WO2000046286A1

WO2000046286A1 - Utilisation of aluminium compounds for improving antistatic properties

Info

Publication number: WO2000046286A1
Application number: PCT/EP2000/000604
Authority: WO
Inventors: Michael Zobel; Thomas Eckel; Dieter Wittmann
Original assignee: Bayer Aktiengesellschaft
Priority date: 1999-02-04
Filing date: 2000-01-27
Publication date: 2000-08-10
Also published as: AR022467A1; CN1146625C; HK1044555A1; DE19904393A1; CN1339046A; AU3421200A; KR20010101978A; BR0007951A; JP2002536483A; EP1151032A1; CA2368236A1

Abstract

The present invention relates to the utilisation of aluminium compounds for producing molding materials, shaped parts and plates with antistatic properties.

Description

Use of aluminum compounds to improve the antistatic properties

The present invention relates to the use of aluminum compounds for

Production of molding compounds, molded parts, sheets and foils with antistatic properties, which result in improved mechanical properties and an improved antistatic effect.

Thermoplastic molding compositions, in particular those which contain homo- and / or copolymers of one or more ethylenically unsaturated monomers, polycarbonates and polyesters, are known from a large number of publications. This applies in particular to the use of ABS polymers. The following documents are only mentioned by way of example: DE-A-19616, WO 97/40092, EP-A-728811, EP-A-315868 (= US-A-4937285), EP-A 0174493 (US-P 4983658), US-P 5030675,

JA 59202240, EP-A 0363608 (= US-P 5204394), EP-A 0767204, EP-A 0611798, WO 96/27600, EP-A 0754.

The antistatic properties of the thermoplastic molding compositions described in this prior art are still in need of improvement.

Surprisingly, it has now been found that molding compositions, moldings, plates and films have an antistatic effect when aluminum compounds are added to them.

The present invention accordingly relates to the use of aluminum compounds for the production of molding compositions, moldings, plates with antistatic properties. According to the invention, use for thermoplastic molding compositions is preferred. These preferably contain thermoplastic polycarbonate and 0.01 to 30, preferably 0.01-20, particularly preferably 0.01-10 parts by weight per 100 parts by weight (polycarbonate) of aluminum compounds with an average particle diameter of lnm-20 μm, preferably lnm - 10 μm, particularly preferably 5 - 500 nm, most preferably 5 - 200 nm.

Compounds of aluminum with one or more metals of the 1st to 5th main group and 1st to 8th subgroup of the periodic system, preferably 2nd to 5th main group and 4th to 8th subgroup, particularly preferably 3rd to 4th, are suitable according to the invention 5th main group and 4th to 8th subgroup or compounds with the elements oxygen, carbon, nitrogen, hydrogen, sulfur and silicon.

According to the invention, oxides, water-containing oxides, phosphates, sulfates, sulfides,

Hydroxides, borates, boron phosphates, of aluminum can be used. Aluminum oxide hydroxide, aluminum phosphate and aluminum borate are particularly preferred. Aluminum oxide hydroxide is most preferred.

Water-containing compounds are preferred.

Particle size and particle diameter always mean the average particle diameter d ₅₀ , determined by ultracentrifuge measurements according to W. Scholtan et al. Colloid-Z. and Z. Polymers 250 (1972), pp. 782 to 796.

The aluminum compounds can be present as powders, pastes, brine, dispersions or suspensions. Precipitation can be used to obtain powders from dispersions, brine or suspensions. The thermoplastic molding compositions contain in particular

A. 40 to 99 parts by weight, preferably 50 to 95 parts by weight, particularly preferably 60 to 90 parts by weight of an aromatic polycarbonate,

B. 0 to 50, preferably 1 to 30 parts by weight of a vinyl (co) polymer (B1) from at least one monomer selected from the series styrene, α-methylstyrene, nucleus-substituted styrenes, Ci-Cg-alkyl methacrylates, C \ - Cg-alkyl acrylates with at least one monomer from the series acrylonitrile, methacrylonitrile, Ci-Cg-alkyl methacrylates, Cj-Cg-alkyl acrylates,

Maleic anhydride, N-substituted maleimides and / or polyalkylene terephthalate (B2),

C. 0.5 to 60 parts by weight, preferably 1 to 40 parts by weight, particularly preferably 2 to 30 parts by weight, of a graft polymer consisting of at least two monomers from the group of the mono- or polyunsaturated olefins, such as Ethylene, propylene, chloroprene, butadiene, isoprene, vinyl acetate, styrene, α-methylstyrene, nucleus-substituted styrenes, vinyl cyanides, such as, for. B. acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted-maleimides,

D. 0.01 to 30 parts by weight, preferably 0.01 to 20 parts by weight, particularly preferably 0.01 to 10 parts by weight of aluminum compound with an average particle diameter of lnm - 20 microns, preferably lnm - 10 microns , particularly preferably 5 - 500 nm, most preferably 5 - 200 nm and optionally

E. Common additives such as flame retardants, anti-dripping agents, very fine inorganic compounds, stabilizers, dyes, pigments, lubricants and mold release agents, nucleating agents, fillers and reinforcing materials. The sum of all parts by weight A + B + C + D + E is 100.

Component A

Thermoplastic aromatic polycarbonates according to component A which are suitable according to the invention are those based on the diphenols of the formula (I)

wherein

A is a single bond-C5-alkylene, C2-C5-alkylidene, C5-Cö-cycloalkylene, -S- or -SO2-,

B chlorine, bromine,

0, 1 or 2 and

Are 1 or 0,

or alkyl-substituted dihydroxyphenylcycloalkanes of the formula (II),

woπn

R ^ and R ° independently of one another, each hydrogen, halogen, preferably chlorine or bromine, Ci-Cg-alkyl, Cs-Cg-cycloalkyl, Cö-Cio-aryl, preferably phenyl, and C -C ^ -Nralkyl, preferred Phenyl-C 1 -C 4 -alkyl, in particular benzyl,

m is an integer of 4, 5, 6 or 7, preferably 4 or 5,

R9 and RO can be selected individually for each Z, independently of one another hydrogen ^• or -CC ₆ alkyl,

and

Z means carbon, with the proviso that at least one atom Z R "and RIO simultaneously mean alkyl.

Suitable diphenols of the formula (I) are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2- methylbutane, l, l-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4 -hydroxyphenyl) propane. Preferred diphenols of the formula (I) are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and 1,1-bis- (4th -hydroxyphenyl) cyclohexane.

Preferred diphenols of the formula (II) are l, l-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 1, 1-bis (4-hydroxyphenyl) -2,4,4-trimethyl-cyclopentane.

Polycarbonates suitable according to the invention are both homopolycarbonates and copolycarbonates.

Component A can also be a mixture of the thermoplastic polycarbonates defined above.

Polycarbonates can be prepared in a known manner from diphenols with phosgene

Phase boundary process or with phosgene according to the process in homogeneous phase, the so-called pyridine process, the molecular weight can be adjusted in a known manner by an appropriate amount of known chain terminators.

Suitable chain terminators are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) phenol according to DE-OS 2842005 or Monoalkylphenol or dialkylphenol with a total of 8 to 20 carbon atoms in the alkyl substituents according to German patent application P 3506472.2, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2 - (3,5-Dimethyl-heptyl) phenol and 4- (3,5-dimethyl 1-heptyl) phenol. The amount of chain terminators is generally between 0.5 and 10 mol%, based on the sum of the diphenols of the formulas (I) and / or (II) used in each case.

The polycarbonates A suitable according to the invention have average molecular weights

(M _w ), weight average, measured, for example, by ultracentrifugation or scattered light measurement) from 10,000 to 200,000, preferably 20,000 to 80,000.

The polycarbonates A suitable according to the invention can be branched in a known manner, preferably by incorporating 0.05 to 2 mol%, based on the sum of the diphenols used, of tri- or more than trifunctional compounds, e.g. those with three or more than three phenolic groups.

In addition to bisphenol A homopolycarbonate, preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and the copolycarbonates of bisphenol A with up to 60 mol%, based on the molar sum of diphenols, l, l-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Some or all of the polycarbonates A can be replaced by aromatic polyester carbonates. The aromatic polycarbonates of component A can also contain polysiloxane blocks. Their production is described for example in DE-OS 3334872 and in US-PS 3821325.

Component B

Vinyl (co) polymers according to component B1 which can be used according to the invention are those composed of at least one monomer from the series: styrene, methylstyrene and / or nucleus-substituted styrenes, Ci-Cg-alkyl methacrylate, Cj-Cg-alkyl acrylate with at least one monomer from the series: Acrylonitrile, methacrylonitrile, C \ - Cg-alkyl methacrylate, Cj-Cg-alkyl acrylate, maleic anhydride and / or N-substituted maleimides (B.2).

Ci-Cg-alkyl acrylates or Cj-Cg-alkyl methacrylates are esters of acrylic acid or methacrylic acid and monohydric alcohols with 1 to 8 carbon atoms. Methacrylic acid methyl esters, ethyl esters and propyl esters are particularly preferred. Methyl methacrylate is mentioned as a particularly preferred methacrylic acid ester.

Thermoplastic (co) polymers with a composition according to component B can be used in the graft polymerization to produce component C as

A by-product is created, especially when large amounts of monomers are combined with small ones

Amounts of rubber are grafted. The amount of to be used according to the invention

(Co) polymer B1 does not include these by-products of the graft polymerization.

The (co) polymers according to component B1 are resin-like, thermoplastic and rubber-free.

Particularly preferred (co) polymers B1 are those made from styrene (B1.) With acrylonitrile and optionally with methyl methacrylate (B1.2), from α-methylstyrene (B1.) With acrylonitrile and optionally with methyl methacrylate (B1.2). , or from styrene (Bl.l) and α-methylstyrene with acrylonitrile and optionally with methyl methacrylate (B1.2).

The thermoplastic (co) polymers B1 contain 50 to 99, preferably 60 to

95 parts by weight of B.1.2 and 50 to 2, preferably 40 to 5 parts by weight of B.1.2.

The styrene-acrylonitrile copolymers according to component B1 are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The copolymers According to component B, molecular weights M _w (weight average, determined by light scattering or sedimentation) preferably have between 15,000 and 200,000.

Particularly preferred copolymers B1 according to the invention are also random copolymers of styrene and maleic anhydride, which can be prepared from the corresponding monomer by continuous mass or solution polymerization with incomplete conversions.

The proportions of the two components of the randomly constructed styrene-maleic anhydride copolymers suitable according to the invention can be varied within wide limits. The preferred content of maleic anhydride is 5 to 25% by weight.

The molecular weights (number average M _n ) of the randomly constructed styrene-maleic anhydride copolymers according to component B which are suitable according to the invention can vary over a wide range. The range from 60,000 to 200,000 is preferred. An intrinsic viscosity of 0.3 to 0.9 is preferred for these products (measured in dimethylformamide at 25 ° C.; see Hoffmann, Krömer, Kuhn, Polymeranalytik I, Stuttgart 1977, page 316 ff).

Instead of styrene, the vinyl (co) polymers B1 can also contain nucleus-substituted styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted styrenes such as α-methylstyrene, which may or may not be substituted.

The polyalkylene terephthalates of component B2 are reaction products made from aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products. Preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component of terephthalic acid residues and at least 80% by weight, preferably at least 90 mol%, based on the diol component of ethylene glycol and / or butanediol -l, 4 residues.

In addition to terephthalic acid residues, the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, of residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as e.g. Residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexane-diacetic acid.

In addition to ethylene glycol or butanediol 1,4-residues, the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 Contain carbon atoms, e.g. Residues of propanediol-1,3,2-ethylpropanediol-1,3, neopentylglycol, pentanediol-1,5, hexanediol-1,6, cyclohexane-dimethanol-1,4,3-ethylpentanediol-2,4,2-methylpentanediol 2,4,2,2,4-trimethylpentanediol-1,3,2-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3, hexanediol-2,5,4,4-di- (β-hydroxyethoxy ) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-l, l, 3,3-tetramethyl-cyclobutane, 2,2-bis

(4-β-hydroxyethoxy-phenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-OS 2 407 674, 2 407 776, 2 715 932).

The polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-OS

1,900,270 and U.S. Patent 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol. Particular preference is given to polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.

Mixtures of polyalkylene terephthalates contain 1 to 50% by weight, preferably 1 to 30% by weight, polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99% by weight, polybutylene terephthalate.

The polyalkylene terephthalates preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. in the Ubbelohde viscometer.

The polyalkylene terephthalates can be prepared by known methods (see e.g. Kunststoff-Handbuch, Volume VIII, p. 695 ff., Carl-Hanser-Verlag, Munich 1973).

Component C

The graft polymers C comprise e.g. Graft copolymers with rubber-elastic properties, consisting essentially of at least two of the following

Monomers available are: chloroprene, 1,3-butadiene, isopropene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth) -acrylic acid esters with 1 to 18 carbon atoms in the alcohol component; i.e. polymers such as in "Methods of Organic Chemistry" (Houben-Weyl), Vol. 14/1, Georg Thieme-Verlag, Stuttgart 1961, pp. 393-406 and in C.B. Bucknall, "Thoughened Plastics", Appl. Science Publishers,

London 1977. Preferred polymers C are partially crosslinked and have gel contents of more than 20% by weight, preferably more than 40% by weight, in particular more than 60% by weight.

Preferred graft polymers C include graft polymers of: Cl 5 to 95, preferably 30 to 80 parts by weight of a mixture of

C.1.1 50 to 95 parts by weight of styrene, α-methylstyrene, styrene substituted with halogen or methyl nucleus, Ci-Cg-alkyl methacrylate, in particular methyl methacrylate, Cj-Cg-alkyl acrylate, in particular methyl methacrylate or mixtures of these compounds and

C.1.2 5 to 50 parts by weight of acrylonitrile, methacrylonitrile, Ci-Cg-alkyl methacrylates, especially methyl methacrylate, Ci-Cg-alkyl acrylate, in particular methacrylate, maleic anhydride, Cj-C - ^ - alkyl or. phenyl-N-substituted maleimides or mixtures of these compounds

C.2 5 to 95, preferably 20 to 70 parts by weight of polymer with a glass transition temperature below - 10 ° C.

Preferred graft polymers C are e.g. polybutadienes, butadiene / styrene copolymers and acrylate rubbers grafted with styrene and / or acrylonitrile and / or (meth) acrylic acid alkyl esters; i.e. Copolymers of the type described in DE-OS 1694173 (= US-PS 3564077); with acrylic or methacrylic acid alkyl esters,

Vinyl acetate, acrylonitrile, styrene and / or alkylstyrenes grafted polybutadienes, butadiene / styrene or butadiene / acrylonitrile copolymers, polyisobutenes or polyisoprenes, such as those e.g. in DE-OS 2348377 (= US-PS 3919353) are described.

Particularly preferred polymers C are, for example, ABS polymers, as described, for example, in DE-OS 2035390 (= US Pat. No. 3644574) or in DE-OS 2248242 (= GB-PS 1409275). Particularly preferred graft polymers C are graft polymers which are obtained by grafting

I. 10 to 70, preferably 15 to 50, in particular 20 to 40% by weight, based on the graft product, of at least one (meth) acrylic acid ester or 10 to 70, preferably 15 to 50, in particular 20 to 40% by weight of one Mixtures of 10 to 50, preferably 20 to 35% by weight, based on the mixture, acrylonitrile or (meth) -acrylic acid ester and 50 to 90, preferably 65 to 80% by weight, based on the mixture, of styrene

II. 30 to 90, preferably 50 to 85, in particular 60 to 80% by weight, based on the graft product, of a butadiene polymer with at least 50% by weight, based on II, butadiene residues as the graft base

are available

wherein the gel fraction of the graft base II is preferably at least 20% by weight, particularly preferably at least 40% by weight (measured in toluene), the degree of graft G 0.15 to 0.55 and the average particle diameter d5Q of the graft polymer 0.05 to 2 μm, preferably 0.1 to 0.6 μm.

(Meth) -acrylic acid esters I are esters of acrylic acid or methacrylic acid and monohydric alcohols with 1 to 18 carbon atoms. Methacrylic acid methyl esters, ethyl esters and propyl esters are particularly preferred.

In addition to butadiene residues, the graft base II can contain up to 50% by weight, based on II, residues of other ethylenically unsaturated monomers, such as styrene, acrylonitrile, esters of acrylic or methacrylic acid with 1 to 4 carbon atoms in the alcohol component (such as methyl acrylate, ethyl acrylate) , Methyl methacrylate, ethyl methacrylate), vinyl ester and / or contain vinyl ether. The preferred graft base II consists of pure polybutadiene.

The degree of grafting G denotes the weight ratio of grafted graft monomers to the graft base and is dimensionless.

The average particle size d5Q is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-796).

Particularly preferred polymers C are e.g. also graft polymers

(a) 20 to 90% by weight, based on C, acrylate rubber with a glass transition temperature below -20 ° C as the graft base and

(b) 10 to 80% by weight, based on C, of at least one polymerizable, ethylenically unsaturated monomer (cf. C. 1) as graft monomers.

The acrylate rubbers (a) of the polymers C are preferably polymers of

Acrylic acid alkyl esters, optionally with up to 40% by weight, based on (a), of other polymerizable, ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include C 1 -C 6 -alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halogen-C _j -Cg alkyl esters, such as chloroethyl acrylate, and mixtures of these

Monomers.

Monomers with more than one polymerizable double bond can be copolymerized for crosslinking. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated mono- high-quality alcohols with 3 to 12 carbon atoms or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, such as ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.

Crosslinking monomers are preferably allyl methacrylate, ethylene glycol dimethyl acrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes.

The amount of crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2% by weight, based on the graft base (a).

In the case of cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base (a).

Preferred “other” polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base (a), are, for example, acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl-Ci-Cg-alkyl ethers, methyl methacrylate, butadiene. Preferred Acrylate rubbers as

Graft base (a) are emulsion polymers which have a gel content of at least 60% by weight. Other suitable graft bases are silicone rubbers with graft-active sites, as are described in published patent applications DE-OS 3704657, DE-OS 3704655, DE-OS 3631540 and DE-OS 3631539.

The gel content of the graft base (a) is determined at 25 ° C. in dimethylformamide

(M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).

According to the invention, since the graft monomers are not necessarily grafted completely onto the graft base in the grafting reaction,

Graft polymers C are also understood to mean those products which are obtained by polymerizing the graft monomers in the presence of the graft base.

Component D

The above-mentioned compounds of aluminum are suitable as component D.

As already explained above, the aluminum compounds can be present as powders, pastes, brine, dispersions or suspensions. Precipitation can be used to obtain powders from dispersions, brine or suspensions.

The powders can be incorporated into the thermoplastic materials by customary methods, for example by direct kneading or extruding the constituents of the molding composition and the very finely divided inorganic powders. Preferred processes are the preparation of a masterbatch, for example in flame retardant additives, other additives, monomers, solvents, in component A or the co-precipitation of dispersions of components B or C with dispersions, suspensions, pastes or sols of the finely divided inorganic materials. Component E

The molding compositions can include conventional additives, such as flame retardants, anti-dripping agents, very finely divided inorganic compounds, lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing materials

Dyes and pigments included. The usual additives such as processing aids are used in the generally known amounts.

The molding compositions can generally contain from 0.01 to 20% by weight, based on the total molding composition, of flame retardants. Examples of flame retardants are organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds such as Mg-Al hydroxide, inorganic compounds such as aluminum oxides, titanium dioxide, antimony oxides, barium metaborate , Hydroxoantimonate,

Zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, tin borate, ammonium borate, barium metaborate and tin oxide as well as siloxane compounds.

Phosphorus compounds as described in EP

A 363608, EP-A 345522 or EP-A 640655 are used.

Such phosphorus compounds are, for example, phosphorus compounds of the formula (III)

in which

R ⁵ , R ⁶ , R ⁷ and R ⁸ , independently of one another in each case optionally halogenated C 1 -C 6 -alkyl, in each case optionally by alkyl, preferably C 1 -C 4 -alkyl, and / or

Halogen, preferably chlorine, bromine, substituted C5-Cg-cycloalkyl, Cg-C g-aryl or Cγ-C ^ aralkyl.

R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably independently of one another C 1 -C 6 -alkyl, phenyl, naphthyl or phenyl-C 1 -C 6 -alkyl. The aromatic groups R ⁵ , R ⁶ , R ⁷ and R ⁸ can in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or Cj-Cj-alkyl. Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.

X in the formula (III) denotes a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms. This is derived from diphenols of the formula (I) or (II), preferably from the suitable and preferred diphenols mentioned therein. X is particularly preferably derived from diphenylphenol, bisphenol A, resorcinol or hydroquinone or their chlorinated or brominated derivatives.

k in the formula (III), independently of one another, can be 0 or 1, preferably n is 1.

N stands for values from 0 to 30, preferably for 0 or an average value of 0.3 to 20, particularly preferably 0.5 to 10, in particular 0.5 to 6. Mixtures of phosphorus compounds of the formula (III) preferably contain 10 to 90% by weight, preferably 12 to 40% by weight, of at least one monophosphorus compound of the formula (III) and at least one oligomeric phosphorus compound or a mixture of oligomeric phosphorus compounds in amounts from 10 to 90% by weight, preferably 60 to 88% by weight, based on the

Total amount of phosphorus compounds used.

Monophosphorus compounds of the formula (III) are, in particular, tributyl phosphate, tris (2-chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethyl cresyl isophosphate, tris ) phosphate, halogen-substituted aryl phosphates, methylphosphonic acid dimethyl ester, methylphosphonic acid diphenyl ester, phenylphosphonic acid diethyl ester, triphenylphosphine oxide or tricresylphosphine oxide.

The mixtures of monomers and oligomeric phosphorus compounds of the formula

(III) have average N values of 0.3 to 20, preferably 0.5 to 10, in particular 0.5 to 6.

The phosphorus compounds of the formula (III) are known (see, for example, EP-A 363608, EP-A 640655, EP-A 542522) or can be prepared analogously by known methods

Manufacture ways (e.g. Ullmann's Encyclopedia of Industrial Chemistry, vol. 18, pp. 301 ff. 1979; Houben-Weyl, Methods of Organic Chemistry, vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).

The molding compositions according to the invention can optionally from compounds of

Formula (III) contain various flame retardants in an amount of up to 20 parts by weight. Synergistic flame retardants are preferred. Examples of other flame retardants are organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde. called hyd resins or siloxane compounds. The molding compositions according to the invention can optionally contain inorganic substances which differ from the inorganic compounds D, such as, for example, inorganic hydroxide compounds such as Mg, Al hydroxide, inorganic compounds such as aluminum oxide, antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide,

Molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metaborate and tin oxide.

In addition to aluminum compounds, the thermoplastic molding compositions according to the invention can contain further very finely divided inorganic compounds which have a favorable effect on the flame retardant properties of the molding compositions according to the invention. These inorganic compounds can be added in an amount of up to 25 parts by weight (based on the total mixture) and comprise compounds of one or more metals of the 1st to 5th main group and the 1st to 8th subgroup of the periodic table, preferably the 2nd to the 5th main group and the 4th to 8th subgroup, particularly preferably the 3rd to 5th main group and the 4th to 8th subgroup with the elements oxygen, sulfur, boron, phosphorus, carbon, nitrogen, hydrogen and / or Silicon.

Preferred compounds are, for example, oxides, hydroxides, water-containing

Oxides, sulfates, sulfites, sulfides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates.

Preferred very finely divided inorganic compounds are, for example, TiN, TiO ₂ , SnO ₂ , WC, ZnO, ZrO ₂ , Sb ₂ O 3, SiO ₂ , iron oxides, NaSO 4 BaSO, vanadium oxides,

Zinc borate, silicates such as Al silicates, Mg silicates, one, two, three-dimensional silicates, mixtures and doped compounds can also be used. Furthermore, these nanoscale particles can be surface-modified with organic molecules in order to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be created. The average particle diameters are less than or equal to 200 nm, preferably less than or equal to 150 nm, in particular 1 to 100 nm.

Particle size and particle diameter always mean the average particle diameter d50, determined by ultracentrifuge measurements according to W. Scholtan et al. Colloid-Z. and Z. Polymers 250 (1972), pp. 782 to 796.

The inorganic compounds can be present as powders, pastes, brine, dispersions or suspensions. Precipitation can be used to obtain powders from dispersions, brine or suspensions.

The powders can be incorporated into the thermoplastic materials by customary methods, for example by direct kneading or extruding the constituents of the molding composition and the very finely divided inorganic powders. Preferred methods are the preparation of a master batch, e.g. in flame retardant additives, other additives, monomers, solvents, in component A or the co-precipitation of dispersions of components B or C with dispersions, suspensions, pastes or sols of the very finely divided inorganic materials.

The thermoplastic molding compositions can contain inorganic fillers and reinforcing materials such as glass fibers, optionally cut or ground, glass beads, glass balls, platelet-shaped reinforcing materials such as kaolin, talc, mica, silicates, quartz, talc, titanium dioxide, wollastonite, mica, carbon fibers or a mixture thereof. Cut or ground glass fibers are preferably used as the reinforcing material. Preferred fillers, which can also have a reinforcing effect, are glass balls, mica, silicates, quartz, talc, titanium dioxide, wollastonite. The filled or reinforced molding compositions can contain up to 60, preferably 10 to 40% by weight, based on the filled or reinforced molding composition, of fillers and / or reinforcing materials.

Furthermore, fluorinated polyolefins can generally be added in an amount of up to 5, preferably 0.1 to 3, in particular 0.1 to 1 part by weight (based on the total molding composition). The fluorinated polyolefins are high molecular weight and have glass transition temperatures of above -30 ° C., generally above 100 ° C., fluorine contents, preferably from 65 to 76, in particular from 70 to 76% by weight, average particle diameter d5 _Q from 0.05 to 1,000 μm, preferably 0.08 to

20 μm. In general, the fluorinated polyolefins E have a density of 1.2 to 2.3 g / cm 4.

Preferred fluorinated polyolefins are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene and ethylene / tetrafluoroethylene copolymers.

The fluorinated polyolefins are known (cf. "Vinyl and Related Polymers" from Schildknecht, John Wiley & Sons, Inc., New York, 1962, pages 484 to 494; "Fluoropolymers" from Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, volume

13, 1970, pages 623-654; "Modern Plastics Encyclopedia", 1970 to 1971, volume 47, No. 10A, October 1970, Mc Grow-Hill, Inc., New York, pages 134 and 774; "Modern Plastics Encyclopedia", 1975 to 1976, October 1975, volume 52, No. 10A, Mc Graw-Hill, Inc., New York, pages 27, 28 and 472 and U.S. Patents 3671487, 3723373 and 338092).

They can be produced by known processes, for example by

Polymerization of tetrafluoroethylene in an aqueous medium with a catalyst which forms free radicals, for example sodium, potassium or ammonium peroxydisulfate, at pressures of 7 to 71 kg / cm 2 and at temperatures of 0 to 200.degree. preferably at temperatures from 20 to 100 ° C. (For more details, see, for example, US Patent 2393967). Depending on the form of use, the density of these materials can be between 1.2 and 2.3 g / cm ^, the average particle size between 0.05 and 1,000 nm.

Fluorinated polyolefins preferred according to the invention are tetrafluoroethylene polymers and have average particle diameters of 0.05 to 20 μm, preferably 0.08 to 10 μm, and a density of 1.2 to 1.9 g / cn. They are preferably in the form of a coagulated mixture of emulsions of the tetrafluoroethylene polymers with emulsions the graft polymer C used.

Suitable fluorinated polyolefins that can be used in powder form are tetrafluoroethylene polymers with average particle diameters of 100 to 1,000 μm and densities of 2.0 g / cm 2 to 2.3 g / cn.

To produce a coagulated mixture of C and the fluorinated polyolefin, an aqueous emulsion (latex) of a graft polymer C with average latex particle diameters from 0.05 to 2 μm, in particular 0.1 to 0.6 μm, with a finely divided emulsion of a fluorinated polyolefin in water with average particle diameters of 0.05 to 20 μm, in particular 0.08 to 10 μm, mixed; Suitable tetrafluoroethylene polymer emulsions usually have

Solids contents of 30 to 70% by weight, in particular 50 to 60% by weight.

The aqueous emulsion of the graft polymer C has solids contents of 25 to 60% by weight, preferably 30 to 45% by weight, in particular 30 to 35% by weight.

The quantity in the description of component C does not include the proportion of the graft polymer in the coagulated mixture of graft polymer and fluorinated polyolefms. In the emulsion mixture, the weight ratio of graft polymer C to the fluorinated polyolefin is 95: 5 to 60:40. The emulsion mixture is coagulated in a known manner, for example by spray drying, freeze-drying or coagulation by adding inorganic or organic salts, acids, bases or organic, water-miscible solvents, such as alcohols.

Ketones, preferably at temperatures from 20 to 150 ° C, in particular from 50 to 100 ° C. If necessary, drying can be carried out at 50 to 200 ° C., preferably 70 to 100 ° C.

Suitable tetrafluoroethylene polymer emulsions are commercially available products and are offered, for example, by DuPont as Teflon® 30 N.

The molding compositions containing components A to E are prepared by mixing the respective constituents in a known manner and melt-compounding or melt-extruding them at temperatures of 200 ° C. to 300 ° C. in conventional units such as internal kneaders, extruders and twin-screw screws, the fluorinated polyolefins preferably in the form of the coagulated mixture already mentioned.

The individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.

The molding compositions of the present invention can be used to produce moldings of any type. In particular, moldings can be produced by injection molding. Examples of moldings that can be produced are: Housing parts of all kinds, for example for household appliances, such as juicers, coffee machines, mixers, for office machines, such as computers, printers, monitors or cover plates for the construction sector and parts for the motor vehicle sector. They are also used in the field of electrical engineering because they have very good electrical properties. The molding compounds are particularly suitable for the production of thin-walled molded parts (eg data technology housing parts), where particularly high demands are placed on the antistatic properties of the plastics used.

Another form of processing is the production of moldings by blow molding or by deep drawing from previously produced sheets or foils.

Examples

Component A

Polycarbonate based on bisphenol A with a relative solution viscosity of 1,252, measured in methylene chloride at 25 ° C and in a concentration of 0.5 g / 100 ml.

Component B

Styrene / acrylonitrile copolymer with a styrene / acrylonitrile ratio of 72:28 and an intrinsic viscosity of 0.55 dl / g (measurement in dimethylformamide at 20 ° C).

Component C

Graft polymer of 40 parts by weight of styrene and acrylonitrile in the ratio of

73:27 to 60 parts by weight of particulate crosslinked polybutadiene rubber (average particle diameter d5Q = 0.3 μm), produced by emulsion polymerization.

Component D

Pural 200, an aluminum oxide hydroxide (from Condea, Hamburg, Germany) is used as the inorganic compound. The average particle size of the material is approx. 20-40 nm.

Component E

Tetrafluoroethylene polymer as a coagulated mixture of a SAN graft polymer emulsion according to component C in water and a tetrafluoroethylene polymer emulsion in water. The weight ratio of graft polymer C to etrafluoroethylene polymer E in the mixture is 90% by weight to 10% by weight. The tetrafluoroethylene polymer emulsion has a solids content of 60% by weight, the average particle diameter is between 0.05 and 0.5 μm. The SAN graft polymer emulsion has a solids content of 34% by weight and an average latex particle diameter of 0.4 μm.

Manufacture of E

The emulsion of the tetrafluoroethylene polymer (Teflon 30 N from DuPont) is mixed with the emulsion of the SAN graft polymer C and stabilized with 1.8% by weight, based on polymer solids, of phenolic antioxidants. At 85 to 95 ° C, the mixture is coagulated with an aqueous solution of MgSO4 (Epsom salt) and acetic acid at pH 4 to 5, filtered and washed until practically free of electrolytes, then freed from the main amount of water by centrifugation and then at 100 ° C dried a powder.

This powder can then be compounded with the other components and optionally together with the flame retardant of the formula (IV) in the units described.

In addition, a flame retardant of the formula (IV) was used.

Components A to E are mixed on a 3 1 internal mixer. The moldings are produced on an Arburg 270E injection molding machine at 260 ° C.

The tensile modulus of elasticity is measured according to method ISO 527.

The elongation at break DR is determined as part of the determination of the tensile modulus of elasticity according to method ISO 527 on F3 shoulder bars.

The antistatic effect is determined after a dust figure test.

For this purpose, round plates are statically charged with a cotton cloth and then dusted with aluminum powder. The assessment is done visually.

The heat resistance according to Vicat B is determined in accordance with DIN 53460.

The MVR was determined in accordance with ISO 1133. a _k Izod was determined in accordance with ISO 1801A.

The composition of the materials tested and the data obtained are summarized in Tables 1 and 2 below.

Table 1

Table 2

* PETS = pentaerythritol tetrastearate

Claims

claims

1. Use of aluminum compounds for the production of molding compounds, moldings, films, plates with antistatic properties.

2. Use according to claim 1, characterized in that oxides, water-containing oxides, phosphates, sulfates, sulfides, sulfites, hydroxides, borates, boron phosphates of aluminum are used.

3. Use according to claim 1, characterized in that aluminum compounds with an average particle diameter of lnm-20 microns are used.

4. Use according to claim 1, characterized in that aluminum compounds with an average particle diameter of lnm- 10 microns are used.

5. Use according to claim 1, characterized in that aluminum compounds with a medium

Particle diameters of 5-500 nm can be used.

6. Use according to claim 1 for the production of thermoplastic molding compositions containing aromatic polycarbonate and / or vinyl copolymer and / or polyalkylene terephthalate and / or graft polymer.

7. Use according to claim 1 for the production of thermoplastic molding compositions containing A. 40 to 99 parts by weight of an aromatic polycarbonate,

B. 0 to 50 parts by weight of a vinyl copolymer and / or a polyalkylene terephthalate,

C. 0.5 to 60 parts by weight of a graft polymer,

D. 0.1 to 30 parts by weight of an aluminum compound,

E. 0 to 25 parts by weight of an additive.

8. Use according to spoke 1 for the production of molding compositions containing 50 to 95 parts by weight of an aromatic polycarbonate A.

9. Use according spoke 1 for the production of molding compositions containing

Graft polymers C produced by copolymerization of

5 to 95 parts by weight of a mixture of

50 to 95 parts by weight styrene, α-methylstyrene, halogen- or alkylkernsub- stituiertem styrene, C _j -CG-alkyl methacrylate, Ci-Cg-alkyl acrylate or mixtures of these compounds and

5 to 50 parts by weight of acrylonitrile, methacrylonitrile, C 1 -C 6 -alkyl methacrylate, C 1 -C 6 -alkyl acrylate, maleic anhydride, C 1 -C 4 -alkyl- or phenyl-N-substituted maleimide or mixtures of these compounds.

10. Use according to spoke 1 for the production of molding compositions containing phosphorus compounds as flame retardants.

11. Use according to spoke 1 for the production of molding compositions containing one or a mixture of phosphorus compound (s) of the formula (III)

in which

R ⁵ , R ⁶ , R ⁷ and R ⁸ , independently of one another in each case optionally halogenated C 1 -C 6 -alkyl, in each case optionally substituted by alkyl, preferably C 1 -C 4 -alkyl, and / or halogen, preferably chlorine, bromine, C5- Cö-cycloalkyl, Cg-C30-aryl or C7-C12-aralkyl,

independently, 0 or 1,

N 0 to 30,

X denotes a mono- or polynuclear aromatic radical with 6 to 30 C atoms.

12. Use according spoke 1 for the production of molding compositions containing 0.01 to 20 wt .-%, based on the total molding composition of at least one further flame retardant.

3. Use according to claim 1 for the production of molding compositions containing at least one additive from the group of stabilizers, pigments, mold release agents, flow aids.