EP3679095A1

EP3679095A1 - Synergistic flame retardant combinations for polymer compositions and use thereof

Info

Publication number: EP3679095A1
Application number: EP18762272.5A
Authority: EP
Inventors: Harald Bauer; Sebastian HÖROLD; Martin Sicken
Original assignee: Clariant Plastics and Coatings Ltd
Current assignee: Clariant International Ltd
Priority date: 2017-09-07
Filing date: 2018-08-29
Publication date: 2020-07-15
Also published as: CN109467747A; WO2019048313A1; CN109467747B; DE102017215780A1; TW201912771A

Abstract

The invention relates to flame retardant combinations containing: phosphinic acid salt of formula (I) as component A in which R1 and R2 represent ethyl, M represents Al, Fe, TiOp or Zn, m represents 2 to 3, and p = (4 - m) / 2; a compound selected from the group consisting of Al-, Fe-, TiOp- or Zn salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid and/or dihexylphosphinic acid as component B; phosphonic acid salt of formula (II) as component C in which R3 represents ethyl, Met represents Al, Fe, TiOq or Zn, n represents 2 to 3, and q = (4 - n) / 2; melamine polyphosphate having an average degree of condensation between 2 to 200 as component D; and melamine cyanurate as component E. The polymer compositions can be used to produce fibres, films, and moulded bodies, in particular for applications in the field of electronics.

Description

Synergistic flame retardant combinations for polymer compositions and their use

description

The present invention relates to novel synergistic combinations of flame retardants and polymer compositions containing these and their use. Flammable plastics generally have to be equipped with flame retardants in order to achieve the high flame retardance requirements demanded by plastics processors and in part by the legislature. Preference - also for ecological reasons - are non-halogenated

Flame retardant systems used that form little or no flue gases.

Among these flame retardants, the salts of phosphinic acids (phosphinates) have proven to be particularly effective for thermoplastic polymers (DE 2 252 258 A and DE 2 447 727 A).

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

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

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

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

X-ray reflections of high-temperature modifications of aluminum salts of phosphinic acids are known from WO 98/03515 A1. These phosphinic acid salts are produced at high temperature. From WO 2014/135256 A1 polyamide molding compositions are known which have a significantly improved thermal stability, a reduced tendency to migrate and good 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.

However, phosphinate-containing flame retardant combinations that impart all the required properties simultaneously to polymer compositions, such as good electrical properties and effective flame retardancy, have hitherto been lacking.

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

To provide flame retardant systems that impart all the aforementioned properties simultaneously to the polymers equipped therewith, in particular good electrical values (GWFI, GWIT, CTI) and an effective flame retardancy, characterized by the shortest possible afterburning times (UL94, time).

The invention provides flame retardant combinations containing

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

wherein Ri and R2 are ethyl,

M is Al, Fe, TiOp or Zn,

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

p = (4 - m) / 2

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

Ethylhexylphosphinsäure, the Butylhexylphosphinsäure and / or the Dihexylphosphinsäure as component 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 3, preferably 2 or 3, and

q = (4-n) / 2

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

Melamine cyanurate as component E.

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 from 5 to 50% by weight, preferably from 10 to 30% by weight. In the flame retardants of the invention, the proportion of component E is usually 5 to 50 wt .-%, preferably 10 to 30 wt .-%.

In this case, the percentages for the proportions of components A to E refer to the total amount of Flamschutzmittelkombinationen.

Preference is given to flame retardant combinations in which

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 is from 0.01 to 10% by weight,

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

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

is, wherein the percentages are based on the total amount of components A to E. 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,

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

the proportion of component E is 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⁺ .

Very particular preference is given to flame retardant combinations in which M and Met are Al, m and n are 3 and in which the compounds of 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 0.2 to 2.5 wt .-% thereof based on the amount of components A, B and C.

The salts used according to the invention as component C of

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. In this Document is also disclosed 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.

The melamine cyanurate used according to the invention as component E is likewise known as synergist in conjunction with diethyl phosphates in flame retardants for polymeric molding compositions, for example from WO 97/39053 A1). In a further preferred embodiment, components A, B, C, D and E 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 F. The use of the invention used as component F.

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 F) preferably corresponds to the general formulas (IV) or (V) [(HO) PO ₂ ] ² -p / 2 cat ^{P +} (IV)

[(HO) ₂ PO] - _P Kat ^{P +} (V) 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 F) is preferably aluminum phosphite [Al (H2PO3) 3], secondary aluminum phosphite [Al2 (H PO3) 3], basic aluminum phosphite [Al (OH) (H2PO3) 2 ^* 2aq],

Aluminum phosphite tetrahydrate [Al 2 (H PO 3) 3 ^* 4aq], aluminum phosphonate, Al7 (HPO 3) 9 (OH) 6 (1, 6-hexanediamine) i, 5 ^* 12H ₂ O, ΑΙ ₂ (ΗΡθ3) ³ * ^* χΑΐ2θ3 ηΗ ₂ Ο with x = 2.27 to 1 and / or AI ₄ HePi6Oi8 ,

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) wherein q is 0 to 4, Al 2, ooMz (HPO 3) y (OH) v X (H ₂ O) w (VII) wherein M is alkali metal cations, e.g. 0.01 to 1.5, and y is 2.63 to 3.5 and v is 0 to 2 and w is 0 to 4;

Al ₂ , oo (HPO 3) u (H ₂ PO 3) t x (H ₂ O) s (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 (HPOs) 3] to give basic aluminum phosphite [Al (OH) (H ₂ PO 3) ₂ ^* 2aq]

Aluminum phosphite tetrahydrate [Al ₂ (HPO 3) 3 ^* 4aq] to give aluminum phosphonate, Al ₇ (HPO ₃ ) 9 (OH) 6 (1,6-hexanediamine) i, ₅ ^* 12H ₂ O, Al ₂ (HPO ₃ ) ^{3 *} xAl ₂ O ₃ ^* nH ₂ O where x = 2.27 - 1 and / or AUHePieOis.

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

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

Particularly preferably, component F is a

Reaction product of phosphorous acid and an aluminum compound. Particularly preferred components F are aluminum phosphites with the

CAS numbers 15099-32-8, 1 19103-85-4, 220689-59-8, 56287-23-1, 156024-71-4, 71449-76-8 and 15099-32-8. The preparation of the preferably used aluminum phosphites is carried out by reacting an aluminum source with a phosphorus source and optionally a template in a solvent at 20-200 ° C for a period of up to 4 days. The aluminum source and the phosphorus source are mixed for 1 to 4 hours, heated under hydrothermal conditions or at reflux, filtered off, washed and z. B. at 1 10 ° C dried.

Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum hydroxide (eg pseudoboehmite). Preferred sources of phosphorus are phosphorous acid, (acidic)

Ammonium phosphite, alkali phosphites or alkaline earth phosphites.

Preferred 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. B. aluminum diethylphosphinate together with aluminum phosphite or zinc diethylphosphinate together with zinc phosphite.

In a preferred embodiment, those described above include

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

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

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

r = (4-o) / 2.

Preferred compounds of the formula (III) are those in which Me ^{0+ denotes} Zn ^{2 '} Fe ³⁺ or in particular Al ³⁺ .

Component F 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 F, 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 G) containing the inventive flame retardant combinations and optionally fillers and reinforcing agents and / or other additives, as below , are hereinafter referred to 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

1 . Polymers of mono- and diolefins, for example polypropylene,

Polyisobutylene, polybutylene, polybutene-1, polyisoproprene or polybutadiene and polymers of cycloolefins such as cyclopentene or norbornene; furthermore polyethylene, which may optionally be crosslinked; z. High density polyethylene (HDPE), high density polyethylene (HDPE-HMW), high density polyethylene and ultra high density polyethylene

Molecular weight (HDPE-UHMW), medium density polyethylene (MDPE),

Low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (VLDPE).

2. 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). Copolymers 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, Acrylnitnl 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 derivatives, such as polyacrylates and polymethacrylates, 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, polyallynine tannin; 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 bonded 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"). Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles. Polyesters which are derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, and block polyether esters derived from hydroxyl-terminated polyethers; also with polycarbonates or MBS modified polyester.

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. 19. Thermoplastic elastomers (TPE), such as block copolymers based on styrene (styrene-butadiene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers), block copolymers based on thermoplastic Polyester elastomers, ether-based and / or ester-based block copolymers consisting of alternating blocks of diisocyanates and short-chain diols and of diisocyanates and long-chain diols, polyether block amides, co-polyamides and / or polyether amides.

Preferred TPEs are elastomer blends, such as thermoplastic olefins containing polypropylene, polyethylene block copolymers; Polypropylene, ethylene-propylene rubber, ethylene-octene copolymers, styrene-ethylene-butadiene-styrene,

Polyolefin-ethylene-propylene-dienes, polyolefin-ethylene-vinyl acetate copolymers and / or polyolefin-polyarylene ethers. Preferred TPE are thermoplastic vulcanizates, eg. B. ethylene-propylene-diene rubber particles in a matrix of polypropylene.

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, propane-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-3,5,5-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 to

Acrylic resins derived from substituted acrylic acid esters, such as. As of epoxy acrylates, urethane acrylates or polyester acrylates.

Further preferred thermoset polymers are alkyd resins,

Polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins. 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 G

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 G) very well against thermal degradation. This is evidenced by the change in the specific viscosity of thermoplastic polymers during compounding and shaping of the polymer compositions according to the invention. 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 E or A to F 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 of the present invention, the content of the component G is usually 25 to 95% by weight, preferably 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 according to the invention, the proportion of component E is usually 1 to 25 wt .-%, preferably 4 to 10 wt .-%.

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

The percentages for the proportions of components A to G are based on 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 G 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 according to the invention used as component A can be prepared by various methods and synthesized from very different building blocks and in a specific application alone or in combination with processing aids, stabilizers or polymeric alloying 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 G 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 11 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 G is at least 75

% By weight of polyamide 6.6 and at most 25% by weight of polyamide 6.

The particularly preferred polyesters of component G 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 G are preferably selected from the group of polyalkylene esters of aromatic and / or aliphatic dicarboxylic acids or their dialkyl esters. Preferably used components G 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 G 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 G 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 G 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 G are polyalkylene terephthalates which are prepared solely from terephthalic acid and its reactive derivatives (eg

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

Polybutylene terephthalate) and mixtures of these polyalkylene terephthalates.

Preferred polybutylene terephthalates contain at least 80 mol%,

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

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

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

Preferably used as component G 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 G 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 H further additives. Preferred components H in the sense of 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, E and F.

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.

Particularly preferred are calcium pyrophosphate,

Calcium dihydrogen pyrophosphate, magnesium pyrophosphate zinc pyrophosphate and / or aluminum pyrophosphate.

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

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

DE-A-102007036465 and EP-A-31331 12 and are expressly among the usable components I. The proportion of component (s) H 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.

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

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

The filler and / or reinforcing material may in a preferred

Be surface-modified embodiment, preferably with a

Adhesive or a primer system, particularly preferably on

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

Fiber processing aids are used. The glass fibers preferably used according to the invention may be short glass fibers and / or long glass fibers. As a short or

Long glass fibers can be used cut fibers. 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 a glass fabric, as a glass braid or as a glass mat.

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

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

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

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

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

Glass fibers can be used as continuous fibers or as cut or ground glass fibers. The glass fibers themselves, regardless of their cross-sectional area and their length, can be selected, for example, from the group of E-glass fibers, A-glass fibers, C-glass fibers, D-glass fibers, M-glass fibers, S-glass fibers,

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

Composition on: S1O2 50-56%; AI2O3 12-16%; CaO 16-25%; MgO <6%; B2O3 6-13%; F <0.7%; Na ₂ O 0.3-2%; K2O 0.2-0.5%; Fe ₂ Os 0.3%.

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

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

The proportion of fillers and / or reinforcing materials in the polymer composition according to the invention is usually 1 to 45 wt .-%, preferably 20 to 40 wt .-%.

The further additives H are known per se as additives to polymer compositions and can be used alone or mixed or in the form of masterbatches. The abovementioned components A, B, C, D, E, G and, if appropriate, F and / or H can be processed in a wide variety of combinations with the flameproofed polymer composition according to the invention. 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. There is also the Possibility, in particular powdery 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

In one embodiment, components thereof may 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 composition according to the invention is preferably in granular form, eg. B. as an extrudate or as a compound before. The granules preferably have cylindrical shape with circular, elliptical or irregular

Base, spherical shape, cushion 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, E and optionally F 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).

A further process for the preparation of flame-retardant thermosetting compositions is characterized in that a thermosetting resin with a flame retardant combination according to the invention comprising the above-defined components A, B, C, D, E and optionally F 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 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, E and G and optionally the components F and / or H. The moldings 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 include injection molding, pressing, foam injection, 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 circuit boards, charging cables for mobile phones, engine covers or textile coatings.

The invention also preferably relates to the use of the flame-retardant Polynnerzusannnnensetzungen invention for the production of molded articles in the form of components for the electrical / electronics sector, in particular for parts of printed circuit boards, housings, foils, cables, 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 . Used components

Flame retardant FM 1 (component A):

Aluminum salt of diethylphosphinic acid 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 butylphosphorate 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 ethylbutyl phosphinate 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 ethylbutyl phosphinate 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 ethylbutyl phosphinate and 5 mol% of aluminum ethyl phosphonate prepared by the process according to US Pat. No. 7,420,007 B2 flame retardant FM 7 (component F):

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

10201 1 120218 A1

Flame retardant FM 8 (component 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

Flame retardant FM 10 (component E):

Melamincyanuarat, Melapur ^® MC (BASF) Commercially available polymers (component G):

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 H):

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 (GWIT Index) has been determined in accordance with standard IEC-60695-2-12.

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 the incorporation of the flame retardant into 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-V12 with PA 6.6 The results of the tests 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 -V12 comparisons; n.b. = not determined)

The polyamide compositions according to the invention of Examples 1 to 5 are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm and at the same time CTI 600 volts, GWFI 960 ° C and GWIT 800 ° C and 825 ° C. The addition of component F in Example 5 leads to a repeated

Improvement of flame retardance expressed by a reduced

After-burn time and to an improvement of the GWIT value.

The omission of component E in Comparative Examples V1 to V5 resulted in a reduction of the flame retardance expressed by an enlarged one

Afterburn time. The GWFI values corresponded to the values for the moldings containing component E. The CTI values decreased in comparison to the moldings containing component E.

The omission of components B and C in Comparative Examples V6 and V7 resulted in reduced CTI and GWIT values in addition to an extended afterburn time compared to Examples 1-4.

The omission of component C in Comparative Examples V8 and V9, in addition to a prolonged afterburn time compared to the examples 1 -4 also resulted in reduced CTI and GWIT values.

Replacing component D with a lower component

Condensation in Comparative Example V10 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 V1 1 resulted in reduced GWIT and GWFI values in addition to a deterioration of the fire protection class compared to Example 2.

In Comparative Example C12, by increasing the concentration of components A, B and C in comparison to Example V1 1, although an improvement in the

Fire protection class achieved. However, this polyamide composition showed still a lower fire protection class compared to Example 2 and reduced GWIT and GWFI values.

Examples 6-10 and Comparative Examples V13-V23 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 (7-10 according to the invention; V13-V23 comparisons; n.b. = not determined)

The polyamide compositions according to the invention of Examples 7 to 10 are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm, while having CTI 600 volts, GWFI 960 ° C and GWIT 800 ° C and 825 ° C, respectively. The addition of component F in Example 10 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time and to an improvement of the GWIT value.

The omission of component E in Comparative Examples V13 to V16 resulted in a reduction of the flame retardance expressed by an enlarged one

The omission of components B and C in Comparative Examples V17 and V18 resulted in reduced CTI and GWIT values in addition to an extended afterburn time as compared to Examples 7-10.

The omission of Component C in Comparative Examples V19 and V20, in addition to a prolonged afterburn time, also resulted in decreased CTI and GWIT values as compared to Examples 7-10.

Replacing component D with a lower component

Condensation in Comparative Example V21 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 V22 resulted in reduced GWIT and GWFI values in addition to a deterioration of the fire protection class compared to Example 8.

In Comparative Example C23, by increasing the concentration of components A, B and C compared to Example V22, although an improvement of the

Fire protection class achieved. However, this polyamide composition showed still a lower fire protection class compared to Example 8 and reduced GWIT and GWFI values.

Examples 13-17 and Comparative Examples V24-V35 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; V24-V35 comparisons; n.b. = not determined)

The polyester compositions according to the invention of Examples 1 1 to 15 are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm and at the same time CTI 600 volts, GWFI 960 ° C and GWIT 775 ° C and 800 ° C. The addition of component F in Example 15 leads to a repeated

Improvement of flame retardance expressed by a reduced

After-burn time and to an improvement of the GWIT value.

The omission of component E in Comparative Examples V24 to V28 resulted in a reduction of the flame retardance expressed by an enlarged one

The omission of components B and C in Comparative Examples V29 and V30 resulted in reduced CTI and GWIT values in addition to an extended afterburn time as compared to Examples 11-14.

The omission of Component C in Comparative Examples V31 and V32, in addition to a prolonged afterburn time, also resulted in decreased CTI and GWIT values compared to Examples 11-14.

Replacing component D with a lower component

Condensation in Comparative Example V33 had the consequence that the

Polyester strand foamed during manufacture and no measurements

could be made.

The omission of component D in Comparative Example C34 resulted in reduced GWIT and GWFI values in addition to a deterioration of the fire protection class compared to Example 12.

In Comparative Example C35, by increasing the concentration of components A, B and C compared to Example V34, although an improvement in the

Fire protection class achieved. However, this polyester composition showed still a lower fire protection rating compared to Example 12 and reduced GWIT and GWFI values.

Comparative Examples V36-V41 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 (n.b. = not determined)

From none of the PA molding compositions of Comparative Examples V36-V41 could

Test specimens are produced because the PA molding compounds as not processable proved. The polyamide strands foamed during production and no test specimens suitable for the measurements could be produced.

Claims

claims

1 . Flammschutzmittelkombinationen containing

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

wherein Ri and R2 are ethyl,

M is Al, Fe, TiOp or Zn,

m means 2 to 3, 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 3 means, and

q = (4-n) / 2

Melamine cyanurate as component E.

2. Flammschutzmittelkombinationen according to claim 1, characterized in that M and Met AI mean, m and n are 3 and that component B a

Aluminum salt is.

3. Flammschutzmittelkonnbinationen according to at least one of claims 1 to 2, 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 is from 0.01 to 10% by weight,

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

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

is, wherein the percentages are based on the total amount of components A to E.

4. Flammschutzmittelkombinationen according to claim 3, 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 0.1 to 2.5% by weight,

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

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

is.

5. Flammschutzmittelkombinationen according to at least one of claims 1 to 4, 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.

6. Flammschutzmittelkombinationen according to at least one of claims 1 to 5, characterized in that the average degree of condensation of Melaminpolyphosphats 2 to 100.

7. Flammschutzmittelkombinationen according to at least one of claims 1 to 6, characterized in that the melamine polyphosphate a

Decomposition temperature greater than or equal to 320 ° C.

8. Flammschutzmittelkonnbinationen according to at least one of claims 1 to 7, characterized in that they contain inorganic phosphonate as further component F.

9. Flammschutzmittelkombinationen according to claim 8, characterized in that the inorganic phosphonate is a compound of formula (III)

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

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

r = (4 - o) / 2, where

the compound of the formula (III) in an amount of 0.01 to 10% by weight,

in particular in an amount of 0.1 to 2.5 wt .-%, based on the

Total amount of components A to F, is present.

10. Polymer compositions comprising thermoplastic and / or thermosetting polymers as component G and a flameproofing agent combination comprising the components A, B, C, D, E and optionally F according to one of claims 1 to 9, where the thermoplastic polymers are amorphous thermoplastic polymers or (partly) crystalline thermoplastic polymers having a melting point of less than or equal to 290 ° C are.

1 1. Polymer compositions according to claim 10, 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.

12 polymer compositions according to at least one of claims 10 to 1 1, 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.

13. Polymer compositions according to at least one of claims 10 to

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

14. Polymer compositions according to at least one of claims 10 to

13, characterized in that component G 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.

15. Polymer compositions according to claim 14, characterized in that component G is selected from the group consisting of PA6, PA6.6 and other aliphatic homo- or copolyamide-based compounds in which 3 to 1 1 come to a polyamide group in the polymer chain 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.

16. Polymer compositions according to at least one of claims 10 to 13, characterized in that component G is a polyalkylene terephthalate, preferably a polyethylene terephthalate or a polybutylene terephthalate.

17. Polymer compositions according to at least one of claims 10 to 16, 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 1 to 25% by weight,

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

the proportion of component G is 25 to 95% by weight

percentages are based on the total amount of

Refer to polymer composition.

18. Polynnerzusannnenungen according to claim 17, characterized in that

the proportion of component A is from 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 4 to 10 wt .-%,

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

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

is.

19. Polymer compositions according to at least one of claims 10 to

18, characterized in that it contains further additives as component H, 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 that differ from components A, B, C, D, E and F.

20. Polymer compositions according to at least one of claims 10 to

19, characterized in that they contain glass fibers.

21. Use of the polymer compositions according to any one of claims 10 to 20 for the production of fibers, films and moldings, in particular for

Applications in the electrical and electronics sector.