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WO1999020693A1 - Thermoplastic moulding materials containing polyesters and polycarbonates - Google Patents

Thermoplastic moulding materials containing polyesters and polycarbonates Download PDF

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Publication number
WO1999020693A1
WO1999020693A1 PCT/EP1998/006537 EP9806537W WO9920693A1 WO 1999020693 A1 WO1999020693 A1 WO 1999020693A1 EP 9806537 W EP9806537 W EP 9806537W WO 9920693 A1 WO9920693 A1 WO 9920693A1
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Prior art keywords
weight
component
graft
molding composition
transition temperature
Prior art date
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PCT/EP1998/006537
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German (de)
French (fr)
Inventor
Martin Weber
Herbert Fisch
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BASF SE
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BASF SE
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Priority to AU11541/99A priority Critical patent/AU1154199A/en
Priority to EP98954419A priority patent/EP1051444A1/en
Publication of WO1999020693A1 publication Critical patent/WO1999020693A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the invention relates to thermoplastic molding compositions containing polyester and polycarbonates, which are impact modified.
  • Polymer blends are gaining increasing interest in technology because they offer tailor-made combinations of properties. Of particular interest are polymer blends made from incompatible polymers that have unusual combinations of properties.
  • Polymer blends based on polyesters and polycarbonates have been known for a long time.
  • the technically important products also contain impact modifiers to improve toughness, especially at low temperatures, butadiene rubber, acrylate graft rubbers and
  • thermoplastic molding compositions the blend of two different polyesters, a polycarbonate and a chew ⁇ tschukelastischen polymer having a glass transition temperature of less than - 25 30 ° C included.
  • An ethylene / n-butyl acrylate / acrylic acid copolymer, ethylene / n-butyl acrylate-glycidyl methacrylate copolymer or a graft copolymer which has a shell made of styrene / acrylonitrile or methyl methacrylate are used as the rubber component.
  • molding compositions which have polycarbonate, an aromatic polyester, a butyl rubber and an acrylic elastomer.
  • the butyl rubber is preferably obtained from isobutene and isoprene.
  • the acrylic elastomer is preferably by Emulsion polymerization of alkyl acrylates, butadiene and methyl methacrylate obtained.
  • DE-A 33 02 124 discloses thermoplastic molding compositions which contain polycarbonates, polyalkenyl terephthalates, rubber-elastic graft polymers and terpolymers made from acrylic esters, vinyl esters and unsaturated nitriles.
  • Resin mixtures comprising a polyester, a polycarbonate and a regulator combination are known from EP-B 0 133 993.
  • the regulator combination contains a graft copolymer with a core of alkyl acrylate and olefin copolymers which contain alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid or mixtures thereof.
  • thermoplastic molding composition containing, based on the total weight of components A to G, which gives a total of 100% by weight
  • a 2 to 98.4% by weight of at least one polyester as component A
  • b 0.5 to 96.9% by weight of at least one polycarbonate as component B
  • c 0.5 to 10 wt .-% of at least one particulate emulsion polymer with a glass transition temperature of below 0 ° C, the has functional groups reactive towards carboxyl groups, as component C,
  • d 0.5 to 10% by weight of at least one particulate emulsion polymer with a glass transition temperature of below 0 ° C., which has no functional groups reactive towards carboxyl groups, as component D,
  • e 0.1 to 10% by weight of at least one ethylene copolymer which has carboxyl groups as component E,
  • f 0 to 60% by weight of at least one fibrous or particulate filler as component F and
  • component G 0 to 20% by weight of further additives as component G.
  • the object is further achieved by a process for the production of such molding compositions, their use for the production of films, fibers and moldings and the films, fibers and moldings obtained therefrom.
  • polyester / polycarbonate molding compositions are obtained by a specific combination of a particulate emulsion polymer which has functional groups which are reactive towards carboxyl groups, a particulate emulsion polymer which has no reactive functional groups against carboxyl groups and an ethylene copolymer which has carboxyl groups, which have a superior property profile compared to known molding compositions.
  • polyesters of component A are used in the molding compositions according to the invention in an amount of 2 to 98.4% by weight, preferably 10 to 90% by weight, in particular 15 to 85% by weight.
  • the polyester is preferably derived from an aromatic dicarboxylic acid.
  • the aromatic ring of the dicarboxylic acid can be further substituted, for example by halogen, such as chlorine or bromine, or C M alkyl, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, i-butyl or tert-butyl.
  • the aromatic dicarboxylic acids can be o-, m- or p-dicarboxylic acids or mixtures thereof. It is preferably p-dicarboxylic acids.
  • Preferred dicarboxylic acids are naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and mixtures thereof.
  • aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids, such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids. Only aliphatic dicarboxylic acids can also be used, but this is not preferred according to the invention.
  • Particularly suitable aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, neopentyl glycol and mixtures thereof.
  • Aromatic dihydroxy compounds which can be used are, for example, those based on diphenols of the general formula I.
  • A is a single bond, C ,. 3 -alkylene-, a C 2 . 3 -alkylidene, C 3 ⁇ - cycloalkylidene group, which can be substituted with up to 4 alkyl radicals, and in particular is in particular a 2,2,4-trimethylcyclohexylidene group, or denotes S or SO 2 .
  • Preferred diphenols of the formula I are, for example, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) 2-methylbutane, 1,1-bis (4- hydroxyphenyl) cyclohexane and bisphenol TMC. 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are particularly preferred.
  • polyesters are polyalkylene terephthalates which are derived from alkane diols having 2 to 6 carbon atoms. Polyethylene terephthalate and polybutylene terephthalate are particularly preferred.
  • the relative viscosity of the polyester A is usually 1.2 to 1.8, measured as a 0.5% by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1) at 25 ° C.
  • At least one polycarbonate is used as component B in an amount of 0.5 to 96.9% by weight, preferably 6.8 to 86.8% by weight, in particular 8 to 78% by weight.
  • the polycarbonate is preferably an aromatic polycarbonate.
  • the polycarbonate is also preferably halogen-free. Suitable halogen-free polycarbonates are, for example, those based on diphenols of the above general formula I. Both homopolycarbonates and copolycarbonates are suitable as component B, besides the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred. Further preferred examples of suitable diphenols are hydroquinone and Resorcinol, as well as the aromatic dihydroxy compounds mentioned under A.
  • the suitable polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having 3 or more than 3 phenolic OH -Groups.
  • the polycarbonates can be produced, for example, by reacting the diphenols with phosgene, using the interfacial process or using phosgene using the homogeneous phase process (the so-called pyridine process), the molecular weight to be adjusted in each case being achieved in a known manner by a corresponding amount of known chain terminators.
  • Polydiorganosiloxane-containing polycarbonates are described, for example, in DE-A 33 34 782.
  • Suitable chain terminators are, for example, phenol, p-tert-butylphenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) phenol according to DE-A 28 42 005, or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the Alkyl substituents according to DE-A 35 06 472, such as p-nonylphenyl, 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) phenol and 4- ( 3,5-dimethylheptyl) phenol.
  • alkylphenols such as 4- (1,3-tetramethylbutyl) phenol according to DE-A 28 42 005, or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the Alkyl substituents according to
  • Halogen-free polycarbonates in the sense of the present invention means that the polycarbonates consist of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of subordinate ppm amounts of saponifiable chlorine, resulting, for example, from the production of the polycarbonates with phosgene by the phase interface process, not to be regarded as containing halogen in the sense of the invention.
  • Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the sense of the present invention.
  • component C 0.5 to 10% by weight, preferably 1 to 8% by weight, in particular 2.5 to 5% by weight, of at least one particulate emulsion polymer having a glass transition temperature of below 0 ° C. which is reactive towards carboxyl groups has functional groups used.
  • the average particle size of the emulsion polymers is preferably in the range from 0.05 to 1 ⁇ m, particularly preferably 0.08 to 0.8 ⁇ m.
  • the particle size is determined from TEM images of the molding compositions, an average of 100 rubber particles being formed.
  • the glass transition temperature is determined by DSC measurement at a heating rate of 20 K / min. The glass transition temperature is preferably below ⁇ 20 ° C.
  • Component C is preferably a graft copolymer
  • cl 20 to 95% by weight of a graft base made of a rubber-elastic polymer with a glass transition temperature below 0 ° C. as component Cl,
  • c2 5 to 80% by weight of a graft pad as component C2 c21: 80 to 99.9% by weight of styrene, substituted styrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid esters or mixtures thereof as component C21,
  • c22 0.1 to 20% by weight of at least one vinylic monomer which has functional groups which are reactive towards carboxyl groups, as component C22.
  • Component Cl the graft base, preferably has a glass transition temperature below 0 ° C., preferably below -20 ° C.
  • suitable graft bases are:
  • Natural rubber synthetic rubber based on conjugated dienes, optionally with other copolymers, and elastomers based on C r to Cg alkyl esters of acrylic acid, which may optionally contain further comonomers.
  • polybutadiene cf. DE-A 14 20 775 and DE-A-14 95 089
  • copolymers of polybutadiene and styrene cf. GB-A 6 49 166
  • graft bases C1 which are composed of
  • cl2 0 to 29.9% by weight, preferably 20 to 30% by weight, of a further copolymerizable monoethylenically unsaturated monomer, such as styrene, acrylonitrile, methyl methacrylate and / or
  • Suitable such bifunctional or polyfunctional crosslinking monomers C13 are monomers which preferably contain two, optionally also three or more, ethylenic double bonds which are capable of copolymerization and which are not conjugated in the 1,3 positions.
  • Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate,
  • Diallyl phthalate, triallyl cyanurate or tricyclodecenyl alcohol (DE-A 12 60 135).
  • graft base is also known per se and is described in the literature, for example in DE-A 31 49 358, US 3,808,180, US 3,843,753 and US 3,562,235.
  • C21 denotes methyl methacrylate, styrene or ⁇ -methylstyrene.
  • the preferred monomer mixtures used are, above all, styrene and acrylonitrile, ⁇ -methylstyrene and acrylonitrile, styrene, acrylonitrile and methyl methacrylate, styrene and maleic anhydride.
  • the grafting pads can be obtained by copolymerizing components C21 and C22.
  • the graft copolymerization can be carried out in solution, suspension or preferably in emulsion.
  • the soft phase of the graft copolymer has an average particle diameter (d 50 value of the integral mass distribution) of 0.03 to 0.95 ⁇ m.
  • the d 50 value can be set in the desired range by enlarging the original particles, for example by agglomeration or when the emulsion is obtained by means of the seed latex method.
  • the polymerizing monomers are at least partially chemically linked to the already polymerized rubber, the linkage probably on the double bonds contained in the rubber.
  • At least some of the monomers are therefore grafted onto the rubber, thus bound to the rubber thread molecules through covalent bonds.
  • the grafting can also be carried out in several stages by first grafting on some of the monomers C2 forming the graft pad and then the rest. If the graft base C1 of the graft polymers C is composed of the components ClI, C13 and, if appropriate, C12, the term ASA rubbers is used. Their manufacture is known per se and is described, for example, in DE-A 28 26 925, DE-A 31 49 358 and DE-A 34 14 118.
  • the graft copolymer C can be prepared, for example, by the method described in DE-B 12 60 135.
  • the proportion of the graft pad (component C2) in the graft copolymer is preferably 10 to 60% by weight, particularly preferably 10 to 40% by weight, in particular 10 to 30% by weight.
  • the graft pad preferably has a glass transition temperature in the range from 50 to 120 ° C., particularly preferably 70 to 115 ° C., in particular 75 to 110 ° C.
  • the proportion of component C22 is preferably 0.2 to 5% by weight, particularly preferably 0.3 to 2% by weight, in particular 0.4 to 1% by weight.
  • component C22 preference is given to vinylic monomers which have epoxy and / or oxazoline groups. Monomers containing epoxy groups are particularly preferred.
  • Epoxy group-bearing monomers can be represented, for example, by the following general formulas II and III.
  • R 1 , R 2 , R 3 , R 4 independently of one another are hydrogen or C 1-4 alkyl, m is an integer from 0 to 20, p is an integer from 0 to 10.
  • the radicals indicated are preferably hydrogen, and m has the value 0 or 1 and p has the value 1.
  • Preferred compounds are alkenyl glycidyl ether and vinyl glycidyl ether.
  • Particularly preferred compounds are epoxy group-containing esters of acrylic acid and / or methacrylic acid, in particular glycidyl acrylate and glycidyl methacrylate.
  • a graft rubber containing oxazoline groups can be prepared by using isopropenyloxazoline as component C22.
  • the graft copolymers of component C can also be prepared as described in US 4,096, 202 or EP-A 0 561 197. They can have a single or multi-layer structure. In the case of a multi-layer structure, shells made of the core material and hard shells can alternate. The outermost shell is preferably compatible with the matrix. Epoxy groups can be present in the outermost shell and optionally in the inner shell.
  • glycidyl ethers of unsaturated alcohols allyl glycidyl ether
  • glycidyl ethers of alkenylphenols can also preferably be used.
  • all compounds can be used which have a polymerizable unsaturated group and an epoxy group.
  • the particulate emulsion polymer used as component D with a glass transition temperature of below 0 ° C., which has no functional groups which are reactive towards carboxyl groups, is in the Thermoplastic molding compositions according to the invention in an amount of 0.5 to 10% by weight, preferably 2 to 8% by weight, in particular 4 to 7% by weight.
  • Component D is preferably a graft copolymer
  • dl 20 to 95% by weight of a graft base made of a rubber-elastic polymer with a glass transition temperature below 0 ° C. as components Dl,
  • d2 5 to 80% by weight of a styrene-substituted graft
  • Styrene acrylonitrile, methacrynitrile, (meth) acrylic acid esters or mixtures thereof as component D2.
  • Component D can be constructed and produced like component C, but there are no functional groups which are reactive towards carboxyl groups. Instead of such monomers, appropriate amounts of the other monomers are used for the graft.
  • the ethylene copolymer used as component E, which has carboxyl groups, is present in the molding compositions according to the invention in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, in particular 0.5 to 1.5% by weight. - % in front.
  • the ethylene copolymer of component E is preferably a copolymer of components E1 to E4, the total weight of which gives a total of 100% by weight
  • el 50 to 98.9% by weight, preferably 60 to 97.8% by weight of ethylene as component El, e2: 1 to 49.9% by weight, preferably 2 to 39.8% by weight of at least one .g-alkyl acrylate as component E2,
  • e3 0.1 to 20% by weight, preferably 0.2 to 15% by weight, of at least one ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof as
  • e4 0 to 10% by weight, preferably 0 to 5% by weight, of further copolymerizable monomers as component E4.
  • Suitable polymers of this type are described, for example, in DE-A 42 27 742.
  • n-butyl acrylate preferably n-butyl acrylate and / or ethylhexyl acrylate, especially n-butyl acrylate, are used.
  • Suitable, ß-unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, maleic acid and fumaric acid. These can also be used in the form of their esters, acid anhydrides, acid halides or amides. Acrylic acid or methacrylic acid are preferably used.
  • Examples of other copolymerizable monomers are polar comonomers, such as aliphatic vinyl monomers containing nitrile groups and halogen atoms.
  • C 3 are further copolymerizable monomers.
  • 8- alk-1-enes such as propene, 1-butene, 1-pentene and 1-hexene.
  • a preferred ethylene copolymer contains only n-butyl acrylate and ethene
  • the proportion of n-butyl acrylate is preferably 25 to 39.8% by weight, acrylic acid 2 to 10% by weight.
  • the ethylene copolymer preferably has a melt flow index of 10 ml / 10 min at 190 ° C and one Load of 2.16 kg.
  • the ethylene copolymers can be prepared by customary high-pressure polymerization processes, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19 (1980), pages 169 to 175, Verlag Chemie, Weinheim.
  • the copolymerization of ethene is preferably carried out at pressures of 350 to 5000 bar, preferably 1500 to 3000 bar.
  • the temperatures are usually 50 to 450 ° C, preferably 150 to 350 ° C. Reference can also be made to EP-A 0 131 707.
  • thermoplastic molding compositions according to the invention contain 0 to 60% by weight, preferably 0 to 20% by weight, in particular 0 to 10% by weight, of at least one fibrous or particulate filler.
  • the glass fibers used can be made of E, A or C glass and are preferably equipped with a size and an adhesion promoter.
  • the diameter is generally between 6 and 20 ⁇ m.
  • Both endless fibers (rovings) and chopped glass fibers with a length of 1 to 10 mm, preferably 3 to 6 mm, can be used.
  • fillers or reinforcing materials such as glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder, talc, kaolin and wollastonite can be added.
  • metal flakes such as metal flakes from Transmed Corp.
  • metal powder such as metal fibers, metal-coated fillers (such as nickel-coated glass fibers) and other additives that shield electromagnetic waves
  • AI flakes K 102 of Transmed
  • EMI Electromagnetic Interference
  • the molding compositions can be coated with additional carbon fibers, Conductivity black or nickel-coated C-fibers can be mixed.
  • thermoplastic molding compositions according to the invention contain, as component G, 0 to 20% by weight, preferably 0 to 10% by weight, in particular 0 to 2% by weight, of further additives.
  • the additives generally used in polyester / polycarbonate blends can be used as further additives.
  • processing aids and stabilizers such as UV stabilizers, lubricants, phosphorus stabilizers and antistatic agents can be involved.
  • Other ingredients are dyes, pigments or antioxidants.
  • Stabilizers can serve to improve thermal stability, increase light stability, increase hydrolysis resistance and chemical resistance. Lubricants and lubricants are particularly useful in the production of moldings or molded parts.
  • metal halides such as chlorides, bromides or iodides, are usually used, which are derived from metals of group I of the periodic table, of the elements, such as Li, Na, K, Cu.
  • Suitable stabilizers are the usual hindered phenols, but also vitamin E or compounds with an analog structure. HALS stabilizers, benzophenones, resorcinols, salicylates, benzotriazoles and other compounds are also suitable.
  • HALS stabilizers such as TINUVIN ® 770 HALS absorber, bis-2,2,6,6-tetramethyl-4-piperidyl sebazate
  • TINUVIN ® P UV absorber, (2H-benzotriazol-2-yl) -4-methylphenol
  • TOPANOL ® TOPANOL ®
  • Suitable lubricants and mold release agents are stearic acids and stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures with 12 to 30 carbon atoms.
  • Silicone oils, oligomeric isobutylene and similar substances can also be used as additives.
  • Pigments, dyes, color brighteners, such as ultramarine blue, phthalocyanines, titanium oxide, cadmium sulfude, derivatives of perylene tetracarboxylic acid can also be used.
  • transesterification protection agents such as Irgaphos ® P-EPQ from Ciba-Geigy or magnesium or zinc phosphate can be used as component G.
  • the molding compositions according to the invention are produced by mixing components A to E and, if appropriate, F and G.
  • the order in which the components are mixed is arbitrary.
  • the molding compositions according to the invention can be produced by processes known per se, for example extrusion.
  • the molding compositions according to the invention can be produced, for example, by mixing the starting components in conventional mixing devices such as screw extruders, preferably twin-screw extruders, Brabender mixers or Banbury mixers and kneaders, and then extruding them. After the extrusion, the extrudate is cooled and crushed.
  • the order of mixing the components can be varied, for example two or possibly three components can be premixed, but all components can also be mixed together.
  • Average mixing times are generally from 0.2 to 30 minutes at temperatures from 230 to 280 ° C., preferably 230 to
  • the molding compositions according to the invention show a good balance of impact strength, damage work, processing stability and weather resistance. Due to the properties mentioned and the high heat resistance, the molding compositions are suitable for the production of moldings, for example in the household. Electrical, automotive and medical technology can be used.
  • thermoplastic molding compositions according to the invention can be processed by the known methods of thermoplastic processing, for example by extrusion, injection molding, calendering, blow molding, pressing or sintering.
  • Polybutylene terephthalate characterized by a tensile modulus of elasticity of 2600 N / mm 2 and a viscosity number of 130 ml / g (VZ measured in 0.5% by weight solution of phenol / o-dichlorobenzene, 1: 1 mixture to 25 ° C), e.g. Ultradur B4500 from BASF AG.
  • Polycarbonate based on bisphenol A characterized by a viscosity number of 61.2 ml / g (measured in 0.5% by weight CH 2 C1 2 solution at 23 ° C).
  • Talc e.g. IT-Extra from Norwegian Tale, average particle size of 4.9 ⁇ m (determined in a suspension cell with demineralized water as a liquid.
  • Component G Irgaphos ® P-EPQ from Ciba-Geigy (tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylene-diphosphonite) with a melting range of 75-95 ° C).
  • a twin screw extruder was used to mix the components.
  • the melt was passed through a water bath and granulated. Furthermore, the mechanical properties of the samples produced using an extruder were determined.
  • the heat resistance was determined according to HDT B.
  • the notched impact strength of the products was determined on ISO bars according to ISO 179 leA.
  • the damage work of the molding compounds was measured according to DIN 53 433 at -30 ° C.
  • the processing stability was determined by measuring the melt viscosity at 270 ° C. over a period of 20 minutes. The specified value is calculated as follows:
  • thermoplastic molding compositions according to the invention demonstrate the excellent range of properties of the thermoplastic molding compositions according to the invention, in particular the balanced toughness level, the improvement in processing stability, the better heat resistance and the better UV resistance.

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Abstract

The inventive thermoplastic moulding material contains the following constituents A-G in relation to their overall weight which totals 100 %: a: 2 to 98.4 wt. % of at least one polyester as constituent A; b: 0.5 to 96.9 wt. % of at least one polycarbonate as constituent B; c: 0.5 to 10 wt. % of at least one particulate emulsion polymerizate which has a glass transition temperature of less than 0 DEG C and which has functional groups which are reactive to carboxyl groups, as constituent C; d: 0.5 to 10 wt. % of at least one particulate emulsion polymerizate which has a glass transition temperature of less than 0 DEG C and which has no functional groups which are reactive to carboxyl groups, as constituent D; e: 0.1 to 10 wt. % of at least one ethylene copolymer which has carboxyl groups, as constituent E; f: 0 to 60 wt. % of at least one fibrous or particulate filler as constituent F and g: 0 to 20 wt. % of other additives as constituent G.

Description

Polyester und Polycarbonate enthaltende thermoplastische Formmassen Thermoplastic molding compositions containing polyester and polycarbonates

55

Die Erfindung betrifft Polyester und Polycarbonate enthaltende thermoplastische Formmassen, die schlagzähmodifiziert sind.The invention relates to thermoplastic molding compositions containing polyester and polycarbonates, which are impact modified.

1010

Polymermischungen finden in der Technik zunehmendes Interesse, da sie maßgeschneiderte Eigenschaftskombinationen bieten. Von besonderem Interesse sind dabei Polymermischungen aus unverträglichen Polymeren, die ungewöhnliche Eigenschaftskombinationen aufweisen.Polymer blends are gaining increasing interest in technology because they offer tailor-made combinations of properties. Of particular interest are polymer blends made from incompatible polymers that have unusual combinations of properties.

1515

Polymermischungen auf Basis von Polyestern und Polycarbonaten sind seit langer Zeit bekannt. Die technisch wichtigen Produkte enthalten zur Verbesserung der Zähigkeit, insbesondere bei tiefen Temperaturen, auch Schlagzähmodifier, wobei insbesondere Butadienkautschuk, Acrylat-Propfkautschuke undPolymer blends based on polyesters and polycarbonates have been known for a long time. The technically important products also contain impact modifiers to improve toughness, especially at low temperatures, butadiene rubber, acrylate graft rubbers and

20 Ethylencopolymere mit polaren Comonomeren eingesetzt werden.20 ethylene copolymers with polar comonomers can be used.

In US 4,764,556 sind thermoplastische Formmassen beschrieben, die Blends aus zwei unterschiedlichen Polyestern, einem Polycarbonat und einem kau¬ tschukelastischen Polymer mit einer Glasubergangstemperatur von weniger als - 25 30°C enthalten. Als Kautschukkomponente kommen ein Ethylen/n-Butyl- acrylat/Acrylsäure-Copolymer, Ethylen/n-Butylacrylat-Glycidylmethacrylat-Copo- lymer oder ein Pfropfcopolymer zur Anwendung, das eine Schale aus Styrol/- Acrylnitril oder Methylmethacrylat aufweist.In US 4,764,556 to thermoplastic molding compositions are described, the blend of two different polyesters, a polycarbonate and a chew ¬ tschukelastischen polymer having a glass transition temperature of less than - 25 30 ° C included. An ethylene / n-butyl acrylate / acrylic acid copolymer, ethylene / n-butyl acrylate-glycidyl methacrylate copolymer or a graft copolymer which has a shell made of styrene / acrylonitrile or methyl methacrylate are used as the rubber component.

30 Aus der JP-A 5 8098 357 sind Formmassen bekannt, die Polycarbonat, einen aromatischen Polyester, einen Butylkautschuk und ein acrylisches Elastomer aufweisen. Der Butylkautschuk wird vorzugsweise aus Isobuten und Isopren erhalten. Das acrylische Elastomer wird vorzugsweise durch Emulsionspolymerisation von Alkylacrylaten, Butadien und Methylmethacrylat erhalten.From JP-A 5 8098 357 molding compositions are known which have polycarbonate, an aromatic polyester, a butyl rubber and an acrylic elastomer. The butyl rubber is preferably obtained from isobutene and isoprene. The acrylic elastomer is preferably by Emulsion polymerization of alkyl acrylates, butadiene and methyl methacrylate obtained.

Aus der DE-A 33 02 124 sind thermoplastische Formmassen bekannt, die Polycarbonate, Polyalkenylterephthalate, kautschukelastische Propfpolymerisate und Terpolymerisate aus Acrylsäureester, Vinylester und ungesättigten Nitrilen enthalten.DE-A 33 02 124 discloses thermoplastic molding compositions which contain polycarbonates, polyalkenyl terephthalates, rubber-elastic graft polymers and terpolymers made from acrylic esters, vinyl esters and unsaturated nitriles.

Aus der EP-B 0 133 993 sind Harzmischungen bekannt, die einen Polyester, ein Polycarbonat und eine Reglerkombinationen umfassen. Die Reglerkombination enthält ein Pfropfcopolymer mit einem Kern aus Alkylacrylat und Olefmcopolymere, die Alkylacrylat, Alkylmethacrylat, Acrylsäure, Meth- acrylsäure oder Gemische davon enthalten.Resin mixtures comprising a polyester, a polycarbonate and a regulator combination are known from EP-B 0 133 993. The regulator combination contains a graft copolymer with a core of alkyl acrylate and olefin copolymers which contain alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid or mixtures thereof.

Die Produkte mit den genannten Kautschukmischungen haben sich bisher jedoch nicht durchsetzen können. Um den immer komplexer werdenden Anforderungen gerecht zu werden, besteht noch immer Bedarf an Polymermischungen auf Basis von Polyestern und Polycarbonaten, die sich durch gute Fließfähigkeit, gute Wärmeformbeständigkeit und gute Witterungsbeständigkeit auzeichnen. Sie sollen zudem eine gute Tieftemperaturzähigkeit und gute Verarbeitungsstabilität haben.However, the products with the rubber mixtures mentioned have so far not been able to establish themselves. In order to meet the increasingly complex requirements, there is still a need for polymer mixtures based on polyesters and polycarbonates which are notable for good flowability, good heat resistance and good weather resistance. They should also have good low-temperature toughness and good processing stability.

Die Aufgabe wird erfindungsgemäß gelöst durch Bereitstellung einer thermoplastischen Formmasse, enthaltend, bezogen auf das Gesamtgewicht der Komponenten A bis G, das insgesamt 100 Gew.- % ergibt,The object is achieved according to the invention by providing a thermoplastic molding composition containing, based on the total weight of components A to G, which gives a total of 100% by weight,

a: 2 bis 98,4 Gew.-% mindestens eines Polyesters als Komponente A, b: 0,5 bis 96,9 Gew.-% mindestens eines Polycarbonats als Komponente B,a: 2 to 98.4% by weight of at least one polyester as component A, b: 0.5 to 96.9% by weight of at least one polycarbonate as component B,

c: 0,5 bis 10 Gew.-% mindestens eines teilchenformigen Emulsionspolymerisats mit einer Glasubergangstemperatur von unter 0°C, das gegenüber Carboxylgruppen reaktionsfähige funktionelle Gruppen aufweist, als Komponente C,c: 0.5 to 10 wt .-% of at least one particulate emulsion polymer with a glass transition temperature of below 0 ° C, the has functional groups reactive towards carboxyl groups, as component C,

d: 0,5 bis 10 Gew.-% mindestens eines teilchenformigen Emulsions- polymerisats mit einer Glasubergangstemperatur von unter 0°C, das keine gegenüber Carboxylgruppen reaktionsfähigen funktionellen Gruppen aufweist, als Komponente D,d: 0.5 to 10% by weight of at least one particulate emulsion polymer with a glass transition temperature of below 0 ° C., which has no functional groups reactive towards carboxyl groups, as component D,

e: 0,1 bis 10 Gew.-% mindestens eines Ethylencopolymers, das Carbox- ylgruppen aufweist, als Komponente E,e: 0.1 to 10% by weight of at least one ethylene copolymer which has carboxyl groups as component E,

f: 0 bis 60 Gew.-% mindestens eines faser- oder teilchenformigen Füllstoffs als Komponente F undf: 0 to 60% by weight of at least one fibrous or particulate filler as component F and

g: 0 bis 20 Gew.-% weiterer Zusatzstoffe als Komponente G.g: 0 to 20% by weight of further additives as component G.

Die Aufgabe wird ferner gelöst durch ein Verfahren zur Herstellung derartiger Formmassen, deren Verwendung zur Herstellung von Folien, Fasern und Formkörpern und die daraus erhaltenen Folien, Fasern und Formkörper.The object is further achieved by a process for the production of such molding compositions, their use for the production of films, fibers and moldings and the films, fibers and moldings obtained therefrom.

Es wurde erfindungsgemäß gefunden, daß durch eine spezifische Kombination eines teilchenformigen Emulsionspolymerisats, das gegenüber Carboxylgruppen reaktionsfähige funktionelle Gruppen aufweist, eines teilchenformigen Emulsionpolymerisats, das gegenüber Carboxylgruppen keine reaktionsfähigen funktionellen Gruppen aufweist und eines Ethylencopolymers, das Carboxylgruppen aufweist, Polyester/Polycarbonat-Formmassen erhalten werden, die gegenüber bekannten Formmassen ein überlegenes Eigenschaftsprofil aufweisen.It has been found according to the invention that polyester / polycarbonate molding compositions are obtained by a specific combination of a particulate emulsion polymer which has functional groups which are reactive towards carboxyl groups, a particulate emulsion polymer which has no reactive functional groups against carboxyl groups and an ethylene copolymer which has carboxyl groups, which have a superior property profile compared to known molding compositions.

Die Komponenten der erfindungsgemäßen Formmasse werden nachstehend näher beschrieben. Komponente AThe components of the molding composition according to the invention are described in more detail below. Component A

Die Polyester der Komponente A werden in den erfmdungsgemäßen Formmassen in einer Menge von 2 bis 98,4 Gew.-%, vorzugsweise 10 bis 90 Gew.- , insbesondere 15 bis 85 Gew.-% eingesetzt.The polyesters of component A are used in the molding compositions according to the invention in an amount of 2 to 98.4% by weight, preferably 10 to 90% by weight, in particular 15 to 85% by weight.

Vorzugsweise leitet sich der Polyester von einer aromatischen Dicarbonsäure ab.The polyester is preferably derived from an aromatic dicarboxylic acid.

Dabei kann der aromatische Ring der Dicarbonsäure weiter substituiert sein, beispielsweise durch Halogen, wie Chlor oder Brom, oder CM-Alkyl, wie Methyl, Ethyl, Isopropyl, n-Propyl, n-Butyl, i-Butyl oder tert-Butyl. Die aromatischen Dicarbonsäuren können o-, m-, oder p-Dicarbonsäuren oder Gemische davon sein. Vorzugsweise handelt es sich um p-Dicarbonsäuren. Bevorzugte Dicarbonsäuren sind Naphthalindicarbonsäure, Terephthalsäure und Isophthalsäure, sowie Gemische davon. Bis zu 10 Mol-% der aromatischen Dicarbonsäuren können dabei durch aliphatische oder cycloaliphatische Dicarbonsäuren ersetzt sein, wie Adipinsäure, Acelainsäure, Sebazinsäure, Dodecandisäuren und Cycloh- exandicarbonsäuren. Es können auch nur aliphatische Dicarbonsäuren eingesetzt werden, was erfindungsgemäß jedoch nicht bevorzugt ist.The aromatic ring of the dicarboxylic acid can be further substituted, for example by halogen, such as chlorine or bromine, or C M alkyl, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, i-butyl or tert-butyl. The aromatic dicarboxylic acids can be o-, m- or p-dicarboxylic acids or mixtures thereof. It is preferably p-dicarboxylic acids. Preferred dicarboxylic acids are naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and mixtures thereof. Up to 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids, such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids. Only aliphatic dicarboxylic acids can also be used, but this is not preferred according to the invention.

Als aliphatische Dihydroxyverbindungen kommen insbesondere Diole mit 2 bis 6 Kohlenstoffatomen in Betracht, insbesondere 1,2-Ethandiol, 1,4-Butandiol, 1,6- Hexandiol, 1,4-Hexandiol, 1,4-Cyclohexandiol, Neopentylglykol und Gemische davon. Verwendbare aromatische Dihydroxyverbindungen sind beispielsweise solche auf Basis von Diphenolen der allgemeinen Formel I.Particularly suitable aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, neopentyl glycol and mixtures thereof. Aromatic dihydroxy compounds which can be used are, for example, those based on diphenols of the general formula I.

HO-H4C6-A-C6H4-OH (I)HO-H 4 C 6 -AC 6 H 4 -OH (I)

worin A eine Einfachbindung, C,.3-Alkylen-, eine C2.3-Alkyliden-, C3^- Cycloalkylidengruppe, die mit bis zu 4 Alkylresten substituiert sein kann, und ins- besondere eine 2,2,4-Trimethylcyclohexylidengruppe ist, oder S oder SO2 bedeutet. Bevorzugte Diphenole der Formel I sind beispielsweise 4,4'- Dihydroxydiphenyl, 2,2-Bis-(4-hydroxyphenyl)propan, 2,4-Bis-(4- hydroxyphenyl)2-methylbutan, 1 , l-Bis(4-hydroxyphenyl)cyclohexan und Bisphenol-TMC. Besonders bevorzugt sind 2,2-Bis(4-hydroxyphenyl)propan und 1 , l-Bis(4-hyxdroxyphenyl)cyclohexan.wherein A is a single bond, C ,. 3 -alkylene-, a C 2 . 3 -alkylidene, C 3 ^ - cycloalkylidene group, which can be substituted with up to 4 alkyl radicals, and in particular is in particular a 2,2,4-trimethylcyclohexylidene group, or denotes S or SO 2 . Preferred diphenols of the formula I are, for example, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) 2-methylbutane, 1,1-bis (4- hydroxyphenyl) cyclohexane and bisphenol TMC. 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are particularly preferred.

Besonders bevorzugte Polyester sind Polyalkylenterephthalate, die sich von Alkandiolen mit 2 bis 6 Kohlenstoffatomen ableiten. Insbesondere bevorzugt sind Polyethylenterephthalat und Polybutylenterephthalat.Particularly preferred polyesters are polyalkylene terephthalates which are derived from alkane diols having 2 to 6 carbon atoms. Polyethylene terephthalate and polybutylene terephthalate are particularly preferred.

Die relative Viskosität der Polyester A beträgt in der Regel 1,2 bis 1,8, gemessen als 0,5 Gew.-%ige Lösung in einem Phenol/o-Dichlorbenzol-Gemisch (Gewichtsverhältnis 1: 1) bei 25°C.The relative viscosity of the polyester A is usually 1.2 to 1.8, measured as a 0.5% by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1) at 25 ° C.

Komponente BComponent B

Als Komponente B wird mindestens ein Polycarbonat in einer Menge von 0,5 bis 96,9 Gew.-% , vorzugsweise 6,8 bis 86,8 Gew.-%, insbesondere 8 bis 78 Gew.-% eingesetzt. Das Polycarbonat ist dabei vorzugsweise ein aromatisches Polycarbonat. Das Polycarbonat ist ferner vorzugsweise halogenfrei. Geeignete halogenfreie Polycarbonate sind beispielsweise solche auf Basis von Diphenolen der vorstehenden allgemeinen Formel I. Sowohl Homopolycarbonate als auch Copolycarbonate sind als Komponente B geeignet, bevorzugt sind neben dem Bisphenol- A-Homopolymerisat die Copolycarbonate von Bisphenol A. Weitere bevorzugte Beispiele geeigneter Diphenole sind Hydrochinon und Resorcin, sowie die unter A genannten aromatischen Dihydroxyverbindungen.At least one polycarbonate is used as component B in an amount of 0.5 to 96.9% by weight, preferably 6.8 to 86.8% by weight, in particular 8 to 78% by weight. The polycarbonate is preferably an aromatic polycarbonate. The polycarbonate is also preferably halogen-free. Suitable halogen-free polycarbonates are, for example, those based on diphenols of the above general formula I. Both homopolycarbonates and copolycarbonates are suitable as component B, besides the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred. Further preferred examples of suitable diphenols are hydroquinone and Resorcinol, as well as the aromatic dihydroxy compounds mentioned under A.

Weitere geeignete Diphenole sind beschrieben in H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, 1964, sowie in US 2,999,835 und DE-A 22 48 817. Verfahren zur Herstellung von Polycarbonaten sind beispielsweise in der US 2,999,835, DE-A 22 48 817, DE-A 13 00 266 und DE- A 14 95 730 beschrieben.Other suitable diphenols are described in H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, 1964, and in US 2,999,835 and DE-A 22 48 817. Processes for producing polycarbonates are described, for example, in US 2,999,835, DE-A 22 48 817, DE-A 13 00 266 and DE-A 14 95 730.

Die geeigneten Polycarbonate können in bekannter Weise verzweigt sein, und zwar vorzugsweise durch Einbau von 0,05 bis 2,0 Mol-%, bezogen auf die Summe der eingesetzten Diphenole, an mindestens trifunktionellen Verbindungen, beispielsweise solchen mit 3 oder mehr als 3 phenolischen OH-Gruppen.The suitable polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having 3 or more than 3 phenolic OH -Groups.

Als besonders geeignet haben sich Polycarbonate erwiesen, die relative Viskositäten von 1,10 bis 1,50, insbesondere von 1,25 bis 1,40 aufweisen. Dies entspricht mittleren Molekulargewichten Mw (Gewichtsmittelwert) von 10000 bis zu 200000, vorzugsweise von 20000 bis 80000.Polycarbonates which have relative viscosities of 1.10 to 1.50, in particular of 1.25 to 1.40, have proven to be particularly suitable. This corresponds to average molecular weights M w (weight average) of 10,000 to 200,000, preferably 20,000 to 80,000.

Die Herstellung der Polycarbonate kann beispielsweise durch Umsetzung der Diphenole mit Phosgen, nach dem Phasengrenzflächenverfahren oder mit Phosgen nach dem Verfahren in homogener Phase (dem sogenannten Pyridinverfahren) erfolgen, wobei das jeweils einzustellende Molekulargewicht in bekannter Weise durch eine entsprechende Menge an bekannten Kettenabbrechern erzielt wird. Polydiorganosiloxanhaltige Polycarbonate sind beispielsweise in der DE-A 33 34 782 beschrieben. Geeignete Kettenabbrecher sind beispielsweise Phenol, p-tert.- Butylphenol, aber auch langkettige Alkylphenole, wie 4-(l,3- Tetramethylbutyl)phenol gemäß DE-A 28 42 005 oder Monoalkylphenole oder Dialkylphenole mit insgesamt 8 bis 20 C-Atomen in den Alkylsubstituenten gemäß DE-A 35 06 472, wie p-Nonylphenyl, 3,5-di-tert.-Butylphenol, p-tert.- Octylphenol, p-Dodecylphenol, 2-(3,5-Dimethylheptyl)phenol und 4-(3,5- Dimethylheptyl)phenol .The polycarbonates can be produced, for example, by reacting the diphenols with phosgene, using the interfacial process or using phosgene using the homogeneous phase process (the so-called pyridine process), the molecular weight to be adjusted in each case being achieved in a known manner by a corresponding amount of known chain terminators. Polydiorganosiloxane-containing polycarbonates are described, for example, in DE-A 33 34 782. Suitable chain terminators are, for example, phenol, p-tert-butylphenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) phenol according to DE-A 28 42 005, or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the Alkyl substituents according to DE-A 35 06 472, such as p-nonylphenyl, 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) phenol and 4- ( 3,5-dimethylheptyl) phenol.

Halogenfreie Polycarbonate im Sinne der vorliegenden Erfindung bedeutet, daß die Polycarbonate aus halogenfreien Diphenolen, halogenfreien Kettenabrechern und gegebenenfalls halogenfreien Verzweigern aufgebaut sind, wobei der Gehalt untergeordneter ppm-Mengen an verseifbarem Chlor, resultierend beispielsweise aus der Herstellung der Polycarbonate mit Phosgen nach dem Phasengrenzflächenverfahren nicht als halogenhaltig im Sinne der Erfindung anzusehen ist. Derartige Polycarbonate mit ppm-Gehalten an verseifbarem Chlor sind halogenfreie Polycarbonate im Sinne der vorliegenden Erfindung.Halogen-free polycarbonates in the sense of the present invention means that the polycarbonates consist of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of subordinate ppm amounts of saponifiable chlorine, resulting, for example, from the production of the polycarbonates with phosgene by the phase interface process, not to be regarded as containing halogen in the sense of the invention. Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the sense of the present invention.

Komponente CComponent C

Als Komponente C werden 0,5 bis 10 Gew.-% , vorzugsweise 1 bis 8 Gew.-%, insbesondere 2,5 bis 5 Gew.-% mindestens eines teilchenformigen Emulsionspolymerisats mit einer Glasubergangstemperatur von unter 0°C, das gegenüber Carboxylgruppen reaktionsfähige funktionelle Gruppen aufweist, eingesetzt.As component C, 0.5 to 10% by weight, preferably 1 to 8% by weight, in particular 2.5 to 5% by weight, of at least one particulate emulsion polymer having a glass transition temperature of below 0 ° C. which is reactive towards carboxyl groups has functional groups used.

Vorzugsweise liegt die mittlere Teilchengröße der Emulsionspolymerisate im Bereich vom 0,05 bis 1 μm, besonders bevorzugt 0,08 bis 0,8 μm. Die Teilchengröße wird dabei aus TEM-Aufnahmen der Formmassen bestimmt, wobei ein Mittelwert aus 100 Kautschukpartikeln gebildet wird. Die Glas- Übergangstemperatur wird durch DSC-Messung bei einer Aufheizrate von 20 K/min bestimmt. Vorzugsweise liegt die Glasubergangstemperatur unterhalb von - 20°C.The average particle size of the emulsion polymers is preferably in the range from 0.05 to 1 μm, particularly preferably 0.08 to 0.8 μm. The particle size is determined from TEM images of the molding compositions, an average of 100 rubber particles being formed. The glass transition temperature is determined by DSC measurement at a heating rate of 20 K / min. The glass transition temperature is preferably below −20 ° C.

Vorzugsweise ist Komponente C ein Pfropfcopolymerisat ausComponent C is preferably a graft copolymer

cl: 20 bis 95 Gew.-% einer Pfropfgrundlage aus einem kautschukelastischen Polymer mit einer Glasubergangstemperatur unterhalb von 0°C als Komponente Cl,cl: 20 to 95% by weight of a graft base made of a rubber-elastic polymer with a glass transition temperature below 0 ° C. as component Cl,

c2: 5 bis 80 Gew.-% einer Pfropfauflage als Komponente C2 aus c21: 80 bis 99,9 Gew.-% Styrol, substituiertem Styrol, Acrylnitril, Methacrylnitril, (Meth)acrylsäureestern oder Gemischen davon als Komponente C21,c2: 5 to 80% by weight of a graft pad as component C2 c21: 80 to 99.9% by weight of styrene, substituted styrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid esters or mixtures thereof as component C21,

c22: 0,1 bis 20 Gew.-% mindestens eines vinylischen Monomers, das gegenüber Carboxylgruppen reaktionsfähige funktionelle Gruppen aufweist, als Komponente C22.c22: 0.1 to 20% by weight of at least one vinylic monomer which has functional groups which are reactive towards carboxyl groups, as component C22.

Vorzugsweise hat Komponente Cl, die Pfropfgrundlage, eine Glasubergangstemperatur unterhalb von 0°C, bevorzugt unterhalb von -20°C. Beispiele geeigneter Pfropfgrundlagen sind:Component Cl, the graft base, preferably has a glass transition temperature below 0 ° C., preferably below -20 ° C. Examples of suitable graft bases are:

Naturkautschuk, Synthesekautschuk auf der Basis von konjugierten Dienen, gegebenenfalls mit anderen Copolymeren, sowie Elastomere auf der Basis von Cr bis Cg-Alkylestern der Acrylsäure, die gegebenenfalls weitere Comonomere enthalten können. Beispielsweise kommen als Pfropfgrundlage Cl Polybutadien (vgl. DE-A 14 20 775 und DE-A- 14 95 089) und Copolymerisate aus Polybutadien und Styrol (vgl. GB-A 6 49 166) in Betracht.Natural rubber, synthetic rubber based on conjugated dienes, optionally with other copolymers, and elastomers based on C r to Cg alkyl esters of acrylic acid, which may optionally contain further comonomers. For example, polybutadiene (cf. DE-A 14 20 775 and DE-A-14 95 089) and copolymers of polybutadiene and styrene (cf. GB-A 6 49 166) are suitable as the graft base C1.

Bevorzugt sind Pfropfgrundlagen Cl, die aufgebaut sind ausPreference is given to graft bases C1 which are composed of

eil: 70 bis 99,9 Gew.-% vorzugsweise 69 bis 79 Gew.-% mindestens eines Alkylacrylates mit 1 bis 8 C-Atomen im Alkylrest, vorzugsweise n-Butylacrylat und/oder 2-Ethyl-hexylacrylat, insbesondere n-rush: 70 to 99.9% by weight, preferably 69 to 79% by weight, of at least one alkyl acrylate having 1 to 8 carbon atoms in the alkyl radical, preferably n-butyl acrylate and / or 2-ethylhexyl acrylate, in particular n-

Butylacrylat als alleinigem Alkylacrylat als Komponente Cll,Butyl acrylate as the sole alkyl acrylate as component Cll,

cl2: 0 bis 29,9 Gew.-%, vorzugsweise 20 bis 30 Gew.-% eines weiteren copolymerisierbaren monoethylenisch ungesättigten Monomeren, wie Styrol, Acrylnitril, Methylmethacrylat und/odercl2: 0 to 29.9% by weight, preferably 20 to 30% by weight, of a further copolymerizable monoethylenically unsaturated monomer, such as styrene, acrylonitrile, methyl methacrylate and / or

Vinylmethy lether als Komponente C12, cl3: 0,1 bis 5 Gew.-%, vorzugsweise 1 bis 4 Gew.-% eines copolymerisier- baren, polyfunktionellen, vorzugsweise bi- oder trifunktionellen, die Vernetzung bewirkenden Monomeren als Komponente C13. Als solche bi- oder polyfunktionellen Vernetzungsmonomeren C13 eignen sich Monomere, die vorzugsweise zwei, gegebenenfalls auch drei oder mehr zur Copolymerisation befähigte ethylenische Doppelbindungen enthalten, die nicht in den 1,3 -Stellungen konjugiert sind. Geeignete Vernetzungsmonomere sind beispielsweise Divinylbenzol, Diallylmaleat, Diallylfumarat,Vinyl methyl ether as component C12, cl3: 0.1 to 5% by weight, preferably 1 to 4% by weight, of a copolymerizable, polyfunctional, preferably bifunctional or trifunctional, crosslinking monomer as component C13. Suitable such bifunctional or polyfunctional crosslinking monomers C13 are monomers which preferably contain two, optionally also three or more, ethylenic double bonds which are capable of copolymerization and which are not conjugated in the 1,3 positions. Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate,

Diallylphthalat, Triallylcyanurat oder Tricyclodecenylalkohol (DE- A 12 60 135).Diallyl phthalate, triallyl cyanurate or tricyclodecenyl alcohol (DE-A 12 60 135).

Auch diese Art von Pfropfgrundlagen ist an sich bekannt und in der Literatur be- schrieben, beispielsweise in der DE-A 31 49 358, US 3,808,180, US 3,843,753 und US 3,562,235. Von den Pfropfauflagen C2 sind diejenigen bevorzugt, in denen C21 Methylmethacrylat, Styrol oder α-Methylstyrol bedeutet. Als bevorzugte Monomeren-Gemische werden vor allem Styrol und Acrylnitril, α- Methylstyrol und Acrylnitril, Styrol, Acrylnitril und Methylmethacrylat, Styrol und Maleinsäureanhydrid eingesetzt. Die Pfropfauflagen sind erhältlich durch Copolymerisation der Komponenten C21 und C22. Die Pfropfmischpolymerisation kann wie aus der DE-A 31 49 358 bekannt in Lösung, Suspension oder vorzugsweise in Emulsion erfolgen. Die Weichphase des Pfropfmischpolymerisats weist bei der bevorzugten Herstellung des Kautschuks und der Pfropfung in Emulsion einen mittleren Teilchendurchmesser (d50-Wert der integralen Massenverteilung) von 0,03 bis 0,95 μm auf. Durch Vergrößerung der ursprünglichen Teilchen, z.B. durch Agglomeration oder bei der Gewinnung der Emulsion im Wege des Saatlatex- Verfahrens, kann der d50-Wert im gewünschten Bereich eingestellt werden. Bei solchen Pfropfcopolymerisationen erfolgt eine zumindest teilweise chemische Verknüpfung der polymerisierenden Monomeren mit dem bereits polymerisierten Kautschuk, wobei die Verknüpfung wahrscheinlich an den im Kautschuk enthaltenen Doppelbindungen erfolgt. Zumindest ein Teil der Monomeren ist also auf den Kautschuk gepfropft, somit durch kovalente Bindungen an den Kautschuk-Fadenmolekülen gebunden. Die Pfropfung kann auch mehrstufig erfolgen, indem zuerst ein Teil der die Pfropfauflage bildenden Monomere C2 aufgepfropft wird und anschließend der Rest. Ist die Pfropfgrundlage Cl der Pfropfpolymerisate C aus den Komponenten Cll, C13 und gegebenenfalls C12 aufgebaut, so spricht man von ASA- Kautschuken. Ihre Herstellung ist an sich bekannt und beispielsweise in der DE-A 28 26 925, der DE-A 31 49 358 und der DE-A 34 14 118 beschrieben. Die Herstellung des Pfropfcopolymerisats C kann beispielsweise nach der in DE-B 12 60 135 beschriebenen Methode erfolgen. Der Anteil der Pfropfauflage (Komponente C2) im Pfropfcopolymerisat beträgt vorzugsweise 10 bis 60 Gew.- %, besonders bevorzugt 10 bis 40 Gew.-% , insbesondere 10 bis 30 Gew.-% . Die Pfropfauflage weist dabei vorzugsweise eine Glasubergangstemperatur im Bereich von 50 bis 120°C, besonders bevorzugt 70 bis 115°C, insbesondere 75 bis 110°C auf. Der Anteil der Komponente C22 beträgt vorzugsweise 0,2 bis 5 Gew.-%, besonders bevorzugt 0,3 bis 2 Gew.-% , insbesondere 0,4 bis 1 Gew.-% . Als Komponente C22 kommen vorzugsweise vinylische Monomere in Betracht, die Epoxy- und/oder Oxazolingruppen aufweisen. Besonders bevorzugt sind dabei Epoxygruppen enthaltende Monomere. Epoxy gruppentragende Monomere sind beispielsweise darstellbar durch folgende allgemeine Formeln II und III.This type of graft base is also known per se and is described in the literature, for example in DE-A 31 49 358, US 3,808,180, US 3,843,753 and US 3,562,235. Of the grafting pads C2, preference is given to those in which C21 denotes methyl methacrylate, styrene or α-methylstyrene. The preferred monomer mixtures used are, above all, styrene and acrylonitrile, α-methylstyrene and acrylonitrile, styrene, acrylonitrile and methyl methacrylate, styrene and maleic anhydride. The grafting pads can be obtained by copolymerizing components C21 and C22. As is known from DE-A 31 49 358, the graft copolymerization can be carried out in solution, suspension or preferably in emulsion. In the preferred production of the rubber and the grafting in emulsion, the soft phase of the graft copolymer has an average particle diameter (d 50 value of the integral mass distribution) of 0.03 to 0.95 μm. The d 50 value can be set in the desired range by enlarging the original particles, for example by agglomeration or when the emulsion is obtained by means of the seed latex method. In such graft copolymerizations, the polymerizing monomers are at least partially chemically linked to the already polymerized rubber, the linkage probably on the double bonds contained in the rubber. At least some of the monomers are therefore grafted onto the rubber, thus bound to the rubber thread molecules through covalent bonds. The grafting can also be carried out in several stages by first grafting on some of the monomers C2 forming the graft pad and then the rest. If the graft base C1 of the graft polymers C is composed of the components ClI, C13 and, if appropriate, C12, the term ASA rubbers is used. Their manufacture is known per se and is described, for example, in DE-A 28 26 925, DE-A 31 49 358 and DE-A 34 14 118. The graft copolymer C can be prepared, for example, by the method described in DE-B 12 60 135. The proportion of the graft pad (component C2) in the graft copolymer is preferably 10 to 60% by weight, particularly preferably 10 to 40% by weight, in particular 10 to 30% by weight. The graft pad preferably has a glass transition temperature in the range from 50 to 120 ° C., particularly preferably 70 to 115 ° C., in particular 75 to 110 ° C. The proportion of component C22 is preferably 0.2 to 5% by weight, particularly preferably 0.3 to 2% by weight, in particular 0.4 to 1% by weight. As component C22, preference is given to vinylic monomers which have epoxy and / or oxazoline groups. Monomers containing epoxy groups are particularly preferred. Epoxy group-bearing monomers can be represented, for example, by the following general formulas II and III.

CHR1 = CH-(CH2-)raO-(CHR-)pCH-CHR7 (II) OCHR 1 = CH- (CH 2 -) ra O- (CHR-) p CH-CHR 7 (II) O

CH2=CR3-COO-(CH2-)pCH-CHR4 (HI)CH 2 = CR 3 -COO- (CH 2 -) p CH-CHR 4 (HI)

OO

worin R1, R2, R3, R4 unabhängig voneinander Wasserstoff oder C^-Alkyl bedeuten, m eine ganze Zahl von 0 bis 20, p eine ganze Zahl von 0 bis 10 ist. Bevorzugt sind die angegebenen Reste Wasserstoff, und m weist den Wert 0 oder 1 und p den Wert 1 auf.wherein R 1 , R 2 , R 3 , R 4 independently of one another are hydrogen or C 1-4 alkyl, m is an integer from 0 to 20, p is an integer from 0 to 10. The radicals indicated are preferably hydrogen, and m has the value 0 or 1 and p has the value 1.

Bevorzugte Verbindungen sind Alkenylglycidy lether und Vinylglycidy lether.Preferred compounds are alkenyl glycidyl ether and vinyl glycidyl ether.

Besonders bevorzugte Verbindungen sind Epoxygruppen enthaltende Ester der Acrylsäure und/oder Methacrylsäure, insbesondere Glycidylacrylat und Glycidylmethacrylat.Particularly preferred compounds are epoxy group-containing esters of acrylic acid and / or methacrylic acid, in particular glycidyl acrylate and glycidyl methacrylate.

Die Herstellung eines Oxazolingruppen enthaltenden Pfropfkautschuks kann durch Verwendung von Isopropenyloxazolin als Komponente C22 erfolgen.A graft rubber containing oxazoline groups can be prepared by using isopropenyloxazoline as component C22.

Die Pfropfcopolymerisate der Komponente C können auch wie in US 4,096, 202 oder EP-A 0 561 197 beschrieben hergestellt werden. Sie können einen ein- oder mehrschaligen Aufbau haben. Beim mehrschaligen Aufbau können Schalen aus dem Kernmaterial und harte Schalen abwechselnd vorliegen. Dabei ist die äußerste Schale vorzugsweise mit der Matrix verträglich. Epoxygruppen können in der äußersten Schale und gegebenenfalls in inneren Schalen vorliegen.The graft copolymers of component C can also be prepared as described in US 4,096, 202 or EP-A 0 561 197. They can have a single or multi-layer structure. In the case of a multi-layer structure, shells made of the core material and hard shells can alternate. The outermost shell is preferably compatible with the matrix. Epoxy groups can be present in the outermost shell and optionally in the inner shell.

Neben Glycidylacrylat und Glycidylmethacrylat können ferner vorzugsweise Glycidylether ungesättigter Alkohole (Allylglycidylether) und Glycidylether von Alkenylphenolen verwendet werden. Allgemein können alle Verbindungen eingesetzt werden, die eine polymerisierbare ungesättigte Gruppe und eine Epoxygruppe aufweisen.In addition to glycidyl acrylate and glycidyl methacrylate, glycidyl ethers of unsaturated alcohols (allyl glycidyl ether) and glycidyl ethers of alkenylphenols can also preferably be used. In general, all compounds can be used which have a polymerizable unsaturated group and an epoxy group.

Komponente DComponent D

Das als Komponente D eingesetzte teilchenförmige Emulsionspolymerisat mit einer Glasubergangstemperatur von unter 0°C, das keine gegenüber Carboxylgruppen reaktionsfähigen funktionellen Gruppen aufweist, liegt in den erfindungsgemäßen thermoplastischen Formmassen in einer Menge von 0,5 bis 10 Gew.-% , vorzugsweise 2 bis 8 Gew.-%, insbesondere 4 bis 7 Gew.-% vor.The particulate emulsion polymer used as component D with a glass transition temperature of below 0 ° C., which has no functional groups which are reactive towards carboxyl groups, is in the Thermoplastic molding compositions according to the invention in an amount of 0.5 to 10% by weight, preferably 2 to 8% by weight, in particular 4 to 7% by weight.

Vorzugsweise ist Komponente D ein Pfropfcopolymerisat ausComponent D is preferably a graft copolymer

dl: 20 bis 95 Gew.-% einer Pfropfgrundlage aus einem kautschukelastischen Polymer mit einer Glasubergangstemperatur unterhalb von 0°C als Kompomente Dl,dl: 20 to 95% by weight of a graft base made of a rubber-elastic polymer with a glass transition temperature below 0 ° C. as components Dl,

d2: 5 bis 80 Gew.-% einer Pfropfauflage aus Styrol, substituiertemd2: 5 to 80% by weight of a styrene-substituted graft

Styrol, Acrylnitril, Methacrynitril, (Meth)acrylsäureestern oder Gemischen davon als Komponente D2.Styrene, acrylonitrile, methacrynitrile, (meth) acrylic acid esters or mixtures thereof as component D2.

Komponente D kann wie Komponente C aufgebaut sein und hergestellt werden, wobei jedoch keine gegenüber Carboxylgruppen reaktionsfähigen funktionellen Gruppen vorliegen. Anstelle derartiger Monomere werden entsprechende Mengen der anderen Monomere für die Pfropfauflage eingesetzt.Component D can be constructed and produced like component C, but there are no functional groups which are reactive towards carboxyl groups. Instead of such monomers, appropriate amounts of the other monomers are used for the graft.

Komponente EComponent E

Das als Komponente E eingesetzte Ethylencopolymer, das Carboxylgruppen aufweist, liegt in den erfindungsgemäßen Formmassen in einer Menge von 0, 1 bis 10 Gew.- , vorzugsweise 0,2 bis 5 Gew.-%, insbesondere 0,5 bis 1,5 Gew.- % vor.The ethylene copolymer used as component E, which has carboxyl groups, is present in the molding compositions according to the invention in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, in particular 0.5 to 1.5% by weight. - % in front.

Vorzugsweise ist das Ethylencopolymer der Komponente E ein Copolymer aus den Komponenten El bis E4, deren Gesamtgewicht insgesamt 100 Gew.-% ergibtThe ethylene copolymer of component E is preferably a copolymer of components E1 to E4, the total weight of which gives a total of 100% by weight

el: 50 bis 98,9 Gew.-%, vorzugsweise 60 bis 97,8 Gew.-% Ethylen als Komponente El, e2: 1 bis 49,9 Gew.-%, vorzugsweise 2 bis 39,8 Gew.-% mindestens eines .g-Alkylacrylats als Komponente E2,el: 50 to 98.9% by weight, preferably 60 to 97.8% by weight of ethylene as component El, e2: 1 to 49.9% by weight, preferably 2 to 39.8% by weight of at least one .g-alkyl acrylate as component E2,

e3: 0,1 bis 20 Gew.-%, vorzugsweise 0,2 bis 15 Gew.-% mindestens einer α, ß-ungesättigen Carbonsäure oder eines Derivats davon alse3: 0.1 to 20% by weight, preferably 0.2 to 15% by weight, of at least one α, β-unsaturated carboxylic acid or a derivative thereof as

Komponente E3 ,Component E3,

e4: 0 bis 10 Gew.-% , vorzugsweise 0 bis 5 Gew.-% weiterer copoly- merisierbarer Monomere als Komponente E4.e4: 0 to 10% by weight, preferably 0 to 5% by weight, of further copolymerizable monomers as component E4.

Geeignete derartige Polymere sind beispielsweise in der DE-A 42 27 742 beschrieben.Suitable polymers of this type are described, for example, in DE-A 42 27 742.

Als C,.8- Alkylacrylat kommen vorzugsweise n-Butylacrylat und/oder Ethylhex- ylacrylat, speziell n-Butylacrylat zum Einsatz.As C ,. 8 - Alkyl acrylate preferably n-butyl acrylate and / or ethylhexyl acrylate, especially n-butyl acrylate, are used.

Beispiele geigneter ,ß-ungesättigter Carbonsäuren sind Acrylsäure, Methacrylsäure, Ethacrylsäure, Maleinsäure und Fumarsäure. Diese können auch in Form ihrer Ester, Säureanhydride, Säurehalogenide oder Amide eingesetzt werden. Bevorzugt werden Acrylsäure oder Methacrylsäure eingesetzt. Als weitere copolymerisierbare Monomere kommen beispielsweise polare Como- nomere, wie Nitrilgruppen und Halogenatome enthaltende aliphatische Vinylmonomere in Betracht.Examples of suitable, ß-unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, maleic acid and fumaric acid. These can also be used in the form of their esters, acid anhydrides, acid halides or amides. Acrylic acid or methacrylic acid are preferably used. Examples of other copolymerizable monomers are polar comonomers, such as aliphatic vinyl monomers containing nitrile groups and halogen atoms.

Als weitere copolymerisierbare Monomere kommen C3.8-Alk-l-ene, wie Propen, 1 -Buten, 1-Penten und 1 -Hexen in Betracht.C 3 are further copolymerizable monomers. 8- alk-1-enes, such as propene, 1-butene, 1-pentene and 1-hexene.

Ein bevorzugtes Ethylencopolymer enthält neben Ethen nur n-Butylacrylat undA preferred ethylene copolymer contains only n-butyl acrylate and ethene

Acrylsäure. Dabei beträgt der Anteil an n-Butylacrylat vorzugsweise 25 bis 39,8 Gew.-%, an Acrylsäure 2 bis 10 Gew.-%. Das Ethylencopolymer weist vorzugsweise einen Schmelzflußindex von 10 ml/10 min bei 190°C und einer Belastung von 2,16 kg auf.Acrylic acid. The proportion of n-butyl acrylate is preferably 25 to 39.8% by weight, acrylic acid 2 to 10% by weight. The ethylene copolymer preferably has a melt flow index of 10 ml / 10 min at 190 ° C and one Load of 2.16 kg.

Die Herstellung der Ethylencopolymere kann nach üblichen Hochdruckpoly- merisationsverfahren erfolgen, wie sie beispielsweise in Ullmann's Enzyklopädie der Technischen Chemie, 4. Auflage, Band 19 (1980), Seite 169 bis 175, Verlag Chemie, Weinheim beschrieben sind. Die Copolymerisation des Ethens erfolgt dabei vorzugsweise bei Drücken von 350 bis 5000 bar, vorzugsweise 1500 bis 3000 bar. Die Temperaturen betragen dabei üblicherweise 50 bis 450°C, vorzugsweise 150 bis 350°C. Es kann ferner auf die EP-A 0 131 707 verwiesen werden.The ethylene copolymers can be prepared by customary high-pressure polymerization processes, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19 (1980), pages 169 to 175, Verlag Chemie, Weinheim. The copolymerization of ethene is preferably carried out at pressures of 350 to 5000 bar, preferably 1500 to 3000 bar. The temperatures are usually 50 to 450 ° C, preferably 150 to 350 ° C. Reference can also be made to EP-A 0 131 707.

Komponente FComponent F

Als Komponente F enthalten die erfindungsgemäßen thermoplastischen Form- massen 0 bis 60 Gew.-% , vorzugsweise 0 bis 20 Gew.-%, insbesondere 0 bis 10 Gew.-% mindestens eines faser- oder teilchenformigen Füllstoffs.As component F, the thermoplastic molding compositions according to the invention contain 0 to 60% by weight, preferably 0 to 20% by weight, in particular 0 to 10% by weight, of at least one fibrous or particulate filler.

Dabei handelt es sich vorzugsweise um Kohlenstofffasern, oder insbesondere Glasfasern. Die verwendeten Glasfasern können aus E-, A- oder C-Glas sein und sind vorzugsweise mit einer Schlichte und einem Haftvermittler ausgerüstet. Der Durchmesser liegt im allgemeinen zwischen 6 und 20 μm. Es können sowohl endlos Fasern (rovings) als auch Schnittglasfasern mit einer Länge von 1 bis 10 mm, vorzugsweise 3 bis 6 mm, eingesetzt werden. Weiterhin können Füll- oder Verstärkungsstoffe, wie Glaskugeln, Mineralfasern, Whisker, Aluminiumoxidfasern, Glimmer, Quarzmehl, Talk, Kaolin und Wollastonit zugesetzt werden. Außerdem können Metallflocken (wie Metallflocken der Transmed Corp.), Metallpulver, Metallfasern, metallbeschichtete Füllstoffe (wie nickelbeschichtete Glasfasern) sowie andere Zuschlagstoffe, die elektromagnetische Wellen abschirmen, eingesetzt werden. Insbesondere kommen AI-Flocken, (K 102 der Transmed) für EMI-Zwecke (Electromagnetic Interference) in Betracht. Ferner können die Formmassen mit zusätzlichen Kohlenstofffasern, Leitfähigkeitsruß oder nickelbeschichteten C-Fasern abgemischt werden.These are preferably carbon fibers, or in particular glass fibers. The glass fibers used can be made of E, A or C glass and are preferably equipped with a size and an adhesion promoter. The diameter is generally between 6 and 20 μm. Both endless fibers (rovings) and chopped glass fibers with a length of 1 to 10 mm, preferably 3 to 6 mm, can be used. Furthermore, fillers or reinforcing materials such as glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder, talc, kaolin and wollastonite can be added. In addition, metal flakes (such as metal flakes from Transmed Corp.), metal powder, metal fibers, metal-coated fillers (such as nickel-coated glass fibers) and other additives that shield electromagnetic waves can be used. AI flakes (K 102 of Transmed) are particularly suitable for EMI (Electromagnetic Interference) purposes. Furthermore, the molding compositions can be coated with additional carbon fibers, Conductivity black or nickel-coated C-fibers can be mixed.

Komponente GComponent G

Die erfindungsgemäßen thermoplastischen Formmassen enthalten als Komponente G 0 bis 20 Gew.-%, vorzugsweise 0 bis 10 Gew.- , insbesondere 0 bis 2 Gew.- % weiterer Zusatzstoffe.The thermoplastic molding compositions according to the invention contain, as component G, 0 to 20% by weight, preferably 0 to 10% by weight, in particular 0 to 2% by weight, of further additives.

Als weitere Zusatzstoffe können die allgemein in Polyester/Polycarbonat-Blends eingesetzten Zusatzstoffe Verwendung finden. Beispielsweise kann es sich dabei um Verarbeitungshilfsmittel und Stabilisatoren, wie UV-Stabilisatoren, Schmiermittel, Phosphorstabilisatoren und Antistatika handeln. Weitere Inhaltstoffe sind Farbstoffe, Pigmente oder Antioxidantien. Stabilisatoren können der Verbesserung der Thermostabilität, Erhöhung der Lichtstabilität, dem Anheben der Hydrolysebeständigkeit und der Chemikalienbeständigkeit dienen. Schmier- und Gleitmittel sind insbesondere bei der Herstellung von Formkörpern oder Formteilen zweckmäßig.The additives generally used in polyester / polycarbonate blends can be used as further additives. For example, processing aids and stabilizers such as UV stabilizers, lubricants, phosphorus stabilizers and antistatic agents can be involved. Other ingredients are dyes, pigments or antioxidants. Stabilizers can serve to improve thermal stability, increase light stability, increase hydrolysis resistance and chemical resistance. Lubricants and lubricants are particularly useful in the production of moldings or molded parts.

Als Wärmestabilisatoren bzw. Antioxidantien werden üblicherweise Metall- halogenide, wie Chloride, Bromide oder lodide eingesetzt, die sich von Metallen der Gruppe I des Periodensystems, der Elemente, wie Li, Na, K, Cu ableiten.As heat stabilizers or antioxidants, metal halides, such as chlorides, bromides or iodides, are usually used, which are derived from metals of group I of the periodic table, of the elements, such as Li, Na, K, Cu.

Geeignete Stabilisatoren sind die üblichen gehinderten Phenole, aber auch Vitamin E bzw. analog aufgebaute Verbindungen. Auch HALS Stabilisatoren, Benzophenone, Resorcine, Salicylate, Benzotriazole und andere Verbindungen sind geeignet. (Beispielsweise IRGANOX®, TINUVIN®, wie TINUVIN® 770 HALS-Absorber, Bis-2,2,6,6-tetramethyl-4-piperidylsebazat) und TINUVIN® P (UV-Absorber,(2H-Benzotriazol-2-yl)-4-methylphenol), TOPANOL®).Suitable stabilizers are the usual hindered phenols, but also vitamin E or compounds with an analog structure. HALS stabilizers, benzophenones, resorcinols, salicylates, benzotriazoles and other compounds are also suitable. (For example IRGANOX ® , TINUVIN ® , such as TINUVIN ® 770 HALS absorber, bis-2,2,6,6-tetramethyl-4-piperidyl sebazate) and TINUVIN ® P (UV absorber, (2H-benzotriazol-2-yl) -4-methylphenol), TOPANOL ® ).

Geeignete Gleit- und Entformungsmittel sind Stearinsäuren und Stearylalkohol, Stearinsäureester bzw. allgemein höhere Fettsäuren, deren Derivate und entsprechende Fettsäuregemische mit 12 bis 30 Kohlenstoffatomen.Suitable lubricants and mold release agents are stearic acids and stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures with 12 to 30 carbon atoms.

Auch Silikonöle, oligomerisches Isobutylen und ähnliche Stoffe kommen als Zusatzstoffe in Frage. Pigmente, Farbstoffe, Farbaufheller, wie Ultramarinblau, Phthalocyanine, Titadoxid, Cadmiumsulfude, Derivate der Perylentetracar- bonsäure sind ebenfalls einsetzbar.Silicone oils, oligomeric isobutylene and similar substances can also be used as additives. Pigments, dyes, color brighteners, such as ultramarine blue, phthalocyanines, titanium oxide, cadmium sulfude, derivatives of perylene tetracarboxylic acid can also be used.

Zudem können als Komponente G Umesterungsschutzmittel wie Irgaphos ® P- EPQ von Ciba-Geigy oder Magnesium- oder Zinkphosphat eingesetzt werden.In addition, transesterification protection agents such as Irgaphos ® P-EPQ from Ciba-Geigy or magnesium or zinc phosphate can be used as component G.

Herstellung der FormmassenProduction of molding compounds

Die erfindungsgemäßen Formmassen werden durch Mischen der Komponenten A bis E und gegebenenfalls F und G hergestellt. Die Reihenfolge, in der die Komponenten gemischt werden, ist beliebig.The molding compositions according to the invention are produced by mixing components A to E and, if appropriate, F and G. The order in which the components are mixed is arbitrary.

Die erfindungsgemäßen Formmassen können nach an sich bekannten Verfahren, beispielsweise Extrusion, hergestellt werden. Die erfindungsgemäßen Formmassen können beispielsweise hergestellt werden, indem man die Ausgangs- komponenten in üblichen Mischvorrichtungen wie Schneckenextrudern, vorzugsweise Zweischneckenextrudern, Brabender-Mischern oder Banbury-Mischern sowie Knetern mischt und anschließend extrudiert. Nach der Extrusion wird das Extrudat abgekühlt und zerkleinert. Die Reihenfolge der Mischung der Komponenten kann variiert werden, so können beispielsweise zwei oder gegebenenfalls drei Komponenten vorgemischt werden, es können aber auch alle Komponenten gemeinsam gemischt werden.The molding compositions according to the invention can be produced by processes known per se, for example extrusion. The molding compositions according to the invention can be produced, for example, by mixing the starting components in conventional mixing devices such as screw extruders, preferably twin-screw extruders, Brabender mixers or Banbury mixers and kneaders, and then extruding them. After the extrusion, the extrudate is cooled and crushed. The order of mixing the components can be varied, for example two or possibly three components can be premixed, but all components can also be mixed together.

Um eine möglichst homogene Durchmischung zu erhalten, ist eine intensiveIn order to achieve the most homogeneous possible mixing, intensive

Durchmischung vorteilhaft. Dabei sind im allgemeinen mittlere Mischzeiten von 0,2 bis 30 Minuten bei Temperaturen von 230 bis 280°C, bevorzugt 230 bisMixing advantageous. Average mixing times are generally from 0.2 to 30 minutes at temperatures from 230 to 280 ° C., preferably 230 to

260°C erforderlich. Nach der Extrusion wird das Extrudat in der Regel abgekühlt und zerkleinert. Die erfindungsgemäßen Formmassen zeigen eine gute Balance von Kerbschlagzähigkeit, Schädigungsarbeit, Verarbeitungsstabilität und Witterungsbeständigkeit. Aufgrund der genannten Eigenschaften und der hohen Wärmeformbeständigkeit sind die Formmassen zur Herstellung von Formkörpern geeignet, die beispielsweise im Haushalts-. Elektro-, Kraftfahrzeug- und Medizintechnikbereich eingesetzt werden können.260 ° C required. After extrusion, the extrudate is usually cooled and crushed. The molding compositions according to the invention show a good balance of impact strength, damage work, processing stability and weather resistance. Due to the properties mentioned and the high heat resistance, the molding compositions are suitable for the production of moldings, for example in the household. Electrical, automotive and medical technology can be used.

Dabei können die erfindungsgemäßen thermoplastischen Formmassen nach den bekannten Verfahren der Thermoplastverarbeitung bearbeitet werden, bei- spielsweise durch Extrudieren, Spritzgießen, Kalandrieren, Hohlkörperblasen, Pressen oder Sintern.The thermoplastic molding compositions according to the invention can be processed by the known methods of thermoplastic processing, for example by extrusion, injection molding, calendering, blow molding, pressing or sintering.

Die Erfindung wird nachstehend anhand von Beispielen näher erläutert.The invention is explained in more detail below with the aid of examples.

BeispieleExamples

Komponente AComponent A

Polybutylenterephthalat, charakterisiert durch einen Zug-E-Modul von 2600 N/mm2 und eine Viskositätszahl von 130 ml/g (VZ gemessen in 0,5 Gew.- -iger Lösung aus Phenol/o-Dichlorbenzol, l:l-Mischung bis 25°C), z.B. Ultradur B4500 der BASF AG.Polybutylene terephthalate, characterized by a tensile modulus of elasticity of 2600 N / mm 2 and a viscosity number of 130 ml / g (VZ measured in 0.5% by weight solution of phenol / o-dichlorobenzene, 1: 1 mixture to 25 ° C), e.g. Ultradur B4500 from BASF AG.

Komponente BComponent B

Polycarbonat auf Basis von Bisphenol A, charakterisiert durch eine Viskositätszahl von 61,2 ml/g (gemessen in 0,5 Gew.-%-iger CH2C12-Lösung bei 23°C).Polycarbonate based on bisphenol A, characterized by a viscosity number of 61.2 ml / g (measured in 0.5% by weight CH 2 C1 2 solution at 23 ° C).

Komponente C Pfropfkautschuk auf Basis von n-Butyacrylat mit einer Methylmethacrylat- Pfropfhülle, die 0,5 Gew.-% Glydicylmethacrylat enthält. Teilchengröße 0,3 μm, Pfropfgrad 20 Gew.-%, hergestellt durch Emulsionspolymerisation, charakterisiert durch Tgl = -44°C (Kern) und Tg2 = 105°C (Schale).Component C Graft rubber based on n-butyacrylate with a methyl methacrylate graft shell which contains 0.5% by weight glydicyl methacrylate. Particle size 0.3 μm, degree of grafting 20% by weight, produced by emulsion polymerization, characterized by Tgl = -44 ° C (core) and Tg2 = 105 ° C (shell).

Komponente DComponent D

Pfropfkautschuk auf Basis von n-Butylacrylat mit einer Methylmethacrylat- Pfropfhülle. Teilchengröße 0,34 μm, Pfropfgrad 30 Gew.-%, hergestellt durch Emulsionspolymerisation, charakterisiert durch Tgl = -44°C (Kern) und Tg2 = 105°C.Graft rubber based on n-butyl acrylate with a methyl methacrylate graft cover. Particle size 0.34 μm, degree of grafting 30% by weight, produced by emulsion polymerization, characterized by Tgl = -44 ° C (core) and Tg2 = 105 ° C.

Komponente EComponent E

Ethylen-Copolymer, enthaltend 35 Gew.-% n-Butylacrylat, 5 Gew.-% Acrylsäure und 0,2 Gew.- Maleinsäureanhydrid, charakterisiert durch einen Schmelzflußindex von 10 ml/10 min bei 190°C und 2,16 kg Belastung.Ethylene copolymer containing 35% by weight of n-butyl acrylate, 5% by weight of acrylic acid and 0.2% by weight of maleic anhydride, characterized by a melt flow index of 10 ml / 10 min at 190 ° C. and a load of 2.16 kg.

Komponente FComponent F

Talkum, z.B. IT-Extra von Norwegian Tale, mittlere Teilchengröße von 4,9 μm (bestimmt in einer Suspensionszelle mit VE- Wasser als Flüssigkeit.Talc, e.g. IT-Extra from Norwegian Tale, average particle size of 4.9 μm (determined in a suspension cell with demineralized water as a liquid.

Komponente G Irgaphos® P-EPQ von Ciba-Geigy (Tetrakis-(2,4-di-tert.-butylphenyl)-4,4- diphenylen-diphosphonit) mit einem Schmelzbereich von 75 - 95°C).Component G Irgaphos ® P-EPQ from Ciba-Geigy (tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylene-diphosphonite) with a melting range of 75-95 ° C).

Herstellung und Prüfung der FormmassenProduction and testing of molding compounds

Zum Mischen der Komponenten wurde ein Zweiwellenextruder verwendet. Die Schmelze wurde durch ein Wasserbad geleitet und granuliert. Desweiteren wurden die mechanischen Eigenschaften der mittels Extruder hergestellten Proben bestimmt. Die Wärmeformbeständigkeit wurde nach HDT B ermittelt. Die Kerbschlagzähigkeit der Produkte wurde an ISO-Stäben nach ISO 179 leA bestimmt. Die Schädigungsarbeit der Formmassen wurde nach DIN 53 433 bei - 30°C gemessen. Die Verarbeitungsstabilität wurde durch Messung der Schmelzeviskosität bei 270°C über einen Zeitraum von 20 Minuten ermittelt. Der angegebene Wert errechnet sich wie folgt:A twin screw extruder was used to mix the components. The The melt was passed through a water bath and granulated. Furthermore, the mechanical properties of the samples produced using an extruder were determined. The heat resistance was determined according to HDT B. The notched impact strength of the products was determined on ISO bars according to ISO 179 leA. The damage work of the molding compounds was measured according to DIN 53 433 at -30 ° C. The processing stability was determined by measuring the melt viscosity at 270 ° C. over a period of 20 minutes. The specified value is calculated as follows:

Δ = η5mm - η2_mi„/η5min * 100%Δ = η 5mm - η 2 _ mi „/ η 5m i n * 100%

Zur Charakterisierung der Witterungsbeständigkeit wurden Rundscheiben für 500 h einem Xenontest nach DIN 53387 Verf. 1-AX (Xenontest 1200 CPS von Atlas) unterzogen. Danach wurde die Schädigungsarbeit bei -30°C bestimmt.To characterize the weather resistance, round disks were subjected to a xenon test according to DIN 53387 procedure 1-AX (Xenon test 1200 CPS from Atlas) for 500 h. The damage work was then determined at -30 ° C.

Die Zusammensetzungen der Formmassen und die Ergebnisse der Prüfungen sind in Tabelle 1 aufgeführt. The compositions of the molding compositions and the results of the tests are listed in Table 1.

Tabelle 1:Table 1:

Figure imgf000022_0003
Figure imgf000022_0001
Figure imgf000022_0002
Figure imgf000022_0003
Figure imgf000022_0001
Figure imgf000022_0002

V1-V4: VergleichsversucheV1-V4: comparison tests

Die Versuche belegen das hervorragende Eigenschaftsspektrum der erfindungsgemäßen thermoplastischen Formmassen, wobei insbesondere das ausgewogene Zähigkeitsniveau, die Verbesserung der Verarbeitungsstabilität, die bessere Wärmeformbeständigkeit und die besssere UV-Beständigkeit hervor- zuheben sind. The tests demonstrate the excellent range of properties of the thermoplastic molding compositions according to the invention, in particular the balanced toughness level, the improvement in processing stability, the better heat resistance and the better UV resistance.

Claims

Patentansprüche claims 1. Thermoplastische Formmasse, enthaltend, bezogen auf das Gesamtgewicht der Komponenten A bis G, das insgesamt 100 Gew.-% ergibt,1. Thermoplastic molding composition containing, based on the total weight of components A to G, which gives a total of 100% by weight, a: 2 bis 98,4 Gew.-% mindestens eines Polyesters als Komponente A,a: 2 to 98.4% by weight of at least one polyester as component A, b: 0,5 bis 96,9 Gew.- mindestens eines Polycarbonats als Komponente B,b: 0.5 to 96.9% by weight of at least one polycarbonate as component B, c: 0,5 bis 10 Gew.-% mindestens eines teilchenformigen Emulsionspolymerisats mit einer Glasubergangstemperatur von unter 0°C, das gegenüber Carboxylgruppen reaktionsfähige funktionelle Gruppen aufweist, als Komponente C,c: 0.5 to 10% by weight of at least one particulate emulsion polymer having a glass transition temperature of below 0 ° C. and having functional groups which are reactive towards carboxyl groups, as component C, d: 0,5 bis 10 Gew.-% mindestens eines teilchenformigen Emulsionspolymerisats mit einer Glasubergangstemperatur von unter 0°C, das keine gegenüber Carboxylgruppen reaktionsfähigen funktionellen Gruppen aufweist, als Komponente D,d: 0.5 to 10% by weight of at least one particulate emulsion polymer with a glass transition temperature of below 0 ° C., which has no functional groups reactive towards carboxyl groups, as component D, e: 0,1 bis 10 Gew.-% mindestens eines Ethylencopolymers, das Carboxylgruppen aufweist, als Komponente E,e: 0.1 to 10% by weight of at least one ethylene copolymer which has carboxyl groups as component E, f: 0 bis 60 Gew.-% mindestens eines faser- oder teilchenformigenf: 0 to 60% by weight of at least one fibrous or particulate Füllstoffs als Komponente F undFiller as component F and g: 0 bis 20 Gew.-% weiterer Zusatzstoffe als Komponente G.g: 0 to 20% by weight of further additives as component G. 2. Formmasse nach Anspruch 1, dadurch gekennzeichnet, daß der Polyester der Komponente A sich von einer aromatischen Dicarbonsäure ableitet. 2. Molding composition according to claim 1, characterized in that the polyester of component A is derived from an aromatic dicarboxylic acid. 3. Formmasse nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Polycarbonat der Komponente B sich von phenolischen Verbindungen ableitet.3. Molding composition according to claim 1 or 2, characterized in that the polycarbonate of component B is derived from phenolic compounds. 4. Formmasse nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß Komponente C ein Pfropfcopolymerisat ist aus4. Molding composition according to one of claims 1 to 3, characterized in that component C is a graft copolymer cl: 20 bis 95 Gew.-% einer Pfropfgrundlage aus einem kautschuk- elastischen Polymer mit einer Glasubergangstemperatur unterhalb von 0°C als Komponente Cl,cl: 20 to 95% by weight of a graft base made of a rubber-elastic polymer with a glass transition temperature below 0 ° C. as component Cl, c2: 5 bis 80 Gew.-% einer Pfropfauflage als Komponente C2 ausc2: 5 to 80% by weight of a graft pad as component C2 c21: 80 bis 99,9 Gew.-% Styrol, substituiertem Styrol, Acrylnitril,c21: 80 to 99.9% by weight of styrene, substituted styrene, acrylonitrile, Methacrylnitril, (Meth)acrylsäureestern oder Gemischen davon als Komponente C21 ,Methacrylonitrile, (meth) acrylic acid esters or mixtures thereof as component C21, c22: 0,1 bis 20 Gew.-% mindestens eines vinylischen Monomers, das gegen- über Carboxylgruppen reaktionsfähige funktionelle Gruppen aufweist, als Komponente C22.c22: 0.1 to 20% by weight of at least one vinylic monomer which has functional groups which are reactive towards carboxyl groups, as component C22. 5. Formmasse nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß Komponente D ein Propfcopolymerisat ist aus5. Molding composition according to one of claims 1 to 4, characterized in that component D is a graft copolymer dl: 20 bis 95 Gew.-% einer Pfropfgrundlage aus einem kautschukelastischen Polymer mit einer Glasubergangstemperatur unterhalb von 0°C als Komponente Dl , d2: 5 bis 80 Gew.-% einer Pfropfauflage aus Styrol, substituiertemdl: 20 to 95% by weight of a graft base made of a rubber-elastic polymer with a glass transition temperature below 0 ° C. as component Dl, d2: 5 to 80% by weight of a styrene-substituted graft Styrol, Acrylnitril, Methacrylnitril, (Meth)acrylsäureestern oder Gemischen davon als Komponente D2.Styrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid esters or mixtures thereof as component D2. 6. Formmasse nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Ethylencopolymer der Komponente E ein Copolymer ist aus den Komponenten El bis E4, deren Gesamtgewicht insgesamt 100 Gew.-% ergibt6. Molding composition according to one of claims 1 to 5, characterized in that the ethylene copolymer of component E is a copolymer of components E1 to E4, the total weight of which gives a total of 100% by weight el: 50 bis 98,9 Gew.-% Ethylen als Komponente El,el: 50 to 98.9% by weight of ethylene as component El, e2: 1 bis 49,9 Gew.-% mindestens eines C,.g-Alkylacrylats als Komponente E2,e2: 1 to 49.9% by weight of at least one C,. g -alkyl acrylate as component E2, e3: 0,1 bis 20 Gew.-% mindestens einer α,ß -ungesättigten Carbon- säure oder eines Derivats davon als Komponente E3,e3: 0.1 to 20% by weight of at least one α, β-unsaturated carboxylic acid or a derivative thereof as component E3, e4: 0 bis 10 Gew.-% weiterer copolymerisierbarer Monomere alse4: 0 to 10% by weight of other copolymerizable monomers than Komponente E4.Component E4. 7. Verfahren zur Herstellung von Formmassen nach einem der Ansprüche 1 bis 6 durch Mischen der Komponenten A bis E und gegebenenfalls F und G.7. A process for the preparation of molding compositions according to any one of claims 1 to 6 by mixing components A to E and optionally F and G. 8. Verwendung von Formmassen nach einem der Ansprüche 1 bis 6 zur Herstellung von Fasern, Folien oder Formkörpern.8. Use of molding compositions according to one of claims 1 to 6 for the production of fibers, films or moldings. 9. Fasern, Folien oder Formkörper aus einer Formmasse nach einem der Ansprüche 1 bis 6.9. Fibers, films or moldings from a molding composition according to one of claims 1 to 6. 10. Verfahren zur Herstellung von Fasern, Folien oder Formkörpern nach Anspruch 9. 10. A method for producing fibers, films or moldings according to claim 9.
PCT/EP1998/006537 1997-10-17 1998-10-15 Thermoplastic moulding materials containing polyesters and polycarbonates Ceased WO1999020693A1 (en)

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DE1997146049 DE19746049A1 (en) 1997-10-17 1997-10-17 Molding material based on polyester and polycarbonate, containing an emulsion polymer with groups that reacts with carboxyl, a polymer with no such groups, and an ethylene copolymer with carboxyl groups
DE19746049.6 1997-10-17

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3302124A1 (en) * 1983-01-22 1984-07-26 Bayer Ag, 5090 Leverkusen THERMOPLASTIC MOLDS
EP0207388A2 (en) * 1985-06-20 1987-01-07 BASF Aktiengesellschaft Cold impact-resistant thermoplastic polyester moulding compositions
US4764556A (en) * 1986-05-21 1988-08-16 Basf Aktiengesellschaft Thermoplastic molding materials of polyester and polycarbonate
US4912163A (en) * 1988-08-13 1990-03-27 Basf Aktiengesellschaft Thermoplastic polyester molding materials having low temperature impact strength

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3302124A1 (en) * 1983-01-22 1984-07-26 Bayer Ag, 5090 Leverkusen THERMOPLASTIC MOLDS
EP0207388A2 (en) * 1985-06-20 1987-01-07 BASF Aktiengesellschaft Cold impact-resistant thermoplastic polyester moulding compositions
US4764556A (en) * 1986-05-21 1988-08-16 Basf Aktiengesellschaft Thermoplastic molding materials of polyester and polycarbonate
US4912163A (en) * 1988-08-13 1990-03-27 Basf Aktiengesellschaft Thermoplastic polyester molding materials having low temperature impact strength

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