DE19904393A1 - Use of aluminum compounds to improve the antistatic properties - Google Patents

Abstract

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

Description

The present invention relates to the use of aluminum compounds for Production of molding compounds, molded parts, sheets and foils with antistatic Properties, the improved mechanical properties and improved antista effect.

Thermoplastic molding compositions, in particular those containing homo- and / or copolymers Risate of one or more ethylenically unsaturated monomers, polycarbo Contain nate and polyester are known from a variety of publications. This applies in particular to the use of ABS polymers. Just be an example referred to the following documents: DE-A-19 616, 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 thermoplastic molding compositions described in this prior art are their antistatic properties still need improvement.

Surprisingly, it has now been found that molding compositions, moldings, plates and Films have an antistatic effect if they have aluminum compounds be added.

The present invention accordingly relates to the use of aluminum nium compounds for the production of molding compounds, molded parts, plates with antista table properties.  

The use according to the invention 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) aluminum compounds with an average particle diameter from 1 nm-20 µm, preferably 1 nm-10 µm, particularly preferably 5-500 nm, most preferably 5-200 nm.

Compounds of aluminum with or are suitable according to the invention several metals of the 1st to 5th main group and 1st to 8th subgroup of the Perio densystems, preferably 2nd to 5th main group and 4th to 8th subgroup, especially preferably 3rd to 5th main group and 4th to 8th subgroup or compounds with the elements oxygen, carbon, nitrogen, hydrogen, sulfur and sili cium.

According to the invention, oxides, water-containing oxides, phosphates, sulfates, sulfides, Hydroxides, borates, boron phosphates, of aluminum can be used. Particularly preferred are aluminum oxide hydroxide, aluminum phosphate and aluminum borate. Maximum alumina hydroxide is preferred.

Water-containing compounds are preferred.

Particle size and particle diameter always means the mean 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 in the form of powders, pastes, brine, dispersions or Suspensions are present. Due to precipitation, dispersions, brine or sus pensions can be obtained.  

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, C ₁ -C ₈ -alkyl methacrylates , C ₁ - C ₈ alkyl acrylates with at least one monomer from the series acrylonitrile, methacrylonitrile, C ₁ -C ₈ alkyl methacrylates, C ₁ -C ₈ 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, especially before adds 2 to 30 parts by weight of a graft polymer consisting of at least at least two monomers from the group of mono- or polyunsaturated Olefins such as e.g. B. ethylene, propylene, chloroprene, butadiene, isoprene, vinyl acetate, styrene, α-methylstyrene, nucleus-substituted styrenes, vinyl cyanides, such as. B. Acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted-maleic imide,
• 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 a medium Particle diameter of 1 nm-20 microns, preferably 1 nm-10 microns, esp preferably 5-500 nm, most preferably 5-200 nm and optionally
• E) common additives such as flame retardants, anti-dripping agents, very finely divided inorganic compounds, stabilizers, dyes, pig elements, lubricants and mold release agents, nucleating agents, fillers and reinforcements 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 C ₁ -C ₅ alkylene, C ₂ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO ₂ -,
B chlorine, bromine,
q 0, 1 or 2 and
p is 1 or 0,
or alkyl-substituted dihydroxyphenylcycloalkanes of the formula (II),

wherein
R ⁷ and R ⁸ independently of one another, in each case hydrogen, halogen, preferably chlorine or bromine, C ₁ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl, C ₆ -C ₁₀ aryl, preferably phenyl, and C ₇ - C ₁₂ aralkyl, preferably phenyl-C ₁ -C ₄ alkyl, in particular benzyl,
m is an integer of 4, 5, 6 or 7, preferably 4 or 5,
R ⁹ and R ^{10 can be} selected individually for each Z, independently of one another hydrogen or C ₁ -C ₆ alkyl,
and
Z means carbon, with the proviso that at least one atom ZR ⁹ and R ¹⁰ simultaneously mean alkyl.

Suitable diphenols of formula (I) are e.g. B. hydroquinone, resorcinol, 4,4'-dihy hydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2- methyl butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxy phenyl) 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 (4-hydroxyphenyl) cyclo hexane.

Preferred diphenols of the formula (II) are 1,1-bis (4-hydroxyphenyl) -3,3-dime thylcyclohexane, 1,1-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 thermoplastics defined above be polycarbonates.

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 in a known manner by a corresponding amount of known chains cancel can be set.

Suitable chain terminators are e.g. B. phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethyl butyl) phenol according to DE-OS 28 42 005 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 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 used in each case (II).

The polycarbonates A suitable according to the invention have average molecular weights (M _w ), weight average, measured for. B. by ultracentrifugation or scattered light measurement) from 10,000 to 200,000, preferably 20,000 to 80,000.

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

In addition to bisphenol A homopolycarbonate, preferred polycarbonates are Copolycarbonates of bisphenol A with up to 15 mol%, based on the molsum 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 molsum of diphenols, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

The polycarbonates A can be partially or completely by aromatic polyesters carbonates to be replaced. The aromatic polycarbonates of component A can also contain polysiloxane blocks. Their manufacture is, for example, in DE-OS 33 34 872 and described 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, α-methylstyrene and / or nucleus-substituted styrenes, C ₁ -C ₈ -alkyl methacrylate, C ₁ -C ₈ -alkyl acrylate with at least one Monomers from the series: acrylonitrile, methacrylonitrile, C ₁ -C ₈ alkyl methacrylate, C ₁ -C ₈ alkyl acrylate, maleic anhydride and / or N-substituted maleimides (B.2).

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

Thermoplastic (co) polymers with a composition according to component B can 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 a.

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

Particularly preferred (co) polymers B1 are those made from styrene (B1.1) with acrylic nitrile and optionally with methyl methacrylate (B1.2), from α-methylstyrene (B1.1) with acrylonitrile and optionally with methyl methacrylate (B1.2), or from styrene (B1.1) 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 preferably have molecular weights M _w (average weight, determined by light scattering or sedimentation) between 15,000 and 200,000.

Particularly preferred copolymers B1 according to the invention are also statistical copolymers of styrene and maleic anhydride built up by a con continuous mass or solution polymerization with incomplete conversions the corresponding monomer can be prepared.

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

The molecular weights (number average M _n ) of the 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 be nucleus-substituted Styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted ones Styrenes such as α-methylstyrene, which may optionally be substituted, contain.

The polyalkylene terephthalates of component B2 are reaction products from aro Matic 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 wt .-%, based on the dicarboxylic acid component terephthalic acid residues and at least 80 wt .-%, preferably at least 90 mol%, based on the diol component ethylene glycol and / or 1,4-butanediol radicals.

The preferred polyalkylene terephthalates can besides terephthalic acid residues to 20 mol%, preferably up to 10 mol%, residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 carbon atoms or aliphatic dicar contain bonic acids with 4 to 12 carbon atoms, such as. B. residues of phthalic acid, Isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, Bern succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexane-diacetic acid.

The preferred polyalkylene terephthalates can be ethylene glycol or butane diol-1,4-residues 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 carbon atoms included, e.g. B. residues of 1,3-propanediol, 2-1,3-propanediol, 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- 1,3-diethyl propanediol, 2,5-hexanediol, 1,4-di (β-hydroxyethoxy) benzene, 2,2-bis (4- hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis (4-β-hydroxyethoxy-phenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-OS 24 07 674, 24 07 776, 27 15 932).

The polyalkylene terephthalates can be 3- or 4- by incorporating relatively small amounts quality alcohols or 3- or 4-basic carboxylic acids, e.g. B. according to DE-OS 19 00 270 and U.S. Patent 3,692,744. Examples of preferred branches trimesic acid, trimellitic acid, trimethylolethane and propane and Pentaerythritol.  

Polyalkylene terephthalates which consist solely of terephthalic acid are particularly preferred and their reactive derivatives (e.g. their dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalate.

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 up to 99% by weight, polybutylene terephthalate.

The preferred polyalkylene terephthalates 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 an 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 include z. B. graft copolymers with elastomer properties essentially consisting 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; thus polymers such as z. B. in "Methods of organization African chemistry "(Houben-Weyl), vol. 14/1, Georg Thieme-Verlag, Stuttgart 1961, p. 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 comprise graft polymers from:

• 1. C.1 5 to 95, preferably 30 to 80 parts by weight of a mixture of
  • 1. C.1.1 50 to 95 parts by weight of styrene, α-methylstyrene, styrene substituted with halogen or methyl nucleus, C ₁ -C ₈ -alkyl methacrylate, in particular methyl methacrylate, C ₁ -C ₈ -alkyl acrylate, in particular methyl methacrylate or mixture against these connections and
  • 2. C.1.2 5 to 50 parts by weight of acrylonitrile, methacrylonitrile, C ₁ -C ₈ alkyl methacrylates, especially methyl methacrylate, C ₁ -C ₈ alkyl acrylate, especially meth acrylate, maleic anhydride, C ₁ -C ₄ alkyl or phenyl-N-substituted maleimides or mixtures of these compounds
• 2. 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. B. with styrene and / or acrylonitrile and / or (Meth) -acrylic acid alkyl esters grafted polybutadienes, butadiene / styrene copoly merisates and acrylate rubbers; d. H. Copolymers of DE-OS 16 94 173 (= US-PS 3564077) described type; with acrylic or methacrylic acid alkyl esters, Vinyl acetate, acrylonitrile, styrene and / or alkylstyrenes grafted polybutadienes, Butadiene / styrene or butadiene / acrylonitrile copolymers, polyisobutenes or Polyisoprene, such as z. B. in DE-OS 23 48 377 (= US-PS 3919353) described are.

Particularly preferred polymers C are e.g. B. ABS polymers, such as. B. in DE-OS 20 35 390 (= US-PS 3644574) or in DE-OS 22 48 242 (= GB-PS 1409275) are described.  

Particularly preferred graft polymers C are graft polymers which are obtained by grafting

• A) 10 to 70, preferably 15 to 50, in particular 20 to 40% by weight on graft product, at least one (meth) acrylic acid ester or 10 to 70, preferably 15 to 50, in particular 20 to 40 wt .-% of a mixture 10 to 50, preferably 20 to 35% by weight, based on the mixture, of acrylonitrile or (meth) acrylic acid ester and 50 to 90, preferably 65 to 80% by weight, based on mixture, styrene
• B) 30 to 90, preferably 50 to 85, in particular 60 to 80% by weight on graft product, a butadiene polymer with at least 50% by weight, based on II, butadiene residues as a 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 grafting G 0.15 to 0.55 and the average particle diameter d ₅₀

of the graft polymer 0.05 to 2 microns, preferably 0.1 to 0.6 microns.

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

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 (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 grafted on nomers to the graft base and is dimensionless.

The average particle size d ₅₀ 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. B. also from graft polymers

• a) 20 to 90 wt .-%, based on C, acrylate rubber with a glass over transition temperature below -20 ° C as a graft base and
• b) 10 to 80 wt .-%, based on C, of at least one polymerizable, ethy lenically unsaturated monomers (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 ₈ alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halogen alkyl esters, preferably halogen C ₁ -C ₈ alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.

Monomers with more than one polymerizable double bond can be used for crosslinking be copolymerized. Preferred examples of crosslinking monomers are Esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated one  valuable alcohols with 3 to 12 carbon atoms or saturated polyols with 2 to 4 OH Groups and 2 to 20 carbon atoms, such as. B. ethylene glycol dimethacrylate, allyl meth acrylate; polyunsaturated heterocyclic compounds, such as. B. 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 containing at least 3 ethyls nisch unsaturated groups.

Cyclic monomers are particularly preferred crosslinking monomers Triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloylhexahydro-s-tria zin, triallylbenzenes.

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

For cyclic crosslinking monomers with at least 3 ethylenically unsaturated It is advantageous for groups to reduce the amount to less than 1% by weight of the graft base (a) restrict.

Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic esters, can optionally be used to prepare the graft base (a) are, for. B. acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C ₁ - C ₆ alkyl ethers, methyl methacrylate, butadiene. Preferred acrylate rubbers as the 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 Make, as in DE-OS 37 04 657, DE-OS 37 04 655, DE-OS 36 31 540 and DE-OS 36 31 539 are described.

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-Ver lag, Stuttgart 1977).

As is known, the graft monomers in the grafting reaction are not necessarily full are constantly grafted onto the graft base, according to the invention Graft polymers C also understood those products which are obtained by polymerization of the graft monomers in the presence of the graft base.

Component D

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

The aluminum connections can - as already explained above - as Pul ver, pastes, brine, dispersions or suspensions are present. Through failures powders can be obtained from dispersions, brine or suspensions.

The powders can be used in the thermoplastic materials by conventional methods can be incorporated, for example by direct kneading or extruding the Components of the molding compound and the very finely divided inorganic powders. Before drafted processes represent the production of a masterbatch, e.g. B. in Flammschutzaddi tive, other additives, monomers, solvents, in component A or the Co-precipitation of dispersions of components B or C with dispersions, suspensions sions, pastes or sols of the finely divided inorganic materials.  

Component E

The molding compositions can be 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 as well Contain dyes and pigments. The usual additives such as processing aids agents are used in the generally known amounts.

The molding compositions can generally 0.01 to 20 wt .-%, based on the Total molding compound, flame retardant included. Be exemplary as a flame preservatives organic halogen compounds such as decabromobisphenyl ether, tetra bromobisphenol, inorganic halogen compounds such as ammonium bromide, stick Compounds such as melamine, melamine formaldehyde resins, inorganic hydro oxide compounds such as Mg-Al-hydroxide, inorganic compounds such as Alumi nium oxides, titanium dioxides, 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 called.

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 ₈ alkyl, in each case optionally substituted by alkyl, C preferably ₁ -C ₄ alkyl and / or halogen, preferably chlorine, bromine, substituted C ₅ -C ₆ cycloalkyl, C ₆ -C ₃₀ aryl or C ₇ -C ₁₂ aralkyl.

R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably, independently of one another, C ₁ -C ₄ -alkyl, phenyl, naphthyl or phenyl-C ₁ -C ₄ -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 C ₁ -C ₄ alkyl. Particularly preferred aryl radicals are Kre syl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding bro mated and chlorinated derivatives thereof.
X in the formula (III) denotes a mono- or polynuclear aromatic radical having 6 to 30 C 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 wt .-%, preferably 12 to 40 wt .-%, 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 of 10 to 90 wt .-%, preferably 60 to 88 wt .-%, 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 phosphate, tri- (isopropylphenyl) phosphate, halogen-substituted arylphos phate, methylphosphonic acid dimethyl ester, methylphosphonic acid diphenyl ester, Phe diethyl nylphosphonate, 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 special from 0.5 to 6.

The phosphorus compounds according to formula (III) are known (cf. e.g. EP-A 363608, EP-A 640655, EP-A 542522) or can be made in a similar manner by known methods Manufacture wise (e.g. Ullmann's Encyclopedia of Industrial Chemistry, Vol. 18, p. 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) various flame retardants in an amount up to 20 parts by weight contain. Synergistic flame retardants are preferred. Exemplary organic halogen compounds such as Decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formals  called hyd-resins or siloxane compounds. The molding compositions according to the invention can optionally differ from the inorganic compounds D anor ganic substances contain such as inorganic hydroxide compounds conditions such as Mg, Al hydroxide, inorganic compounds such as aluminum oxide, anti monoxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, Molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metabo rat and tin oxide.

In addition, the thermoplastic molding compositions according to the invention can be made of aluminum nium compounds contain further very finely divided inorganic compounds which favorably on the flame retardant properties of the molding compositions according to the invention impact. These inorganic compounds can be used in an amount of up to 25 Parts by weight (based on the total mixture) are added and include Compounds of one or more metals of the 1st to 5th main group and the 1st to 8. Subgroup of the periodic table, preferably the 2nd to 5th main group and the 4th to subgroup 8 to 8, particularly preferably the 3rd to 5th main group and the 4th to 8th Sub-group 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 ₄ , 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 diameter is less than or equal to 200 nm, preferred less than or equal to 150 nm, in particular 1 to 100 nm.

Particle size and particle diameter always means the mean 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 inorganic compounds can be in the form of powders, pastes, brine, dispersions or Suspensions are present. Due to precipitation, dispersions, brine or sus pensions can be obtained.

The powders can be used in the thermoplastic materials by conventional methods can be incorporated, for example by direct kneading or extruding the Components of the molding compound and the very finely divided inorganic powders. Before drafted processes represent the production of a masterbatch, e.g. B. in Flammschutzaddi tive, other additives, monomers, solvents, in component A or the Co-precipitation of dispersions of components B or C with dispersions, suspensions sions, pastes or sols of the finely divided inorganic materials.

The thermoplastic molding compositions can contain inorganic fillers and reinforcements materials such as glass fibers, optionally cut or ground, glass beads, Glass balls, lamellar reinforcing material, such as kaolin, talc, mica, Silicates, quartz, talc, titanium dioxide, wollastonite, mica, carbon fibers or their Mix included. Preferably cut as reinforcing material or ground glass fibers used. Preferred fillers that are also reinforcing glass balls, mica, silicates, quartz, talc, titanium dioxide, Wollastonite.  

The filled or reinforced molding compositions can contain up to 60, preferably 10 to 40 wt .-%, based on the filled or reinforced molding compound, filling and / or Ver contain reinforcing substances.

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, usually above 100 ° C, fluorine contents, preferably from 65 to 76, in particular from 70 to 76 wt .-%, average particle diameter d ₅₀ 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 ³ .

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

The fluorinated polyolefins are known (cf. "Vinyl and Related Polymers" by Schildknecht, John Wiley & Sons, Inc., New York, 1962, pages 484 to 494; "Fluorine polymers "by Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, vol 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. Patent 3671487, 3723373 and 338092).

They can be prepared by known processes, for example by polymerizing tetrafluoroethylene in an aqueous medium with a free radical-forming catalyst, for example sodium, potassium or ammonium peroxydi sulfate at pressures from 7 to 71 kg / cm ² and at temperatures from 0 to 200 ° C, preferably at temperatures of 20 to 100 ° C. (For more details, see, e.g., U.S. Patent 2,393,967). Depending on the form of use, the density of these materials can be between 1.2 and 2.3 g / cm ³ , 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 / cm ³ . They are preferably used in the form of a coagulated mixture of emulsions of the tetrafluoroethylene polymers with emulsions of the graft polymers C.

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 ³ to 2.3 g / cm ³ .

To produce a coagulated mixture of C and the fluorinated polyolefin is first an aqueous emulsion (latex) of a graft polymer C with medium 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 medium Particle diameters from 0.05 to 20 µm, in particular from 0.08 to 10 µm, ver mixes; 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 from 30 to 45% by weight, in particular from 30 to 35% by weight.

The quantity in the description of component C includes the proportion of Graft polymer in the coagulated mixture of graft polymer and fluorinated polyolefins.  

The weight ratio of graft polymer C to is in the emulsion mixture fluorinated polyolefins at 95: 5 to 60:40. The emulsion mixture is known in Way coagulates, 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, especially from 50 to 100 ° C. If necessary, can be dried at 50 to 200 ° C, preferably 70 to 100 ° C will.

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 the respective components are mixed in a known manner and at temperatures of 200 ° C to 300 ° C in common units such as internal kneaders, extruders and double wave screws melt-compounded or melt-extruded, the fluorinated Polyolefins preferably in the form of the coagulated mixture already mentioned be set.

The mixing of the individual components can both in a known manner successively as well as simultaneously, both at about 20 ° C (room temperature temperature) as well as at a higher temperature.

The molding compositions of the present invention can be used to produce molded articles pern of any kind can be used. In particular, molded articles can be sprayed cast. Examples of moldings that can be produced are: housing parts any type, e.g. B. for household appliances, such as juicers, coffee machines, blenders, for Office machines, such as computers, printers, monitors or cover plates for the Construction sector and parts for the automotive sector. You will also be in the field of Electrical engineering used because they have very good electrical properties.  

The molding compositions are particularly suitable for producing thin-walled molds share (e.g. data technology housing parts), where particularly high demands on the anti static properties of the plastics used.

Another form of processing is the production of molded articles by blowing shape or by deep drawing from previously made sheets or foils.  

Examples Component A

Bisphenol A based polycarbonate 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 a ratio of 73:27 to 60 parts by weight of particulate crosslinked polybutadiene rubber (mean particle diameter d ₅₀ = 0.3 μm), produced by emulsion polymerization.

Component D

Pural 200, an aluminum oxide hydroxide (Fa. Condea, Hamburg, Germany). The average particle size of the mate rials is approx. 20-40 nm.

Component E

Tetrafluoroethylene polymer as a coagulated mixture from a SAN graft poly Merisat 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 MgSO ₄ (Epsom salt) and acetic acid at pH 4 to 5, filtered and washed until practically free of electrolyte, then freed from the main amount of water by centrifugation and then at 100 ° C dried to a powder.

This powder can then with the other components and, if necessary together with the flame retardant according to formula (IV) in those described Aggregates are compounded.

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

Components A to E are mixed on a 3 l internal mixer. The Moldings are made on an Arburg 270E injection molding machine at 260 ° C posed.

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 Method ISO 527 determined 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 Vicat B heat resistance is determined in accordance with DIN 53460.

The MVR was determined according to ISO 1133.

a _k Izod was determined according to ISO 1801 A.

The composition of the tested materials and the data obtained are shown in the following tables 1 and 2 summarized.  

Table 1

Table 2

Claims (13)

1. Use of aluminum compounds for the production of molding compositions, Molded parts, foils, sheets 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 will. 3. Use according to claim 1, characterized in that aluminum compounds with a medium Particle diameters of 1 nm-20 µm can be used. 4. Use according to claim 1, characterized in that aluminum compounds with a medium Particle diameters of 1 nm-10 µm can be 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 claim 1 for the production of molding compositions containing 50 to 95 parts by weight of an aromatic polycarbonate A. 9. Use according to claim 1 for the production of molding compositions containing graft polymers C prepared by copolymerization of
5 to 95 parts by weight of a mixture of
50 to 95 parts by weight of styrene, α-methylstyrene, halogen- or alkyl nucleus-substituted styrene, C ₁ -C ₈ -alkyl methacrylate, C ₁ -C ₈ -alkyl acrylate or mixtures of these compounds and
5 to 50 parts by weight acrylonitrile, methacrylonitrile, C ₁ -C ₈ alkyl methacrylate, C ₁ -C ₈ alkyl acrylate, maleic anhydride, C alkyl- or phenyl-C ₁ -C ₄ N-sub stituiertem maleimide or mixtures of these compounds . 10. Use according to claim 1 for the production of molding compositions containing as flame retardant phosphorus compounds.   11. Use according to claim 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 ₈ -alkyl, in each case optionally by alkyl, preferably C ₁ -C ₄ -alkyl, and / or halogen, preferably chlorine, bromine, substituted C ₅ -C ₆ cycloalkyl, C ₆ -C ₃₀ aryl or C ₇ -C ₁₂ aralkyl,
k independently of one another, 0 or 1,
N 0 to 30,
X represents a mono- or polynuclear aromatic radical with 6 to 30 C atoms. 12. Use according to claim 1 for the production of molding compositions containing 0.01 to 20 wt .-%, based on the total molding compound at least one another flame retardant.   13. Use according to claim 1 for the production of molding compositions containing at least one additive from the group of stabilizers, pigments, ent molding agents, flow aids.