 - compound selected from the group of Al, Fe, TiO _p - or Zn-salts of Ethylbutylphosphinsäure, the dibutylphosphinic, the Ethylhexylphosphinsäure, the Butylhexylphosphinsäure and / or the Dihexylphosphinsäure as component D, and - phosphonic acid salt of formula (II) as component e,

wherein R _{3 is} ethyl, Met is Al, Fe, TiO _q or Zn, n is 2 to 3, and q = (4-n) / 2, wherein the powder X-ray diffraction pattern of the compositions contains the following reflections: in the angle range 2θ of 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 from 5.125 ° 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 of 9.117 ° to 9.317 ° and of 18.537 ° to 18.737 ° and / or in the angular range 2θ of 8.300 ° to 8.500 °. Flame retardant polyamide compositions according to Claim 1 , characterized in that its X-ray powder diffraction gram contains the following reflections: in the angular range 2θ from 9.099 ° to 9.442 °, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 °. Flame retardant polyester compositions according to at least one of Claims 1 to 2 , characterized in that M and Met are Al, m and n are 3 and that component D is an aluminum salt. Flame retardant polyester compositions according to at least one of Claims 1 to 3 , characterized in that - the proportion of component A 25 to 95 wt .-%, - the proportion of component B is from 1 to 45% by weight, the proportion of component C is from 1 to 35% by weight, the proportion of component D is from 0.01 to 3% by weight, and the proportion of component E 0.001 to 1% by weight, the percentages being based on the total amount of the polyester composition. Flame retardant polyester compositions according to Claim 4 , characterized in that - the proportion of component A 25 to 75 wt .-%, - the proportion of component B 20 to 40 wt .-%, - the proportion of component C 5 to 20 wt .-%, - the proportion from component D 0.05 to 1.5 wt .-%, and - the proportion of component E 0.01 to 0.6 wt .-%, is. 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. Flame retardant polyester compositions according to Claim 6 , characterized in that the inorganic phosphonate is a compound of formula (III)

wherein Me is Fe, TiO _r , 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) in an amount of 0.005 to 10% by weight, based on the total amount of the polyester composition. 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 greater than or equal to 20, preferably a melamine polyphosphate whose average degree of condensation is 20 to 200. Flame retardant polyester compositions according to at least one of Claims 1 to 8th , characterized in that they contain as component I melamine cyanurate. Flame retardant polyester compositions according to at least one of Claims 1 to 9 , characterized in that it has a Comparative Tracking Index measured according to the International Electrotechnical Commission Standard IEC-60112/3 of greater than or equal to 500 volts. Flame retardant polyester compositions according to at least one of Claims 1 to 10 , characterized in that they achieve a rating of V0 to UL-94 of 3.2 mm to 0.4 mm thickness. Flame retardant polyester compositions according to at least one of Claims 1 to 11 , 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. Flame retardant polyester compositions according to at least one of Claims 1 to 12 , characterized in that they have a glow wire ignition temperature according to IEC-60695-2-13 of at least 775 ° C at 0.75 - 3 mm thickness. 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. Flame retardant polyester compositions according to Claim 14 , characterized in that component A is a polybutylene terephthalate. Flame retardant polyester compositions according to at least one of Claims 1 to 16 , characterized in that glass fibers are used as component B. 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 microns. Flame retardant polyester compositions according to at least one of Claims 1 to 18 characterized in that it contains further additives as component G, the further additives being 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 that differ from components C, D, E, F, H and I. Use of the polyester compositions according to one of the Claims 1 to 19 for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector.