WO2019048311A1

WO2019048311A1 - Flame retardant combinations for polymer compositions and use thereof

Info

Publication number: WO2019048311A1
Application number: PCT/EP2018/073234
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: CN109467748A; TW201920633A; DE102017215777A1; CN112409638B; CN112409638A; EP3679093A1

Abstract

The invention relates to flame retardant combinations containing - phosphinic acid salt of the formula (I) as component A, wherein R1 and R2 represent ethyl, M represents Al, Fe, TiOp or Zn, m is 2 to < 4, 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 dihexylphosphinic acid as component B, phosphonic acid salt of formula (II) as component C, wherein R3 represents ethyl, Met represents Al, Fe, TiOq or Zn, n is 2 to < 4, and q = (4 - n) /2, wherein the melamine polyphosphate has an average degree of condensation from 2 - 200 as component D, wherein the x-ray diffractogram of the flame retardant combinations contain the following reflections: in the angle range 2θ from 9.099° to 9.442°, from 14.765° to 15.076°, 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°, from 14.765° to 15.076° and/or in the angle range 2θ from 9.117° to 9.317°, from 14.765° to 15.076° and from 18.537° to 18.737° and/or in the angle range 2θ from 8.300° to 8.500° and from 14.765° to 15.076°. The polymer compositions can be used to produce fibres, films and moulded bodies, in particular for electrical and electronic applications.

Description

Flammschutzmittelkonnbinationen for polymer compositions and their use

description

The present invention relates to novel acting combinations of

Flame retardants and polymer compositions containing these and their use. Due to their chemical composition, many plastics are easily combustible. In order to be able to achieve the high flame retardance requirements demanded by plastics processors and partly by the legislator, plastics generally have to be equipped with flame retardants. These are a variety of different flame retardants and

Flammschutzmittelsynergisten known and commercially available. Due to the more favorable fire side effects with respect to smoke gas density and flue gas composition, as well as for ecological reasons, non-halogenated flame retardant systems have been used for some time. Among the non-halogenated flame retardants, the salts of phosphinic acids (phosphinates) have proven particularly effective for thermoplastic polymers (DE 2 252 258 A and DE 2 447 727 A). Some derivatives of this flame retardant class are estimated, in particular because of their low negative impact on the mechanical properties of the thermoplastic molding compositions.

In addition, synergistic combinations of phosphinates with certain nitrogen-containing compounds, in particular with melamine derivatives, 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). Also, synergistic combinations of phosphinates with melamine cyanurate are known, which also act more effectively as flame retardants in many polymers than the phosphinates alone (DE 196 14 424 A1 and DE 103 31 889 A1). It is known from US Pat. No. 7,420,007 B2 that dialkylphosphinates containing a small amount of selected telomers are outstandingly suitable

Flame retardants are suitable for polymers, wherein the polymer is subject to the incorporation of the flame retardant in the polymer matrix only a small degradation.

In CN 104371 142 A corresponding to WO 2016/065971 A1

Flame retardant additives for polymers described in addition to Mg, Ca, Al, Zn or Fe salts of dialkylphosphinates up to 20 wt .-% of Mg, Ca, Al, Zn or Fe salts of alkyl phosphinates and optionally small amounts of Mg, Ca, Al, Zn or Fe salts of the phosphonic acid. These additives cause in polymer molding compositions a very good flame retardant and a reduction in the corrosion of extruder components in the processing of the molding compositions.

Finally, WO 2006/027340 A1 and WO 2000/002869 A1 disclose polyphosphate derivatives of 1,3,5-triazine compounds which can be used as

Flame retardants for polymer molding compounds are suitable.

The processing of plastics takes place predominantly in the melt or at elevated temperatures. The associated structural and

State changes hardly survive a plastic without changing its chemical structure. Crosslinking, oxidation,

Molecular weight changes and thus also changes in the physical and technical properties can be the result. In order to reduce the load on the polymers during processing, different additives are used, depending on the plastic.

Often different additives are used simultaneously, each of which performs a specific task. So become antioxidants and stabilizers used so that the plastic survives the processing without chemical damage and then for a long time against external influences such as heat,

UV light, weather and oxygen (air) is stable. In addition to improving the flow behavior, lubricants prevent too much sticking

Plastic melt on hot machine parts and act as a dispersant for pigments, fillers and reinforcing materials.

Through the use of flame retardants, the stability of

Plastics are processed during processing in the melt.

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 retardants affect the processing stability of plastics. For example, increased polymer degradation, crosslinking reactions, outgassing or discoloration may occur.

From WO 2014/135256 A1 polyamide molding compositions are known which have a significantly improved thermal stability, a reduced

Migration tendency and a balanced property profile with regard to electrical and mechanical properties.

From DE 10 2005 041 966 A1 are polyamide molding compositions with high

Glow wire resistance is known, which in addition to phosphinates nitrogen-containing

Synergists contain as flame retardants.

There is a lack of flame retardant combinations based on

selected phosphinates which achieve very good electrical values and excellent flame retardancy in polymer compositions.

It was therefore an object of the present invention, phosphinate-containing

Flammschutzmittelysteme with the property profile described above to provide, ie that the invention phosphinathaltigen Flammschutzmittelysteme good electrical values (GWFI, CTI) and effective flame retardancy characterized by the shortest possible afterburning. (UL-94, post-combustion time / time). The invention therefore relates to containing flame retardant combinations

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

wherein Ri and R2 are ethyl,

M is Al, Fe, TiOp or Zn,

m 2 to <4, preferably 2 or 3, means, 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 B

Phosphonic acid salt of the formula II as component C.

wherein R 3 is ethyl,

Met is Al, Fe, TiOq or Zn,

n is 2 to <4, preferably 2 or 3, and

q = (4-n) / 2, and

Melaminpolyphosphat with an average degree of condensation of 2 to 200 as component D, wherein the X-ray diffractogram of the flame retardant combinations contains the following reflexes:

in the angular range 2Θ from 9.099 ° to 9.442 °, from 14.765 ° to 15.076 °, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 ° and / or

in the angular range 2Θ from 5.1 12 ° to 5.312 °, from 6.097 ° to 6.297 °, of

10,082 ° to 10,282 °, from 10,350 ° to 10,550 °, from 12,308 ° to 12,508 ° and / or from 14,765 ° to 15,076 °

in the angular range 2Θ from 9.1 17 ° to 9.317 °, from 14.765 ° to 15.076 ° and from 18.537 ° to 18.737 ° and / or

in the angular range 2Θ from 8,300 ° to 8,500 ° and from 14,765 ° to 15,076 °.

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 flame retardant combinations according to the invention are those whose X-ray diffractogram contains the following reflections: in the angular range 2Θ of 9.099 ° to 9.442 °, of 14.765 ° to 15.076 °, of 18.619 ° to 18.984 ° and of 26.268 ° to 26.679 °.

In the flame retardants of the invention, the proportion of component A is usually 5 to 85 wt .-%, preferably 10 to 60 wt .-%. In the flame retardants of the invention, the proportion of component B is usually 0.01 to 10 wt .-%, preferably 0.1 to 2.5 wt .-%.

In the flame retardants of the invention, the proportion of component C is usually 0.01 to 10 wt .-%, preferably 0.1 to 2.5 wt .-%.

In the flame retardants of the invention, the proportion of component D is usually 5 to 50 wt .-%, preferably 10 to 30 wt .-%. The percentages for the proportions of components A to D relate to the total amount of the flame retardant combinations.

Preference is given to flame retardant combinations in which

the proportion of component A is 5 to 85% by weight,

the proportion of component B is from 0.01 to 10% by weight,

the proportion of component C 0.01 to 10 wt .-%, and

the proportion of component D is from 5 to 50% by weight,

is, wherein the percentages relate to the total amount of components A to D.

Particularly preferred are flame retardant combinations in which

the proportion of component A is from 10 to 60% by weight,

the proportion of component B is from 0.1 to 2.5% by weight,

the proportion of component C is from 0.1 to 2.5% by weight, and

the proportion of component D is from 10 to 30% by weight,

is.

Preferred salts of component A are those in which M ^{m +} Zn ²⁺ , Fe ³⁺ or in particular Al ³⁺ .

Preferably used salts of component B are zinc, iron or

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

Flame retardant combinations are particularly preferred in which M and Met are AI, m and n are 3 and in which the compounds of the

Component B are present as aluminum salts.

The salts used according to the invention as component A of

Diethylphosphoric acid are known flame retardants for polymeric molding compositions. Salts of diethylphosphinic acid with fractions of the phosphinic and phosphonic acid salts used according to the invention as components B and C 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 A may contain small amounts of salts of component B and of salts of component C, for example up to 10% by weight

Component B, preferably 0.01 to 6 wt.%, And in particular 0.2 to 2.5 wt.% Thereof, and up to 10 wt.% Of component C, preferably 0.01 to 6 wt. and in particular from 0.2 to 2.5% by weight thereof, based on the amount of components A, B and C. The salts of the invention used as component C

Ethylphosphonic acid are as additives to diethylphosphinates in

Flame retardants for polymeric molding compositions also known, for example from WO 2016/065971 A1. The use of the polyphosphate derivatives of melamine according to the invention as component D with a degree of condensation of greater than or equal to 20 as flame retardants is also 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 flame retardant combinations according to the invention comprise as component D 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 flame retardant combinations according to the invention contain as component D a melamine polyphosphate which has 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.

As component D, preference is given to using melamine 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).

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.

It is likewise preferred to use melamine polyphosphates whose mean condensation ridge (number average) is> 20 whose decomposition temperature is greater than 320 ° C., the molar ratio of 1,3,5-triazine compound to phosphorus being 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 a further preferred embodiment, components A, B, C and D are in particulate form, the average particle size (dso) being 1 to 100 μm. In a preferred embodiment, those described above include

Flammschutzmittelkombinationen inorganic Phosponat as further

Component E.

The use of the present invention used as component E.

inorganic phosphonates or salts of phosphorous acid

(Phosphites) are known as flame retardants. Thus WO discloses

2012/045414 A1 Flammschutzmittelkombinationen, in addition to Phosphinic acid salts also salts of phosphorous acid (= phosphites) included.

The inorganic phosphonate (component E) preferably corresponds to the general formula (IV) or (V)

[(HO) PO ₂ ] ² -p / 2 cat ^{P +} (IV)

[(HO) ₂ PO] - _P Kat ^{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 particular AI including the cation AI ( OH) or Al (OH) 2, and p is 1, 2, 3 or 4.

The inorganic phosphonate (component E) 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 (ΗΡO ³ ) ³ * χΑΐ 2θ ³ ^* ηΗ ₂ Ο where x = 2.27-1 and / or AI ₄ HePi6Oi8.

The inorganic phosphonate (component E) 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, ooMz (HPO ₃ ) y (OH) v x (H ₂ O) w (VII) where 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 0 to 4 means;

Al ₂ , oo (HPO 3) u (H ₂ PO 3) t x (H ₂ O) s (VIII), 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 to Al7 (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 E) are water-insoluble or sparingly soluble salts.

Particularly preferred inorganic phosphonates are aluminum, calcium and zinc salts. Most preferably, component E is a

Reaction product of phosphorous acid and an aluminum compound.

Particularly preferred components E 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, Dinathumphosphithydrat, 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, those described above include

Flame retardant combinations as component E a compound of formula (III)

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

o is 2 to <4, preferably 2 or 3, and

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

Component E is preferably in an amount of 0.01 to 10 wt .-%, in particular in an amount of 0.1 to 2.5 wt .-%, based on the

Total amount of components A to E, before.

The invention also relates to the use of the invention

Flame retardant combination for flameproofing of

thermoplastic and thermosetting polymers as well as with these

Flame retardant combinations flame retardant equipped

polymer compositions

Thermoplastic and / or thermosetting polymers (hereinafter component F) which contain the flame retardant combinations according to the invention and optionally fillers and reinforcing agents and / or other additives as defined below are referred to below as polymer compositions. In the thermoplastic polymers in which the inventive

Flame retardant combinations can be effectively used, it is amorphous thermoplastic polymers or semi-crystalline

thermoplastic polymers having a melting point of less than or equal to 290 ° C, preferably less than or equal to 280 ° C, and most preferably less than or equal to 250 ° C. Such polymers have already been described in detail in the literature and are known to the person skilled in the art.

Melting points of thermoplastic polymers used according to the invention are determined by means of differential scanning caloimetry (DSC) at a heating rate of 10 K / second.

The thermoplastic polymers used according to the invention include, for example Polymers of mono- and diolefins, for example polypropylene,

Polyisobutylene, polybutylene, polybutene-1, polyisoproprene or

Polybutadiene and polymers of cycloolefins such as

Cyclopentene or norbornene; also polyethylene, which

optionally can be crosslinked; z. High density polyethylene (HDPE), high density polyethylene (HDPE-HMW), high density polyethylene and ultrahigh molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene Density (LLDPE), branched low density polyethylene (VLDPE).

Mixtures of the aforementioned polymers, for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (eg.

PP / HDPE, PP / LDP) and blends of various types of polyethylene such as LDPE / HDPE.

Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as. B. ethylene-propylene copolymers, linear

Low density polyethylene (LLDPE) and blends thereof with low density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, etc. Further ethylene-alkyl acrylate copolymers, ethylene-vinyl acetate -Copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene; furthermore mixtures of such copolymers with one another and with those under 1. mentioned polymers, for. Polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers,

LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers, and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such. B. polyamides. Polystyrene, poly (p-methylstyrene), poly (alpha-methylstyrene). Copolyners of styrene or alpha-methylstyrene with dienes or

Acrylic derivatives, such as. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile methacrylate; Blends of high impact strength of styrene copolymers and another polymer, such as. A polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; as well as block copolymers of styrene such. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene. Graft copolymers of styrene or alpha-methylstyrene, such as. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and

Maleic anhydride or maleimide on polybutadiene, styrene and maleimide on polybutadiene; Styrene and alkyl acrylates or

Alkyl methacrylates on polybutadiene; Styrene and acrylonitrile on ethylene-propylene-diene terpolymers; Styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates; Styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof with those mentioned under 5.

Polymers, such as. B. known as so-called ABS, MBS, ASA or AES polymers. Halogen-containing polymers, such as. As polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene

(Halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, Epichlorhydrinhomo- and copolymers, especially polymers of halogen-containing

Vinyl compounds, such as. As polyvinyl chloride, polyvinylidene chloride, Polyvinyl fluoride, polyvinylidene fluoride; and their copolymers, such as

Vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate. Polymers derived from alpha-, beta-unsaturated acids and their

Derive derivatives such as polyacrylates and polymethacrylates, with butyl acrylate impact-modified polymethyl methacrylates, polyacrylamides and polyacrylonitriles.

Copolymers of the monomers mentioned under 8 with each other or with other unsaturated monomers, such as. For example, acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol,

Polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral,

Polyallyl phthalate, polyallylmelamine; and their copolymers with those under 1. olefins mentioned.

Polyacetals, such as polyoxymethylene, as well as those polyoxymethylenes, the comonomers, such as. B. contain ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

Polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.

Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12 / 12, polyamide 1 1, polyamide 12; Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers, or chemically bound or grafted elastomers; or with polyethers, such as. B. with polyethylene glycol, polypropylene glycol or

Polytetramethylene glycol. Further modified with EPDM or ABS

Polyamides or copolyamides; as well as during processing

condensed polyamides ("IM polyamide systems").

14. Polyureas, polyimides, polyamide-imides, polyether-imides, polyester-imides, polyhydantoins and polybenzimidazoles. 15. Polyesters derived from dicarboxylic acids and dialcohols and / or from

Derived hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexanterephthalat, and block polyether esters derived from polyethers having hydroxyl end groups; also with polycarbonates or MBS modified polyester.

16. polycarbonates and polyestercarbonates.

17. Polysulfones, polyethersulfones and polyether ketones.

18. mixtures (polyblends) of the aforementioned polymers, such as. PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate,

POM / Thermoplastic PUR, PC / Thermoplastic PUR, POM / Acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and Copolymers.

The thermosetting polymers in which the inventive

Flame retardant combinations can be used effectively, are also already described in detail in the literature and are known in the art.

The thermosetting polymers are preferably unsaturated polyester resins (UP resins) which are more saturated and more stable to copolyesters derived unsaturated dicarboxylic acids or their anhydrides with polyhydric alcohols, and vinyl compounds as crosslinking agents. UP resins are cured by free-radical polymerization with initiators (eg peroxides) and accelerators.

Preferred unsaturated dicarboxylic acids and derivatives for the preparation of the UP resins are maleic anhydride and fumaric acid.

Preferred saturated dicarboxylic acids are phthalic acid, isophthalic acid,

Terephthalic acid, tetrahydrophthalic acid, adipic acid.

Preferred diols are 1, 2 propanediol, ethylene glycol, diethylene glycol and

Neopentyl glycol, neopentyl glycol, ethoxylated or propoxylated bisphenol A. Preferred vinyl compound for crosslinking is styrene.

Preferred hardener systems are peroxides and metal co-initiators, e.g. B.

Hydroperoxides and cobalt octanoate and / or benzoyl peroxide and aromatic amines and / or UV light and photosensitizers, e.g. B. benzoin ethers.

Preferred hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permalate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-chlorobenzoyl peroxide and dicyclohexyl peroxide dicarbonate ,

Preferred metal co-initiators are cobalt, manganese, iron, vanadium, nickel or lead compounds.

Preferred aromatic amines are dimethylaniline, dimethyl-p-toluene, diethylaniline and phenyldiethanolamine.

Further preferred thermosetting polymers are epoxy resins which are aliphatic, cycloaliphatic, heterocyclic or aromatic Derive glycidyl compounds, for. B. of bisphenol A diglycidyl ethers and

Bisphenol-F-di-glycidyl ethers, which by means of conventional hardeners and / or

Accelerators are networked. Suitable glycidyl compounds are bisphenol A diglycidyl esters, bisphenol F diglycidyl esters, polyglycidyl esters of phenol formaldehyde resins and cresol formaldehyde resins, polyglycidyl esters of pthalthalene, isophthalic and

Terephthalic acid and trimellitic acid, N-glycidyl compounds of

aromatic amines and heterocyclic nitrogen bases and di- and

Polyglycidyl compounds of polyhydric aliphatic alcohols.

Suitable hardeners are aliphatic, cycloaliphatic, aromatic and

heterocyclic amines or polyamines such as ethylenediamine, diethylenetriamine triethylenetetramine, propan-1,3-diamine, hexamethylenediamine, aminoethylpiperazine, isophoronediamine, polyamidoamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenol sulfones, aniline-formaldehyde resins, 2,2,4-trimethylhexane-1,6 diamine, m-xylylenediamine, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 3-aminomethyl-3,55-trimethylcyclohexylamine

(Isophorone diamine), polyamidoamines, cyanoguanidine and dicyandiamide, as well as polybasic acids or their anhydrides such. Phthalic anhydride,

Maleic anhydride, tetrahydrophthalic anhydride,

Methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and

Methylhexahydrophthalsäureanhydrid and phenols such. Phenol novolac resin, cresol novolak resin, dicyclopentadiene-phenol adduct resin, phenol aralkyl resin, cresolar alkyl resin, naphthol aralkyl resin, biphenol-modified

Phenol aralkyl resin, phenoltrimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol kocondensate resin, naphthol cresol kocondensate resin, biphenol-modified phenol resin, and aminotriazine-modified phenol resin. The hardeners can be used alone or in combination

be used together.

Suitable catalysts or accelerators for the crosslinking in the

Polymerization are tertiary amines, benzyldimethylamine, N-alkylpyridines, imidazole, 1-Methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, metal salts of organic acids, Lewis acids and amine complex salts. The thermoset polymers are preferably those which are derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins. Also preferably, the thermosetting polymers are acrylic resins derived from substituted acrylic acid esters, such as. As of epoxy acrylates, urethane acrylates or polyester acrylates.

Further thermoset polymers which are preferably used are alkyd resins, polyester resins and acrylate resins which are blended with melamine resins, urea resins,

Isocyanates, isocyanurates, polyisocyanates or epoxy resins are crosslinked.

Further preferred thermoset polymers are polyurethanes or polyureas obtained by reacting polyisocyanates or ureas with polyols or polyamines.

Preferred polyols are alkene oxide adducts of ethylene glycol, 1, 2-propanediol, bisphenol A, trimethylolpropane, glycerol, pentaerythrol, sorbitol, sugar or degraded starch. It is also possible to use polyester polyols. These can be obtained by polycondensation of a polyalcohol such as ethylene glycol,

Diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, methyl pentanediol, 1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, diglycerol,

Dextrose and / or sorbitol with a dibasic acid such as oxalic acid, malonic acid, succinic acid, tartaric acid, adipic acid, sebacic acid,

Maleic acid, fumaric acid, phthalic acid and / or terephthalic acid. Suitable polyisocyanates are aromatic, alicyclic or aliphatic

Polyisocyanates having not less than two isocyanate groups and mixtures thereof. Preference is given to aromatic polyisocyanates, such as tolyl diisocyanate,

Methylene diphenyl diisocyanate, naphthylene diisocyanates, xylylene diisocyanate, tris-4-isocyanatophenyl) methane and polymethylene polyphenylene diisocyanates; alicyclic polyisocyanates such as methylene diphenyl diisocyanate, tolylene diisocyanate; aliphatic polyisocyanates, and hexamethylene diisocyanate, isophorone diisocyanate, Demeryldiisocyanat, 1, 1-methylenebis (4-isocyanatocyclohexane-4,4'-diisocyanato dicyclohexylmethane isomer mixture, 1, 4-cyclohexyl diisocyanate, Desmodur ^® - types (Bayer) and lysine diisocyanate and mixtures thereof.

Suitable polyisocyanates are also modified products obtained by reaction of polyisocyanate with polyol, urea, carbodiimide and / or biuret.

It is preferable that the invention as component F

used polymers to thermoplastic polymers, particularly preferably polystyrene HI, polyphenylene ethers, polyamides, polyesters, polycarbonates and blends or polymer blends of the type ABS (acrylonitrile-butadiene-styrene) or PC / ABS (polycarbonate / acrylonitrile-butadiene-styrene) or PPE / HIPS

(Polyphenylene ether / polystyrene Hl). Polystyrene HI is a polystyrene with increased impact strength.

Particularly preferred thermoplastic polymers used are polyamides, polyesters and PPE / HIPS blends.

The flame retardant combinations used according to the invention stabilize the polymers (component F) very well against thermal degradation. This is reflected in the change in the specific viscosity of thermoplastic polymers in compounding and shaping of the invention

Polymer compositions. The resulting thermal stress has a partial degradation of the polymer chains result, resulting in a reduction of average molecular weight and associated therewith expresses a reduction in the viscosity of a polymer solution.

Thus, for example, be typical values for the specific viscosity of polybutylene terephthalate, measured as 0.5% strength solution in phenol / dichlorobenzene (1: 1) at 25 ° C according to ISO 1628 with a capillary viscometer, about 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 1 10 and 129 cm ³ / g.

Preference is given to the said use the

Flame retardant components A to D or A to E in one

Total concentration of 1 to 40 wt .-%, in particular from 3 to 30 wt .-%, based on the polymer composition used.

In the polymer composition according to the invention, the proportion of component F is usually from 25 to 95% by weight, preferably from 25 to 75% by weight. In the polymer composition of the invention, the proportion of

Component A usually 1 to 35 wt .-%, preferably 5 to 20 wt .-%.

In the polymer composition of the invention, the proportion of component B is usually 0.01 to 3 wt .-%, preferably 0.05 to 1, 5 wt .-%.

In the polymer composition according to the invention, the proportion of component C is usually 0.001 to 1% by weight, preferably 0.01 to

0.6% by weight.

In the polymer composition of the invention, the proportion of component D is usually 1 to 25 wt .-%, preferably 4 to 10 wt .-%. In the polymer composition of the invention, the proportion of component E is usually 0 to 10 wt .-%, preferably 1 to 8 wt .-%.

The percentages for the proportions of components A to F relate to the total amount of the polymer composition.

Preference is given to flame-retardant according to the invention

Polymer 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

Polymer 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

Polymer compositions have a Glow Wire Flammability Index according to IEC-60695-2-12 greater than or equal to 960 ° C, in particular measured on molded parts of 0.75 - 3 mm thickness.

The particularly preferred polyamides of component F are generally homo- or copolyamides derived from (cyclo) aliphatic

Dicarboxylic acids or their polyamide-forming derivatives, such as their salts, and of (cyclo) aliphatic diamines or of (cyclo) aliphatic

Aminocarboxylic acids or their polyamide-forming derivatives, such as their salts derived.

The polyamides used according to the invention as component F can be prepared by various processes and synthesized from very different building blocks and, in a specific application, alone or in combination with processing aids, stabilizers or even polymers

Alloy partners, preferably elastomers, to materials equipped with specially selected property combinations. For the preparation of polyamides, a variety of procedures have become known, depending on the desired end product different

Monomerbausteine, various chain regulators for setting a desired molecular weight or monomers with reactive groups for later intended post-treatments can be used.

The technically relevant processes for the preparation of polyamides usually run via the polycondensation in the melt. In this context, the hydrolytic polymerization of lactams is understood as a polycondensation.

Polyamides to be used as component F are preferably partially crystalline aliphatic polyamides having a melting point of less than or equal to 290 ° C., preferably less than or equal to 280 ° C. These can be based on

aliphatic diamines and aliphatic dicarboxylic acids and / or

cycloaliphatic lactams with at least 5 ring members or corresponding amino acids.

Suitable starting materials are aliphatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and / or sebacic acid, aliphatic diamines, preferably tetramethylenediamine, hexamethylenediamine, 1, 9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bisaminomethylcyclohexane,

Aminocarboxylic acids, preferably aminocaproic acid or the corresponding lactams into consideration. Copolyamides of several of the monomers mentioned are included. Particularly preferred are caprolactams, most preferably ε-caprolactam is used.

The aliphatic homo- or copolyamides used according to the invention are preferably polyamide 12, polyamide 4, polyamide 4.6, polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.10, polyamide 6.12, polyamide 6.66, polyamide 7.7, polyamide 8.8, polyamide 9.9, Polyamide 10.9, polyamide 10.10, polyamide 1 1 or polyamide 12. These are known, for example, under the trade names ^Nylon® , Fa. DuPont, Ultramid ^®, Fa. BASF, Akulon ^® K122, Fa. DSM, Zytel ^® 7301,

Fa. DuPont; Durethan ^® B 29, Messrs. Bayer and Grillamid® ^®, Fa. Ems Chemie.

Also particularly suitable are PA6, PA6.6 and other aliphatic homo- or copolyamide-based compounds in which a

Polyamide group in the polymer chain 3 to 1 1 come methylene groups.

Flame retardant polyamide compositions in which one or more polyamides is selected as component G from the group consisting of PA 6, PA 6.6, PA 4.6, PA 12, PA 6.10 are preferably used.

Flame-retardant polyamide compositions in which polyamide 6.6 or polymer blends of polyamide 6.6 and polyamide 6 are used as component G are particularly preferred.

Very particular preference is given to flame retardants

Polyamide compositions in which component F consists of at least 75% by weight of polyamide 6,6 and at most 25% by weight of polyamide 6. The particularly preferred polyesters of component F 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 of (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. The term

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

The thermoplastic polyesters of component F are preferably selected from the group of polyalkylene esters of aromatic and / or aliphatic dicarboxylic acids or their dialkyl esters. Preferably used components F 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 the invention preferably used components F 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 F 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 F 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 F 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 (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 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 F 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 F according to the invention

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

The polymer compositions according to the invention may contain as component G further additives. Preferred components G 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,

Fillers, reinforcing agents and / or other flame retardants that differ from components A, B, C, D and E. 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 that have a four- or six-bond 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, very particular preference is given to 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 hydrogen phosphate, calcium hydrogen phosphate dihydrate, magnesium hydrogen phosphate, titanium hydrogen phosphate (TIHC) and / or zinc hydrogen phosphate

Preference is given to aluminum dihydrogen phosphate, magnesium dihydrogen phosphate, calcium dihydrogen phosphate, zinc dihydrogen phosphate, zinc dihydrogen phosphate dihydrate and / or aluminum dihydrogen phosphate.

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 mentioned and belong expressly to the usable components I. The proportion of component (s) G in the inventive

Polymer composition is usually up to 60 wt .-%, preferably between 10 and 50 wt .-%, based on the total amount of

Polymer composition. Particular preference is given to polymer compositions according to the invention which contain fillers and / or in particular reinforcing materials, preferably glass fibers. It can also be mixtures of two or more

different fillers and / or reinforcing materials are used. The proportion of fillers and / or reinforcing materials in the novel Polynnerzusannnensetzung is usually 1 to 45 wt .-%, preferably 20 to 40 wt .-%.

The further additives G are known per se as additives to Polynnerzusannnnensetzungen and can be used alone or in admixture or in the form of masterbatches. The abovementioned components A, B, C, D, F and, if appropriate, E and / or G can be used in a wide variety of combinations to form the invention

flame-retarded polymer composition are processed. It is thus possible to mix the components into the polymer melt already 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 polymer compositions of the present invention may be combined by mixing prior to incorporation into the polymer 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

Polymer compositions can also be prepared granules, which can then be introduced into the polymer matrix.

For this purpose, two or more components of the invention

Polymer 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 polymer composition according to the invention or two or more components thereof may be prepared by roll compaction in one embodiment.

The polymer 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 polymer composition according to the invention or two or more components thereof can be prepared in one embodiment by spray granulation.

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.

When using polymers or precursors thereof, which are processed into thermosetting polymer compositions, different manufacturing processes can be used. A process for the preparation of flame-retardant thermosetting compositions is characterized in that a thermosetting resin having a

Flammschutzmittelkombination invention comprising the above-defined components A, B, C, D and optionally E and optionally with other flame retardants, synergists, stabilizers, additives and fillers or

Reinforcing mixed and the resulting mixture at elevated pressure, for example at pressures of 3 to 10 bar and at moderate

Temperatures, for example at temperatures of 20 to 60 ° C, wet presses (cold pressing).

Another process for the preparation of flame-retardant thermoset compositions is characterized in that a thermosetting resin with a flame retardant combination according to the invention containing the above-defined components A, B, C, D and optionally F and optionally with other flame retardants, synergists, stabilizers, additives and Filling or

Reinforcing mixed and the resulting mixture at elevated pressure, for example at pressures of 3 to 10 bar and at elevated

Temperatures, for example at temperatures of 80 to 150 ° C, wet presses (hot or hot pressing).

The invention also relates to moldings produced from the above-described flame-retardant polymer composition comprising the components A, B, C, D and F and optionally the components E 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 polymer molding compositions by any desired molding processes, in particular by injection molding or extrusion.

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

Film casting, calendering, laminating or coating at higher temperatures with the flame-retardant polyamide molding compound. The molded parts are preferably injection-molded parts or extruded parts.

The flame-retardant polymer 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 polymer 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 polymer compositions according to the invention for the production 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 control 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 . Components used Flame retardant FM 1 (component A):

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

Flame retardant FM 2 (components A and B):

Aluminum salt of diethylphosphinic acid containing 0.9 mol% of aluminum ethylbutylphospinate prepared in analogy to Example 1 of DE 10 2014 001 222 A1

Flame retardant FM 3 (components A, B and C):

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

Flame retardant FM 4 (components A, B and C):

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

Flame retardant FM 5 (components A, B and C):

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 6 (components A, B and C):

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 7 (component E):

Aluminum salt of phosphonic acid prepared according to Example 1 of DE

10201 1 120218 A1 Flame retardant FM 8 (component D):

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

Flame retardant FM 9 (not according to the invention):

Melamine polyphosphate having an average degree of condensation of 18 prepared in analogy to WO 2000/002869 A1

Commercially available polymers (component F):

Polyamide 6.6 (PA 6.6-GV; melting range of 255-260 ° C): Ultramid ^® A27 (BASF)

Polyamide 6 (melting range of 217-222 ° C): Durethan ^® B29 (Lanxess)

Polyamide 6T / 6.6 (melting range 310-320 ° C): Vestamid ^® HAT plus 1000 (Evonik)

Polybutylene terephthalate (PBT): Ultradur ^® 4500 (BASF) glass fibers (component G):

Glass fibers PPG HP 3610 10μηη diameter, 4.5 mm length (PPG, NL),

2. Manufacture, processing and testing of flame retardants

thermoplastic molding compounds

2.1 Polyamide molding compounds

The flame retardant components were mixed in the proportions shown in the tables and on the side feeder of a twin-screw extruder (Leistritz ZSE 27 / 44D) at temperatures of 260 to 310 ° C in PA 6.6 and at 250 to 275 ° C in PA 6 resp at 310 to 330 ° C PA 6T / 6.6 incorporated. The glass fibers were over a second side feed added. 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 Allrounder) at mass temperatures of 250 to 320 ° C to test specimens processed and based on the UL 94 test

(Underwriter Laboratories) tested for 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-601 12/3.

The Glow Wire Flammability Index (GWFI Index) has been determined in accordance with standard IEC-60695-2-12.

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

Polymer compositions are measured with 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.

2.2 Polyester molding compounds

The procedure was as in the polyamide molding compositions. Only this happened

Incorporation of the flame retardant components in the polymer in the twin-screw extruder at temperatures of 240 to 280 ° C.

The processing of the dried molding compounds to test specimens on the

Injection molding machine was carried out at melt temperatures of 260 to 280 ° C. Examples 1 -5 and Comparative Examples V1-V5 with PA 6.6

The results of the experiments with PA 6.6 molding compositions are listed in the examples listed in the table below. All amounts are given as wt .-% and are based on the polyamide molding composition

including flame retardants and reinforcing agents.

Table 1: PA 6.6 GF 30 test results (1 -5 according to the invention; V1 -V5 comparisons; n.b. = not determined)

The polyamide 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 and at the same time have CTI 500 volts and GWFI 960 ° C. The addition of component E in Example 5 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time.

The omission of components B and C in Comparative Example V1 resulted in a prolonged afterburn time as compared to Example 2. The omission of Component C in Comparative Example V2 resulted in a prolonged afterburn time as compared to Example 2.

Replacing component D with a lower component

Condensation in Comparative Example V3 had the consequence that the

Polyamide strand in the production foamed and no measurements

could be made.

The omission of component D in Comparative Example V4 resulted in a prolongation of the afterburn time compared to Example 2.

In Comparative Example C5, a shortening of the afterburning time was achieved by increasing the concentration of components A, B and C compared to Example V4. However, this polyamide composition still showed a prolonged afterburn time compared to Example 2.

Examples 6-10 and Comparative Examples V6-V10 with PA 6.6 / PA6

The results of the experiments with PA 6 / PA6.6 molding compounds are listed in the examples listed in the table below. All amounts are expressed as weight percent and refer to the polyamide molding compound including the flame retardants and reinforcing agents. Table 2: PA 6 / PA 6.6 GF 30 test results (6-10 according to the invention; V6-V10 comparisons; nb = not determined)

The polyamide compositions of Examples 6 to 10 according to the invention are, for example, at the same time having CTI 500 volts and GWFI 960 ° C., which reach the UL 94 V-0 fire rating at 0.4 mm. The addition of component E in

Example 10 leads to a further improvement of the flame retardant

expressed by a reduced afterburning time.

The omission of components B and C in Comparative Example V6 resulted in a prolonged afterburn time as compared to Example 7. The omission of Component C in Comparative Example V7 resulted in a prolonged afterburn time as compared to Example 7.

Replacing component D with a lower component

Condensation in Comparative Example V8 had the consequence that the

Polyamide strand in the production foamed and no measurements

could be made.

The omission of component D in Comparative Example V9 resulted in an extension of the afterburn time compared to Example 7.

In Comparative Example C10 was by increasing the concentration of

Although components A, B and C achieved a shortening of the afterburning time in comparison with example V9. However, this polyamide composition still exhibited an extended afterburn time compared to Example 7.

Examples 1 1 -15 and Comparative Examples V1 1 -V15 with PBT

The results of the experiments with PBT molding compositions are listed in the examples listed in the table below. All amounts are by weight

and refer to the polyester molding composition including the flame retardants and reinforcing agents. Table 3: PBT GF 30 experimental results (1 1 -15 according to the invention, V1 1 -V 15 comparisons, nb = not determined)

The polyester compositions according to the invention of Examples 1 1 to 15 are molding compositions which reach the fire class UL 94 V-0 at 0.4 mm and at the same time have CTI 500 volts and GWFI 960 ° C. The addition of component E in Example 15 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time.

The omission of components B and C in Comparative Example V1 1 resulted in a prolonged afterburn time compared to Example 12. The omission of Component C in Comparative Example V12 resulted in a prolonged afterburn time compared to Example 12.

Replacing component D with a lower component

Condensation in Comparative Example V13 had the consequence that the

Polyester strand foamed during manufacture and no measurements

could be made.

The omission of component D in Comparative Example V14 resulted in an extension of the afterburn time compared to Example 12.

In Comparative Example V15, by increasing the concentration of components A, B and C compared to Example V14, although a shortening of the afterburning time. However, this polyester composition still exhibited an extended afterburn time compared to Example 12.

Comparative Examples V16-V18 with PA 6T / 6.6

The results of the experiments with PA 6T / 6.6 molding compositions are listed in the examples listed in the table below. All amounts are expressed as weight percent and refer to the polyamide molding compound including the flame retardants and reinforcing agents. Table 4: PA 6T / 6.6 GF 30 test results (nb. = Not determined)

Test specimens could not be produced from any of the PA molding wettings of Comparative Examples V16-V18, since the PA molding nosings proved to be unprocessable. The polyamide strands foamed during production and no test specimens suitable for the measurements could be produced.

Claims

claims

Flammschutzmittelkombinationen containing

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

[] M - *

m

wherein Ri and R2 are ethyl,

M is Al, Fe, TiOp or Zn,

m 2 to <4 means, and

p = (4 - m) / 2

Ethylhexylphosphinsäure, the Butylhexylphosphinsäure and / or the

Dihexylphosphinic acid as component B

Phosphonic acid salt of the formula (II) as component C.

wherein R 3 is ethyl,

Met is Al, Fe, TiOq or Zn,

n 2 to <4 means, and

q = (4-n) / 2, and

Melaminpolyphosphat with an average degree of condensation of 2 to 200 as component D, wherein

the X-ray diffractogram of the flame retardant combinations contains the following reflexes:

in the angular range 2Θ from 9.099 ° to 9.442 °, from 14.765 ° to 15.076 °, 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 °, from 12.308 ° to 12.508 °, from 14.765 ° to 15.076 ° and / or

2. Flammschutzmittelkombinationen according to claim 1, characterized in that the Rontgendiffraktrogramm contains the following reflexes: in the angular range 2Θ of 9.099 ° to 9.442 °, from 10.802 to 1 1, 004, from 18.619 ° to 18.984 ° and from 26.268 ° to 26.679 °.

3. Flammschutzmittelkombinationen according to at least one of claims 1 to 2, characterized in that M and Met AI, m and n are 3 and that component B is an aluminum salt.

4. Flammschutzmittelkombinationen according to at least one of claims 1 to 3, characterized in that

the proportion of component A is from 5 to 85% by weight,

the proportion of component B is from 0.01 to 10% by weight,

the proportion of component C 0.01 to 10 wt .-%, and

the proportion of component D is from 5 to 50% by weight,

is, wherein the percentages relate to the total amount of components A to D.

5. Flammschutzmittelkombinationen according to claim 4, characterized in that

the proportion of component A is from 10 to 60% by weight,

the proportion of component B is from 0.1 to 2.5% by weight,

the proportion of component C is from 0.1 to 2.5% by weight, and

the proportion of component D is from 10 to 30% by weight,

is.

6. Flammschutzmittelkonnbinationen according to at least one of claims 1 to 5, characterized in that components A, B, C and D are in particulate form, wherein the average particle size dso of these components is 1 to 100 μιτι.

7. Flammschutzmittelkombinationen according to at least one of claims 1 to 6, characterized in that the average degree of condensation of Melaminpolyphosphats is 2 to 100.

8. Flammschutzmittelkombinationen according to at least one of claims 1 to 7, characterized in that the melamine polyphosphate a

Decomposition temperature greater than or equal to 320 ° C.

9. Flammschutzmittelkombinationen according to at least one of claims 1 to 8, characterized in that these inorganic phosphonate as further

Component E included.

10. Flammschutzmittelkombinationen according to claim 9, characterized in that the inorganic phosphonate is a compound of formula (III)

wherein

Me Fe, TiOr, Zn or in particular AI,

o is 2 to <4, preferably 2 or 3, and

r = (4-o) / 2,

wherein the compound of formula III in an amount of 0.01 to 10 wt .-%, in particular in an amount of 0.1 to 2.5 wt .-%, based on the

Total amount of components A to E, is present.

1 1. Polymer compositions comprising thermoplastic and / or thermosetting polymers as component F and a flame retardant combination containing the components A, B, C, D and optionally E according to any one of claims 1 to 10, wherein the thermoplastic polymers are amorphous

thermoplastic polymers or (partially) crystalline thermoplastic polymers having a melting point of less than or equal to 290 ° C.

12. Polymer compositions according to claim 1 1, characterized in that they have a Comparative Tracking Index, measured according to the International Electrotechnical Commission Standard IEC-601 12/3, of greater than or equal to 500 volts.

13 polymer compositions according to at least one of claims 1 1 to

12, characterized in that they reach a rating of V0 to UL-94, in particular measured on moldings of 3.2 mm to 0.4 mm thickness.

14. Polymer compositions according to at least one of claims 1 to 1

13, characterized in that they have a Glow Wire Flammability Index according to IEC-60695-2-12 of greater than or equal to 960 ° C, in particular measured on moldings of 0.75 - 3 mm thickness.

15. Polymer compositions according to at least one of claims 1 to 1

14, characterized in that component F is a partially crystalline aliphatic polyamide having a melting point of less than or equal to 290 ° C, preferably less than or equal to 280 ° C.

16. Polymer compositions according to claim 15, characterized in that component F is selected from the group consisting of PA 6, PA 6.6 and other aliphatic homo- or copolyamide-based compounds in which come to a polyamide group in the polymer chain 3 to 1 1 methylene groups, in particular is selected from the group consisting of PA 6, PA 6.6, PA 4.6, PA 12 and PA 6.10.

17. Polymer compositions according to claim 11, characterized in that component F is a polyalkylene terephthalate, preferably a

Polyethylene terephthalate or a polybutylene terephthalate.

18. Polymer compositions according to at least one of claims 1 to 17, characterized in that

the proportion of component A 1 to 35 wt .-%,

the proportion of component B is from 0.01 to 3% by weight,

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

the proportion of component D 1 to 25 wt .-%,

the proportion of component E 0 to 10 wt .-%, and

the proportion of component F 25 to 95% by weight

percentages are based on the total amount of

Refer to polymer composition.

19. Polymer compositions according to claim 18, characterized in that

the proportion of component A is 5 to 20% by weight,

the proportion of component B is from 0.05 to 1, 5% by weight,

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

the proportion of component D is 4 to 10% by weight,

the proportion of component E 1 to 8 wt .-%, and

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

is.

20. Polymer compositions according to at least one of claims 1 to 1

19, 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, fillers, reinforcing agents and / or other flame retardants which differ from components A, B, C, D and E.

21. Polymer compositions according to at least one of Claims 1 to

20, characterized in that they contain glass fibers.

22. Use of Polynnerzusannnensein according to any one of claims 1 1 to 21 for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector.