HK1030789B - Flame-resistant reinforced polycarbonate abs moulding materials - Google Patents

Description

Flame-resistant reinforced polycarbonate ABS moulding materials

The invention relates to reinforced polycarbonate ABS moulding compositions which are flame-resistant with organic phosphorus compounds and have excellent mechanical properties.

Reinforced flame-retardant polycarbonate ABS moulding compositions are known.

In particular, EP-A-0754531 describes flame-resistant molding compositions composed of polycarbonate, ABS graft polymer and optionally SAN copolymers, which are reinforced with inorganic materials in the form of platelets.

Flame-retardant polymer mixtures consisting of aromatic polycarbonates, styrene-containing copolymers and/or graft polymers, oligomeric phosphates as flame retardants and fibers as reinforcing agents are known from EP-A-0363608.

The teaching of EP-A-0640655 relates to flame-retardant molding compositions consisting of aromatic polycarbonate, styrene-containing copolymer, graft polymer, and ｃA mixture of mono-and oligomeric phosphates, which may optionally contain glass fibers as reinforcing agents.

For certain applications, such as the production of moldings or thin-walled moldings having high mechanical stress, the known molding compositions exhibit an inadequate level of properties, in particular too low a hardness or inadequate flowability.

It was therefore an object of the present invention to provide flame-resistant reinforced polycarbonate ABS moulding compositions which, in addition to very good flame resistance, very good processability and a high level of mechanical properties, also have an excellent E modulus.

It has now surprisingly been found that by using certain mixtures of polycarbonates, each having a distinctly different solution viscosity, polycarbonate ABS moulding compositions are obtained which have a distinctly better E modulus, a higher notched impact strength and a better processing behaviour than moulding compositions which comprise as polycarbonate component only polycarbonates having the corresponding average solution viscosity.

Accordingly, the present invention provides flame-retardant reinforced thermoplastic molding compositions comprising

A.5 to 95, preferably 10 to 90, particularly preferably 20 to 80 parts by weight of a mixture of two aromatic polycarbonates A.1 and A.2 having different solution viscosities

A.1 has a relative solution viscosity of 1.18 to 1.24,

a.2 has a relative solution viscosity of 1.24 to 1.34

The difference between the relative solution viscosities of A.1 and A.2 is not less than 0.06,

wherein one or more further polycarbonates can be added to the mixture of A.1 and A.2,

b.0 to 50, preferably 1 to 30, particularly preferably 2 to 25 parts by weight of a vinyl (co) polymer composed of one or at least two ethylenically unsaturated monomers,

c.0.5 to 60, preferably 1 to 40, particularly preferably 2 to 30 parts by weight of a graft polymer having a glass transition temperature of < -10 ℃ which is obtainable by graft polymerization of at least two monomers selected from the group consisting of chloroprene, butadiene, isoprene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth) acrylates having 1 to 18 carbon atoms in the alcohol component,

d.0.5 to 20, preferably 1 to 18, particularly preferably 2 to 15 parts by weight of phosphorus compounds of the formula (I)

Wherein

R¹、R²、R³And R⁴Independently of one another, represents optionally halogenated C₁-C₄-alkyl radical, C₅-C₆-cycloalkyl, C₆-C₂₀-aryl or C₇-C₁₂Aralkyl, in each case optionally substituted by halogen and/or C₁-C₄-an alkyl substitution,

n represents independently of one another 0 or 1,

n represents 0 to 30 and

x represents a mono-or polynuclear aromatic radical having 6 to 30 carbon atoms,

e.0.05 to 5, preferably 0.1 to 1, particularly preferably 0.1 to 0.5 parts by weight of fluorinated polyolefin and

f.1 to 40, preferably 3 to 30, particularly preferably 5 to 20 parts by weight of an inorganic, preferably fiber-reinforced material.

The sum A + B + C + D + E + F of all parts by weight is 100.

Component A

The thermoplastic aromatic polycarbonates suitable according to the invention for use as component A are those based on bisphenols of the formula (II) or alkyl-substituted dihydroxyphenylcycloalkanes of the formula (III),

in the formula (II)

A represents a single bond, C₁-C₅Alkylene radical, C₂-C₅- (1, 1-) alkylene, C₅-C₆-cyclo (1, 1-) alkylene, -S-, -SO₂-, -O-, -CO-or-C₆-C₁₂-arylene, said group being optionalOptionally fused with an aromatic ring additionally containing heteroatoms,

b in each case independently of one another represents C₁-C₈-alkyl, preferably methyl, ethyl; c₆-C₁₀-aryl, preferably phenyl; c₇-C₁₂-aralkyl, preferably benzyl; the halogen, preferably chlorine, bromine,

x in each case independently of one another represents 0, 1 or 2 and

p represents 1 or 0, and p represents a group,

in the formula (III)

R⁵And R⁶In each case independently of one another, represents hydrogen; halogen, preferably chlorine or bromine; c₁-C₈-alkyl, preferably methyl, ethyl; c₅-C₆-a cycloalkyl group; c₆-C₁₀-aryl, preferably phenyl; and C₇-C₁₂Aralkyl, preferably phenyl-C₁-C₄-an alkyl group, in particular a benzyl group,

m represents an integer from 4 to 7, preferably 4 or 5,

for each Z, R⁷And R⁸May be selected respectively and independently of one another represent hydrogen or C₁-C₆-alkyl, preferably hydrogen, methyl or ethyl, and

z represents carbon, with the proviso that R is on at least one atom Z⁷And R⁸Simultaneously represents an alkyl group.

Examples of suitable bisphenols of the formula (II) are hydroquinone, resorcinol, 4' -dihydroxybiphenyl, 2-bis- (4-hydroxyphenyl) -propane, 2, 4-bis- (4-hydroxyphenyl) -2-methylbutane, 1-bis- (4-hydroxyphenyl) -cyclohexane, 2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2-bis- (3, 5-dibromo-4-hydroxyphenyl) -propane.

Preferred diphenols of the formula (II) are 2, 2-bis- (4-hydroxyphenyl) -propane, 2-bis- (3, 5-dichloro-4-hydroxyphenyl) -propane and 1, 1-bis- (4-hydroxyphenyl) -cyclohexane.

Preferred bisphenols of the formula (III) are dihydroxydiphenylcycloalkanes having 5 and 6 ring carbon atoms in the cycloaliphatic radical [ m ═ 4 or 5 in the formula (III) ] such as, for example, bisphenols of the formula:

and

of these, 1-bis- (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane (formula IIIa) is particularly preferred.

The polycarbonates suitable as component A according to the invention can be branched in a known manner, preferably in practice by introducing from 0.05 to 2.0 mol%, relative to the sum of the diphenols used, of compounds having three or more functional groups, such as those having three or more phenolic groups, examples being:

phloroglucinol, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) -heptene-2, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) -heptane, 1, 3, 5-tris- (4-hydroxyphenyl) -benzene, 1, 1, 1-tris- (4-hydroxyphenyl) -ethane, tris- (4-hydroxyphenyl) -phenylmethane, 2-bis- (4, 4-bis- (4-hydroxyphenyl) -cyclohexyl) -propane, 2, 4-bis- (4-hydroxyphenyl) -isopropyl) -phenol, 2, 6-bis- (2-hydroxy-5' -methylbenzyl) -4-methylphenol, methyl-p-phenylene-ethyl-phenyl, 2- (4-hydroxyphenyl) -2- (2, 4-dihydroxyphenyl) -propane, hexa- (4- (4-hydroxyphenyl-isopropyl) -phenyl) -phthalate, tetrakis- (4-hydroxyphenyl) -methane, tetrakis- (4- (4-hydroxyphenyl-isopropyl) -phenoxy) -methane and 1, 4-di- ((4', 4 "-dihydroxytriphenyl) -methyl) -benzene.

Some other trifunctional compounds are 2, 4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3, 3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2, 3-dihydroindole.

Preferred polycarbonates, in addition to bisphenol A homopolycarbonates, are the copolycarbonates of bisphenol A with up to 15 mol%, relative to the molar sum of diphenols, of 2, 2-bis- (3, 5-dibromo-4-hydroxyphenyl) -propane.

The aromatic polycarbonates of component A may be partially substituted by aromatic polyester carbonates.

The aromatic polycarbonates of component A may also contain polysiloxane blocks. The production thereof is described, for example, in DE-OS 3334872 and US-PS 3821325.

The aromatic polycarbonates and/or aromatic polyester carbonates according to component A are known in the literature or can be produced by methods known in the literature (for the production of aromatic polycarbonates see, for example, Schnell, "chemistry and Physics of polycarbonates", Interscience Publishers, 1964 and DE-AS 1495626, DE-OS 2232877, DE-OS 2703376, DE-OS 2714544, DE-OS 3000610, DE-OS 3832396; for the production of aromatic polyester carbonates see, for example, DE-OS 3077934).

Aromatic polycarbonates and/or aromatic polyester carbonates may be produced, for example, by reacting bisphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, by the phase interface method, optionally using chain terminators and optionally using trifunctional or more than trifunctional branching agents.

The content of A.1 is from 5 to 95, preferably from 25 to 75, in particular from 35 to 65,% by weight, and the content of A.2 is from 95 to 5, preferably from 75 to 25, in particular from 65 to 35,% by weight, based on the mixture of polycarbonates A.1 and A.2.

The mixtures of polycarbonates A.1 and A.2 differ in that the relative solution viscosity of A.1 is from 1.18 to 1.24, the relative solution viscosity of A.2 is from 1.24 to 1.34, and the difference between the relative solution viscosities of A.1 and A.2 is not less than 0.06, in particular not less than 0.09, i.e.the relative solution viscosity of A.2 minus the relative solution viscosity of A.1 is not less than 0.06, in particular not less than 0.09. Relative solution viscosity is in CH₂Cl₂Measured at 25 ℃ and at a concentration of 0.5g/100ml of solvent.

Preferably, the polycarbonates A.1 and A.2 have the same structure, i.e.they are synthesized from the same monomers. It is particularly preferred that the polycarbonates A.1 and A.2 and the polycarbonates added in addition (as described above for A.1 and A.2) are synthesized from the same monomers and have the same structure. The additional polycarbonate is preferably added in an amount of 30% by weight (relative to the amounts of A.1 and A.2).

One or both of the polycarbonate components A.1 or A.2 in the mixture may be recycled polycarbonate. Recycled polycarbonate refers to a product that has undergone processing and use cycles and has undergone special reprocessing processes to remove attached impurities to an amount suitable for further use.

Component B

The thermoplastic polymers B optionally present in the molding compositions according to the invention comprise (co) polymers of one or at least two ethylenically unsaturated monomers (vinyl monomers), such as styrene, alpha-methylstyrene, styrene substituted in the benzene ring (for example halogen and/or alkyl-substituted in the ring), acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, N-substituted maleimides and (meth) acrylates having from 1 to 18 carbon atoms in the alcohol component.

The copolymer of component B is resin-like, thermoplastic and rubber-free. The molding compositions may also comprise various (co) polymers B.

Preferred vinyl (co) polymers B are (co) polymers composed of at least one monomer from the series (B.1) of styrene, alpha-methylstyrene and/or ring-substituted styrene and/or methyl methacrylate and at least one monomer from the series (B.2) of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride and/or N-alkyl-and N-aryl-substituted maleimides.

The content of monomer B.1 in the (co) polymer is preferably from 50 to 99, particularly preferably from 60 to 95,% by weight, and the content of monomer B.2 is preferably from 1 to 50, particularly preferably from 40 to 5,% by weight.

Particularly preferred copolymers B are those composed of styrene and acrylonitrile and optionally methyl methacrylate, of alpha-methylstyrene and acrylonitrile and optionally methyl methacrylate, or of styrene and alpha-methylstyrene and acrylonitrile and optionally methyl methacrylate.

The (co) polymers of component B are known and can be produced by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The copolymers of component B preferably have molecular weights Mw (weight average, determined by light scattering or sedimentation) of 15,000-200,000.

Particularly preferred copolymers B according to the invention are also statistically synthesized copolymers of styrene and maleic anhydride, which can preferably be produced from the corresponding monomers by continuous bulk or solution polymerization with incomplete reaction.

The content of the two components of the statistically synthesized styrene/maleic anhydride copolymers suitable according to the invention can vary within wide limits. The preferred maleic anhydride content is 5 to 25 wt.%.

The polymer may also contain ring-substituted styrenes such as p-methylstyrene, 2, 4-dimethylstyrene and other substituted styrenes such as alpha-methylstyrene in place of styrene.

The molecular weight (number average Mn) of the statistically synthesized styrene/maleic anhydride copolymers suitable for component B according to the invention can vary within wide limits. The preferred range is 60,000-200,000. The intrinsic viscosity of these products is preferably in the range from 0.3 to 0.9 (measured in dimethylformamide at 25 ℃; see Hoffmann, Kr * mer, Kuhn, Polymer analysis I, Stuttgart1977, p.316 and the following).

Component C

Component C according to the invention represents a graft polymer which may also be contained as a mixture in the molding composition. They comprise graft copolymers having rubber-elastic properties, obtainable essentially from at least two of the following monomers: chloroprene, butadiene-1, 3-diene, isoprene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth) acrylates having 1 to 18 carbon atoms in the alcohol component; i.e.for example in "organic chemistry methods" (Houben-Weyl), volume 14/1, Georg Thieme Verlag Press, Stuttgart 1961, page 393-406 and "toughened plastics" in C.B.Bucknall, using the polymers described in scientific Press, London 1977. Preferred polymers C are partially crosslinked and have a gel content of more than 20% by weight, preferably more than 40% by weight, in particular more than 60% by weight.

Preferred graft polymers C include those consisting of the following C.1 grafted onto C.2:

c.15-95, preferably 30-80 parts by weight of a mixture comprising:

c.1.150-99 parts by weight of styrene, alpha-methylstyrene, halogen-or methyl ring-substituted styrene, methyl methacrylate or mixtures of these compounds and

c.1.21-50 weight portions of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride and C₁-C₄-alkyl and/or phenyl-N-substituted maleimides or mixtures of these compounds

C.25-95, preferably 20-70 parts by weight of a diene and/or alkylacrylate based polymer having a glass transition temperature below-10 ℃.

Examples of preferred graft polymers C are substrates C.2 grafted with styrene and/or acrylonitrile and/or alkyl (meth) acrylates, such as polybutadiene, butadiene/styrene copolymers and acrylate rubbers; copolymers of the type described in DE-OS 169473 (═ US-PS 3564077); polybutadiene, butadiene/styrene or butadiene/acrylonitrile copolymers, polyisobutylene or polyisoprene grafted with alkyl acrylates or methacrylates, vinyl acetate, acrylonitrile, styrene and/or other alkylstyrenes, as described in DE-OS 2348377 (US-PS 3919353).

Examples of particularly preferred polymers C are ABS polymers, as described, for example, in DE-OS 2035390 (US-PS 3644574) or DE-OS 2248242 (GB-PS 1409275).

Particularly preferred graft polymers C are obtainable by grafting reaction of the following compounds:

alpha to the graft polymer C, 10 to 70, preferably 15 to 50, in particular 20 to 40 wt.% of at least one (meth) acrylate or 10 to 70, preferably 15 to 50, in particular 20 to 40 wt.% of a mixture of 10 to 50, preferably 20 to 35 wt.% (relative to the mixture) of acrylonitrile or (meth) acrylate and 50 to 90, preferably 65 to 80 wt.% (relative to the mixture) of styrene as graft shell C.1,

beta to the graft polymer C, 30 to 90, preferably 50 to 85, in particular 60 to 80 wt.% of a butadiene polymer (containing at least 50 wt.% of butadiene groups relative to beta) as graft base C.2,

wherein the gel content of the graft base beta is preferably at least 70 wt.% (measured in toluene), the degree of grafting G is 0.15 to 0.55 and the mean particle diameter d of the graft polymer C.2₅₀Is 0.05-2 μm, preferably 0.1-0.6 μm.

The (meth) acrylic acid ester α is an ester of acrylic acid or methacrylic acid with a monohydric alcohol having from 1 to 18 carbon atoms. Methyl, ethyl and propyl methacrylate, n-butyl acrylate, t-butyl acrylate and t-butyl methacrylate are particularly preferred.

In addition to the butadiene groups, the grafting base β may contain up to 50% by weight, relative to β, of other ethylenically unsaturated monomers, such as styrene, acrylonitrile, acrylic or methacrylic esters having 1 to 4 carbon atoms in the alcohol component (e.g. methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate), vinyl esters and/or vinyl ethers. The preferred grafting base β consists of pure polybutadiene.

The degree of grafting G refers to the weight ratio between grafted grafting monomer and grafting base and is dimensionless.

Average particle size d₅₀The particles each account for 50 wt% of the diameter above and below this diameter. It can be determined by ultracentrifuge measurement techniques (W.Scholtan, H.Lange, Kolloid, Z.und Z.Polymer 250(1972), 782-796).

Examples of particularly preferred polymers C are graft polymers comprising the following compounds:

tau.20-90 wt.%, relative to component C, of an acrylate rubber having a glass transition temperature < -20 ℃, as graft base C.2, and

10-80% by weight, relative to component C, of at least one polymerizable ethylenically unsaturated monomer as graft monomer C.1.

The acrylate rubber tau of the polymer C is preferably a polymer of an alkyl acrylate, optionally containing up to 40 wt.% (relative to tau) of other polymerizable ethylenically unsaturated monomers. C₁-C₈Alkyl esters, such as methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters, haloalkyl esters, preferably halo-C₁-C₈Alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers, are among the preferred polymerizable acrylates.

For crosslinking, monomers with more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms with unsaturated monohydric alcohols having 3 to 12 carbon atoms or saturated polyols having 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 tri-vinylbenzenes; and triallyl phosphate and diallyl phthalate.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least three ethylenically unsaturated groups.

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

The amount of crosslinking monomer is preferably from 0.02 to 5, in particular from 0.05 to 2,% by weight, based on the graft base τ.

In the case of ring-crosslinking monomers containing at least three ethylenically unsaturated groups, it is advantageous to limit the amount of graft base τ to less than 1% by weight.

Examples of preferred "other" polymerizable ethylenically unsaturated monomers which can optionally also be used in addition to the acrylate for producing the graft base tau are acrylonitrile, styrene, alpha-methylstyrene, acrylamide, vinyl-C₁-C₆Alkyl ethers, methyl methacrylate, butadiene. Preferred acrylate rubbers as graft base τ are emulsion polymers having a gel content of at least 60% by weight.

Further suitable graft bases according to C.2 are silicone rubbers with graft-active sites, as described in DE-OS 3704657, DE-OS 3704655, DE-OS 3631540 and DE-OS 3631539.

The gel content of the grafting base C.2 was determined at 25 ℃ in dimethylformamide (M.Hoffmann, H.Kr * mer, R.Kuhn, Polymer analysis I and II, George Thieme-Verlag Press, Stuttgart 1977).

The graft polymers C can be produced by known processes, such as the bulk, suspension, emulsion or bulk-emulsion process.

Since it is known that the graft monomers do not have to be completely grafted onto the graft base in the grafting reaction, graft polymers C are also understood according to the invention as meaning products which are obtained by polymerization of the graft monomers in the presence of the graft base.

Component D

The inventive molding compositions contain, as flame retardants, at least one organic phosphorus compound and/or a mixture of organic phosphorus compounds of the formula (I)

In the formula, R¹、R²、R³And R⁴Have the same meaning as described above. Preferably R¹、R²、R³And R⁴Independently of one another represent C₁-C₄-alkyl, phenyl, naphthyl or phenyl-C₁-C₄-an alkyl group. For aromatic radicals R¹、R²、R³And R⁴They may be substituted by halogen, preferably chlorine or bromine, and/or by alkyl, preferably C₁-C₄Alkyl such as methyl, ethyl. Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated or chlorinated derivatives thereof.

In formula (I), X represents a mono-or polynuclear aromatic radical having 6 to 30 carbon atoms. Preference is given to bisphenol derived from formula (II) such as bisphenol A, resorcinol or hydroquinone or chlorinated or brominated derivatives thereof.

In formula (I), n may be 0 or 1 independently of one another, preferably n is equal to 1.

N represents a value of 0 to 30, preferably 0.3 to 20, particularly preferably 0.5 to 10, very particularly preferably 0.5 to 6.

The average value of N in the mixture of phosphorus compounds is 0 to 30, preferably 0.3 to 20, particularly preferably 0.5 to 10, very particularly preferably 0.5 to 6.

The mixture may comprise monophosphorus compounds and/or oligomeric and/or polymeric phosphorus compounds.

When N is 0, formula (I) describes monophosphorus compounds.

Organic monophosphates such as tributyl phosphate, tris- (2-chloroethyl) -phosphate, tris- (2, 3-dibromopropyl) -phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri- (isopropylphenyl) -phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl phenylphosphonate, triphenylphosphine oxide or tricresylphosphine oxide and/or mixtures thereof are particularly useful as phosphorus compounds of the formula (I).

The mono-and oligomeric phosphorus compounds of the formula (I) in the mixture are preferably selected in such a way that a synergistic effect is obtained. The mixture generally consists of 10 to 90 wt.% of oligomeric phosphorus compounds and 90 to 10 wt.% of monophosphorus compounds, preferably monophosphorus compounds of the formula (I). The monophosphorus compounds are preferably mixed in amounts in the range from 12 to 50, in particular from 14 to 40, very particularly preferably from 15 to 40,% by weight with a complementary amount of the oligophosphorus compound.

Component E

The fluorinated polyolefins E are of high molecular weight and have a glass transition temperature of more than-30 ℃ and generally more than 100 ℃, a fluorine content of preferably 65 to 76, in particular 70 to 76,% by weight, and an average particle diameter d₅₀Is 0.05-1,000, preferably 0.08-20 μm. In general, the fluorinated polyolefins E have a density of from 1.2 to 2.3g/cm³。

Preferred fluorinated polyolefins E are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene/hexafluoroethylene and/or ethylene/tetrafluoroethylene copolymers. Fluorinated polyolefins are known (cf. Schildknecht "vinyl and related polymers", John Wiley & Sons, Inc., New York, 1962, 484-494 page; Wall "fluoropolymers", Wiley Interscience, John Wiley & Sons, Inc., New York, volume 13, 1970, 623-654 page), "modern plastics encyclopedia", 1970-1971, 47, 10A, 10 months 1970, McGraw-Hill, Inc., New York, 134 and 774 pages; modern plastics encyclopedia ", 1975-1976, 10 months 1975, 52, 10A, McGraw-Hill, New York, pages 27, 28 and 472 and US-PS 3671487, 3723373 and 3838092).

They can be produced by known methods, for example by using free-radical-forming catalysts such as sodium, potassium or ammonium peroxodisulfate in an aqueous mediumIn the range of 7-71kg/cm²And a temperature of from 0 to 200 c, preferably from 20 to 100 c. (see, for example, U.S. Pat. No. 2,2393967 for further details). Depending on the form of application, these materials may have a density of 1.2 to 2.3g/cm³And the average particle size is 0.05 to 1,000. mu.m.

Preferred fluorinated polyolefins E 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 densities of 1.2 to 1.9g/cm³. They are preferably used in the form of a coagulated mixture of emulsions of tetrafluoroethylene polymers E and emulsions of graft polymers C.

Suitable fluorinated polyolefins E which can be used in powder form are those having an average particle diameter of 100-1,000 μm and a density of 2.0 to 2.3g/cm³The tetrafluoroethylene polymer of (1).

To prepare a coagulated mixture of C and E, an aqueous emulsion (latex) of a graft polymer C having an average latex particle diameter of 0.05 to 2 μm, in particular 0.1 to 0.6 μm, is first mixed with a fine emulsion of a fluorinated polyolefin E having an average particle diameter of 0.05 to 20 μm, in particular 0.08 to 10 μm, in water; suitable tetrafluoroethylene polymer emulsions generally have solids contents of from 30 to 70% by weight, in particular from 50 to 60% by weight.

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

The amounts mentioned in the description of component C do not include the content of graft polymer in the coagulated mixture of graft polymer and fluorinated polyolefin.

The weight ratio of graft polymer C to fluorinated polyolefin E in the emulsion mixture is from 95: 5 to 60: 40. The emulsion mixture is coagulated in a known manner, for example by spray drying, freeze drying or coagulation by addition of inorganic or organic salts, acids, bases or water-miscible organic solvents such as alcohols, ketones, preferably at from 20 to 150 ℃ and in particular from 50 to 100 ℃. If desired, drying may be carried out at 50 to 200 ℃ and preferably 70 to 100 ℃.

Suitable tetrafluoroethylene polymer emulsions are conventional commercially available products and are supplied, for example, by DuPont as Teflon * 30N.

Component F

Inorganic reinforcing materials such as glass fibers (which optionally have been cut or ground), glass beads, glass spheres, reinforcing materials in the form of platelets such as kaolin, talc, mica, carbon fibers or mixtures thereof are used as component F. Cut or ground glass fibers preferably having a length of 1 to 10mm and a diameter of < 20 μm are preferably used as reinforcing material in an amount of 1 to 40 parts by weight; the glass fibers are preferably surface treated.

The moulding compositions according to the invention may further comprise at least one of the conventional additives, such as lubricants and mould release agents, nucleating agents, antistatic agents, stabilisers and also dyes and pigments.

Furthermore, the moulding compositions according to the invention may further comprise fine inorganic powders in amounts of up to 50 parts by weight, preferably up to 20, in particular from 0.5 to 10 parts by weight.

The fine inorganic compounds consist of compounds of one or more metals of main groups 1 to 5 or transition groups 1 to 8, preferably main groups 2 to 5 or transition groups 4 to 8, particularly preferably main groups 3 to 5 or transition groups 4 to 8 of the periodic Table with at least one element selected from the group consisting of oxygen, sulfur, boron, phosphorus, carbon, nitrogen, hydrogen or silicon.

Examples of preferred compounds are oxides, hydroxides, hydrated oxides, sulphates, sulphites, sulphides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates.

Examples of preferred fine inorganic compounds are TiN, TiO₂，SnO₂，WC，ZnO，Al₂O₃，AlO(OH)，ZrO₂，Sb₂O₃，SiO₂Iron oxide, Na₂SO₄，BaSO₄Vanadium oxide, zinc borate, silicates such as aluminum silicate, magnesium silicate, mono-, di-and three-dimensional silicates, it being possible to use mixtures and doped compounds. And can be usedOrganic molecules surface modify these very small particles to obtain better compatibility with the polymer. In this way hydrophobic or hydrophilic surfaces can be obtained.

The average particle diameter is not more than 200nm, preferably not more than 150nm, in particular from 1 to 100 nm.

Particle size and particle diameter always mean the average particle diameter d₅₀Determined by the ultracentrifuge measurement method according to Kolloid-Z.und Z.Polymer 250(1972), 782-796, W.Scholtan et al.

The inorganic compounds may be present as powders, slurries, sols, dispersions or suspensions. Powders can be obtained by precipitation from dispersions, sols or suspensions.

The powder can be incorporated into the thermoplastic by conventional methods, for example by direct mixing or extrusion of the molding composition components and the fine inorganic powder. Preferred methods are the production of masterbatch formulations, for example comprising flame retardant additives, further additives, monomers and solvents in component A, or coprecipitation from a graft rubber dispersion together with a dispersion, suspension, slurry or sol of a fine inorganic material.

The moulding compositions according to the invention may comprise from 0.01 to 20% by weight, relative to the total moulding composition, of a further flame retardant optionally having a synergistic effect. Examples of suitable further flame retardants are organic halides such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halides such as ammonium bromide, nitrogen compounds such as melamine, melamine-formaldehyde resins, inorganic hydroxides such as magnesium hydroxide or aluminum, inorganic compounds such as aluminum oxide, titanium dioxide, antimony oxide, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate and tin oxide and also siloxane compounds.

The molding compositions according to the invention comprising components A to F and optionally further known additives such as stabilizers, dyes, pigments, lubricants and mold release agents, nucleating agents and antistatics are produced by mixing the particular components in a known manner and melt compounding and melt extrusion at 200-300 ℃ in conventional equipment such as internal mixers, extruders and twin-screw extruders, where component E is preferably used in the form of the abovementioned coagulated mixture. Extruders and twin screw extruders are preferred equipment.

The individual components can be mixed in a known manner, either continuously or simultaneously, and mixed at temperatures of about 20 c (room temperature) and above.

The molding compositions of the invention can be used to produce moldings by injection molding. Examples of producible mouldings are: various household parts, for example household articles such as juice makers, coffee makers, blenders, office machines such as monitors, printers, copiers or panels of building parts and motor vehicle parts. They can also be used in the field of electrical engineering, since they have very good electrical properties.

Another form of processing is the production of molded bodies by thermoforming from previously produced sheets or films.

Owing to their excellent flame resistance, their very good processability and their very good mechanical properties, in particular their outstanding rigidity, the thermoplastic molding compositions according to the invention are suitable for the production of moldings of all kinds, in particular moldings requiring a high degree of breaking strength.

The present invention therefore also provides the use of the molding compositions according to the invention for the production of various moldings, preferably those described above, and also moldings produced from the molding compositions according to the invention.

Examples

Component A

A

Linear polycarbonate based on bisphenol A with a relative solution viscosity of 1.249, the viscosity being CH₂Cl₂Measured at 25 ℃ and at a concentration of 0.5g/100ml of solvent.

A.1

Linear polycarbonate based on bisphenol A with a relative solution viscosity of 1.26 in CH₂Cl₂Measured at 25 ℃ and at a concentration of 0.5g/100ml of solvent.

A.2

Linear polycarbonate based on bisphenol A with a relative solution viscosity of 1.19 in CH₂Cl₂Measured at 25 ℃ and at a concentration of 0.5g/100ml of solvent.

Component C

45 parts by weight of a copolymer of styrene and acrylonitrile in a ratio of 72: 28 to 55 parts by weight of a particulate crosslinked polybutadiene rubber (average particle diameter d)₅₀═ 0.4 μm), produced by emulsion polymerization.

Component D

Component E

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

Preparation of E

The emulsion of tetrafluoroethylene polymer (Teflon 30N, DuPont) was mixed with the emulsion of graft polymer C and stabilized with 1.8% by weight, based on polymer solids, of a phenolic antioxidant. At 85-95 deg.C with MgSO₄(epsom salt) water solution and acetic acid at a pH of 4-5 to coagulate the mixture, filter and wash until substantially free of electrolytes;most of the water was then centrifuged off and the mixture was dried to a powder at 100 ℃. This powder can then be compounded with the additional components in the equipment described above.

Component F

Glass fibers (CS 7942, Bayer Corp., Leverkusen, Germany) (cut, average length 4.5 mm).

Preparation and testing of the moulding compositions according to the invention

Components A to F and conventional processing aids were mixed in a ZSK 32 twin-screw extruder. The mouldings were produced in an injection moulding machine of the Arburg 270E type at 260 ℃.

80X 10X 4mm at room temperature according to ISO method 1801A³Notched impact strength was measured on the bars.

The heat deflection temperature of Vicat B is 80X 10X 4mm in accordance with DIN 53460³Measured on a rod.

Tensile E modulus was determined according to ISO 527/DIN 53457.

Flame retardancy is measured according to UL 94V.

The burning behavior of the samples was determined according to UL-Subj.94V on bars of 127mm by 12.7mm by 3.2mm and/or 1.6 mm.

The sample bar was placed vertically with the lower surface of the test body 305mm above the strip of bonding material. Each test rod was fired separately by two sequential firing methods (each of 10 second duration). The combustion performance after each ignition was observed and then the sample was evaluated. Bunsen burner with 10mm (3.8 inch) high blue natural gas flame at 3.73X 10⁴kJ/m³(1000BTU per cubic foot) the thermal unit ignited the sample.

To evaluate the burning behavior, two flames were applied to each test body for 10 seconds each. The smoldering time after the fire source was removed was measured. Five test bodies were used for each test and the sum of 10 burning times and the respective smoldering times was determined.

The compositions of the test materials and the results obtained are summarized in Table 1 below.

TABLE 1 composition and Properties of polycarbonate ABS moulding compositions

Example 12

Comparative example the invention

Composition [ parts by weight ]

A 70 -

A1 and A2-70:

wherein the A185.7wt.%,

A2 14.3wt.％

C 5 5

D 11 11

E 4 4

F 10 10

performance:

Vicat B[℃] 97 96

notched impact Strength [ kJ/m²] 5 8

Melt viscosity [ Pa.s ] at 260 DEG C

At 100s^-1 539 440

At 1000s^-1 275 241

At 1500s^-1 223 193

MVR 240℃/5kg[ml/10mins] 16.2 17.6

Tensile E modulus [ N/mm ]²] 3293 3349

UL 94V 3.2mm/RT V0 V0

Total fumigation time [ s ] 134

UL 94V 1.6mm/RT V0 V0

Total fumigation time [ s ] 159

Claims (15)

1. Flame-retardant reinforced thermoplastic molding compositions comprising

A.5 to 95 parts by weight of a mixture of two aromatic polycarbonates A.1 and A.2 having different solution viscosities

A.1 has a relative solution viscosity of 1.18 to 1.24,

a.2 has a relative solution viscosity of 1.24 to 1.34

The difference between the relative solution viscosities of A.1 and A.2 is not less than 0.06,

wherein one or more further polycarbonates can be added to the mixture of A.1 and A.2,

b.0 to 50 parts by weight of a vinyl (co) polymer consisting of one or at least two ethylenically unsaturated monomers,

c.0.5-60 parts by weight of a graft polymer selected from the group consisting of chloroprene, butadiene, isoprene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth) acrylic acid-C₁-C₁₈At least two monomers of alkyl esters by graft polymerization,

d.0.5 to 20 parts by weight of a phosphorus compound of the formula (I)

Wherein

R¹、R²、R³And R⁴In each case independently of one another represent optionally halogenated C₁-C₄-alkyl radical, C₅-C₆-cycloalkyl, C₆-C₂₀-aryl or C₇-C₁₂Aralkyl, in each case optionally substituted by halogen and/or C₁-C₄-an alkyl substitution,

n represents independently of one another 0 or 1,

n represents 0 to 30 and

x represents a mono-or polynuclear aromatic radical having 6 to 30 carbon atoms,

e.0.05 to 5 parts by weight of at least one fluorinated polyolefin, and

f.1 to 40 parts by weight of an inorganic reinforcing material,

wherein the sum of parts by weight of A + B + C + D + E + F is 100 parts by weight.

2. The molding composition according to claim 1, wherein N in formula (I) is from 0.3 to 20.

3.A molding composition according to claim 1 or 2, wherein R in the formula (I)¹、R²、R³And R⁴In each case independently of one another represent C₁-C₄Alkyl, phenyl, naphthyl or phenyl-C in each case optionally substituted by halogen and/or alkyl₁-C₄-alkyl and X is derived from a bisphenol selected from bisphenol a, resorcinol or hydroquinone, optionally chlorinated or brominated.

4. Moulding compositions according to claim 1 or 2, wherein the monophosphorus compound of formula (I) is selected from the group consisting of tributyl phosphate, tris- (2-chloroethyl) -phosphate, tris- (2, 3-dibromopropyl) -phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri- (isopropylphenyl) -phosphate, halogen-substituted aryl phosphates, methylphosphonic acid dimethyl ester, methylphosphonic acid diphenyl ester, phenylphosphonic acid diethyl ester, triphenylphosphine oxide and/or tricresylphosphine oxide.

5. Moulding compositions according to claim 1, wherein polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene/hexafluoroethylene and/or ethylene/tetrafluoroethylene copolymers are used as fluorinated polyolefins E).

6. Moulding compositions according to claim 1, wherein the inorganic reinforcing material is selected from glass fibres, optionally cut or ground, glass beads, carbon fibres, lamellar reinforcing materials or mixtures thereof.

7. Moulding compositions according to claim 1 or 2, wherein the composition comprises at most 20 wt.%, relative to the total moulding composition, of at least one further flame retardant.

8. A molding composition according to claim 1 or 2, wherein the composition comprises from 10 to 90 parts by weight of component A, from 1 to 40 parts by weight of component C, from 1 to 18 parts by weight of component D and from 3 to 30 parts by weight of component F.

9. A molding composition according to claim 8, wherein the composition comprises from 20 to 80 parts by weight of component A, from 2 to 30 parts by weight of component C, from 2 to 15 parts by weight of component D and from 5 to 20 parts by weight of component F.

10. A molding composition according to claim 1 or 2, wherein component B is a (co) polymer comprising the following monomers:

from 150 to 99 parts by weight of monomers selected from styrene, alpha-methylstyrene, ring-substituted styrene and/or methyl methacrylate, and

b.21 to 50 parts by weight of monomers selected from the group consisting of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride and/or N-alkyl-or N-aryl-substituted maleimides.

11. A molding composition as claimed in claim 1 or 2, in which component C is a graft polymer obtainable by graft polymerization of the following compounds C.1 on C.2:

c.15-95 parts by weight of a mixture comprising:

c.1.150 to 99 parts by weight of styrene, alpha-methylstyrene, halogen-or methyl ring-substituted styrene, methyl methacrylate or mixtures of these compounds, and

c.1.21-50 weight portions of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride and C₁-C₄-alkyl and/or phenyl-N-substituted maleimides or mixtures of these compounds,

c.25-95 parts by weight of a diene and/or alkyl acrylate based polymer having a glass transition temperature below-10 ℃.

12. A molding composition according to claim 1 or 2, comprising fine compounds of main groups 1 to 5 or sub-groups 1 to 8 of the periodic Table with at least one element selected from the group consisting of oxygen, sulfur, boron, carbon, phosphorus, nitrogen, hydrogen and silicon.

13. Moulding compositions according to claim 1 or 2, characterized in that they comprise at least one additive from the group consisting of stabilizers, pigments, mould release agents, nucleating agents and antistatic agents.

14. Use of a molding composition according to one of the preceding claims for the production of molded bodies.

15. A molded body made from the molding composition according to one of the preceding claims.