EP3313920A1

EP3313920A1 - Anticorrosive flame retardant formulations for thermoplastic polymers

Info

Publication number: EP3313920A1
Application number: EP16730832.9A
Authority: EP
Inventors: Muriel Rakotomalala; Elke Schlosser; Sebastian HÖROLD; Wolfgang Wanzke
Original assignee: Clariant Plastics and Coatings Ltd
Current assignee: Clariant International Ltd
Priority date: 2015-06-24
Filing date: 2016-06-20
Publication date: 2018-05-02
Also published as: US20180171112A1; CN107250267A; WO2016207087A1; DE102015211728A1; JP6986450B2; TWI707903B; US11053375B2; KR20180020282A; CN107250267B; TW201718744A; JP2018525449A; KR102546391B1

Abstract

The invention provides anticorrosive flame retardant formulations for thermoplastic polymers, comprising from 20 to 97.9% by weight of a (di)phosphinic acid salt of formula (I) and/or (II) where R¹, R² are the same or different and are H or C₁-C₆-alkyl, linear or branched, and/or aryl; R³ is C₁-C₁₀-alkylene, linear or branched, C₆-C₁₀-arylene, C₆-C₁₀-alkylarylene or C₇-C₂₀-arylalkylene; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogen base; m is from 1 to 4; n is from 1 to 4; x is from 1 to 4, and as component B from 2 to 50% by weight of a phosphazene of the general formula (III) or (IV) wherein R⁴ and R^4' are the same or different and are C₁-C₂₀-alkyl, C₆-C₃₀-aryl, C₆-C₃₀-arylalkyl or C₆-C₃₀-alkyl-substituted aryl, and X is a -N=P(OPh)₃ or -N=P(O)OPh group and Y is the -P(OPh)₄ or -P(O)(OPh)₂ group; as component C from 0.1 to 30% by weight of an inorganic zinc compound, and as component D from 0 to 50% by weight of a nitrogen-containing flame retardant.

Description

Anti-corrosive flame retardant formulations for thermoplastic polymers

The invention relates to flame retardant formulations that can be used in polymers to flame-retardant compounds with outstanding

produce mechanical and electrical properties, and show no measurable wear during their incorporation.

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 in part by the legislature, plastics must therefore generally be equipped with flame retardants.

For this purpose, a variety of different flame retardants and

Flammschutzmittelsynergisten known and commercially available. Non-halogenated flame retardant systems have been used for some time because of their more favorable fire by-products with respect to smoke density and

Flue gas composition and preferably used for environmental reasons. Among the non-halogenated flame retardants have for thermoplastic polyesters in particular the salts of phosphinic acids

(Phosphinates) proved to be particularly effective (DE-A-2 252 258 and

DE-A-2 447 727). Calcium and aluminum phosphinates have been described in polyesters as very effective and affect the material properties of the polymer molding compositions less than z. As the alkali metal salts (EP-A-0 699 708). In addition, synergistic combinations of phosphinates with various nitrogen-containing compounds have been found to be more effective than flame retardants in a whole series of polymers as the phosphinates alone (PCT / EP97 / 01664, DE-A-197 34 437, DE-A-197 37 727 and

US-A-6,255,371).

WO-A-2005/059 018 describes a polybutylene terephthalate with a nitrogen-containing flame retardant, a phosphinate and a

ash-forming polymer. Ash-forming polymers are here polyetherimides, Polyphenylene ethers, polyphenylene sulfide, polysulfones, polyethersulfones,

Polyphenylene sulfide oxides or phenolic resins. The addition of the ash-forming polymer improves the flame retardancy. Disadvantages are the high price of the ash-forming polymers and their tendency to discoloration.

DE-A-10 2005 050956 describes thermoplastic molding compositions of a polybutylene terephthalate, a polyester different from

Polybutylene terephthalate, and phosphinates and a reaction product of a nitrogen-containing compound with phosphoric acid. Preferred are

Polyethylene terephthalate (PET) and polytrimethylene terephthalate. Only the addition of PET already achieves UL94 V-0 (Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pages 14-18, Northbrook 1998) and a good one

Creep resistance and good mechanical properties. A GWIT (Glow Wire Ignition Temperature) according to IEC 60695-2-13 of 775 ° C with a thickness of 1.5 mm is achieved.

If phosphinates are used alone or in combination with other flame retardants in polyesters, it usually comes to a certain extent

Polymer degradation, which adversely affects the mechanical properties of

Polymer system affects. Even with phosphazenes alone or in combination with other flame retardants, flame retardant polyesters with good mechanical properties can not be obtained. In addition, unsafe UL 94 V-0 classifications due to too long afterburning times of individual specimens, no safe GWIT 775 ° C classification with thin wall thicknesses are disadvantageous

(<1, 5 mm) and elongation at break below 2%, especially in glass (fiber) kept from 25 to 35%.

DE-A-10 2010 049968 describes flame-retardant polyesters with phosphinate, a phosphazene and a condensate of a nitrogen-containing compound with phosphoric acid as flame retardant. Only the addition of phosphazene achieves UL 94 V-0 and an elongation at break of more than 2% simultaneously. It will be a GWIT (Glow Wire Ignition Temperature) according to IEC 60695-2-13 of 775 ° C with 1 mm material thickness achieved.

A disadvantage of the described additives of flame retardants is a stronger wear of metal parts of the plasticizing unit and the nozzle during compounding. Similar problems can occur in the injection molding of polyester or high temperature polyamide compounds with certain phosphinates.

WO-A-2009/109318 describes the preparation of flame-retardant, non-corrosive and readily flowable polyamide and polyester molding compositions. The flame retardant mixture used there consists of a phosphinic acid salt and a metal salt. Through a special combination of aluminum diethylphosphinate and zinc stannate, a PA6T / 66 molding compound achieves UL94 V-0 (PA = polyamide) with concomitant low corrosion.

DE-A-10 2010 048025 describes a flame retardant stabilizer combination for thermoplastics. The aforesaid combination consists of a salt of a dialkylphosphinic acid, a salt of a

phosphorous acid, a nitrogenous synergist and a zinc salt stabilizer. Polyesters with this combination achieve UL94 V-0 with higher elongation at break, with a slight addition of phosphorous acid in PA6T / 66 resulting in low corrosion. Evidence of positive effects of such combination in polyester on the wear can not be found. It was therefore an object of the present invention to find flame retardant formulations for polymers which show a very good flame retardancy even with thin material thicknesses (applications), with which good mechanical properties of compounds are achieved and which have no detectable increased corrosion during processing.

It has now surprisingly been found that mixtures of metal phosphinates, phosphazene, a nitrogen-containing synergist and a zinc-containing

Compound effective flame retardants, in their processing no Corrosion is detectable and lead to compounds with good mechanical properties.

It was also surprisingly found that electrical characteristics such as tracking resistance of the compounds are significantly improved and that no corrosion is detectable in application tests.

The invention therefore provides a flame retardant formulation for

thermoplastic polymers comprising, as component A, from 20 to 97.9% by weight of a phosphinic acid salt of the formula (I) and / or of a diphosphinic acid salt of the formula (II) and / or polymers thereof,

wherein

R ¹ , R ^{2 are the} same or different and are H or Ci-C6-alkyl, linear or

branched and / or aryl;

R ^{3 is} C 1 -C 10 -alkylene, linear or branched, C 6 -C 10 -arylene, C 6 -C 10 -alkylarylene or C 7 -C 20 -arylalkylene;

M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;

m 1 to 4; n 1 to 4; x is 1 to 4,

and as component B from 2 to 50% by weight of a phosphazenes of the general formula (III) or (IV)

wherein

R ⁴ and R ^{4 'are} identical or different and are C 1 -C 20 -alkyl, C 6 -C 30 -aryl,

C6-C3o-arylalkyl or C6-C3o-alkyl substituted aryl, and X is a group -N = P (OPh) 3 or -N = P (O) OPh and

Y represents the group -P (OPh) ₄ or -P (O) (OPh) ₂ ;

as component C 0.1 to 30 wt .-% of an inorganic zinc compound and as component D 0 to 50 wt .-% of a nitrogen-containing flame retardant.

Preferably, R ¹ and R ^{2 are the} same or different and are methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

Preferably, R ^{3 is} methylene, ethylene, n-propylene, iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene; Phenylene or naphthylene; Methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene,

Ethylnaphthylene or tert-butylnaphthylene; Phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene. Preferably, it contains flame retardant formulation

From 30 to 97.5% by weight of component A,

From 2 to 40% by weight of component B,

0.5 to 30 wt .-% of component C and

0 to 40 wt .-% of component D,

wherein the sum of the weight components gives 100 wt .-%.

Most preferably, the flame retardant formulation contains

From 40 to 94% by weight of component A,

From 5 to 40% by weight of component B,

1 to 20 wt .-% of component C and

0 to 35 wt .-% of component D,

wherein the sum of the weight components gives 100 wt .-%. In particular, the flame retardant formulation contains

From 50 to 82% by weight of component A,

10 to 30% by weight of component B,

2 to 19 wt .-% of component C and

From 1 to 30% by weight of component D,

wherein the sum of the weight components gives 100 wt .-%.

Most preferably, the flame retardant formulation contains

60 to 86% by weight of component A,

10 to 20% by weight of component B,

2 to 18 wt .-% of component C and

From 2 to 20% by weight of component D,

wherein the sum of the weight components gives 100 wt .-%.

Preferably, the phosphazenes are phenoxyphosphazenes.

It is preferable that the component D

a) melamine phosphate, dimelamine phosphate, melamine pyrophosphate,

Melamine polyphosphates, melampolyphosphates, melem polyphosphates and / or Melon polyphosphates and / or melamine condensation products such as melam, melem and / or melon;

and / or b) nitrogen compounds of the formulas (VII) to (XII) or mixtures thereof

(VII) (VIII) (IX)

(X) (XI)

OH

(XII) wherein

R ⁵ to R ^{7 are} hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or -alkylcycloalkyl, optionally

substituted with a hydroxy or a C 1 -C 4 hydroxyalkyl function, C 2 -C 8 alkenyl, C 1 -C 8 alkoxy, acyl, acyloxy, C 6 -C 12 -aryl or arylalkyl, -OR ⁸ and -N (R ⁸ ) R ⁹ , as well as N-alicyclic or

N-aromatic,

R ^{8 is} hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or -alkylcycloalkyl, if appropriate

substituted with a hydroxy or a C 1 -C 4 -hydroxyalkyl function, C 2 -C 8 -alkenyl, C 1 -C -alkoxy, -acyl, -acyloxy or C 6 -C 12 -aryl or -arylalkyl,

R ⁹ to R ^{13 have} the same groups as R ⁸ and -OR ⁸ ,

m and n independently of one another 1, 2, 3 or 4,

X acids which can form adducts with triazine compounds (VII) mean

and / or c) oligomeric esters of tris (hydroxyethyl) isocyanurate with

aromatic polycarboxylic acids, benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycouril, melamine, melamine cyanurate, dicyandiamide and / or guanidine; and / or d) nitrogen-containing phosphates of the formulas (NH ₄ ) _y H3- _y PO4 or

(NH ₄ PO 3) z, where y is 1 to 3 and z is 1 to 10,000.

Component C is preferably zinc oxide, zinc hydroxide, zinc oxide hydrate, zinc borate, basic zinc silicate and / or zinc stannate.

Most preferably, component C is zinc stannate.

The invention also relates to the use of a flame retardant formulation according to one or more of claims 1 to 11 as flame retardant,

especially as a flame retardant for clearcoats and

Intumescent coatings, as flame retardants for wood and other cellulosic products, as reactive and / or non-reactive

Flame retardant for polymers, for the production of flame-retardant

Polymer form mass, for the production of flame-retardant polymer form bodies and / or for the flame-retardant finishing of polyester and cellulose pure and mixed fabrics by impregnation.

More particularly, the invention relates to the use of the flame retardant formulations according to the invention according to one or more of claims 1 to 12 in or for connectors, current-contacting parts in power distributors (Fl protection), circuit boards, potting compounds, power connectors, circuit breaker, lamp housing, LED lamp housing, capacitor housing , Bobbins, fans, protective contacts, plugs, in / on boards, housings for plugs, cables, flexible circuit boards, charging cables, engine covers, textile coatings and other products.

The invention also encompasses a flame-retardant thermoplastic or thermosetting polymer molding composition, polymer moldings, films, filaments and fibers containing 0.5 to 45% by weight of flame retardant formulation according to one or more of claims 1 to 11, 10 to 95% by weight. % thermoplastic or thermosetting polymer or mixtures thereof, 0 to 55% by weight of additives and 0 to 55% by weight of filler or reinforcing materials, the sum of the components being 100% by weight.

In particular, the invention comprises flame-retardant thermoplastic or thermosetting polymer molding compositions, polymer moldings, films, filaments and fibers, containing 5 to 30% by weight of flame retardant formulation according to one or more of claims 1 to 11, 20 to 95% by weight. thermoplastic or thermosetting polymer or mixtures thereof, 5 to 55 wt .-% additives and 10 to 55 wt .-% filler or reinforcing materials, wherein the sum of the components is 100 wt .-%.

The flame-retardant thermoplastic or thermoset is preferred

Polymer molding composition, polymer moldings, films, filaments and fibers, characterized in that these are polyesters, polyamides and / or

Polymer blends containing polyamides or polyesters is. The preparation of phosphazenes is described in EP-A-0945478.

Particular preference is given to cyclic phenoxyphosphazenes of the formula

PsNsCse (V)

PhO OPh or linear phenoxyphosphazenes according to formula (VI). The phenyl radicals may optionally be substituted.

Phosphazenes for the purposes of the present application are described in Mark, J.A., Allcock, H.R., West, R., "Inorganic Polymers", Prentice Hall International, 1992, pages 61-141.

The invention also relates to a flameproof plastic molding composition comprising an inventive anticorrosive flame retardant formulation, wherein the plastic is thermoplastic polymers of the type polystyrene HI (high-impact), 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) plastics. Suitable phosphinates are described in PCT / WO97 / 39053, which is incorporated herein by reference.

Preferably, M in formula (I) or (II) is magnesium, calcium, aluminum or zinc, more preferably aluminum or zinc.

Hereinafter, the term "phosphinic acid salt" includes salts of phosphinic and diphosphinic acids and their polymers.

The phosphinic acid salts prepared in aqueous medium are essentially monomeric compounds. Depending on the

Reaction conditions may also be polymeric

Phosphinic salts arise.

Suitable phosphinic acids as a constituent of the phosphinic acid salts are, for example:

Dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propyl-phosphinic acid, methane-di (methylphosphinic acid), benzene-1, 4- (dimethyl-phosphinic acid), methyl-phenyl-phosphinic acid, diphenylphosphinic acid. The salts of the phosphinic acids according to the invention can be prepared by known methods, as described in more detail, for example, in EP-A-0699708. The phosphinic acids are reacted, for example, in aqueous solution with metal carbonates, metal hydroxides or metal oxides. The aforementioned phosphinic acid salts can be used for the inventive

Polyester compounds depending on the type of polymer used and the

desired properties are applied in various physical form. Thus, the phosphinic acid salts z. B. to achieve a better Dispersion in the polymer are ground to a finely divided form. If desired, it is also possible to use mixtures of different phosphinic acid salts. The phosphinic salts according to the invention are thermally stable, do not decompose the polymers during processing nor do they affect the production process of the plastic molding compound. The phosphinic acid salts are non-volatile under the usual polyester manufacturing and processing conditions. The polymers preferably originate from the group of thermoplastic polymers such as polyester, polystyrene or polyamide and / or the group of thermosetting polymers.

Particularly preferably, the thermoset polymers are epoxy resins.

The thermoset polymers are particularly preferably epoxy resins which have been cured with phenols, dicyandiamide, phenol derivatives (resoles), alcohols or amines, in particular phenol derivatives and dicyandiamide.

The thermoset polymers are particularly preferably epoxy resins which are mixed with phenols and / or dicyandiamide and / or a

Catalyst are cured.

The catalysts are preferably imidazole compounds.

The epoxy resins are preferably polyepoxide compounds. The epoxy resins are preferably resins based on novolac.

Preferably, the epoxy resins are resins on the base

Bisphenol-A. Polymers which can be used according to the invention are thermosetting and thermoplastic polymers. Preferably, the polymers are polymers of mono- and

Diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methyl-pentene-1, polyisoprene or polybutadiene and polymers of

Cycloolefins such. From cyclopentene or norbornene; also polyethylene (which may be optionally crosslinked), e.g. 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), as well as mixtures thereof.

Preferably, the polymers are 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,

Ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers,

Isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate 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; further

Mixtures of such copolymers with one another, 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 construction

Polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such. B. polyamides. The polymers are preferably hydrocarbon resins (eg C5-C9) including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.

The polymers are preferably polystyrene (polystyrene 143E (BASF), poly (p-methylstyrene), poly (alpha-methylstyrene).

Preferably, the polymers are 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-methyl acrylate;

Blends of high impact strength of styrene copolymers and another polymer, such as. A polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.

Preferably, the polymers are graft copolymers of styrene or alpha-methylstyrene, such as. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (resp.

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, such as they z. B. known as so-called ABS, MBS, ASA or AES polymers.

The polymers are preferably 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,

Epichlorohydrin homopolymers and copolymers, in particular polymers

halogen-containing vinyl compounds, such as. B. polyvinyl chloride,

Polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; As well as their

Copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

The polymers are preferably polymers which are derived from alpha, beta-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polymethyl methacrylates which have been modified with butyl acrylate, polyacrylamides and polyacrylonitriles and copolymers of said monomers with one another or with other unsaturated monomers, such as Acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

The polymers are preferably polymers which are 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 olefins.

The polymers are preferably homo- and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

The polymers are preferably polyacetals, such as

Polyoxymethylene, as well as those polyoxymethylenes, the comonomers, such as. For example, ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

The polymers are preferably polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides. The polymers are preferably polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and precursors thereof.

The polymers are preferably polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 2/12, polyamide 4 (poly-4-aminobutyric acid, ^Nylon® 4, Fa. DuPont), polyamide 4/6

(Poly (tetramethylene adipamide), poly (tetramethylene-adipamide), Nylon ^® 4/6, Fa. DuPont), polyamide 6 (polycaprolactam, poly-6-aminohexanoic acid, Nylon ^® 6, Fa. DuPont, Akulon ^® K122, from DSM;. Zytel ^® 7301, from DuPont;.. Durethan B 29, from Bayer), polyamide 6/6 ((poly (N, N'-hexamethyleneadipinediamid), nylon ^® 6/6, DuPont, Zytel ^® one hundred and first , from DuPont;. Durethan ^® A30, Durethan ^® AKV, Durethan ^® AM, from Bayer;. Ultramid ^® A3, BASF), polyamide 6/9 (poly (hexamethylene nonanediamid), nylon 6/9 ^®, DuPont). , Polyamide 6/10 (poly (hexamethylene sebacamide), nylon ^® 6/10, from DuPont), polyamide 6/12 (poly (hexamethylene dodecanediamide), nylon ^® 6/12, from DuPont), polyamide 6/66 ( poly (hexamethylene adipamide-co-caprolactam), nylon ^® 6/66, Fa. DuPont), polyamide 7 aminoheptanoic acid (poly-7, nylon ^® 7, Fa. DuPont), polyamide 7.7

(Polyheptamethylenpimelamid, Nylon ^® 7.7, Fa. DuPont), polyamide (poly aminooctanoic acid-8, nylon ^® 8, Fa. DuPont) 8, polyamide 8.8

(Polyoctamethylensuberamid, Nylon ^® 8.8, Fa. DuPont), polyamide (poly-9- aminononanoic acid, Nylon ^® 9, Fa. DuPont) 9, polyamide 9.9

(Polynonamethylenazelamid, Nylon ^® 9.9, Fa. DuPont), polyamide 10 (poly-10-amino-decanoic acid, Nylon ^® 10, Fa. DuPont), polyamide 10.9

(Poly (decamethylene azelamide), nylon ^® 10.9, Fa. DuPont), polyamide 10,10

(Polydecamethylensebacamid, Nylon ^® 10,10, from DuPont.), Polyamide 1 1 (Poly-1 1 - aminoundecanoic acid, nylon ^® 1 1, from DuPont.), Polyamide 12 (polylauryllactam,

. Nylon ^® 12, DuPont, Grillamid ^® L20, from Ems Chemie), aromatic polyamides starting from m-xylene, diamine and adipic acid. Polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid (Polyhexamethylene isophthalamide polyhexamethylene terephthalamide) and

optionally an elastomer as modifier, e.g. As poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide.

Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted

elastomers; or with polyethers, such as. With polyethylene glycol,

Polypropylene glycol or polytetramethylene glycol. Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM polyamide systems").

The polymers are preferably polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and

Polybenzimidazoles. The polymers are preferably polyesters which differ from

Derive dicarboxylic acids and dialcohols and / or hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate,

Polybutylene terephthalate (Celanex ^® 2500, Celanex ^® 2002, from Celanese;. Ultradur ^®, BASF), poly-1, 4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and also block polyether esters derived from polyethers having hydroxyl end groups; also with polycarbonates or MBS modified polyester.

The polymers are preferably polycarbonates and

Polyester.

The polymers are preferably polysulfones, polyethersulfones and polyether ketones.

The polymers are preferably crosslinked polymers 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. Preferably, the polymers are drying and non-drying alkyd resins.

The polymers are preferably unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, as well as their halogen-containing, hardly combustible modifications.

Preferably, the polymers are crosslinkable acrylic resins derived from substituted acrylic acid esters, such as. As of epoxy acrylates, urethane acrylates or polyester acrylates.

The polymers are preferably alkyd resins, polyester resins and acrylate resins which are blended with melamine resins, urea resins, isocyanates,

Isocyanurates, polyisocyanates or epoxy resins are crosslinked.

The polymers are preferably crosslinked epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic

Derive glycidyl compounds, for. B. products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, by conventional hardeners such. As anhydrides or amines can be crosslinked with or without accelerators.

The polymers are preferably mixtures (polyblends) of the abovementioned polymers, such as e.g. PP / EPDM (polypropylene / ethylene-propylene-diene rubber), polyamide / EPDM or ABS (polyamide / ethylene-propylene-diene rubber or acrylonitrile-butadiene-styrene), PVC / EVA (polyvinyl chloride /

Ethylene vinyl acetate), PVC / ABS (polyvinyl chloride / acrylonitrile-butadiene-styrene), PVC / MBS (polyvinyl chloride / methacrylate-butadiene-styrene), PC / ABS

(Polycarbonate / acrylonitrile-butadiene-styrene), PBTP / ABS (polybutylene terephthalate / acrylonitrile-butadiene-styrene), PC / ASA (polycarbonate / acrylic ester-styrene-acrylonitrile), PC / PBT (polycarbonate polybutylene terephthalate), PVC / CPE

(Polyvinyl chloride / chlorinated polyethylene), PVC / acrylates (polyvinyl chloride / acrylates, POM / thermoplastic PUR (polyoxymethylene / thermoplastic polyurethane), PC / Thermoplastic PUR (Polycarbonate / Thermoplastic Polyurethane), POM / Acrylate (Polyoxymethylene / Acrylate), POM / MBS (Polyoxymethylene / Acrylic)

Methacrylate-butadiene-styrene), PPO / HIPS (polyphenylene oxide / high impact

Polystyrene), PPO / PA 6.6 (polyphenylene oxide / polyamide 6.6) and copolymers, PA / HDPE (polyamide / high density polyethylene), PA / PP (polyamide / polyethylene), PA / PPO (polyamide / polyphenylene oxide), PBT / PC / ABS (Polybutylene terephthalate / polycarbonate / acrylonitrile-butadiene-styrene) and / or PBT / PET / PC

(Polybutylene terephthalate / polyethylene terephthalate / polycarbonate). The inventive combination of the components A and B and C and optionally D additives may be added, such. As antioxidants, UV absorbers and light stabilizers, metal deactivators, peroxide-destroying compounds, polyamide stabilizers, basic co-stabilizers, nucleating agents, fillers and reinforcing agents, other flame retardants and other additives.

Suitable antioxidants include alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol; 1 .2 Alkylthiomethylphenole, z. B. 2,4-dioctylthiomethyl-6-tert-butylphenol; Hydroquinones and alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol; Tocopherols, e.g. For example, α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E); Hydroxylated thiodiphenyl ethers, e.g. B. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio-bis (6-tert-butyl) butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec-amylphenol), 4,4'-bis (2,6-di-methyl-4-hydroxyphenyl) -disulfic acid; Alkylidene Bisphenols, e.g. B. 2,2'-methylenebis (6-tert-butyl-4-methylphenol;

O, N and S benzyl compounds, e.g. B. 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydi benzyl ether; Hydroxybenzylated malonates, e.g. Dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydrorybenzyl) -malonate; Hydroxybenzyl aromatics, e.g. B. 1, 3,5-tris- (3,5-di-tert-butyl) -4-hydroxybenzyl) -2,4,6-trimethylbenzoyl, 1,4-bis- (3,5-di-tert-butyl) butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzoic 2,4,6-tris- (3,5-di-tert-butyl-4-butylbenzyl) phenol; Triazine compounds, e.g. B. 2,4-bis-octylmercapto-6 (3,5-di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine; Benzylphosphonates, e.g. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate; Acylaminophenols, 4-hydroxylaurin acid amide, 4-hydroxystearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamic acid octyl ester; Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols; Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols; Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols; Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols; Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as. N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylenediamine, N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine.

Suitable UV absorbers and light stabilizers are, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole;

2-hydroxybenzophenones, such as. For example, 4-hydroxy, 4-methoxy, 4-octoxy,

4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivative;

Esters of optionally substituted benzoic acids, such as. B. 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4- di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid acid 2-methyl-4,6-di-tert-butylphenyl ester; Acrylates, such as. B. α-cyano-ß, ß-diphenylacrylic acid ethyl ester or -isooctylester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-.beta.-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, a-carbomethoxy-p- methyl methoxycinnamate, N- (β-carbomethoxy-β-cyanovinyl) -2-methyl-indoline.

Furthermore, nickel compounds, such as. As nickel complexes of 2,2'-thio-bis [4 (1, 1, 3,3-tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as methyl or ethyl esters, nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands; Sterically hindered amines, such as. Bis (2,2,6,6-tetramethylpiperidyl) sebacate; Oxidesäurediamide, such as. 4,4'-dioctyloxy-oxanilide; 2- (2-hydroxyphenyl) -1, 3,5-triazines, such as. B. 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazine.

Suitable metal deactivators are, for. B. Ν, Ν '-Diphenyloxalsäurediamid, N-salicylal-N'-salicyloylhydrazin, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4 -hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) -oxalic dihydrazide, oxanilide, isophthalic dihydrazide, sebacic acid bis-phenylhydrazide, Ν, Ν'-diacetyl-adipic acid dihydrazide, N , N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic dihydrazide. Suitable peroxide-destroying compounds are, for. B. esters of .beta.-thionipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulphide, pentaerythritol tetrakis (.beta.-dodecylmercapto), propionate.

Suitable polyamide stabilizers are, for. As copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

Suitable basic co-stabilizers are melamine, polyvinylpyrrolidone,

Dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate, K palmitate, Antimony catechinate or tin catechinate. Suitable nucleating agents are for. For example, 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid. The fillers and reinforcing agents include, for. As calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite and others. As further flame retardants z. As aryl phosphates, phosphonates, salts of hypophosphorous acid and red phosphorus suitable.

To the other additives counts z. As plasticizers, expandable graphite, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents and blowing agents.

These additional additives can be added to the polymers before, together with or after addition of the flame retardants. The dosage of these additives as well as the flame retardants can be carried out as a solid, in solution or melt, as well as in the form of solid or liquid mixtures or as masterbatches / concentrates.

Lubricants and / or mold release agents may additionally be used as additives. The lubricants and / or mold release agents are long-chain fatty acids, their salts, their ester derivatives and / or amide derivatives,

Montan waxes and / or low molecular weight polyethylene and / or

Polypropylene waxes.

Preferably, the lubricants and / or mold release agents are esters or salts of stearic acid, such as. As glycerol monostearate or calcium stearate.

Preferably, the lubricants and / or mold release agents are

Reaction products of montan wax acids with ethylene glycol. The reaction products are preferably a mixture of ethylene glycol mono-montan wax acid ester, ethylene glycol dimontane wax acid ester, montan wax acids and ethylene glycol. Preferably, the lubricants and / or mold release agents are

Reaction products of montan wax acids with a calcium salt.

The reaction products are particularly preferably a mixture of 1,3-budanediol mono-montan wax acid ester, 1,3-budanediol di-montan wax acid ester, montan wax acids, 1,3-butanediol, calcium montanate and the calcium salt.

The abovementioned additives can be introduced into the plastic in a wide variety of process steps. Thus it is possible with polyamides, already at the beginning or at the end of the polymerization / polycondensation or in a subsequent compounding process, the additives in the polymer melt

interfere. Furthermore, there are processing processes in which the additives are added later. This is especially practiced when using pigment or additive masterbatches. In addition, it is possible, in particular pulverulent additives aufzutrommeln on the possibly through the drying process warm polymer granules.

The polymer is particularly preferably one or more polyesters and / or polyamides which may be provided with fillers and / or reinforcing materials.

The polyesters and polyamides are preferably in the form of shaped bodies, films, threads and / or fibers.

Surprisingly, it has been found that inventive combinations of salts of dialkylphosphinic acids and phosphazenes with zinc-containing additives have a good flame retardancy, combined with improved stability in the processing of the molding compositions. This corrosion prevention effect has not been found to this extent in the prior art in any combination so far described. Preferably, the flame retardant polyester compounds continue to contain

Carbodiimides.

The flame-retardant polyester compounds preferably contain more than one thermoplastic polyester. Particularly preferably, the flame-retardant polyester compounds contain PBT and PET in blends.

The flame-resistant polyester compounds preferably also contain polycarbonates. The invention also relates to a process for the preparation of the flame-retardant polyester compounds or polyamide compounds according to the invention, characterized in that the components A to D in the abovementioned

Parts by weight mixed by melt extrusion. Finally, the invention relates to the use of fibers, films and

Moldings of the flame-retardant polyester compounds or polyamide compounds according to the invention in the household, industry, in medicine, in

Motor vehicles, in airplanes, in ships, in spaceships and other means of transport, in office equipment and in objects; and

Buildings requiring increased fire protection.

The thermoplastic polyesters are selected from the group of

Polyalkylene. Polyalkylene terephthalates according to the invention are reaction products of aromatic dicarboxylic acids or their reactive derivatives (eg dimethyl esters or anhydrides) and aliphatic,

cydoaliphatic or araliphatic diols and mixtures of these

Reaction products.

Polyalkylene terephthalates preferably to be used according to the invention can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Vol. VIII, pages 695-710, Karl-Hanser-Verlag, Munich 1973). Polyalkylene terephthalates preferably to be used according to the invention contain at least 80 mol%, preferably 90 mol%, based on the dicarboxylic acid, of terephthalic acid residues.

The polyalkylene terephthalates which are preferably used according to the invention may contain, in addition to terephthalic acid residues, up to 20 mol% of other aromatic dicarboxylic acids containing 8 to 14 carbon atoms or aliphatic dicarboxylic acids containing 4 to 12 carbon atoms, such as phthalic acid, isophthalic acid, naphthalene-2,6 dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic, cyclohexanediacetic, cyclohexanedicarboxylic acid.

The polyalkylene terephthalates to be used according to the invention can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or

4-basic carboxylic acids, e.g. in DE-A-19 00 270 are branched. Examples of preferred branching agents are

Trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.

Especially preferred according to the invention 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 mole% of other aliphatic diols having 2 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, e.g. Remains of

Ethylene glycol, propanediol 1, 3, 2-ethylpropanediol-1, 3, neopentyl glycol, pentanediol 1, 5, hexanediol-1 .6, cyclohexane-dimethanol-1, 4, 3-methylpentanediol-2,4,

2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1, 3 and -1, 6,2-ethylhexanediol-1,3-2,2-diethylpropanediol-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 (DE-A-24 07 674, DE-A-24 07 776,

DE-A-27 15 932).

Polyalkylene terephthalates which are preferably used according to the invention are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components and / or butanediol-1,4. Particularly preferred copolyesters are poly (ethylene glycol / butanediol-1, 4) terephthalates. Suitable components C (phosphazenes) are those described in Mark, J.A., Allcock, H.R., West, R., "Inorganic Polymers", Prentice Hall International, 1992,

Pages 61-141.

The phosphazenes may also be a cross-linked phosphazene wherein at least one of the foregoing phosphazenes (V) and (VI) is cross-linked to at least one cross-linking group. The cross-linking group consists of an o-phenylene group, an m-phenylene group, a p-phenylene group, a biphenyl group or a group represented by the formula (XIII)

wherein

A is a group -SO2, a group -S-, a group -O- or a group -C- (CH3) 2-, wherein each of said cross-linking groups is located between the two oxygen atoms that after the removal of the group R ¹ , wherein the number of R ¹ groups in the cross-linked phosphazene is 50 to 99.9%, based on the total number of R ¹ groups in said phosphazene before cross-linking. The foregoing examples of the halogen-free phosphazene can be used either alone or in combination.

Specific examples of cyclic phosphazene and straight-chain

Phosphazene includes a mixture of phosphazene compounds in which a phenoxy group and / or an alkoxy group has been introduced in a mixture of the cyclic and straight-chain chlorophosphazenes, e.g. B.

Hexachlorocyclotriphosphazenes, octachlorocyclotetraphosphazenes and the like. The chlorophosphazenes are prepared by reacting ammonium chloride and phosphorus pentachloride at 120 - 130 ° C with each other.

Specific examples of the cross-linked phosphazene are

Phenoxyphosphazenes having a structure cross-linked by 4,4'-sulfonyldiphenylenes (bisphenol-S-residue); Phenoxyphosphazenes having a 2,2- (4,4'-diphenylenes) isopropylidene group cross-linked structure;

Phenoxyphosphazenes having a 4,4'-diphenylene group cross-linked structure and the like.

Specific examples of the preferred phosphazenes are

Hexaphenoxycyclotriphosphazenes, octaphenoxycyclotetraphosphazenes,

Cyclopentaphosphazenes and similar cyclophosphazenes with

Phenoxy groups are substituted; and straight-chain phosphazenes substituted by phenoxy groups.

Among the reaction products with phosphoric acid or condensed

Phosphoric acids are compounds which are formed by reacting melamine or the condensed melamine compounds, such as melam, Meiern or melon, etc., with phosphoric acid. Examples of these are dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, Melamine polyphosphate, melampolyphosphate, melon polyphosphate and

Melempolyphosphat or mixed polysalts, as z. B. in the

WO-A-98/39306 are described. Most preferably, component D is um

Melaminpolyphosphat or melamine cyanurate.

Mineral particulate fillers based on talc, wollastonite, kaolin and / or glass fibers are particularly preferably used according to the invention.

In particular, for applications in which isotropy in dimensional stability and high thermal dimensional stability are required, such as

For example, in automotive applications for exterior body parts, mineral fillers are preferably used, in particular talc, wollastonite or kaolin.

Furthermore, needle-shaped mineral fillers may also be used with particular preference. Under needle-shaped mineral fillers is

According to the invention, a mineral filler with pronounced

acicular character understood. By way of example, acicular wollastonites are mentioned. Preferably, the mineral has a length to diameter ratio of from 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, most preferably from 4: 1 to 12: 1. The mean particle size of the suitable acicular minerals according to the invention is preferably less than 20 microns, more preferably less than 15 microns, most preferably less than 10 microns.

The filler and / or reinforcing material may optionally

be surface-modified, for example, with a bonding agent or

Primer system, based on silane. However, pretreatment is not essential. In particular, when using glass fibers, polymer dispersions, film formers, branching agents and / or glass fiber processing aids may be used in addition to silanes. Particularly preferred reinforcing materials are glass fibers, generally having a fiber diameter between 7 and 18 microns, preferably between 9 and 15 microns, are added as continuous filaments or as cut or ground glass fibers. The fibers can with a suitable sizing system and a primer or adhesion promoter system z. B. silane-based

be equipped.

Preferred adhesion promoters are silane compounds from the group

Aminopropyltrimethoxysilane, aminobutyltrimethoxysilane,

Aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as a substituent.

For the equipment of the fillers, the silane compounds are generally used in amounts of 0.05 to 2 wt .-%, preferably 0.25 to 1, 5 wt .-% and in particular 0.5 to 1 wt .-% based on the mineral Filler, used for surface coating.

The particulate fillers may have a smaller d97 or d50 value than those originally used due to the processing into the molding compound or molding in the molding compound or in the molding

Fillers. Due to the processing, the glass fibers can be shorter due to the molding composition or molding in the molding compound or in the molding

Have length distributions than originally used. In a further alternative preferred embodiment, the

Molding compositions in addition to the components A to D contain at least one lubricant and mold release agent. Long-chain fatty acids (for example stearic acid or behenic acid), their salts (for example Ca or Zn stearate) and their ester derivatives or amide derivatives (for example ethylene bisstearylamide), montan waxes (mixtures from straight-chain, saturated

Carboxylic acids with chain lengths of 28 to 32 carbon atoms) and low molecular weight polyethylene or polypropylene waxes. According to the invention, preference is given to lubricants and / or mold release agents from the group of low molecular weight Polyethylene waxes and esters of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with aliphatic saturated alcohols having 2 to 40 carbon atoms used, with pentaerythritol tetrastearate (PETS) is very particularly preferred.

In a further alternative preferred embodiment, the

Molding compounds in addition to the components A to D contain other additives. Usual additives are for. B. stabilizers (for example

UV stabilizers, heat stabilizers, gamma ray stabilizers,

Hydrolysis stabilizers), antistatic agents, other flame retardants, emulsifiers, nucleating agents, plasticizers, processing aids,

Impact modifiers, dyes and pigments. The additives can be used alone or mixed or in the form of masterbatches, or can be premixed in the melt or applied to the surface thereof.

As stabilizers, for example, sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, as well as various substituted representatives of these groups and mixtures thereof can be used. As suitable UV stabilizers are various

substituted resorcinols, salicylates, benzotriazoles and benzophenones.

In the case of impact modifiers (elastomer modifiers, modifiers) are generally copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or

Methacrylic acid esters having 1 to 18 carbon atoms in the alcohol component.

Inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide, zinc sulfide and carbon black, furthermore organic pigments, such as phthalocyanines,

Quinacridones, perylenes and dyes such as nigrosine and anthraquinones are added as colorants and other colorants. As part of the

present invention, the use of carbon black is preferred. As a nucleating agent z. For example, sodium or calcium phenylphosphinate, alumina or silica and preferably talc can be used. As processing aids, for example, copolymers of at least one [ct] olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol can be used. Preference is given here

Copolymers in which the [ct] olefin is composed of ethene and / or propene and the methacrylic acid ester or acrylic ester contains as alcohol component linear or branched alkyl groups having 4 to 20 carbon atoms. Particularly preferred is butyl acrylate and (2-ethyl) hexyl acrylate.

Examples of plasticizers are dioctyl phthalate,

Dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils and N- (n-butyl) benzenesulfonamide.

The flame-retardant polyester compounds according to the invention preferably also contain carbodiimides. The components A, B, C and D can be in thermoplastic polyester

can be incorporated by premixing all components as a powder and / or granules in a mixer and then homogenized in a polymer compounding unit (eg a twin-screw extruder) in the polymer melt. The melt is usually withdrawn as a strand, cooled and granulated. The components C and D can also be separated via a

Dosing be introduced directly into the compounding.

It is also possible to admix the flame-retardant additives A, B, C and D to a finished polymer granulate or powder and to process the mixture directly on an injection molding machine to form parts. In the case of polyesters, for example, the flame-retardant additives A, B, C and D can also already be added to the polyester composition during the polycondensation. The flame-retardant polyester compounds are suitable for the production of

Moldings, films, threads and fibers, z. B. by injection molding, extrusion or compression.

Examples

1 . Used components

Commercially available polyesters (granules), component A:

Polybutylene terephthalate (PBT): Ultradur ^® 4500 (BASF, D).

Component B:

Aluminum salt of diethylphosphinic acid, hereinafter referred to as Depal. Component C:

Phosphazen SPB 100, Otsuka Chemical Co., Japan

Phosphazene Rabitle ^® FP 1 10, Fushimi Pharmaceuticals, Japan

Component D:

Melapur ^® MC (melamine cyanurate), Messrs. Ciba Specialty Chemicals, CH

Melapur ^® 200/70 (melamine), Messrs. Ciba Specialty Chemicals, CH Delacal ^® M350 (Meiern), Fa. Delamin, UK

Component E: Flamtard ^® H, stannate, from William Blythe, UK.

Component F: PPG fiberglass HP 3786 EC 10 4, 5 MM component G: lubricants: Licowax E ^®, montan wax, Clariant, CH. 2. Preparation, Processing and Testing of Flame Resistant Polyester Compounds The flameproofing components were mixed with the polymer granules and possibly additives in the ratio indicated in the tables and on a twin-screw extruder (Leistritz ZSE 27 HP-44D type) at temperatures of 240 to 280 ° C incorporated. The homogenized polymer strand was

withdrawn, cooled in a water bath and then granulated.

After sufficient drying, the molding materials were on a

Injection molding machine (type Arburg 320C / KT) at mass temperatures of 260 to 280 ° C processed into test specimens. The flame retardance of the molding compositions was determined by the UL94 V method (Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pages 14 to 18, Northbrook 1998).

The flammability of the specimens was assessed by determining the oxygen index (LOI according to ASTM D 2863-77).

Corrosion was examined by the platelet method. The platelet method set up at DKI (Deutsches Kunststoffinstitut, Darmstadt) is used for model investigations for the comparative evaluation of metallic materials and the corrosion and wear intensity of plasticizing molding compounds. In this test, two specimens are placed in pairs in the nozzle so that they have a rectangular gap of 12 mm length, 10 mm width and a height of 0.1 to a maximum of 1 mm adjustable height for the passage of

Form plastic melt. Through this gap, plastic melt is extruded (or sprayed) from a plasticizing unit with the appearance of large local

Shear stresses and shear rates in the gap (Günther Menning, Markus Lake "Wear Reduction in Plastics Processing - Phenomena and Protective Measures" 2nd edition Carl Hanser Verlag, Munich 2008, pages 281-284, Eggering, P et al.: "Wear on metal surfaces with fast flowing plastic melts in contact "Kunststofftechnik 10 (1971) 5, pages 159-168). A wear parameter is the weight loss of the specimens, which is determined by differential weighing of the specimens with an A & D "Electronic Balance"

Analytical balance is determined with a deviation of 0.1 mg. The

Mass determination of the specimens was carried out before and after the corrosion test with 25 or 10 kg polymer throughput.

After a previously defined throughput (25 or 10 kg), the

Sample plate removed and physically / chemically cleaned of the adhering plastic. The physical cleaning is done by removing the hot plastic mass by rubbing with a soft material (cotton). The chemical cleaning is carried out by heating the specimens at 60 ° C in m-cresol for 10 minutes. After boiling still adhering plastic mass is removed by rubbing with a soft cotton swab.

The glow-wire resistance was determined by means of the glow-wire test GWIT (GlowWire-Ignition-Temperature) according to IEC 60695-2-13. The GWIT test is performed on 3 test specimens (for example on 60 x 60 X geometry plates

1, 5 mm) with a glowing wire at temperatures between 550 and 960 ° C indicates the glow wire ignition temperature which is 25K (30K between 900 ° C and 960 ° C higher than the maximum glow wire temperature, which in 3 consecutive tests also during the The ignition time of the filament does not lead to ignition, igniting with a flame of> = (greater than or equal to) 5 seconds.

To assess copper corrosion, UL 94 specimens were tightly wrapped with a copper foil (0.1-0.2 mm) and stored in fully desalted water at 120 ° C for 72 hours. If neither the specimens nor the copper foil show any change after storage, the flame retardant formulation will not cause any

Copper corrosion. Comparative Examples: PBT GF 30 with combination of Depal with melamine polyphosphate and phosphazene

Example V1 V2 V3 V4

PBT (% by weight) 49.7 49.7 49.7 49.7

Glass fibers (% by weight) 30 30 30 30

Depal (wt%) 13.3 13.3 12 18

Phosphazene SPB 100 (wt%) 2.7

Melamine polyphosphate (% by weight) 6.7 3.3 6

Lubricant (% by weight) 0.3 0.3 0.3 0.3

Corrosion Clear Low Clear Low

UL94 (0.8 mm) VO VO VO V1

UL94 (0.8 mm) VO VO VO V1 after furnace storage

GWIT (1 mm) (° C) 750 775 750 750

LOI (% 0 ₂ ) 35.4 41, 1 40.0 42.0

CTI (V) 575 550 575 575

Elongation at break (% by weight) 1, 9 2.5 2.0 1, 8

Impact strength at room (kJ / m ² ) 37 51 50 38 temperature (20 ° C)

Notched impact strength at room (kJ / m ² ) 6.2 6.4 6.9 5.0 temperature (20 ° C)

Copper Corrosion Greenish Greenish Greenish Greener

Flooring Flooring Flooring Flooring Table 2: Comparative examples and inventive combination of Depal with phosphazene, melamine polyphosphate and zinc stannate

From Comparative Examples V1 to V6 shows that it is not possible by the sole use of Depal, phosphazene or melamine polyphosphate or by the combination of Depal with melamine polyphosphate and the combination of phosphazene with melamine polyphosphate, UL 94 V-0, GWIT 775 ° C, an elongation at break of greater than 2% and a non-measurable wear to achieve at the same time. The inventive combination of Depal with phosphazene, with melamine polyphosphate and zinc stannate, an elongation at break of greater than 2%, a safe UL 94 V-0 classification and a GWIT of 775 ° C is achieved in PBT. During processing, no wear could be detected. The compounds showed no copper corrosion.

The flame-retardant polyester compounds according to the invention are also distinguished by a high oxygen index and high tracking resistance. Preferably, the flame retardant polyamide composition has a

Tracking immunity [Tracking Index (CTI)] measured according to the International Electrotechnical Commission Standard IEC-601 12/3 of greater than or equal to 600 volts.

Claims

claims

1 . Flame retardant formulation for thermoplastic polymers comprising, as component A, from 20 to 97.9% by weight of a phosphinic acid salt of the formula (I) and / or of a diphosphinic acid salt of the formula (II) and / or polymers thereof,

wherein

R ¹ , R ^{2 are the} same or different and are H or Ci-C6-alkyl, linear or

branched and / or aryl;

m 1 to 4; n 1 to 4; x is 1 to 4,

wherein

Y represents the group -P (OPh) ₄ or -P (O) (OPh) ₂ ;

2. flame retardant formulation according to claim 1, characterized in that R ¹ , R ^{2 are the} same or different and are methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-pentyl and / or phenyl ,

3. Flame retardant formulation according to claim 1 or 2, characterized

characterized in that R ^{3 is} methylene, ethylene, n-propylene, iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene; Phenylene or naphthylene; Methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene,

Ethylnaphthylene or tert-butylnaphthylene; Phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene means.

4. Flame retardant formulation according to one or more of claims 1 to 3, comprising

From 30 to 97.5% by weight of component A,

From 2 to 40% by weight of component B,

0.5 to 30 wt .-% of component C and

0 to 40 wt .-% of component D,

wherein the sum of the weight components gives 100 wt .-%.

5. Flame retardant formulation according to one or more of claims 1 to 4, comprising

From 40 to 94% by weight of component A,

From 5 to 40% by weight of component B,

1 to 20 wt .-% of component C and

0 to 35 wt .-% of component D,

wherein the sum of the weight components gives 100 wt .-%.

6. Flame retardant formulation according to one or more of claims 1 to 5, comprising

From 50 to 82% by weight of component A,

10 to 30% by weight of component B,

2 to 19 wt .-% of component C and

From 1 to 30% by weight of component D,

wherein the sum of the weight components gives 100 wt .-%.

7. Flame retardant formulation according to one or more of claims 1 to 6, comprising

60 to 86% by weight of component A,

10 to 20% by weight of component B,

2 to 18 wt .-% of component C and

From 2 to 20% by weight of component D,

wherein the sum of the weight components gives 100 wt .-%.

8. Flame retardant formulation according to one or more of claims 1 to

7, characterized in that it is in the Phosphazenen to

Phenoxyphosphazene acts.

9. flame retardant formulation according to one or more of claims 1 to

8, characterized in that it is at the component D a) to

Melamine phosphate, dimelamine phosphate, melamine pyrophosphate,

Melamine polyphosphates, melam polyphosphates, melem polyphosphates and / or melon polyphosphates and / or melamine condensation products such as melam, Meiern and / or melon;

(VII) (VIII) (IX)

(X) (XI) OH

(XII) where

substituted with a hydroxy or a Ci-C4-hydroxyalkyl

Function, C 2 -C 8 alkenyl, C 1 -C 8 alkoxy, acyl, acyloxy, C 6 -C 12 aryl or arylalkyl, -OR ⁸ and -N (R ⁸ ) R ⁹ , as well as N-alicyclic or

N-aromatic,

substituted with a hydroxy or a Ci-C4-hydroxyalkyl

Function, C 2 -C 8 alkenyl, C 1 -C 8 alkoxy, acyl, acyloxy or C 6 -C 12 aryl or arylalkyl,

R ⁹ to R ^{13 have} the same groups as R ⁸ and -OR ⁸ ,

m and n independently of one another 1, 2, 3 or 4,

X acids which can form adducts with triazine compounds (VII) mean

and / or c) oligomeric esters of tris (hydroxyethyl) isocyanurate with

(NH ₄ PO 3) z, where y is 1 to 3 and z is 1 to 10,000.

10. flame retardant formulation according to one or more of claims 1 to 9, characterized in that it is at the component C to zinc oxide, zinc hydroxide, zinc oxide, zinc borate, basic zinc silicate and / or

Zinc stannate acts.

1 1. Flame retardant formulation according to one or more of claims 1 to 10, characterized in that component C is zinc stannate.

12. Use of a flame retardant formulation according to one or more of claims 1 to 1 1 as a flame retardant, in particular as

Flame retardants for clearcoats and intumescent coatings, as

Flame retardants for wood and other cellulosic products, as reactive and / or non-reactive flame retardants for polymers, for the production of flame-retardant polymer molding compositions, for the production of flame-retardant polymer moldings bodies and / or for flame retardant finishing of polyester and cellulose pure and blended fabrics by impregnation.

13. Use according to claim 12, characterized in that the

Flame retardant formulations according to one or more of claims 1 to 17 in or for connectors, current-contacting parts in power distributors (Fl-protection), circuit boards, potting compounds, power connectors, circuit breaker, lamp housing, LED lamp housing, capacitor housing, bobbins, fans, protective contacts, plugs , can be used in / on circuit boards, housings for plugs, cables, flexible circuit boards, charging cables, engine covers, textile coatings and other products

14. Flame retardant thermoplastic or thermosetting

Polymer molding composition, polymer moldings, films, filaments and fibers containing 0.5 to 45 wt .-% flame retardant formulation according to one or more of claims 1 to 1 1, 10 to 95 wt .-% thermoplastic or thermosetting polymer or mixtures the same, 0 to 55 wt .-% of additives and 0 to

55 wt .-% filler or reinforcing materials, the sum of the

Components 100 wt .-% is.

15. Flame-Retardant Thermoplastic or Thermosetting Polymer Shaped Articles, Films, Threads and Fibers Containing 5 to 30% by Weight Flame retardant formulation according to one or more of claims 1 to 1 1, 20 to 95 wt .-% thermoplastic or thermosetting polymer or mixtures thereof, 5 to 55 wt .-% additives and 10 to 55 wt .-% filler or reinforcing materials, wherein the Sum of components 100 wt .-% is.

16. flame-retardant thermoplastic or thermosetting polymer molding composition according to claim 14 or 15, characterized in that it is polyester, polyamides and / or polymer blends containing polyamides or polyesters is.