EP1567581A1 - Polymer compositions with a modified impact-resistance - Google Patents

Polymer compositions with a modified impact-resistance

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Publication number
EP1567581A1
EP1567581A1 EP03772333A EP03772333A EP1567581A1 EP 1567581 A1 EP1567581 A1 EP 1567581A1 EP 03772333 A EP03772333 A EP 03772333A EP 03772333 A EP03772333 A EP 03772333A EP 1567581 A1 EP1567581 A1 EP 1567581A1
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EP
European Patent Office
Prior art keywords
weight
parts
composition according
polymer
spoke
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03772333A
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German (de)
French (fr)
Inventor
Marc Vathauer
Gerwolf Quaas
Andreas Seidel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Priority claimed from DE2002154877 external-priority patent/DE10254877A1/en
Priority claimed from DE2002157077 external-priority patent/DE10257077A1/en
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP1567581A1 publication Critical patent/EP1567581A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions 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
    • C08L51/04Compositions 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions 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
    • C08L51/06Compositions 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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/10Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences

Definitions

  • the invention relates. Impact-modified polyamide compositions and molded parts made therefrom, which are particularly suitable for direct online painting without prior treatment of the molded part with an electrically conductive primer system, as well as the online coated molded parts.
  • DE-A 101 019 225 generally describes polymer compositions. Containing polyamide, graft polymer, vinyl (co) polymer, compatibility agent and very fine mineral particles with anisotropic particle geometry. DE-A 101 019 225 does not mention that the compositions described there can be painted online.
  • EP 0202 214 A discloses polymer blends made from a polyamide, a styrene / acrylonitrile copolymer and a compatibilizer.
  • a copolymer consisting of a vinyl aromatic monomer and acrylonitrile, methacrylonitrile, C- is used as a compatibilizer.
  • Increased impact strength is to be achieved through the use of compatibility agents.
  • a disadvantage of the polymer blends described in this publication is that they have too low a stiffness and a too high coefficient of expansion for thin-wall applications.
  • JP 11 241 016.A2 discloses polyamide molding compositions which, in addition to polyamide, contain rubber-modified styrene polymers, graft polymers based on ethylene / propylene rubbers and talc with a particle diameter of 1 to 4 ⁇ m.
  • EP-A 0 718 350 describes polymer blends consisting of a crystalline and an amorphous or semi-crystalline polymer and 2 to 7% by weight of electrically conductive Carbon (soot) for the production of molded, thermoplastic objects that are electrostatically painted in a further step. Highly heat-resistant polymer blends with conductive finish are not described here.
  • thermoplastic and elastomeric are antistatically treated
  • the antistatic agents consist of polyethers, polyesters, polyester ether amides, polyether esters or mixtures and copolymers of these as well as an organic or inorganic. Salt.
  • a large number of polymers are listed as thermoplastic and elastomeric polymers. However, the compositions of the present invention are not described.
  • antistatic compositions of polyether ester amides and polyether esters are described in WO 02/055411 and EP-A 613 919.
  • inorganic materials in certain polymer compositions, in particular in polycarbonate compositions, are also generally known.
  • the inorganic materials are used, for example, as reinforcing materials to increase the rigidity and tensile strength, to increase the dimensional stability in the event of temperature fluctuations, to improve the surface properties or - in flame-retardant materials - also as a flame retardant synergist. Both mineral and artificially obtained materials are used.
  • US Pat . No. 5,714,537 describes polycarbonate bi-ends which contain certain inorganic fillers to improve the rigidity and linear thermal expansion resistance.
  • WO 01/34703 discloses impact-modified polyethylene terephthalate / polycarbonate blends which are suitable for online coating. Polyamide blends are not described.
  • Noryl ® GTX from General Electric Plastics is known for some directly paintable inline applications (cf. EP-A 685 527). It is a
  • Blend containing polyamide and polyphenylene ether (PA / PPO blend).
  • Body parts made of plastics usually have to be painted.
  • the body attachments made from them are usually covered with one or more layers of transparent lacquer.
  • the body attachments made from them are coated with several layers of paint, with at least one of the layers giving color (top coat).
  • top coat Depending on the heat resistance of the plastics, a distinction is made here between different processes that differ at the time the plastic add-on parts are attached to the outer part of the body. If the plastic add-on parts go through the entire painting process, one speaks generally of an "online" painting, which places the highest demands on the heat resistance of the plastic.
  • the plastic add-on part is called the cathode dip painting (KTL) the outer part of the body is assembled and placed in the painting line.
  • KTL cathode dip painting
  • the entire plastic add-on part is painted outside the painting line at low temperatures and only then mounted on the outer part of the body.
  • the "online” process is preferred by the automotive industry because it minimizes the work steps and also achieves the best color matching of plastic and sheet metal. With this process, temperatures of up to 205 ° C are reached, so that high demands are placed on the Heat resistance of the molded part can be provided.
  • a plastic can be modified in such a way that its specific resistance becomes so low that it can be used in electrostatic painting without prior treatment with a conductive primer system, a production step is avoided.
  • plastic body parts Additional requirements placed on plastic body parts are good rigidity, low thermal expansion and post-vibration. dung, good surface quality, good paintability and good chemical resistance.
  • the molding compounds used to produce the exterior parts of the body must have good fluidity in the melt.
  • the task . was solved by containing a polymer composition
  • composition may contain, as further components, compatibilizer (component F) and / or vinyl (co) polymer (component G), phenolic
  • the invention furthermore also relates to the online lacquered moldings obtainable from the compositions mentioned above. It has been found that a plastic with the above composition shows excellent heat resistance and can therefore be used in "online” painting processes. It also has a Class-A surface, high rigidity and excellent chemical resistance.
  • Polyamides (component A) which are suitable according to the invention are known or can be prepared by processes known from the literature.
  • Polyamides suitable according to the invention are known homopolyamides, copolyamides and mixtures of these polyamides. These can be partially crystalline and or amorphous polyamides.
  • the partially crystalline polyamides are polyamide 6, polyamide
  • 6,6, mixtures and corresponding copolymers of these components are suitable.
  • partially crystalline polyamides the acid component of which is wholly or partly composed of terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or adipic acid and / or cyclohexanedicarboxylic acid, the diamine component wholly or partly of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4-trimethylhexamethylenediamine and / or 2,4,4-trimethymexamethylenediamine and / or isophoronediamine and the composition of which is known in principle.
  • polyamides which are wholly or partly prepared from lactams with 7 to 12 carbon atoms in the ring, optionally with the use of one or more of the above-mentioned starting components.
  • Particularly preferred partially crystalline polyamides are polyamide 6 and polyamide 6,6 and their mixtures.
  • Known products can be used as amorphous polyamides. They are obtained by polycondensation of diamines such as ethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4- and / or 2,4,4-trimethylhexamemylenediamine, m- and / or p-xylylenediamine, bis- (4-aminocyclohexyl ) - methane, bis- (4-aminocyclohexyl) propane, 3,3'-dimethyl * -4,4'-diamino-dicyclohexyl-methane, 3 ** aminomethyl-3,5,5-trimethylcyclohexylamine, 2,5- and or 2,6-bis (aminomethyl) norbornane and / or 1,4-diaminomethylcyclohexane with dicarboxylic acids such as
  • Copolymers obtained by polycondensation of several monomers are also suitable, as are copolymers which are prepared with the addition of ammocarboxylic acids such as e-aminocaproic acid, w-aminoundecanoic acid or w-aminolauric acid or their lactams.
  • ammocarboxylic acids such as e-aminocaproic acid, w-aminoundecanoic acid or w-aminolauric acid or their lactams.
  • Particularly suitable amorphous polyamides are the polyamides made from isophthalic acid, hexamethylenediamine and other diamines such as 4,4-diaminodicyclohexylmethane, isophoronediamine, 2,2,4- and / or 2,4,4-trimethylhexa-methylenediamine, 2, 5- and / or 2,6-bis (aminomethyl) norbornene; or from isophthalic acid,
  • 4,4'-diamino-dicyclohexylmethane and ⁇ -caprolactam or from isophthalic acid, 3,3'-dimethyl-4,4 '- (hamino-dicyclohexylmethane and laurolactam; or from terephthalic acid and the isomer mixture of 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine.
  • isophthalic acid 3,3'-dimethyl-4,4 '- (hamino-dicyclohexylmethane and laurolactam
  • terephthalic acid and the isomer mixture of 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine instead of the pure 4,4'-diaminodicyclohexylmethane, it is also possible to use mixtures of the positional isomers diamine dicyclohexalmethane, which are composed of
  • the polyamides preferably have a relative viscosity (measured on a 1% strength by weight solution in m-cresol at 25 ° C.) from 2.0 to 5.0, particularly preferably from 2.5 to 4.0.
  • the polyamides can be contained in component A alone or in any mixture with one another.
  • Component B comprises one or more rubber-modified graft polymers.
  • the rubber-modified graft polymer B comprises a statistical (co) polymer made from vinyl monomers B.l, preferably according to B.l.l and B.l.2, and one grafted with vinyl monomers, preferably according to B.l.l and B.l.2
  • Rubber B.2. B is prepared in a known manner by free-radical polymerization, for example by an emulsion, bulk or solution or bulk suspension polymerization process, such as, for example, in US Pat. Nos. 3,243,481, 3,509,237, US Pat. A 3 660 535, US-A 4 221 833 and US-A 4 239 863.
  • Particularly suitable graft rubbers are also ABS polymers that pass through Redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285 are available.
  • Preferred monomers B1 are styrene, ⁇ -methylstyrene, halogen- or alkyl nucleus-substituted styrenes such as p-methylstyrene, p-chlorostyrene, (meth) acrylic acid-C 8 -C 8 -alkyl esters such as methyl methacrylate, n-butyl acylate and tert-butyl acrylate.
  • Preferred monomers B1 are unsaturated nitriles such as acrylonitrile, methacrylonitrile, (meth) acrylic C 8 -C 8 alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, derivatives (such as anhydrides and imides) of unsaturated carboxylic acids such as maleic anhydride and N-phenyl-maleimide or mixtures thereof.
  • unsaturated nitriles such as acrylonitrile, methacrylonitrile, (meth) acrylic C 8 -C 8 alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, derivatives (such as anhydrides and imides) of unsaturated carboxylic acids such as maleic anhydride and N-phenyl-maleimide or mixtures thereof.
  • Particularly preferred monomers B.l.l are styrene, ⁇ -methylstyrene and / or methyl methacrylate, particularly preferred monomers B.l.2 are acrylonitrile, maleic anhydride and or methyl methacrylate.
  • Particularly preferred monomers are B.l.l styrene and B.1.2 acrylonitrile.
  • Rubbers B.2 suitable for the rubber-modified graft polymers B are, for example, diene rubbers, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers. Composites made from various of the rubbers mentioned are also suitable as graft bases.
  • Preferred rubbers B.2 are diene rubbers (e.g. based on butadiene, isoprene
  • glass transition temperature component B.2 is below 10 ° C, preferably below -10 ° C.
  • Pure polybutadiene rubber is particularly preferred.
  • Further copolymerizable monomers can contain up to 50% by weight, preferably up to 30, in particular up to 20% by weight (based on the rubber base B.2) in the rubber base.
  • Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers made from acrylic acid alkyl esters, optionally with up to 40% by weight, based on B.2, of other polymerizable, ethylenically unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include Cj to Cg-
  • Alkyl esters for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halgoenalkyl esters, preferably halogen-C; * - Cg-alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base B.2 are, for. B. acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl C-- C 6 alkyl ether methyl methacrylate, butadiene.
  • Preferred acrylate rubbers as graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • graft bases according to B.2 are silicone rubbers with graft-active sites, as described in DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631 539.
  • the graft polymers according to the present invention particularly preferably contain no graft bases (rubbers) based on ethylene / propylene rubbers (EPR) or ethylene / propylene and non-conjugated diene (EPDM), as described, for example, in JP 11 24 10 16 A2.
  • EPR ethylene / propylene rubbers
  • EPDM ethylene / propylene and non-conjugated diene
  • the gel content of the graft base B.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and U, Georg Thieme-Verlag, Stuttgart 1977).
  • the average particle size dso is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-1796).
  • component B can additionally contain small amounts, usually less than 5% by weight, preferably less than 2% by weight, based on B.2, contain cross-linking ethylenically unsaturated monomers.
  • crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with
  • polystyrene resin 3 to 12 carbon atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, polyunsaturated heterocyclic compounds, polyfunctional vinyl compounds, such as alkylene diol di (meth) acrylates, polyester di (meth) - acrylates, divinylbenzene, trivinylbenzene, trivinylcyanurate, triallylcyanurate, allyl (meth) acrylate, diallyl maleate, diallyl fumarate, triallyphosphate and iallyl phthalate.
  • alkylene diol di (meth) acrylates polyester di (meth) - acrylates
  • divinylbenzene trivinylbenzene
  • trivinylcyanurate trivinylcyanurate
  • triallylcyanurate triallylcyanurate
  • allyl (meth) acrylate diallyl maleate, diallyl fumarate, triallyphosphate and iallyl
  • Preferred crosslinking monomers are allyl methacrylate, emylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least three ethylenically unsaturated groups.
  • the rubber-modified graft polymer B is obtained by graft polymerization from 50 to 99, preferably 65 to 98, particularly preferably 75 to 97 parts by weight of a mixture of 50 to 99 60 to 95 parts by weight of monomers according to B1 and 1 to 50, preferably 5 to 40 parts by weight of monomers according to B.1.2 in the presence of 1 to 50, preferably 2 to 35, particularly preferably 2 to 15, in particular 2 to 13 parts by weight of the rubber component B.2.
  • the average particle diameter d 5 Q of the grafted rubber particles generally has values from 0.05 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m, particularly preferably 0.2 to 1 ⁇ m.
  • the average particle diameter d 5 o of the resulting grafted rubber particles by bulk or solution or bulk-suspension polymerization method are available, (determined by counting on electron microscopy
  • Recordings is generally in the range from 0.5 to 5 ⁇ m, preferably from 0.8 to 2.5 ⁇ m.
  • the graft copolymers can be present in component B alone or in any mixture with one another.
  • Component B is contained in the polymer composition according to the invention preferably in an amount of 0.5 to 50 parts by weight, particularly preferably 1 to 40 parts by weight and very particularly preferably 1 to 35 parts by weight.
  • Mineral particles suitable according to the invention are inorganic materials with a flaky or platelet-like and fibrous character such as talc, mica / clay layer minerals, montmorrilonite, the latter also in an organophilic form modified by ion exchange, and furthermore kaolin, vermiculite and wollastonite
  • Talc and wollastonite are particularly preferred.
  • Talc is understood to mean a naturally occurring or synthetically produced talc.
  • Pure talc has the chemical composition 3MgO4SiO 2 'H 2 O and thus an MgO content of 31.9% by weight, an SiO 2 content of 63.4% by weight and a chemically bound water content of 4.8% by weight. It is a silicate with poor structure.
  • Talc types of high purity are particularly preferred. These contain, for example, an MgO content of 28 to 35% by weight, preferably 30 to 33% by weight, particularly preferably 30.5 to 32% by weight and an SiO 2 content of 55 to 65% by weight , preferably 58 to 64% by weight, particularly preferably 60 to 62.5% by weight.
  • Preferred types of talc are further characterized by an Al 2 O 3 content of ⁇ 5% by weight, particularly preferably ⁇ 1% by weight, in particular ⁇ 0.7% by weight.
  • Preferred mineral particles are also those with anisotropic particle geometry. These are understood to mean those particles whose so-called aspect ratio - the ratio of the largest and the smallest particle size - is greater than 1, preferably greater than 2 and particularly preferably greater than about 5. Such particles are at least in the broadest sense platelet-shaped or fibrous.
  • Such materials include, for example, certain talcs and certain (alionimino) silicates with a layer or fiber geometry such as bentonite, wollastonite, mica (mica), kaolin, hydrotalcite, hectorite or montmorillonite.
  • talc in the form of finely ground types with an average particle size d o 5 microns of ⁇ 10, preferably ⁇ 5 micrometers, more preferably ⁇ 2.5 microns, very preferably ⁇ 1.5 microns.
  • talc having an average particle size is d 5 o of 350 nm to 1.5 microns.
  • Preferred wollastonites have an average aspect ratio of> 6, in particular> 7 and an average fiber diameter of 1 to 15 ⁇ m, preferably 2 to 10 ⁇ m, in particular 4 to 8 ⁇ m.
  • the average aspect ratio in the sense of the invention is the ratio of the average length of the fiber to the average diameter.
  • Particle size and particle diameter in the sense of this invention means the average particle diameter d 50 , determined by ultracentrifuge measurements
  • the mineral particles can be surface-modified with organic molecules, for example silanized, in order to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be created.
  • elongated or plate-like materials with the specified small particles are particularly suitable, compared to fibril-shaped or spherical fillers. Those are highly preferred
  • D / T average diameter / thickness
  • the mineral particles can be present as powders, pastes, brine dispersions or suspensions. By precipitation, powders can be obtained from dispersions, brine or suspensions.
  • thermoplastic molding compositions can be incorporated into the thermoplastic molding compositions by customary processes, for example by directly kneading or extruding molding compositions and the finely divided inorganic powders.
  • Preferred procedure Ren represent the production of a masterbatch, for example in flame retardant additives and at least one component of the molding compositions according to the invention in monomers or solvents, or the co-precipitation of a thermoplastic component and the finely divided inorganic powders, for example by co-precipitation of an aqueous emulsion and the finely divided inorganic powders, optionally in Form of dispersions, suspensions, pastes or sols of the finest inorganic materials.
  • Examples of substances which can preferably be used according to the invention as mineral particles are Tremin® 939-300EST from Quarzwerke GmbH, Frechen, Germany
  • Aluminum silicate with a particle size d 50 1.3 ⁇ m), Naintsch A3 (see examples, component CI), Nyglos ® 4-10013 (see examples C2).
  • the mineral particles of component C can be present in the composition according to the invention in an amount of preferably up to 30 parts by weight, particularly preferably up to 20 parts by weight and, if present, preferably from 1.5 to 13 parts by weight. Share, be included.
  • the compositions according to the invention can contain particulate carbon compounds such as carbon black, which is suitable for producing conductivity and is also referred to by the person skilled in the art as conductivity black, graphite powder and / or carbon nanofibrils.
  • carbon black which is suitable for producing conductivity and is also referred to by the person skilled in the art as conductivity black, graphite powder and / or carbon nanofibrils.
  • graphite powders are comminuted graphite.
  • the person skilled in the art understands graphite as a modification of the carbon as described, for example, in AF Hollemann, E. Wieberg, N. Wieberg, “Textbook of Inorganic Chemistry”, 91st-100th ed., Pp. 701-702.
  • Graphite consists of planar carbon layers arranged one above the other.
  • graphite can be comminuted, for example, by grinding.
  • the particle size is in the range from 0.1 ⁇ m to 1 mm, preferably in the range from 1 to 300 ⁇ m, most preferably in the range from 2 to 20 ⁇ m.
  • the dibutyl phthalate adsorption of the conductivity carbon blacks is between 40 and 1000 ml per 100 g of carbon black, preferably between 90 and 600 ml per 100 g of carbon black.
  • a large number of oxygen-containing groups such as, for example, carboxyl, lactol, phenol groups, quinoid carbonyl groups and / or pyrone structures, can be located on the surface of the carbon black.
  • Conductivity carbon blacks can be produced from acetylene, from synthesis gas or from the furnace process from oil, carrier gases and air. Manufacturing processes are described, for example, in R.G. Gilg, "Carbon black for conductive plastics" in: Electrically conductive plastics, ed .: H.J. Mair, S. Roth, 2nd ed., Carl Hanser
  • the carbon blacks and / or graphites according to the invention can be added before, during or after the polymerization of the monomers to give the thermoplastics of component A).
  • the additions of the carbon black and or graphite according to the invention are carried out according to the
  • the carbon blacks and / or graphites can also be metered in as highly concentrated masterbatches in thermoplastics, which are preferably chosen from the group of thermoplastics used as component A).
  • concentration of the carbon blacks and / or graphites in the masterbatches is in the range from 5 to 70, preferably 8 to 50, particularly preferably in Range from 12 to 30 wt .-% (based on the masterbatch).
  • the carbon blacks and / or graphites can also be mixed with binders such as waxes, fatty acid esters or polyolefins for better meterability.
  • the carbon blacks and / or graphites can also be pelletized or granulated with or without additional additives, for example by pressing or printing processes, which likewise serves to improve meterability.
  • Carbon nanofibrils according to the invention typically have the form of tubes which are formed from graphite layers.
  • the graphite layers are arranged in a concentric manner around the cylinder axis.
  • Carbon nanofibrils have a length-to-diameter ratio of at least 5, preferably at least 100, particularly preferably at least 1000.
  • the diameter of the nanofibrils is typically in the range from 0.003 to 0.5 ⁇ m, preferably in the range from 0.005 to 0.08 ⁇ m, particularly preferably in the range from 0.006 to 0.05 ⁇ m.
  • the length of the carbon nanofibrils is typically 0.5 to 1000 ⁇ m, preferably 0.8 to 100 ⁇ m, particularly preferably 1 to 10 ⁇ m.
  • the carbon nanofibrils have a hollow, cylindrical core around which the graphite layers are formally wrapped.
  • This cavity typically has a diameter of 0.001 to 0.1 ⁇ m, preferably a diameter of 0.008 to 0.015 ⁇ m.
  • the wall of the fibril around the cavity consists, for example, of 8 graphite layers.
  • the carbon nanofibrils can be present as aggregates of up to 1000 ⁇ m in diameter, preferably up to 500 ⁇ m in diameter, of several nanofibrils.
  • the aggregates can take the form of bird nests, combed yarn or open net structures.
  • the carbon nanofibrils can be added before, during or after the polymerization of the monomers to give thermoplastics of component A). If the nanofibrils according to the invention are added after the polymerization, they are preferably added to the thermoplastic melt in an extruder or in a kneader. By means of the compounding process in the kneader or extruder, the aggregates already described can in particular be largely or even completely crushed and the carbon nanofibrils can be dispersed in the thermoplastic matrix.
  • the carbon nanofibrils can be metered in as highly concentrated masterbatches in thermoplastics, which are preferably selected from the group of thermoplastics used as component A).
  • concentration of the carbon nanofibrils in the masterbatches is in the range from 5 to 50, preferably 8 to 30, particularly preferably in the range from 12 to 22% by weight.
  • the production of masterbatches is described, for example, in US Pat. No. 5,643,502.
  • the use of masterbatches can particularly improve the size reduction of the aggregates.
  • the carbon nanofibrils can have shorter length distributions than originally used due to the processing into the molding composition or molding in the molding composition or in the molding.
  • mixtures of the individual components can also be used.
  • Conductivity invention for example, under the name Ketjenblack ® by the company AKZO Nobel, under the name Vulcan ® by the company. Cabot or under the name Printex ® by the company. Degussa be obtained.
  • Graphites according to the invention can be used as powders, for example from Vogel &
  • Carbon nanofibrils are offered, for example, by Hyperion Catalysis or Applied Sciences Inc.
  • the carbon nanofibrils are synthesized, for example, in a reactor which contains a carbon Contains gas and a metal catalyst, as described for example in US-A 5 643 502.
  • polyester-ether block copolymers contain the reaction product of ethylene glycol, terephthalic acid or dimethyl terephthalate and polyethylene glycol.
  • Polyester ether copolymers are described, for example, in Encyclopedia of Polymer Science and Engineering, Vol. 12, John Wiley & Sons, Inc., N.Y., 1988, pages 49-52.
  • Preferred polyether ester amides are block copolymers in which the polyether segments are polyethylene glycol units with a molecular weight M n of 200 to 6,000 daltons and the polyamide segments have a molecular weight M n generally of 200 to 6,000 daltons.
  • the block copolymer preferably contains 4 to 14 polyamide segments.
  • Suitable polyether ester amides are described, for example, in EP-A 613 919.
  • the polyamides mentioned in the description of component A) are suitable as polyamide segments.
  • the polymers according to component E) are preferably used in the form of antistatic preparations, which for example may additionally contain inorganic or organic salts.
  • antistatic preparations or antistatic agents include in WO 02/055411 and US-A 5,965,206 and the references cited therein.
  • WO 02/055411 and US-A 5,965,206 are explicitly included as a disclosure in the present application.
  • Antistatic compositions are, for example under the names hgastat ® P 18 and P 22 Irgastat ® commercially available from Ciba Specialty Chemicals Company.
  • Antistatic mixtures or preparations preferably contain inorganic salts selected from the group consisting of LiQO, LiCF 3 S ⁇ 3 , NaQO 4 , LiBF 4 , NaBF 4 , KBF 4 , NaCF 3 SO 3 , KClO 4 , KPF 6 , KCF 3 SO 3 , KC4F 9 SO 3 , Ca (ClO 4 ) 2 , Ca (PF 6 ) 2 , Mg (ClO 4 ) 2 , Mg (CF 3 SO 3 ) 2 , Zn (ClO 4 ) 2 , Zn (PF 6 ) 2 or Ca (CF 3 SO 3 ) 2 , which are generally used in polyether ester amide, polyether ester block copolymers or
  • Polyamide-polyether block copolymers or mixtures thereof are complexed or solvated.
  • Suitable organic salts are preferably selected from organic zinc, barium, cadmium, aluminum, calcium, magnesium or a rare one
  • Earth metal salts with aliphatic saturated C -C 2 carboxylates, aliphatic unsaturated C 3 -C 22 carboxylates, aliphatic C 2 -C 2 carboxylates which are substituted by at least one hydroxyl group or whose chain is substituted by at least one oxygen atom is interrupted, further cyclic or bicyclic C5-C22 carboxylates, respectively unsubstirusammlungs or by at least one OH
  • an organic fibrous or fiber-forming polymer such as polyamide, copolyamide, polyester, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid ester, modified cellulose, and furthermore those which are described in US
  • Polyester, polyamide 4.6, polyamide 6.6, polyamide 6 or copolyamide 6 / 6.6 are preferably used as the fibrous material.
  • Thermoplastic polymers with polar groups are preferably used as compatibilizers.
  • F.2 at least one monomer selected from the group C 2 to C 12 alkyl methacrylates, C 2 to C 12 alkyl acrylates, methacrylonitriles and acrylonitriles and
  • F.3 contain ⁇ , ⁇ -unsaturated components containing dicarboxylic anhydrides.
  • Styrene is particularly preferred as vinyl aromatic monomer F.l.
  • Maleic anhydride is particularly preferred for ⁇ , ⁇ -unsaturated "components containing dicarboxylic anhydrides F.3.
  • Terpolymers of the monomers mentioned are preferably used as component F.l, F.2 and F.3. Accordingly, terpolymers of styrene preferably
  • Acrylonitrile and maleic anhydride are used. These terpolymers contribute in particular to improving the mechanical properties, such as tensile strength and elongation at break.
  • the amount of maleic anhydride in the terpolymer can vary within wide limits. The amount is preferably 0.2 to 5 mol%. Amounts between 0.5 and 1.5 mol% are particularly preferred. In this area particularly good mechanical properties with regard to tensile strength and elongation at break are achieved.
  • the terpolymer can be produced in a manner known per se.
  • a suitable method is to dissolve monomer components of the terpolymer, e.g. of
  • Styrene, maleic anhydride or acrylonitrile in a suitable solvent e.g. Methyl ethyl ketone (MEK).
  • a suitable solvent e.g. Methyl ethyl ketone (MEK).
  • One or optionally several chemical initiators are added to this solution. Suitable initiators are e.g. Peroxides.
  • the mixture is then polymerized for several hours at elevated temperatures. The solvent and the unreacted monomers are then removed in a manner known per se.
  • the ratio between component F.l (vinyl aromatic monomer) and component F.2, e.g. the acrylonitrile monomer in the terpolymer is preferably between 80:20 and 50:50.
  • an amount of vinyl aromatic monomer F.l is preferably selected which corresponds to the amount of vinyl monomer B.l in graft copolymer B.
  • EP-A 785 234 and EP-A-202 214 According to the invention, particular preference is given to the polymers mentioned in EP-A 785 234.
  • Compatibility mediators can be contained in component F alone or in any mixture with one another.
  • Another substance which is particularly preferred as a compatibilizer is a terpolymer of styrene and acrylonitrile in a weight ratio of 2.1: 1 containing 1 mol% of maleic anhydride.
  • the amount of component F in the polymer compositions according to the invention is preferably between 0.5 and 30 parts by weight, in particular between 1 and 20 parts by weight and particularly preferably between 2 and 10 parts by weight. Amounts between 3 and 7 parts by weight are most preferred.
  • Component G comprises one or more thermoplastic vinyl (co) polymers.
  • Suitable vinyl (co) polymers for component G are polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C 1 -C 8 ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides ) unsaturated carboxylic acids.
  • (Co) polymers of are particularly suitable
  • Gl 50 to 99 preferably 60 to 80 parts by weight of vinyl aromatics and / or core-substituted vinyl aromatics (such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (-CC 8 ) alkyl esters (such as methyl methacrylate, ethyl methacrylate), and
  • G.2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated
  • Nitriles such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid
  • (C - C 8 ) alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate
  • unsaturated carboxylic acids eg N-phenylmaleimide
  • the (co) polymers G are resin-like, thermoplastic and rubber-free.
  • the copolymer of Gl styrene and G.2 acrylonitrile is particularly preferred.
  • the (co) polymers G are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers preferably have average molecular weights Mw (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
  • the vinyl (co) polymers can be contained in component G alone or in any mixture with one another.
  • Component G is preferably in one in the polymer composition
  • Contain amount of 0 to 30 parts by weight in particular from 0 to 25 parts by weight and particularly preferably from 0 to 20 parts by weight, in particular 0.5 to 10 parts by weight.
  • Phenol-formaldehyde resins according to the invention are obtained by condensation reaction from phenols with aldehydes, preferably formaldehyde, by derivatization of the resulting condensates or by addition of phenols to unsaturated compounds, e.g. Acetylene, terpenes etc. produced
  • the condensation can be acidic or basic and the molar ratio of aldehyde to phenol can be from 1: 0.4 to 1: 2.0. This produces oligomers or polymers with a molar mass of 150-5000 g / mol.
  • the resins are known or can be prepared by processes known from the literature.
  • compositions preferably contain phenol-formaldehyde resins which are generally added in an amount of up to 15 parts by weight, preferably 1 to 12 and in particular 2 to 8 parts by weight.
  • Component J phenol-formaldehyde resins which are generally added in an amount of up to 15 parts by weight, preferably 1 to 12 and in particular 2 to 8 parts by weight.
  • the polymer compositions according to the invention can contain conventional additives, such as flame retardants, anti-dripping agents, fillers and reinforcing materials, different from components C and D, lubricants and. Mold release agents, nucleating agents,
  • Contain antistatic agents different from component E, stabilizers as well as dyes and pigments.
  • compositions according to the invention can generally contain from 0.01 to 20% by weight, based on the overall composition, of flame retardants.
  • flame retardants are organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds such as Mg-Al-hydroxide, inorganic compounds such as Aliminium oxides, titanium dioxide, antimony oxides, barium meta-borate, zirconium meta borate, hydroxyl Zirconium hydroxide, molybdenum oxide, ammonium molybdate, tin riborate, ammonium borate and tin oxide as well as siloxane compounds.
  • flame retardant compounds can also phosphorus compounds, as in the
  • EP-A 363 608, EP-A 345 522 and / or EP-A 640 655 are used.
  • Glass fibers optionally cut or ground, glass beads and glass balls are suitable as further filling and reinforcing materials.
  • compositions according to the invention are prepared by mixing the respective constituents in a known manner and at temperatures of 200 ° C to 300 ° C in conventional units such as kneaders, extruders and twin-screw extruders, melt-compounded and melt-extruded, the mold release agent being used in the form of a coagulated mixture.
  • the individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
  • the polymer compositions according to the invention can be used for the production of moldings of any kind.
  • molded parts can by
  • molded parts are: Housing parts of all kinds, for example for household appliances such as electric shavers, flat screens, monitors, printers, copiers or cover plates for the construction sector and parts for motor vehicles and rail vehicles. They can also be used in the field of electrical engineering because they have very good electrical properties.
  • polymer compositions according to the invention can be used, for example, to produce the following moldings:
  • Another form of processing is the production of molded parts by deep drawing from previously produced sheets or foils.
  • Another object of the present invention is therefore also the use of the compositions according to the invention for the production of moldings of any kind, preferably those mentioned above, and the moldings from the compositions according to the invention.
  • the online-painted molded parts preferably online-painted automotive exterior parts, for example wheel arches, fenders, outer mirror housings, etc., are also the subject of the present invention.
  • compositions are prepared, processed into test specimens and tested in accordance with the information in Table 1.
  • Polyamide 6.6 (Ultramid ® A 3, BASF, Ludwigshafen, Germany).
  • Graft polymer of 40 parts by weight of a copolymer of styrene and acrylonitrile in a ratio of 73:27 to 60 parts by weight of particulate crosslinked polybutadiene rubber (average particle diameter d 50 0.28 ⁇ m), produced by emulsion polymerization.
  • Nyglos ® 4-10013 silica wollastonite with a particle size according to manufacturer's specifications of 4.8 ⁇ m
  • Ketjenblack ® EC 600 (Akzo Nobel, Düren sales office, 52349 Düren, Germany (electrically conductive carbon black)
  • Styrene / acrylonitrile copolymer with a Slyrol / AcryMtril weight ratio of 72:28 and an intrinsic viscosity of 0.55 dl / g (measurement in dimethylformamide at 20 ° C).
  • compositions are mixed on a 3-1 internal kneader.
  • the moldings are produced on an Arburg 270 E injection molding machine at 280 ° C.
  • Vicat B's dimensional stability under heat is determined in accordance with ISO 306 on rods measuring 80 x 10 x 4 mm.
  • the impact strength a ⁇ is determined in accordance with ISO 180/1 U.
  • the MVR (Melt Volume Rate) is determined according to ISO 1133 at 280 ° C using a stamp load of 5 kg.
  • the surface resistance is determined according to DL IEC 60167.
  • the elongation at break is determined in a tensile test according to ISO 527.
  • component E shows positive properties with regard to the toughness of the molding composition and the flow behavior.
  • the combination of E and D has a positive effect.
  • Comparative example 1 Comparative example 1
  • a very good surface resistance is achieved, but the MVR value drops so much that it can no longer be determined under the given conditions.
  • less carbon black is used (comparative example 2)
  • the surface resistance is very high and, in contrast to examples 1 and 2 according to the invention, the MVR value is significantly lower.
  • Example 3 The advantageous properties as in Example 1 are also evident with wollastonite as filler (Example 3)
  • the value of the surface resistance in Examples 1, 2 and 3 is for electrostatic painting of a molded part without prior treatment with a

Abstract

A conductive, impact-strength-modified polyamide molding composition is disclosed. The composition contains A) 40 to 99 parts by weight polyamide, B) 0.5 to 50 parts by weight graft polymer, C) 0.1 to 30 parts by weight mineral in particulate form, D) 0 to 1.5 parts by weight electrically conductive carbon particles, E) 0.1 to 15 parts by weight of at least one member selected from the group consisting of polyester ether amide, polyester/ether block copolymer and polyamide/polyester block copolymer. Embodiments that further contain any of compatibility promoter, vinyl (co)polymer, phenolformaldehyde resin and polymer additive are also disclosed. The composition is particularly suitable for online lacquering.

Description

Schlagzähmodifizierte Polymer-ZusammensetzungenImpact-modified polymer compositions
Die Erfindung betrifft . schlagzänmodifizierte Polyamid-Zusammensetzungen und daraus hergestellte Formteile, die sich insbesondere zur direkten Online-Lackierung ohne vorherige Behandlung des Formteiles mit einem elektrisch leitfähigen Primer- system eignen sowie die online lackierten Formteile.The invention relates. Impact-modified polyamide compositions and molded parts made therefrom, which are particularly suitable for direct online painting without prior treatment of the molded part with an electrically conductive primer system, as well as the online coated molded parts.
DE-A 101 019 225 beschreibt allgemein Polymer-Zusammensetzungen . enthaltend Polyamid, Pfropfpolymerisat, Vinyl(co)polymerisat, Verträglichkeitsvermittler und feinstteilige mineralische Partikel mit anisotroper Partikelgeometrie. In DE-A 101 019 225 wird nicht erwähnt, dass die dort beschriebene Zusammensetzungen online lackiert werden können.DE-A 101 019 225 generally describes polymer compositions. Containing polyamide, graft polymer, vinyl (co) polymer, compatibility agent and very fine mineral particles with anisotropic particle geometry. DE-A 101 019 225 does not mention that the compositions described there can be painted online.
Aus der EP 0202 214 A sind Polymerblends aus einem Polyamid, einem Sty- rol/Acrylnitril-Copolymerisat und einem Verträglichkeitsvermittler bekannt. Als Verträglichkeitsvermittler wird ein Copolymer aus einem vinylaromatischen Monomer und Acrylnitril, Methacrylnitril, C-. bis C4-Alkylmethacrylat oder C- bis C4- Alkylacrylat in einem Gewichtsverhältnis von 85:15 bis 15:85 eingesetzt. Durch den Einsatz von Verträglichkeitsvermittlern soll eine erhöhte Schlagzähigkeit erreicht werden. Nachteilig an den in dieser Druckschrift beschriebenen Polymerblends ist, dass sie für Dünnwandapplikationen eine zu geringe Steifigkeit und einen zu hohen Ausdehnungskoeffizienten aufweisen.EP 0202 214 A discloses polymer blends made from a polyamide, a styrene / acrylonitrile copolymer and a compatibilizer. A copolymer consisting of a vinyl aromatic monomer and acrylonitrile, methacrylonitrile, C- is used as a compatibilizer. to C 4 alkyl methacrylate or C to C 4 alkyl acrylate in a weight ratio of 85:15 to 15:85. Increased impact strength is to be achieved through the use of compatibility agents. A disadvantage of the polymer blends described in this publication is that they have too low a stiffness and a too high coefficient of expansion for thin-wall applications.
Aus JP 11 241 016.A2 sind Polyamid-Formmassen bekannt, die neben Polyamid kautschukmodifizierte Styrolpolymere, Pfropφolymere auf Basis von Ethylen/Pro- pylen-Kautschuken und Talk mit einem Teilchendurchmesser von 1 bis 4 μm enthalten.JP 11 241 016.A2 discloses polyamide molding compositions which, in addition to polyamide, contain rubber-modified styrene polymers, graft polymers based on ethylene / propylene rubbers and talc with a particle diameter of 1 to 4 μm.
EP-A 0 718 350 beschreibt Polymerblends aus einem kristallinen und einem amorphen bzw. halbkristallinen Polymer sowie 2 bis 7 Gew.-% elektrisch leitfähigem Kohlenstoff (Ruß) zur Herstellung geformter, thermoplastischer Gegenstände, die in einem weiteren Schritt elektrostatisch lackiert werden. Besonders hoch wärmeformbeständige Polymerblends mit leitfabiger Ausrüstung werden hier nicht beschrieben.EP-A 0 718 350 describes polymer blends consisting of a crystalline and an amorphous or semi-crystalline polymer and 2 to 7% by weight of electrically conductive Carbon (soot) for the production of molded, thermoplastic objects that are electrostatically painted in a further step. Highly heat-resistant polymer blends with conductive finish are not described here.
In US-A 5 965 206 werden thermoplastische und elastomere antistatisch ausgerüsteteIn US-A 5 965 206 thermoplastic and elastomeric are antistatically treated
Zusammensetzungen beschrieben. Die Antistatika bestehen aus Polyethern, Poly- estern, Polyester-Ether Amiden, Polyetherestern oder Mischungen und Copolymeren aus diesen sowie einem organischen oder anorganischem. Salz. Als thermoplastische und elastomere Polymeren werden eine Vielzahl von .Polymeren aufgeführt. Die Zusammensetzungen der vorliegenden Erfindung wird jedoch nicht beschrieben.Compositions described. The antistatic agents consist of polyethers, polyesters, polyester ether amides, polyether esters or mixtures and copolymers of these as well as an organic or inorganic. Salt. A large number of polymers are listed as thermoplastic and elastomeric polymers. However, the compositions of the present invention are not described.
Weiterhin werden antistatische Zusammensetzungen aus Polyetheresteramiden und Polyetherestern in WO 02/055411 und EP-A 613 919 beschrieben.Furthermore, antistatic compositions of polyether ester amides and polyether esters are described in WO 02/055411 and EP-A 613 919.
Allgemein bekannt ist ferner der Einsatz von feinteiligen anorganischen Materialien in bestimmten Polymer-Zusammensetzungen, insbesondere in Polycarbonat-Zusam- mensetzungen. Die anorganischen Materialien werden in diesen Zusammensetzungen beispielsweise als Verstärkungsstoff zur Erhöhung der Steifigkeit und Zugfestigkeit, zur Erhöhung der Dimensionsstabilität bei Temperaturschwankungen, zur Verbesserung der Oberflächeneigenschaften oder - in flammwidrigen Materialien - auch als Flammschutzsynergist eingesetzt. Verwendet werden sowohl mineralische als auch künstlich gewonnene Materialien. So werden in der US-A 5 714 537 beispielsweise Polycarbonat-Bi'ends beschrieben, die zur Verbesserung der Steifigkeit und linearen Wärmeausdehnungsfestigkeit bestimmte anorganische Füllstoffe enthalten.The use of finely divided inorganic materials in certain polymer compositions, in particular in polycarbonate compositions, is also generally known. In these compositions, the inorganic materials are used, for example, as reinforcing materials to increase the rigidity and tensile strength, to increase the dimensional stability in the event of temperature fluctuations, to improve the surface properties or - in flame-retardant materials - also as a flame retardant synergist. Both mineral and artificially obtained materials are used. For example, US Pat . No. 5,714,537 describes polycarbonate bi-ends which contain certain inorganic fillers to improve the rigidity and linear thermal expansion resistance.
Aus der WO 01/34703 sind schlagzähmodifizierte Polyethylenterephthalat/Poly- carbonat Blends bekannt, die sich zur Online-Lackierung eignen. Polyamid-Blends werden nicht beschrieben.WO 01/34703 discloses impact-modified polyethylene terephthalate / polycarbonate blends which are suitable for online coating. Polyamide blends are not described.
Bekannt für einige direkt lackierbare onh inline-Anwendungen ist das Noryl® GTX der General Electric Plastics (vgl. EP-A 685 527). Es handelt sich dabei um einThe Noryl ® GTX from General Electric Plastics is known for some directly paintable inline applications (cf. EP-A 685 527). It is a
Blend enthaltend Polyamid und Polyphenylenether (PA/PPO Blend). Karosserieaußenteile aus Kunststoffen müssen in der Regel lackiert werden. Im Falle wagenfarbig eingefärbter Kunststoffe werden die daraus hergestellten Karosserieanbauteile in der Regel mit einer oder mehreren Schichten durchsichtiger Lacke überzogen. Im Falle nicht wagenfarbig eingefärbter Kunststoffe werden' die daraus hergestellten Karosserieanbauteile mit mehreren Lackschichten lackiert, wobei mindestens eine der Schichten farbgebend ist (Decklack). Je nach Wärmeformbeständigkeit der Kunststoffe wird hier zwischen unterschiedlichen Verfahren unterschieden, die im Zeitpunkt der Anbringung der Kunststoffanbauteile an das Karosserieaußen- teil differieren. Wenn die Kunststoffanbauteile den gesamten Lackierprozeß mit durchlaufen, spricht man allgemein von einer „online" Lackierung, die die höchste Anforderung an die Wärmeformbständigkeit des Kunststoffes stellt. Bei der sogenannten „inline" Lackierung wird das Kunststoffanbauteil nach der sogenannten Kathoden Tauch Lackierung (KTL) an das Karosserieaußenteil montiert und in die Lackierstraße eingebracht. Bei der sogenannten „off-line" Lackierung wird das gesamte Kunststoffanbauteil außerhalb der Lackierstraße bei geringen Temperaturen lackiert und erst anschließend an das Karosserieaußenteil montiert.Blend containing polyamide and polyphenylene ether (PA / PPO blend). Body parts made of plastics usually have to be painted. In the case of car-colored plastics, the body attachments made from them are usually covered with one or more layers of transparent lacquer. In the case of plastics that are not colored in the color of a car, the body attachments made from them are coated with several layers of paint, with at least one of the layers giving color (top coat). Depending on the heat resistance of the plastics, a distinction is made here between different processes that differ at the time the plastic add-on parts are attached to the outer part of the body. If the plastic add-on parts go through the entire painting process, one speaks generally of an "online" painting, which places the highest demands on the heat resistance of the plastic. In the so-called "inline" painting, the plastic add-on part is called the cathode dip painting (KTL) the outer part of the body is assembled and placed in the painting line. In the so-called "off-line" painting, the entire plastic add-on part is painted outside the painting line at low temperatures and only then mounted on the outer part of the body.
Der „online"-Prozess wird von der Automobilindustrie bevorzugt, da er die Arbeits- schritte rninimiert und außerdem die beste Farbanpassung von Kunststoff und Blech erreicht wird. Bei diesem Verfahren werden Temperaturen von bis zu 205 °C erreicht, so dass hohe Anforderungen an die Wärmeformbeständigkeit des Formteils gestellt werden.The "online" process is preferred by the automotive industry because it minimizes the work steps and also achieves the best color matching of plastic and sheet metal. With this process, temperatures of up to 205 ° C are reached, so that high demands are placed on the Heat resistance of the molded part can be provided.
Wenn es gelingt einen Kunststoff so zu modifizieren, dass sein spezifischer Widerstand so gering wird, dass er, ohne vorherige Behandlung mit einem leitfähigen Primersystem, in der elektrostatischen Lackierung verwendet werden kann, so umgeht man einen Produktionsschritt.If a plastic can be modified in such a way that its specific resistance becomes so low that it can be used in electrostatic painting without prior treatment with a conductive primer system, a production step is avoided.
Zusätzliche Anforderungen, die an Karosserieanbauteile aus Kunsstoff gestellt werden, sind gute Steifigkeit, geringe thermische Ausdehnung sowie Nachschwin- dung, gute Oberflächenqualität, gute Lackierbarkeitund gute Chemikalienbeständigkeit. Zudem müssen die zur Herstellung der Karosserieaußenteile verwendeten Formassen eine gute Fließfahigkeit in der Schmelze aufweisen.Additional requirements placed on plastic body parts are good rigidity, low thermal expansion and post-vibration. dung, good surface quality, good paintability and good chemical resistance. In addition, the molding compounds used to produce the exterior parts of the body must have good fluidity in the melt.
Aufgäbe der vorliegenden Erfindung war es, Polyamidformmassen mit reduziertem spezifischen Widerstand zur Verfügung zu stellen, die eine Eigenschaftskombination von guter Wärmeformbeständigkeit, Schlagzähigkeit erhöhter Reißdehnung bei gleichzeitig gutem Verarbeitungsverhalten aufweisen.It was an object of the present invention to provide polyamide molding compositions with reduced specific resistance, which have a combination of properties of good heat resistance, impact strength, increased elongation at break and, at the same time, good processing behavior.
Die Aufgabe . wurde gelöst durch eine Polymer-Zusammensetzung enthaltendThe task . was solved by containing a polymer composition
(A) 40-99, vorzugsweise 45 -95, besonders bevorzugt 50 - 85, insbesondere 50 bis 80 Gew.-Teile Polyamid(A) 40-99, preferably 45-95, particularly preferably 50-85, in particular 50 to 80 parts by weight of polyamide
(B) 0,5 - 50, vorzugsweise 1 - 40, besonders bevorzugt 1 - 30, insbesondere 5 bis 25 Gew.-Teile Pfropfpolymerisat(B) 0.5-50, preferably 1-40, particularly preferably 1-30, in particular 5 to 25 parts by weight of graft polymer
(C) 0,1 - 30, vorzugsweise 1 - 20, besonders bevorzugt 2 - 15, insbesondere 4 - 13 Gew.-Teile mineralische Partikel(C) 0.1-30, preferably 1-20, particularly preferably 2-15, in particular 4-13 parts by weight of mineral particles
(D) 0 - 1,5 Gew.-Teile elektrisch leitfähige Kohlenstoffpartikel(D) 0-1.5 parts by weight of electrically conductive carbon particles
(E) 0,1 - 15, vorzugsweise 1 - 12 besonders bevorzugt 2 - 10 Gew. Teile ent- haltend mindestens ein Polymer ausgewählt aus der Gruppe der Polyester- etheramide, Polyester-ether-Blockcopolymeren, Polyamid-Polyetherblock- polymere.(E) 0.1-15, preferably 1-12, particularly preferably 2-10 parts by weight containing at least one polymer selected from the group consisting of polyester ether amides, polyester ether block copolymers and polyamide-polyether block polymers.
Die Zusammensetzung kann als weitere Komponenten Verträglichkeitsvermittler (Komponente F) und/oder Vinyl(co)polymerisat (Komponente G) enthalten, Phenol-The composition may contain, as further components, compatibilizer (component F) and / or vinyl (co) polymer (component G), phenolic
Formaldehyd-Harz (H) und übliche Polymeradditive (J) enthalten.Contain formaldehyde resin (H) and common polymer additives (J).
Gegenstand der Erfindung sind weiterhin auch die Online-lackierten Formteile erhältlich aus den obengenannten Zusammensetzungen. Es wurde gefunden, dass ein Kunststoff mit obiger Zusammensetzung eine ausgezeichnete Wärmeformbeständigkeit zeigt und aufgrund dieser ein Einsatz in „online"-Lackierprozessen gut möglich ist. Außerdem weist er eine Class-A Oberfläche, hohe Steifigkeit und hervorragende Chemikalienresistenz auf.The invention furthermore also relates to the online lacquered moldings obtainable from the compositions mentioned above. It has been found that a plastic with the above composition shows excellent heat resistance and can therefore be used in "online" painting processes. It also has a Class-A surface, high rigidity and excellent chemical resistance.
Weiterhin wurde gefunden, dass die Kombination von Leitrußen mit mindestens einem Polymer ausgewählt aus Polyesteretheramiden und Polyether-Ester-Block- copolymeren für die Leitfähigkeitsausrüstung besonders gut geeignet sind.Furthermore, it was found that the combination of conductive carbon blacks with at least one polymer selected from polyester ether amides and polyether ester block copolymers are particularly suitable for the conductivity equipment.
Die erfindungsgemäß geeigneten Komponenten der Polymer-Zusammensetzung werden nachfolgend beispielhaft erläutert.The components of the polymer composition suitable according to the invention are explained below by way of example.
Komponente AComponent A
Erfindungsgemäß geeignete Polyamide (Komponente A) sind bekannt oder nach literaturbekannten Verfahren herstellbar.Polyamides (component A) which are suitable according to the invention are known or can be prepared by processes known from the literature.
Erfindungsgemäß geeignete Polyamide sind bekannte Homopolyamide, Copoly- amide und Mischungen dieser Polyamide. Es können dies teilkristalline und oder amorphe Polyamide sein. Als teilkristalline Polyamide sind Polyamid-6, Polyamid-Polyamides suitable according to the invention are known homopolyamides, copolyamides and mixtures of these polyamides. These can be partially crystalline and or amorphous polyamides. The partially crystalline polyamides are polyamide 6, polyamide
6,6, Mischungen und entsprechende Copolymerisate aus diesen Komponenten geeignet. Weiterhin kommen teilkristalline Polyamide in Betracht, deren Säurekomponente ganz oder teilweise aus Terephthalsäure und/oder Isophthalsäure und/oder Korksäure und/oder Sebacinsäure und/oder Azelainsäure und/oder Adipinsäure und/oder Cyclohexandicarbonsäure, deren Diaminkomponente ganz oder teilweise aus m- und/oder p-Xylylendiamin und/oder Hexamethylendiamin und/oder 2,2,4- Trimethylhexa-methylendiamin und/oder 2,4,4-Trimethymexamemylendiamin und/oder Isophorondiamin besteht und deren Zusammensetzung prinzipiell bekannt ist. Außerdem sind Polyamide zu nennen, die ganz oder teilweise aus Lactamen mit 7 bis 12 Kohlenstoffatomen im Ring, gegebenenfalls unter Mitverwendung einer oder mehrerer der oben genannten Ausgangskomponenten, hergestellt werden.6,6, mixtures and corresponding copolymers of these components are suitable. Also suitable are partially crystalline polyamides, the acid component of which is wholly or partly composed of terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or adipic acid and / or cyclohexanedicarboxylic acid, the diamine component wholly or partly of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4-trimethylhexamethylenediamine and / or 2,4,4-trimethymexamethylenediamine and / or isophoronediamine and the composition of which is known in principle. Also to be mentioned are polyamides which are wholly or partly prepared from lactams with 7 to 12 carbon atoms in the ring, optionally with the use of one or more of the above-mentioned starting components.
Besonders bevorzugte teilkristalline Polyamide sind Polyamid-6 und Polyamid-6,6 und ihre Mischungen. Als amorphe Polyamide können bekannte Produkte eingesetzt werden. Sie werden erhalten durch Polykondensation von Diaminen wie Ethylendi- amin, Hexamethylendiamin, Decamethylendiamin, 2,2,4- und/oder 2,4,4-Trimethyl- hexamemylendiamin, m- und/oder p-Xylylendiamin, Bis-(4-aminocyclohexyl)- methan, Bis-(4-aminocyclohexyl)-propan, 3,3'-Dimethyl*-4,4'-diamino-dicyclohexyl- methan, 3**Aminomethyl-3,5,5-trimethylcyclohexylamin, 2,5- und oder 2,6-Bis- (aminomethyl)-norbornan und/oder 1,4-Diaminomethylcyclohexan mit Dicarbon- säuren wie Oxalsäure, Adipinsäure, Azelainsäure, Decandicarbonsäure, Heptadecan- dicarbonsäure, 2,2,4- und/oder 2,4,4-Trimethyladipinsäure, Isophthalsäure und Terephthalsäure.Particularly preferred partially crystalline polyamides are polyamide 6 and polyamide 6,6 and their mixtures. Known products can be used as amorphous polyamides. They are obtained by polycondensation of diamines such as ethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4- and / or 2,4,4-trimethylhexamemylenediamine, m- and / or p-xylylenediamine, bis- (4-aminocyclohexyl ) - methane, bis- (4-aminocyclohexyl) propane, 3,3'-dimethyl * -4,4'-diamino-dicyclohexyl-methane, 3 ** aminomethyl-3,5,5-trimethylcyclohexylamine, 2,5- and or 2,6-bis (aminomethyl) norbornane and / or 1,4-diaminomethylcyclohexane with dicarboxylic acids such as oxalic acid, adipic acid, azelaic acid, decanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4- and / or 2,4 , 4-trimethyladipic acid, isophthalic acid and terephthalic acid.
Auch Copolymere, die durch Polykondensation mehrerer Monomere erhalten werden, sind geeignet, ferner Copolymere, die unter Zusatz von Ammocarbonsäuren wie e-Aminocapronsäure, w-Aminoundecansäure oder w-Aminolaurinsäure oder ihren Lactamen, hergestellt werden.Copolymers obtained by polycondensation of several monomers are also suitable, as are copolymers which are prepared with the addition of ammocarboxylic acids such as e-aminocaproic acid, w-aminoundecanoic acid or w-aminolauric acid or their lactams.
Besonders geeignete amorphe Polyamide sind die Polyamide hergestellt "aus Isophthalsäure, Hexamethylendiamin und weiteren Diaminen wie 4,4-Diaminodicyclo- hexylmethan, Isophorondiamin, 2,2,4- und/oder 2,4,4-Trimethylhexa-methylen- diamin, 2,5- und/oder 2,6-Bis-(aminomethyl)-norbornen; oder aus Isophthalsäure,Particularly suitable amorphous polyamides are the polyamides made from isophthalic acid, hexamethylenediamine and other diamines such as 4,4-diaminodicyclohexylmethane, isophoronediamine, 2,2,4- and / or 2,4,4-trimethylhexa-methylenediamine, 2, 5- and / or 2,6-bis (aminomethyl) norbornene; or from isophthalic acid,
4,4'-Diamino-dicyclohexylmethan und ε-Caprolactam; oder aus Isophthalsäure, 3,3'- Dimethyl-4,4'-(hamino-dicyclohexylmethan und Laurinlactam; oder aus Terephthalsäure und dem Isomerengemisch aus 2,2,4- und/oder 2,4,4-Trimethylhexamethylen- diamin. Anstelle des reinen 4,4'-Diaminodicyclohexylmethans können auch Gemische der Stellungsisomeren Diamindicyclohexalmethane eingesetzt werden, die sich zusammensetzen aus4,4'-diamino-dicyclohexylmethane and ε-caprolactam; or from isophthalic acid, 3,3'-dimethyl-4,4 '- (hamino-dicyclohexylmethane and laurolactam; or from terephthalic acid and the isomer mixture of 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine. Instead of the pure 4,4'-diaminodicyclohexylmethane, it is also possible to use mixtures of the positional isomers diamine dicyclohexalmethane, which are composed of
70 bis 99 Mol% des 4,4'-Diamino-Isomeren,70 to 99 mol% of the 4,4'-diamino isomer,
1 bis 30 Mol% des 2,4'-Diamino-Isomeren und1 to 30 mol% of the 2,4'-diamino isomer and
O bis 2 Mol% des 2,2'-Diamino-Isomeren,0 to 2 mol% of the 2,2'-diamino isomer,
gegebenenfalls entsprechend höher kondensierten Diaminen, die durch Hydrierung von Diaminodiphenylmethan technischer Qualität erhalten werden. Die Isophthalsäure kann bis zu 30 % durch Terephthalsäure ersetzt sein.if appropriate, correspondingly more highly condensed diamines obtained by hydrogenating technical-grade diaminodiphenylmethane. Up to 30% of the isophthalic acid can be replaced by terephthalic acid.
Die Polyamide weisen vorzugsweise eine relative Viskosität (gemessen an einer 1 gew.-%igen Lösung in m-Kresol bei 25°C) von 2,0 bis 5,0, besonders bevorzugt von 2,5 bis 4,0 auf.The polyamides preferably have a relative viscosity (measured on a 1% strength by weight solution in m-cresol at 25 ° C.) from 2.0 to 5.0, particularly preferably from 2.5 to 4.0.
Die Polyamide können allein oder in beliebiger Mischung untereinander in Komponente A enthalten sein.The polyamides can be contained in component A alone or in any mixture with one another.
Komponente BComponent B
Die Komponente B umfasst ein oder mehrere kautschukmodifizierte Pfropfpolymerisate. Das kautschukmodifizierte Pfropf olymerisat B umfasst ein statistisches (Co)- polymerisat aus Vinylmonomeren B.l, vorzugsweise gemäß B.l.l und B.l.2, sowie einen mit Vinylmonomeren, vorzugsweise gemäß B.l.l und B.l.2 gepfropftenComponent B comprises one or more rubber-modified graft polymers. The rubber-modified graft polymer B comprises a statistical (co) polymer made from vinyl monomers B.l, preferably according to B.l.l and B.l.2, and one grafted with vinyl monomers, preferably according to B.l.l and B.l.2
Kautschuk B.2. Die Herstellung von B erfolgt in bekannter Weise durch radikalische Polymerisation, z.B. nach einem Emulsions-, Masse- oder Lösungs- oder Masse- Suspensions-Polymerisationsverfahren , wie z.B. in den US-A 3 243 481, US-A 3 509 237, US-A 3 660 535, US-A 4 221 833 und US-A 4 239 863 beschrieben. Besonders geeignete Pfropfkautschuke sind auch ABS-Polymerisate, die durch Redox-Initiierung mit einem Initiatorsystem aus organischem Hydroperoxid und Ascorbinsäure gemäß US-A 4 937 285 erhältlich sind.Rubber B.2. B is prepared in a known manner by free-radical polymerization, for example by an emulsion, bulk or solution or bulk suspension polymerization process, such as, for example, in US Pat. Nos. 3,243,481, 3,509,237, US Pat. A 3 660 535, US-A 4 221 833 and US-A 4 239 863. Particularly suitable graft rubbers are also ABS polymers that pass through Redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285 are available.
Bevorzugt sind ein oder mehrere Pfropfpolymerisate von 5 bis 95, vorzugsweise 20 bis 90 Gew.-% wenigstens eines Vinylmonomeren B.l auf 95 bis 5, vorzugsweiseOne or more graft polymers of 5 to 95, preferably 20 to 90% by weight of at least one vinyl monomer B.l to 95 to 5, preferably, are preferred
80 bis 10 Gew.-% einer oder mehrerer Pf opfgrundlagen B.2 mit Glasübergangs- temperaturen < 10°C, vorzugsweise <-10°C.80 to 10 wt .-% of one or more Pf opfgrundlagen B.2 with glass transition temperatures <10 ° C, preferably <-10 ° C.
Bevorzugte Monomere B.l.l sind Styrol, α-Methylstyrol, halogen- oder alkylkern- substituierte Styrole wie p-Methylstyrol, p-Chlorstyrol, (Meth)acrylsäure-C--C8- alkylester wie Methylmethacrylat, n-Butylaciylat und tert.-Butylacrylat. Bevorzugte Monomere B.l.2 sind ungesättigte Nitrile wie Acrylnitril, Methacrylnitril, (Meth)- Acrylsäure-C--C8-alkylester wie Methylmethacrylat, n-Butylacrylat, tert.-Butylacrylat, Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren wie Malein- säureanhydrid und N-Phenyl-maleinimid oder Mischungen davon.Preferred monomers B1 are styrene, α-methylstyrene, halogen- or alkyl nucleus-substituted styrenes such as p-methylstyrene, p-chlorostyrene, (meth) acrylic acid-C 8 -C 8 -alkyl esters such as methyl methacrylate, n-butyl acylate and tert-butyl acrylate. Preferred monomers B1 are unsaturated nitriles such as acrylonitrile, methacrylonitrile, (meth) acrylic C 8 -C 8 alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, derivatives (such as anhydrides and imides) of unsaturated carboxylic acids such as maleic anhydride and N-phenyl-maleimide or mixtures thereof.
Besonders bevorzugte Monomere B.l.l sind Styrol, α-Methylstyrol und/oder Methylmethacrylat, besonders bevorzugte Monomere B.l.2 sind Acrylnitril, Maleinsäureanhydrid und oder Methylmethacrylat.Particularly preferred monomers B.l.l are styrene, α-methylstyrene and / or methyl methacrylate, particularly preferred monomers B.l.2 are acrylonitrile, maleic anhydride and or methyl methacrylate.
Besonders bevorzugte Monomere sind B.l.l Styrol und B.1.2 Acrylnitril.Particularly preferred monomers are B.l.l styrene and B.1.2 acrylonitrile.
Für die kautschukmodifizierten Pfropfpolymerisate B geeignete Kautschuke B.2 sind beispielsweise Dienkautschuke, Acrylat-, Polyurethan-, Silikon-, Chloropren- und Ethylen/Vinylacetat-Kautschuke. Ebenso sind Komposite aus verschiedenen der genannten Kautschuke als Pfropfgrundlagen geeignet.Rubbers B.2 suitable for the rubber-modified graft polymers B are, for example, diene rubbers, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers. Composites made from various of the rubbers mentioned are also suitable as graft bases.
Bevorzugte Kautschuke B.2 sind Dienkautschuke (z.B. auf Basis Butadien, IsoprenPreferred rubbers B.2 are diene rubbers (e.g. based on butadiene, isoprene
. etc.) oder Gemische von Dienkautschuken oder Copolymerisate von Dienkau- tschuken oder deren Gemischen mit weiteren copolymerisierbaren Vinylmonomeren, etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable vinyl monomers
(z.B. gemäß B.l.l und B.l.2), mit der Maßgabe, dass die Glasübergangstemperatur der Komponente B.2 unterhalb 10°C, vorzugsweise unterhalb -10°C liegt. Besonders bevorzugt wird reiner Polybutadienkautschuk. Weitere copolymerisierbare Monomere können bis zu 50 Gew.-%, vorzugsweise bis zu 30, insbesondere bis zu 20 Gew.-% (bezogen auf die Kautschukgrundlage B.2) in der Kautschukgrundlage enthalten sein.(eg according to Bll and Bl2), with the proviso that the glass transition temperature component B.2 is below 10 ° C, preferably below -10 ° C. Pure polybutadiene rubber is particularly preferred. Further copolymerizable monomers can contain up to 50% by weight, preferably up to 30, in particular up to 20% by weight (based on the rubber base B.2) in the rubber base.
Geeignete Acrylatkautschuke gemäß B.2 der Polymerisate B sind vorzugsweise Polymerisate aus Acrylsäurealkylestern, gegebenenfalls mit bis zu 40 Gew.-%, bezogen auf B.2 anderen polymerisierbaren, ethylenisch ungesättigten Monomeren. Zu den bevorzugten polymerisierbaren Acrylsäureestern gehören Cj bis Cg-Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers made from acrylic acid alkyl esters, optionally with up to 40% by weight, based on B.2, of other polymerizable, ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include Cj to Cg-
Alkylester. beispielsweise Methyl-, Ethyl-, Butyl-, n-Octyl- und 2-Ethylhexylester; Halgoenalkylester, vorzugsweise Halogen-C;*-Cg-alkylester, wie Chlorethylacrylat sowie Mischungen dieser Monomeren.Alkyl esters. for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halgoenalkyl esters, preferably halogen-C; * - Cg-alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
Bevorzugte "andere" polymerisierbare, ethylenisch ungesättigte Monomere, die neben den Acrylsäureestern gegebenenfalls zur Herstellung der Pfropfgrundlage B.2 dienen können, sind z. B. Acrylnitril, Styrol, α-Methylstyrol, Acrylamide, Vinyl-C-- C6-alkylether Methylmethacrylat, Butadien. Bevorzugte Acrylatkautschuke als Pfropfgrundlage B.2 sind Emulsionspolymerisate, die einen Gelgehalt von minde- stens 60 Gew.% aufweisen.Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base B.2 are, for. B. acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C-- C 6 alkyl ether methyl methacrylate, butadiene. Preferred acrylate rubbers as graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight.
Weitere geeignete Pfropfgrundlagen gemäß B.2 sind Silikonkautschuke mit pfropfaktiven Stellen, wie sie in den DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 und DE-A 3 631 539 beschrieben werden.Further suitable graft bases according to B.2 are silicone rubbers with graft-active sites, as described in DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631 539.
Besonders bevorzugt enthalten die Pfropfpolmere gemäß vorliegender Erfindung keine Pfropfgrundlagen (Kautschuke) auf Basis Ethylen/Propylen-Kautschuken (EPR) oder Ethylen/Propylen und nicht konjugiertem Dien (EPDM) wie sie z.B. in JP 11 24 10 16 A2 beschrieben sind. Der Gelgehalt der Pfropfgrundlage B.2 wird bei 25°C in einem geeigneten Lösungsmittel bestimmt (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I und U, Georg Thieme- Verlag, Stuttgart 1977).The graft polymers according to the present invention particularly preferably contain no graft bases (rubbers) based on ethylene / propylene rubbers (EPR) or ethylene / propylene and non-conjugated diene (EPDM), as described, for example, in JP 11 24 10 16 A2. The gel content of the graft base B.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and U, Georg Thieme-Verlag, Stuttgart 1977).
Die mittlere Teilchengröße dso ist der Durchmesser, oberhalb und unterhalb dessen jeweils 50 Gew.-% der Teilchen liegen. Er kann mittels Ultrazentrifugenmessung (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796) bestimmt werden.The average particle size dso is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-1796).
Die Komponente B kann, falls erforderlich und wenn dadurch die Kautschukeigenschaften der Komponente B.2 nicht beeinträchtigt werden, zusätzlich noch geringe Mengen, üblicherweise weniger als 5 Gew.-%, vorzugsweise weniger als 2 Gew.-%, bezogen auf B.2, vernetzend wirkender ethylenisch ungesättigter Monomeren enthalten. Beispiele für solche vernetzend wirkenden Monomere sind Ester ungesättigter Monocarbonsäuren mit 3 bis 8 C- Atomen und ungesättigter einwertiger Alkohole mitIf necessary and if this does not impair the rubber properties of component B.2, component B can additionally contain small amounts, usually less than 5% by weight, preferably less than 2% by weight, based on B.2, contain cross-linking ethylenically unsaturated monomers. Examples of such crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with
3 bis 12 C- Atomen, oder gesättigter Polyole mit 2 bis 4 OH-Gruppen und 2 bis 20 C- Atomen, mehrfach ungesättigte heterocyclische Verbindungen, polyfunktionelle Vinylverbindungen, wie Alkylendiol-di(meth)-acrylate, Polyester-di(meth)-acrylate, Divinylbenzol, Trivinylbenzol, Trivinylcyanurat, Triallylcyanurat, Allyl-(meth)- acrylat, Diallylmaleat, Diallylfumarat, Triallyphosphat und iallylphthalat.3 to 12 carbon atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, polyunsaturated heterocyclic compounds, polyfunctional vinyl compounds, such as alkylene diol di (meth) acrylates, polyester di (meth) - acrylates, divinylbenzene, trivinylbenzene, trivinylcyanurate, triallylcyanurate, allyl (meth) acrylate, diallyl maleate, diallyl fumarate, triallyphosphate and iallyl phthalate.
Bevorzugte vernetzende Monomere sind Allylmethacrylat, Emylenglykoldimethacry- lat, Diallylphthalat und heterocyclische Verbindungen, die mindestens drei ethylenisch ungesättigte Gruppen aufweisen.Preferred crosslinking monomers are allyl methacrylate, emylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least three ethylenically unsaturated groups.
Das kautschukmodifizierte Pfropfpolymerisat B wird im Falle der Herstellung mittels Masse- oder Lösungs- oder Masse-Suspensionspolymerisation erhalten durch Pf opfpolymerisation von 50 bis 99, bevorzugt 65 bis 98, besonders bevorzugt 75 bis 97 Gew.-Teilen eines Gemischs aus 50 bis 99, bevorzugt 60 bis 95 Gew.-Teilen Monomeren gemäß B.l.l und 1 bis 50, bevorzugt 5 bis 40 Gew.-Teilen Monomeren gemäß B.1.2 in Gegenwart von 1 bis 50, vorzugsweise 2 bis 35, besonders bevorzugt 2 bis 15, insbesondere 2 bis 13 Gew.-Teilen der Kautschukkomponente B.2.In the case of production by bulk or solution or bulk suspension polymerization, the rubber-modified graft polymer B is obtained by graft polymerization from 50 to 99, preferably 65 to 98, particularly preferably 75 to 97 parts by weight of a mixture of 50 to 99 60 to 95 parts by weight of monomers according to B1 and 1 to 50, preferably 5 to 40 parts by weight of monomers according to B.1.2 in the presence of 1 to 50, preferably 2 to 35, particularly preferably 2 to 15, in particular 2 to 13 parts by weight of the rubber component B.2.
Der mittlere Teilchendurchmesser d5Q der gepfropften Kautschukteilchen weist im Allgemeinen Werte von 0,05 bis 10 μm, vorzugsweise 0,1 bis 5 μm, besonders bevorzugt 0,2 bis 1 μm auf.The average particle diameter d 5 Q of the grafted rubber particles generally has values from 0.05 to 10 μm, preferably 0.1 to 5 μm, particularly preferably 0.2 to 1 μm.
Der mittlere Teilchendurchmesser d5o der resultierenden gepfropften Kautschukteilchen, die mittels Masse- oder Lösungs- oder Masse-Suspensionspolymerisations- verfahren erhältlich sind, (ermittelt durch Auszählung an elektronenmikroskopischenThe average particle diameter d 5 o of the resulting grafted rubber particles by bulk or solution or bulk-suspension polymerization method are available, (determined by counting on electron microscopy
Aufnahmen) liegt im Allgemeinen im Bereich von 0,5 bis 5 μm, vorzugsweise von 0,8 bis 2,5 μm.Recordings) is generally in the range from 0.5 to 5 μm, preferably from 0.8 to 2.5 μm.
Die Pfropfcopolymerisate können allein oder in beliebiger Mischung untereinander in Komponente B enthalten sein.The graft copolymers can be present in component B alone or in any mixture with one another.
Komponente B ist in der erfindungsgemäßen Polymer-Zusammensetzung vorzugsweise in einer Menge von 0,5 bis 50 Gew.-Teilen, besonders bevorzugt von 1 bis 40 Gew.-Teilen und ganz besonders bevorzugt von 1 bis 35 Gew.-Teilen enthalten.Component B is contained in the polymer composition according to the invention preferably in an amount of 0.5 to 50 parts by weight, particularly preferably 1 to 40 parts by weight and very particularly preferably 1 to 35 parts by weight.
Komponente CComponent C
Erfindungsgemäß geeignete mineralische Partikel sind anorganische Materialien mit schuppen- oder plättchenförmigem sowie faserfb'rmigem Charakter wie Talk, Glim- mer/Tonschichtmineralien, Montmorrilonit, letztere auch in einer durch Ionenaustausch modifizierten, organophilen Form, weiterhin Kaolin, Vermiculit und WollastonitMineral particles suitable according to the invention are inorganic materials with a flaky or platelet-like and fibrous character such as talc, mica / clay layer minerals, montmorrilonite, the latter also in an organophilic form modified by ion exchange, and furthermore kaolin, vermiculite and wollastonite
Besonders bevorzugt sind Talk und Wollastonit Unter Talk wird ein natürlich vorkommender oder synthetisch hergestellter Talk verstanden. Reiner Talk hat die chemische Zusammensetzung 3MgO4SiO2'H2O und somit einen MgO-Gehalt von 31,9 Gew.-%, einen SiO2-Gehalt von 63,4 Gew.-% und einen Gehalt an chemisch gebundenem Wasser von 4,8 Gew.-%. Es handelt sich um ein Silikat mit ScMchtstruktur.Talc and wollastonite are particularly preferred. Talc is understood to mean a naturally occurring or synthetically produced talc. Pure talc has the chemical composition 3MgO4SiO 2 'H 2 O and thus an MgO content of 31.9% by weight, an SiO 2 content of 63.4% by weight and a chemically bound water content of 4.8% by weight. It is a silicate with poor structure.
Besonders bevorzugt sind Talktypen hoher Reinheit. Diese enthalten beispielsweise einen MgO-Gehalt von 28 bis 35 Gew.-%, bevorzugt 30 bis 33 Gew.-%, besonders bevorzugt 30,5 bis 32 Gew.-% und einen SiO2-Gehalt von 55 bis 65 Gew.-%, bevorzugt 58 bis 64 Gew.-%, besonders bevorzugt 60 bis 62,5 Gew.-%. Bevorzugte Talktypen zeichnen sich des Weiteren durch einen Al2O3-Gehalt von < 5 Gew.-%, besonders bevorzugt von < 1 Gew.-%, insbesondere von < 0,7 Gew.-% aus.Talc types of high purity are particularly preferred. These contain, for example, an MgO content of 28 to 35% by weight, preferably 30 to 33% by weight, particularly preferably 30.5 to 32% by weight and an SiO 2 content of 55 to 65% by weight , preferably 58 to 64% by weight, particularly preferably 60 to 62.5% by weight. Preferred types of talc are further characterized by an Al 2 O 3 content of <5% by weight, particularly preferably <1% by weight, in particular <0.7% by weight.
Bevorzugte mineralische Partikel sind ferner auch solche mit anisotroper Partikelgeometrie. Darunter werden solche Teilchen verstanden, deren sogenanntes Aspekt- Verhältnis - Verhältnis aus größter und kleinster Partikeläbrnessung - größer als 1, vor- zugsweise größer als 2 und besonders bevorzugt größer als etwa 5 ist. Solche Teilchen sind zumindest im weitesten Sinne plättchen- oder faserformig. Zu solchen Materialien gehören beispielsweise bestimmte Talke und bestimmte (Alιιmino)Sili- -cate mit Schicht oder Fasergeometrie wie Bentonit, Wollastonit, Glimmer (Mica), Kaolin, Hydrotalcit, Hektorit oder Montmorillonit.Preferred mineral particles are also those with anisotropic particle geometry. These are understood to mean those particles whose so-called aspect ratio - the ratio of the largest and the smallest particle size - is greater than 1, preferably greater than 2 and particularly preferably greater than about 5. Such particles are at least in the broadest sense platelet-shaped or fibrous. Such materials include, for example, certain talcs and certain (alionimino) silicates with a layer or fiber geometry such as bentonite, wollastonite, mica (mica), kaolin, hydrotalcite, hectorite or montmorillonite.
-Vorteilhaft ist insbesondere auch der Einsatz von Talk in Form von feinvermahlenen Typen mit einer mittleren Teilchengröße d5o von < 10 μm, bevorzugt < 5 μm, besonders bevorzugt < 2,5 μm, ganz besonders bevorzugt < 1,5 μm. Insbesondere bevorzugt ist der Einsatz von Talk mit einer mittleren Teilchengröße d5o von 350 nm bis 1,5 μm.-Vorteilhaft particular, the use of talc in the form of finely ground types with an average particle size d o 5 microns of <10, preferably <5 micrometers, more preferably <2.5 microns, very preferably <1.5 microns. Especially preferred is the use of talc having an average particle size is d 5 o of 350 nm to 1.5 microns.
Bevorzugte Wollastonite haben ein mittleres Aspekt- Verhältnis von >6, insbesondere >7 und einen mittleren Faserdurchmesser von 1 bis 15 μm, bevorzugt 2 bis 10 μm, insbesondere von 4 bis 8 μm. Das mittlere Aspekt- Verhältnis im Sinne der Erfindung ist das Verhältnis der mittleren Länge der Faser zum mittleren Durchmesser.Preferred wollastonites have an average aspect ratio of> 6, in particular> 7 and an average fiber diameter of 1 to 15 μm, preferably 2 to 10 μm, in particular 4 to 8 μm. The average aspect ratio in the sense of the invention is the ratio of the average length of the fiber to the average diameter.
Teilchengröße und Teilchendurchmesser im Sinne dieser Erfindung bedeutet den mittleren Teilchendurchmesser d50, ermittelt durch Ultrazentrifugenmessungen nachParticle size and particle diameter in the sense of this invention means the average particle diameter d 50 , determined by ultracentrifuge measurements
W. Scholtan et al., Kolloid-Z. und Z. Polymere 250 (1972), S. 782-796.W. Scholtan et al., Kolloid-Z. and Z. Polymer 250 (1972), pp. 782-796.
Des Weiteren können die mineralischen Teilchen mit organischen Molekülen oberflächenmodifiziert, beispielsweise silanisiert, sein, um eine bessere Verträglichkeit mit den Polymeren zu erzielen. Auf diese Weise lassen sich hydrophobe oder hydrophile Oberflächen erzeugen.Furthermore, the mineral particles can be surface-modified with organic molecules, for example silanized, in order to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be created.
Wie in der US-A 5 091 461 beschrieben, eignen sich insbesondere längliche oder plattenfbrmige Materialien mit den angegebenen kleinen Teilchen, verglichen mit fibrillenformigen oder kugelförmigen Füllstoffen. Hoch bevorzugt sind solcheAs described in US Pat. No. 5,091,461, elongated or plate-like materials with the specified small particles are particularly suitable, compared to fibril-shaped or spherical fillers. Those are highly preferred
Zusammensetzungen, welche Partikel enthalten, die ein Verhältnis Durchschnittsdurchmesser/Dicke (D/T), gemessen nach der in der US-A 5 714 537 beschriebenen Weise von wenigstens 4, bevorzugt wenigstens 6, mehr bevorzugt wenigstens 7, haben. Hinsichtlich des Maximalwertes für das Verhältnis D/T wurde es als wün- sehenswert gefunden, einen Wert bis zu und einschließlich 30 zu haben, bevorzugt bis zu und einschließlich 24, mehr bevorzugt bis zu und einschheßlich 18, noch mehr bevorzugt bis zu und einschließlich 13 und am meisten bevorzugt bis zu und einschließlich 10.Compositions containing particles having an average diameter / thickness (D / T) ratio as measured in the manner described in US-A 5,714,537 of at least 4, preferably at least 6, more preferably at least 7. With regard to the maximum value for the ratio D / T, it was found desirable to have a value up to and including 30, preferably up to and including 24, more preferably up to and including 18, even more preferably up to and including 13 and most preferably up to and including 10.
Die mineralischen Partikel können als Pulver, Pasten, Sole Dispersionen oder Suspensionen vorliegen. Durch Ausfallen können aus Dispersionen, Sole oder Suspensionen Pulver erhalten werden.The mineral particles can be present as powders, pastes, brine dispersions or suspensions. By precipitation, powders can be obtained from dispersions, brine or suspensions.
Die Materialien können nach üblichen Verfahren in die thermoplastischen Form- massen eingearbeitet werden, beispielsweise durch direktes Kneten oder Extrudieren von Formmassen und den feinstteiligen anorganischen Pulvern. Bevorzugte Verfah- ren stellen die Herstellung eines Masterbatch, z.B. in Flammschutzadditiven und wenigstens einer Komponente der erfindungsgemäßen Formmassen in Monomeren oder Lösungsmitteln, oder die Cofällung von einer thermoplastischen Komponente und den feinstteihgen anorganischen Pulvern, z.B. durch Cofällung einer wässrigen Emulsion und den feinstteihgen anorganischen Pulvern dar, gegebenenfalls in Form von Dispersionen, Suspensionen, Pasten oder Solen der feinstteihgen anorganischen Materialien.The materials can be incorporated into the thermoplastic molding compositions by customary processes, for example by directly kneading or extruding molding compositions and the finely divided inorganic powders. Preferred procedure Ren represent the production of a masterbatch, for example in flame retardant additives and at least one component of the molding compositions according to the invention in monomers or solvents, or the co-precipitation of a thermoplastic component and the finely divided inorganic powders, for example by co-precipitation of an aqueous emulsion and the finely divided inorganic powders, optionally in Form of dispersions, suspensions, pastes or sols of the finest inorganic materials.
Beispiele für erfindungsgemäß bevorzugt als mineralische Partikel einsetzbare Sub- stanzen sind Tremin® 939-300EST der Quarzwerke GmbH, Frechen, DeutschlandExamples of substances which can preferably be used according to the invention as mineral particles are Tremin® 939-300EST from Quarzwerke GmbH, Frechen, Germany
(aminosilan-beschichtetes Wollastonit mit einem mittleren Nadeldurchmesser von 3 μm), Finntalc® M30SL der Omya GmbH, Köln, Deutschland (imbeschichteter Talk mit einer Partikelgröße d5o = 8,5 μm) Wicroll® 40PA der Omya GmbH, Köln, Deutschland (silanisierter Wollastonit mit einer Partikelgröße d50 = 1,3 μm) sowie Burgess® 2211 der Omya GmbH, Köln, Deutschland (aminosilan-beschichtetes(aminosilane-coated wollastonite with an average needle diameter of 3 μm), Finntalc® M30SL from Omya GmbH, Cologne, Germany (coated talc with a particle size d 5 o = 8.5 μm) Wicroll® 40PA from Omya GmbH, Cologne, Germany ( silanized wollastonite with a particle size d 50 = 1.3 μm) and Burgess ® 2211 from Omya GmbH, Cologne, Germany (aminosilane-coated
Aluminiumsilikat mit einer Partikelgröße d50 = 1,3 μm), Naintsch A3 (siehe Beispiele, Komponente CI), Nyglos® 4-10013 (Siehe Beispiele C2).Aluminum silicate with a particle size d 50 = 1.3 μm), Naintsch A3 (see examples, component CI), Nyglos ® 4-10013 (see examples C2).
Die mineralischen Partikel der Komponente C können in der erfindungsgemäßen Zu- sammensetzung in einer Menge von vorzugsweise bis zu 30 Gew.-Teilen, besonders bevorzugt bis zu 20 Gew.-Teilen und, falls enthalten, bevorzugt von 1,5 bis 13 Gew.-Teilen, enthalten sein.The mineral particles of component C can be present in the composition according to the invention in an amount of preferably up to 30 parts by weight, particularly preferably up to 20 parts by weight and, if present, preferably from 1.5 to 13 parts by weight. Share, be included.
Komponente DComponent D
Als Komponente D) können die Zusammensetzungen erfindungsgemäß teilchen- förmige Kohlenverbindungen wie Ruß, der zur Herstellung von Leitfähigkeit geeignet ist und vom Fachmann auch als Leitfahigkeitsruß bezeichnet wird, Graphitpulver und/oder Kohlenstoff-Nanofibrillen enthalten. Bei Graphitpulvern handelt es sich im Sinne der vorliegenden Erfindung um zerkleinerten Graphit. Unter Graphit versteht der Fachmann eine Modifikation des Kohlenstoffs wie sie beispielweise in A.F. Hollemann, E. Wieberg, N. Wieberg, „Lehrbuch der anorganischen Chemie", 91.-100. Aufl., S. 701-702 beschrieben ist. Graphit besteht aus planaren Kohlenstoffschichten, die übereinander angeordnet sind.As component D), the compositions according to the invention can contain particulate carbon compounds such as carbon black, which is suitable for producing conductivity and is also referred to by the person skilled in the art as conductivity black, graphite powder and / or carbon nanofibrils. For the purposes of the present invention, graphite powders are comminuted graphite. The person skilled in the art understands graphite as a modification of the carbon as described, for example, in AF Hollemann, E. Wieberg, N. Wieberg, “Textbook of Inorganic Chemistry”, 91st-100th ed., Pp. 701-702. Graphite consists of planar carbon layers arranged one above the other.
Graphit kann erfindungsgemäß beispielsweise durch Mahlen zerkleinert werden. Die Partikelgröße liegt im Bereich von bis 0,1 μm - 1 mm, bevorzugt im Bereich von 1 bis 300 μm, am meisten bevorzugt im Bereich von 2 bis 20 μm.According to the invention, graphite can be comminuted, for example, by grinding. The particle size is in the range from 0.1 μm to 1 mm, preferably in the range from 1 to 300 μm, most preferably in the range from 2 to 20 μm.
Bei erfindungsgemäßen Leitfähigkeitsrußen hegt die Primärteilchengröße zwischenIn the case of conductivity blacks according to the invention the primary particle size lies between
0,005 und 0,2 μm, bevorzugt zwischen 0,01 und 0,1 μm. Die Dibutylphthalat- Adsorption der Leitfähigkeitsruße liegt zwischen 40 und 1000ml pro 100g Ruß, bevorzugt zwischen 90 und 600 ml pro 100g Ruß. Auf der Rußoberfläche können eine Vielzahl von sauerstoffhaltigen Gruppen, wie zum Beispiel Carboxyl-, Lactol-, Phenolgruppen, chinoide Carbonylgruppen und/oder Pyronstrukturen befinden.0.005 and 0.2 μm, preferably between 0.01 and 0.1 μm. The dibutyl phthalate adsorption of the conductivity carbon blacks is between 40 and 1000 ml per 100 g of carbon black, preferably between 90 and 600 ml per 100 g of carbon black. A large number of oxygen-containing groups, such as, for example, carboxyl, lactol, phenol groups, quinoid carbonyl groups and / or pyrone structures, can be located on the surface of the carbon black.
Leitfähigkeitsruße können beispielsweise aus Acetylen, aus Synthesegas oder aus dem Furnace-Process aus Öl, Trägergase und Luft „hergestellt werden. Herstellungsprozesse sind beispielsweise in R.G. Gilg, „Ruß für leitfähige Kunststoffe " in: Elektrisch leitende Kunststoffe, Hrsg.: H.J. Mair, S. Roth, 2. Aufl., Carl HanserConductivity carbon blacks can be produced from acetylene, from synthesis gas or from the furnace process from oil, carrier gases and air. Manufacturing processes are described, for example, in R.G. Gilg, "Carbon black for conductive plastics" in: Electrically conductive plastics, ed .: H.J. Mair, S. Roth, 2nd ed., Carl Hanser
Verlag, 1989, München, Wien, S. 21 - 36 und darin zitierter Literatur beschrieben.Verlag, 1989, Munich, Vienna, pp. 21 - 36 and the literature cited therein.
Die Zugabe der erfindungsgemäßen Ruße und/oder Graphite kann vor, während oder nach der Polymerisation der Monomere zum Thermoplasten der Komponte A) erfolgen. Erfolgt die Zugäbe der erfindungsgemäßen Ruße und oder Graphite nach derThe carbon blacks and / or graphites according to the invention can be added before, during or after the polymerization of the monomers to give the thermoplastics of component A). The additions of the carbon black and or graphite according to the invention are carried out according to the
Polymerisation, so erfolgt sie vorzugsweise durch Zugäbe zur Thermoplastenschmelze in einem Extruder oder in einem Kneter. Erfindungsgemäß können die Ruße und/oder Graphite auch als hochkonzentrierte Masterbatche in Thermoplasten, die bevorzugt aus der Gruppe der als Komponente A) eingesetzten Thermoplaste gewählt werden, zudosiert werden. Die Konzentration der Ruße und/oder Graphite des in den Master- batchen liegt im Bereich von 5 bis 70, bevorzugt 8 bis 50, besonders bevorzugt im Bereich von 12 bis 30 Gew.-% (bezogen auf das Masterbatch). Erfindungsgemäß können die Ruße und/oder Graphite zur besseren Dosierbarkeit auch mit Bindemitteln wie beispielsweise Wachsen, Fettsäureestern oder Polyolefinen versetzt sein. Erfindungsgemäß können die Ruße und/oder Graphite auch mit oder ohne zusätzlichen Bmdemittehi beispielsweise durch Press- oder Druckverfahren pelletisiert oder granuliert sein, was ebenfalls der besseren Dosierbarkeit dient.Polymerization, it is preferably carried out by additions to the thermoplastic melt in an extruder or in a kneader. According to the invention, the carbon blacks and / or graphites can also be metered in as highly concentrated masterbatches in thermoplastics, which are preferably chosen from the group of thermoplastics used as component A). The concentration of the carbon blacks and / or graphites in the masterbatches is in the range from 5 to 70, preferably 8 to 50, particularly preferably in Range from 12 to 30 wt .-% (based on the masterbatch). According to the invention, the carbon blacks and / or graphites can also be mixed with binders such as waxes, fatty acid esters or polyolefins for better meterability. According to the invention, the carbon blacks and / or graphites can also be pelletized or granulated with or without additional additives, for example by pressing or printing processes, which likewise serves to improve meterability.
Erfindungsgemäße Kohlenstoff-Nanofibrillen haben typischerweise die Form von Röhren, die aus Graphit-Schichten gebildet werden. Die Graphitlagen sind in kon- zentrischer Art um die Zylinderachse angeordnet.Carbon nanofibrils according to the invention typically have the form of tubes which are formed from graphite layers. The graphite layers are arranged in a concentric manner around the cylinder axis.
Kohlenstoff-Nanofibrillen haben einen Längen-zu-Durchmesserverhältms von wenigstens 5, vorzugsweise von mindestens 100, besonders bevorzugt von mindestens 1000. Der Durchmesser der Nanofibrillen liegt typischerweise im Bereich von 0,003 bis 0,5 μm, vorzugsweise im Bereich von 0,005 bis 0,08 μm, besonders bevorzugt im Bereich von 0,006 bis 0,05 μm. Die Länge der Kohlenstoff-Nanofibrillen beträgt typischerweise 0,5 bis 1000 μm, vorzugsweise 0,8 bis 100 μm, besonders bevorzugt 1 bis 10 μm. Die Kohlenstoff-Nanofibrillen besitzen einen hohlen, zylinderförmigen Kern, um den die Graphitlagen formal gewickelt sind. Dieser Hohlraum hat typischerweise einen Durchmesser von 0,001 bis 0,1 μm, bevorzugt einen Durchmesser von 0,008 bis 0,015 μm. In einer typischen Ausführungsform der Kohlenstoff-Nanofibrillen besteht die Wand der Fibrille um den Hohlraum beispielsweise aus 8 Graphitlagen. Die Kohlenstoff-Nanofibrillen können dabei als Aggregate von bis zu 1000 μm Durchmesser, vorzugsweise bis zu 500 μm Durchmesser aus mehreren Nanofibrillen vorliegen. Die Aggregate können die Form von Vogelnestern, von gekämmtem Garn oder von offenen Netzstrukturen besitzen.Carbon nanofibrils have a length-to-diameter ratio of at least 5, preferably at least 100, particularly preferably at least 1000. The diameter of the nanofibrils is typically in the range from 0.003 to 0.5 μm, preferably in the range from 0.005 to 0.08 μm, particularly preferably in the range from 0.006 to 0.05 μm. The length of the carbon nanofibrils is typically 0.5 to 1000 μm, preferably 0.8 to 100 μm, particularly preferably 1 to 10 μm. The carbon nanofibrils have a hollow, cylindrical core around which the graphite layers are formally wrapped. This cavity typically has a diameter of 0.001 to 0.1 μm, preferably a diameter of 0.008 to 0.015 μm. In a typical embodiment of the carbon nanofibrils, the wall of the fibril around the cavity consists, for example, of 8 graphite layers. The carbon nanofibrils can be present as aggregates of up to 1000 μm in diameter, preferably up to 500 μm in diameter, of several nanofibrils. The aggregates can take the form of bird nests, combed yarn or open net structures.
Die Zugäbe der Kohlenstoff-Nanofibrillen kann vor, während oder nach der Polymerisation der Monomere zum Thermoplasten der Komponente A) erfolgen. Erfolgt die Zugabe der erfindungsgemäßen Nanofibrillen nach der Polymerisation, so erfolgt sie vorzugsweise durch Zugäbe zur Thermoplastenschmelze in einem Extruder oder in einem Kneter. Durch den Compoundiervorgang im Kneter oder Extruder können insbesondere die bereits beschriebenen Aggregate weitgehend oder sogar vollständig zerkleinert werden und die Kohlenstoff-Nanofibrillen in der Thermoplastenmatrix disper- giert werden.The carbon nanofibrils can be added before, during or after the polymerization of the monomers to give thermoplastics of component A). If the nanofibrils according to the invention are added after the polymerization, they are preferably added to the thermoplastic melt in an extruder or in a kneader. By means of the compounding process in the kneader or extruder, the aggregates already described can in particular be largely or even completely crushed and the carbon nanofibrils can be dispersed in the thermoplastic matrix.
In einer bevorzugten Ausführungsform können die Kohlenstoff-Nanofibrillen als hochkonzentrierte Masterbatche in Thermoplasten, die bevorzugt aus der Gruppe der als Komponente A) eingesetzen Thermoplaste gewählt werden, zudosiert werden. Die Konzentration der Kohlenstoff-Nanofibrillen in den Masterbatchen liegt im Bereich von 5 bis 50, bevorzugt 8 bis 30, besonders bevorzugt im Bereich von 12 bis 22 Gew.-In a preferred embodiment, the carbon nanofibrils can be metered in as highly concentrated masterbatches in thermoplastics, which are preferably selected from the group of thermoplastics used as component A). The concentration of the carbon nanofibrils in the masterbatches is in the range from 5 to 50, preferably 8 to 30, particularly preferably in the range from 12 to 22% by weight.
%. Die Herstellung von Masterbatchen ist beispielsweise in US-A 5 643 502 beschrieben. Durch den Einsatz von Masterbatchen kann insbesondere die Zerkleinerung der Aggregate verbessert werden. Die Kohlenstoff-Nanofibrillen können bedingt durch die Verarbeitung zur Formmasse bzw. Formkörper in der Formmasse bzw. im Formkörper kürzere Längenverteilungen als ursprünglich eingesetzt aufweisen.%. The production of masterbatches is described, for example, in US Pat. No. 5,643,502. The use of masterbatches can particularly improve the size reduction of the aggregates. The carbon nanofibrils can have shorter length distributions than originally used due to the processing into the molding composition or molding in the molding composition or in the molding.
In einer bevorzugten Ausführungsform können auch Mischungen aus den einzelnen Komponenten verwendet werden.In a preferred embodiment, mixtures of the individual components can also be used.
Erfindungsgemäße Leitfähigkeitsruße können beispielsweise unter dem Namen Ketjenblack® von der Fa AKZO Nobel, unter dem Namen Vulcan® von der Fa. Cabot oder unter dem Namen Printex® von der Fa. Degussa bezogen werden.Conductivity invention, for example, under the name Ketjenblack ® by the company AKZO Nobel, under the name Vulcan ® by the company. Cabot or under the name Printex ® by the company. Degussa be obtained.
Erfindungsgemäße Graphite können als Pulver beispielsweise von der Fa. Vogel &Graphites according to the invention can be used as powders, for example from Vogel &
Prenner Nachf., Wiesbaden, Deutschland bezogen werden.Prenner Nachf., Wiesbaden, Germany.
Kohlenstoff-Nanofibrillen werden beispielsweise von der Fa. Hyperion Catalysis oder der Fa. Applied Sciences Inc. angeboten. Die Synthese der Kohlenstoff-Nano- fibrillen erfolgt beispielsweise in einem Reaktor, der ein Kohlenstoff enthaltendes Gas und einen Metallkatalysator enthält, wie es z.B. in US-A 5 643 502 beschrieben wird.Carbon nanofibrils are offered, for example, by Hyperion Catalysis or Applied Sciences Inc. The carbon nanofibrils are synthesized, for example, in a reactor which contains a carbon Contains gas and a metal catalyst, as described for example in US-A 5 643 502.
Komponente EComponent E
Bevorzugte Polyester-ether-Blockcopolymere enthalten das Reaktionsprodukt von Ethylenglykol, Terephthalsäure oder Dimethylterephthalat und Polyethylenglykol. Polyester-ether-Copolymere sind beispielsweise in Encyclopedia of Polymer Science and Engineering, Vol. 12, John Wiley & Sons, Inc., N.Y., 1988, Seiten 49-52 beschrieben.Preferred polyester-ether block copolymers contain the reaction product of ethylene glycol, terephthalic acid or dimethyl terephthalate and polyethylene glycol. Polyester ether copolymers are described, for example, in Encyclopedia of Polymer Science and Engineering, Vol. 12, John Wiley & Sons, Inc., N.Y., 1988, pages 49-52.
Bevorzugte Polyetheresteramide sind Blockcopolymere, in dem die Polyether- Segmente Polyethylenglykol-Einheiten mit einem Molekulargewicht Mn von 200 bis 6 000 Dalton sind und die Polyamid-Segmente ein Molekulargewicht Mn im Allgemeinen von 200 bis 6000 Dalton aufweisen. Das Blockcopolymer enthält vorzugsweise 4 bis 14 Polyamid-Segemente. Geeignete Polyetheresteramide sind beispielsweise in EP-A 613 919 beschrieben. Als Polyamide-Segmente kommen die bei der Beschreibung der Komponente A) genannten Polyamide in Frage.Preferred polyether ester amides are block copolymers in which the polyether segments are polyethylene glycol units with a molecular weight M n of 200 to 6,000 daltons and the polyamide segments have a molecular weight M n generally of 200 to 6,000 daltons. The block copolymer preferably contains 4 to 14 polyamide segments. Suitable polyether ester amides are described, for example, in EP-A 613 919. The polyamides mentioned in the description of component A) are suitable as polyamide segments.
Die Polymere gemäß Komponente E) werden vorzugsweise in Form von antistatischen Zubereitungen, die beispielsweise zusätzlich- anorganische oder organische Salze enthalten können, eingesetzt. Solche antistatischen Zubereitungen oder antistatischen Mittel sind u.a. in WO 02/055411 und US-A 5,965,206 sowie den darin zitierten Referenzen beschrieben.The polymers according to component E) are preferably used in the form of antistatic preparations, which for example may additionally contain inorganic or organic salts. Such antistatic preparations or antistatic agents include in WO 02/055411 and US-A 5,965,206 and the references cited therein.
WO 02/055411 und US-A 5,965,206 werden explizit als Offenbarung in die vorliegende Anmeldung aufgenommen.WO 02/055411 and US-A 5,965,206 are explicitly included as a disclosure in the present application.
Solche antistatischen Zusammensetzungen sind z.B. unter den Namen hgastat® P 18 und Irgastat® P 22 kommerziell bei der Ciba Specialty Chemicals Company erhältlich. Antistatische Mischungen bzw. Zubereitungen enthalten vorzugsweise anorganische Salze ausgewählt aus der Gruppe bestehend aus LiQO , LiCF33, NaQO4, LiBF4, NaBF4, KBF4, NaCF3SO3, KClO4, KPF6, KCF3SO3, KC4F9SO3, Ca(ClO4)2, Ca(PF6)2, Mg(ClO4)2, Mg(CF3SO3)2, Zn(ClO4)2, Zn(PF6)2 oder Ca(CF3SO3)2, die im Allgemeinen im Polyetheresteramid, Polyether-Ester-Blockcopolymeren bzw.Such anti-static compositions are, for example under the names hgastat ® P 18 and P 22 Irgastat ® commercially available from Ciba Specialty Chemicals Company. Antistatic mixtures or preparations preferably contain inorganic salts selected from the group consisting of LiQO, LiCF 33 , NaQO 4 , LiBF 4 , NaBF 4 , KBF 4 , NaCF 3 SO 3 , KClO 4 , KPF 6 , KCF 3 SO 3 , KC4F 9 SO 3 , Ca (ClO 4 ) 2 , Ca (PF 6 ) 2 , Mg (ClO 4 ) 2 , Mg (CF 3 SO 3 ) 2 , Zn (ClO 4 ) 2 , Zn (PF 6 ) 2 or Ca (CF 3 SO 3 ) 2 , which are generally used in polyether ester amide, polyether ester block copolymers or
Polyamid-Polyetherblockcopolymere oder Mischungen hieraus komplexiert oder solvatisiert vorliegen.Polyamide-polyether block copolymers or mixtures thereof are complexed or solvated.
Geeignete organische Salze sind vorzugsweise ausgewählt aus organischen Zink-, Barium-, Cadmium-, Aluminium-, Calcium-, Magnesium- oder einem seltenenSuitable organic salts are preferably selected from organic zinc, barium, cadmium, aluminum, calcium, magnesium or a rare one
Erdmetall-Salzen, mit aliphatischen gesättigten C -C22-Carboxylaten, aliphatischen ungesättigten C3-C22-Carboxylaten, aliphatischen C2-C2 -Carboxylaten, welche durch mindestens eine Hydroxyl-Gmppe substituiert sind oder deren Kette durch mindestens ein Sauerstoff- Atom unterbrochen ist, femer cyclischen oder bicyclischen C5-C22-Carboxylaten, jeweils unsubstiruiertes oder durch mindestens eine OH-Earth metal salts, with aliphatic saturated C -C 2 carboxylates, aliphatic unsaturated C 3 -C 22 carboxylates, aliphatic C 2 -C 2 carboxylates which are substituted by at least one hydroxyl group or whose chain is substituted by at least one oxygen atom is interrupted, further cyclic or bicyclic C5-C22 carboxylates, respectively unsubstiruiertes or by at least one OH
Gruppe und/oder Cj-Cig-Alkyl substituiertes Phenylcarboxylat, Phenyl-Ci-Cig- alkylcarboxylat, Naphthyl-Ci-Cig-alkylcarboxylat oder unsubstituiertes oder durch rCi2-Alkyl substituiertes Phenolat. Mischungen dieser Salze sind ebenfalls geeignet.Group and / or C j -Cig-alkyl substituted phenyl carboxylate, phenyl-Ci-Cig-alkyl carboxylate, naphthyl-Ci-Cig-alkyl carboxylate or unsubstituted or substituted by rCi 2 alkyl. Mixtures of these salts are also suitable.
Besonders bevorzugte antistatische Zubereitungen sind Mischungen enthaltendMixtures containing particularly preferred antistatic preparations
1. ein organisches faserformiges oder faserbildendes Polymer wie Polyamid, Copolyamid, Polyester, Polyvinylacetat, Polyvinylalkohol, Polyacryl- säureester, modifizierte Cellulose, und weiterhin solche, die in US-1. an organic fibrous or fiber-forming polymer such as polyamide, copolyamide, polyester, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid ester, modified cellulose, and furthermore those which are described in US
A 5,965,206, Spalte 6, Zeile 10 bis 17 aufgezählt sind. Als faserformiges Material wird bevorzugt Polyester, Polyamid 4,6, Polyamid 6,6, Polyamid 6 oder Copolyamid 6/6,6 eingesetzt.A 5,965,206, column 6, lines 10 to 17 are listed. Polyester, polyamide 4.6, polyamide 6.6, polyamide 6 or copolyamide 6 / 6.6 are preferably used as the fibrous material.
2. die als Komponente E) genannten Copolymere und 3. oben genannte organische oder anorganische Salze oder Mischungen davon.2. the copolymers mentioned as component E) and 3. The above-mentioned organic or inorganic salts or mixtures thereof.
Komponente FComponent F
Als Verträghchkeitsvermittler werden vorzugsweise thermoplastische Polymere mit polaren Gruppen eingesetzt.Thermoplastic polymers with polar groups are preferably used as compatibilizers.
Erfindungsgemäß kommen dem gemäß Polymere zum Einsatz, dieAccording to the invention, polymers are used that
F.l ein vinylaromatisches Monomer,F.l a vinyl aromatic monomer,
F.2 wenigstens ein Monomer ausgewählt aus der Gruppe C2 bis C12-Alkyl- methacrylate, C2 bis C12-Alkylacrylate, Methacrylnitrile und Acrylnitrile undF.2 at least one monomer selected from the group C 2 to C 12 alkyl methacrylates, C 2 to C 12 alkyl acrylates, methacrylonitriles and acrylonitriles and
F.3 α,ß-ungesättigte Komponenten enthaltend Dicarbonsäureanhydride enthalten.F.3 contain α, β-unsaturated components containing dicarboxylic anhydrides.
Als vinylaromatische Monomere F.l ist Styrol besonders bevorzugt.Styrene is particularly preferred as vinyl aromatic monomer F.l.
Für die Komponente F.2 ist besonders bevorzugt Acrylnitril.Acrylonitrile is particularly preferred for component F.2.
Für α,ß-ungesättigte "Komponenten enthaltend Dicarbonsäureanhydride F.3 ist besonders bevorzugt Maleinsäureanhydrid.Maleic anhydride is particularly preferred for α, β-unsaturated "components containing dicarboxylic anhydrides F.3.
Vorzugsweise werden als Komponente F.l, F.2 und F.3 Terpolymere der genannten Monomeren eingesetzt. Demgemäß kommen vorzugsweise Terpolymere von Styrol,Terpolymers of the monomers mentioned are preferably used as component F.l, F.2 and F.3. Accordingly, terpolymers of styrene preferably
Acrylnitril und Maleinsäureanhydrid zum Einsatz. Diese Terpolymere tragen insbesondere zur Verbesserung der mechanischen Eigenschaften, wie Zugfestigkeit und Reißdehnung bei. Die Menge an Malemsäureanhydrid in dem Terpolymer kann in weiten Grenzen schwanken. Vorzugsweise beträgt die Menge 0,2 bis 5 Mol%. Besonders bevorzugt sind Mengen zwischen 0,5 und 1,5 Mol%. In diesem Bereich werden besonders gute mechanische Eigenschaften bezüglich Zugfestigkeit und Reißdehnung erzielt.Acrylonitrile and maleic anhydride are used. These terpolymers contribute in particular to improving the mechanical properties, such as tensile strength and elongation at break. The amount of maleic anhydride in the terpolymer can vary within wide limits. The amount is preferably 0.2 to 5 mol%. Amounts between 0.5 and 1.5 mol% are particularly preferred. In this area particularly good mechanical properties with regard to tensile strength and elongation at break are achieved.
Das Terpolymer kann in an sich bekannter Weise hergestellt werden. Eine geeignete Methode ist das Lösen von Monomerkomponenten des Terpolymers, z.B. desThe terpolymer can be produced in a manner known per se. A suitable method is to dissolve monomer components of the terpolymer, e.g. of
Styrols, Maleinsäureanhydrids oder Acrylnitrils in einem geeigneten Lösemittel, z.B. Methylethylketon (MEK). Zu dieser Lösung werden ein oder gegebenenfalls mehrere chemische Initiatoren hinzugesetzt. Geeignete Initiatoren sind z.B. Peroxide. Sodann wird das Gemisch für mehrere Stunden bei erhöhten Temperaturen polymerisiert. Anschließend werden das Lösemittel und die nicht umgesetzten Monomere in an sich bekannter Weise entfernt.Styrene, maleic anhydride or acrylonitrile in a suitable solvent, e.g. Methyl ethyl ketone (MEK). One or optionally several chemical initiators are added to this solution. Suitable initiators are e.g. Peroxides. The mixture is then polymerized for several hours at elevated temperatures. The solvent and the unreacted monomers are then removed in a manner known per se.
Das Verhältnis zwischen der Komponente F.l (vinylaromatisches Monomer) und der Komponente F.2, z.B. dem Acrylnitrilmonomer in dem Terpolymer liegt vorzugs- weise zwischen 80:20 und 50:50. Um die Mischbarkeit des Terpolymers mit demThe ratio between component F.l (vinyl aromatic monomer) and component F.2, e.g. the acrylonitrile monomer in the terpolymer is preferably between 80:20 and 50:50. To determine the miscibility of the terpolymer with the
Pfropfcopolymer B zu verbessern, wird vorzugsweise eine Menge an vinylaroma- tischen Monomer F.l ausgewählt, die der Menge des Vinylmonomeren B.l in dem Pf opfcopolymer B entspricht.To improve graft copolymer B, an amount of vinyl aromatic monomer F.l is preferably selected which corresponds to the amount of vinyl monomer B.l in graft copolymer B.
Beispiele für erfindungsgemäß einsetzbare Verträglichkeitsverrnittler F sind in denExamples of compatibilizers F which can be used according to the invention are shown in FIGS
EP-A 785 234 und EP-A- 202 214 beschrieben. Erfindungsgemäß bevorzugt sind insbesondere die in der EP-A 785 234 genannten Polymere.EP-A 785 234 and EP-A-202 214. According to the invention, particular preference is given to the polymers mentioned in EP-A 785 234.
Die Verttäglichkeitsvermittler können in Komponente F allein oder in beliebiger Mi- schung untereinander enthalten sein.Compatibility mediators can be contained in component F alone or in any mixture with one another.
Eine weitere, als Verträglichkeitsvermittler besonders bevorzugte Substanz ist ein Terpolymer von Styrol und Acrylnitril im Gewichts Verhältnis 2,1:1 enthaltend 1 Mol% Maleinsäureanhydrid. Die Menge der Komponente F in den erfindungsgemäßen Polymer-Zusammensetzungen liegt vorzugsweise zwischen 0,5 und 30 Gew.-Teilen, insbesondere zwischen 1 und 20 Gew.-Teilen und besonders bevorzugt zwischen 2 und 10 Gew.- Teilen. Höchst bevorzugt sind Mengen zwischen 3 und 7 Gew.-Teilen.Another substance which is particularly preferred as a compatibilizer is a terpolymer of styrene and acrylonitrile in a weight ratio of 2.1: 1 containing 1 mol% of maleic anhydride. The amount of component F in the polymer compositions according to the invention is preferably between 0.5 and 30 parts by weight, in particular between 1 and 20 parts by weight and particularly preferably between 2 and 10 parts by weight. Amounts between 3 and 7 parts by weight are most preferred.
Komponente GComponent G
Die Komponente G umfasst ein oder mehrere thermoplastische Vinyl(Co)Polymeri- sate.Component G comprises one or more thermoplastic vinyl (co) polymers.
Geeignete Vinyl(Co)Polymerisate für Komponente G sind Polymerisate von mindestens einem Monomeren aus der Gruppe der Vinylaromaten, Vinylcyanide (ungesättigte Nitrile), (Meth)Acrylsäure-(Cι-C8)-Alkylester, ungesättigte Carbonsäuren sowie Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren. Insbesondere geeignet sind (Co)Polymerisate ausSuitable vinyl (co) polymers for component G are polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C 1 -C 8 ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides ) unsaturated carboxylic acids. (Co) polymers of are particularly suitable
G.l 50 bis 99, vorzugsweise 60 bis 80 Gew.-Teilen Vinylaromaten und/oder kernsübstituierten Vinylaromaten (wie Styrol, α-Methylstyrol, p-Methyl- styrol, p-Chlorstyrol) und/oder Methacrylsäure-(Cι-C8)-Alkylester (wie Methylmethacrylat, Ethylmethacrylat), undGl 50 to 99, preferably 60 to 80 parts by weight of vinyl aromatics and / or core-substituted vinyl aromatics (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (-CC 8 ) alkyl esters (such as methyl methacrylate, ethyl methacrylate), and
G.2 1 bis 50, vorzugsweise 20 bis 40 Gew.-Teilen Vinylcyanide (ungesättigteG.2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated
Nitrile) wie Acrylnitril und Methacrylnitril und/oder (Meth)Acrylsäure-Nitriles) such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid
(C--C8)-Alkylester (wie Methylmethacrylat, n-Butylacrylat, tert.-Butyl- acrylat) und/oder Imide ungesättigter Carbonsäuren (z.B. N-Phenylmalein- imid).(C - C 8 ) alkyl esters (such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and / or imides of unsaturated carboxylic acids (eg N-phenylmaleimide).
Die (Co)Polymerisate G sind harzartig, thermoplastisch und kautschukfrei.The (co) polymers G are resin-like, thermoplastic and rubber-free.
Besonders bevorzugt ist das Copolymerisat aus G.l Styrol und G.2 Acrylnitril. Die (Co)Polymerisate G sind bekannt und lassen sich durch radikalische Polymerisation, insbesondere durch Emulsions-, Suspensions-, Lösungs- oder Massepolymerisation herstellen. Die (Co)Polymerisate besitzen vorzugsweise mittlere Molekulargewichte Mw (Gewichtsmittel, ermittelt durch Lichtstreuung oder Sedimentation) zwischen 15 000 und 200 000.The copolymer of Gl styrene and G.2 acrylonitrile is particularly preferred. The (co) polymers G are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co) polymers preferably have average molecular weights Mw (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
Die Vinyl(Co)Polymerisate können in Komponente G allein oder in beliebiger Mischung untereinander enthalten sein.The vinyl (co) polymers can be contained in component G alone or in any mixture with one another.
Die Komponente G ist in der Polymer-Zusammensetzung vorzugsweise in einerComponent G is preferably in one in the polymer composition
Menge von 0 bis 30 Gew.-Teilen, insbesondere von 0 bis 25 Gew.-Teilen und besonders bevorzugt von 0 bis 20 Gew.-Teilen, insbesondere 0,5 bis 10 Gew.-Teilen enthalten.Contain amount of 0 to 30 parts by weight, in particular from 0 to 25 parts by weight and particularly preferably from 0 to 20 parts by weight, in particular 0.5 to 10 parts by weight.
Komponente HComponent H
Erfindungsgemäße Phenol-Formaldehyd-Harze werden durch Kondensationsreaktion aus Phenolen mit Aldehyden, bevorzugt Formaldehyd, durch Derivatisierung der dabei resultierenden Kondensate oder durch Addition von Phenolen an ungesättigten Verbindungen, wie z.B. Acetylen, Terpene etc. hergestelltPhenol-formaldehyde resins according to the invention are obtained by condensation reaction from phenols with aldehydes, preferably formaldehyde, by derivatization of the resulting condensates or by addition of phenols to unsaturated compounds, e.g. Acetylene, terpenes etc. produced
Die Kondensation kann dabei sauer oder basisch erfolgen und das Molverhältnis von Aldehyd zu Phenol von 1:0,4 bis 1:2,0 betragen. Hierbei fallen Oligomere bzw. Polymere mit einer Molmasse von 150 - 5000 g/Mol an. Die Harze sind bekannt oder nach literaturbekannten Verfahren herstellbar.The condensation can be acidic or basic and the molar ratio of aldehyde to phenol can be from 1: 0.4 to 1: 2.0. This produces oligomers or polymers with a molar mass of 150-5000 g / mol. The resins are known or can be prepared by processes known from the literature.
Bevorzugt enthalten die Zusammensetzungen Phenol-Formaldeyd-Harze, die im Allgemeinen in einer Menge von bis zu 15 Gew.-Teilen, vorzugsweise 1 bis 12 und insbesondere 2 bis 8 Gew.-Teile, zugesetzt werden. Komponente JThe compositions preferably contain phenol-formaldehyde resins which are generally added in an amount of up to 15 parts by weight, preferably 1 to 12 and in particular 2 to 8 parts by weight. Component J
Die erfindungsgemäßen Polymer-Zusammensetzungen können übliche Additive, wie Flammschutzmittel, Anti-Dripping-Mittel, Füll- und Verstärkungsstoffe, verschieden von Komponente C und D, Gleit- und. Entformungsmittel, Nukleierungsmittel,The polymer compositions according to the invention can contain conventional additives, such as flame retardants, anti-dripping agents, fillers and reinforcing materials, different from components C and D, lubricants and. Mold release agents, nucleating agents,
Antistatika, verschieden von Komponente E, Stabilisatoren sowie Farbstoffe und Pigmente enthalten.Contain antistatic agents, different from component E, stabilizers as well as dyes and pigments.
Die erfindungsgemäßen Zusammensetzungen können im Allgemeinen 0,01 bis 20 Gew.-%, bezogen auf die Gesamt-Zusammensetzung, Flammschutzmittel enthalten. Beispielhaft werden als Flammschutzmittel organische Halogenverbindungen wie Decabrombisphenylether, Teträbrombisphenol, anorganische Halogenverbindungen wie Ammoniumbromid, Stickstoffverbindungen wie Melamin, Melaminformaldehyd-Harze, anorganische Hydroxidverbindungen wie Mg-Al- Hydroxid, anorganische Verbindungen wie AJiiminiumoxide, Titandioxide, Antimonoxide, Barium-metäborat, Hydroxoantimonat, Zirkonoxid, Zirkonhydroxid, Molybdänoxid, Ammoniummolybdat, Zinriborat, Ammoniumborat und Zinnoxid sowie Siloxanverbindungen genannt.The compositions according to the invention can generally contain from 0.01 to 20% by weight, based on the overall composition, of flame retardants. Examples of flame retardants are organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds such as Mg-Al-hydroxide, inorganic compounds such as Aliminium oxides, titanium dioxide, antimony oxides, barium meta-borate, zirconium meta borate, hydroxyl Zirconium hydroxide, molybdenum oxide, ammonium molybdate, tin riborate, ammonium borate and tin oxide as well as siloxane compounds.
Als Flammschutzverbindungen können ferner Phosphorverbindungen, wie sie in derAs flame retardant compounds can also phosphorus compounds, as in the
EP-A 363 608, EP-A 345 522 und/oder EP-A 640 655 beschrieben sind, eingesetzt werden.EP-A 363 608, EP-A 345 522 and / or EP-A 640 655 are used.
Als weitere Füll- und Verstärkungsmaterialien kommen beispielsweise Glasfasern, gegebenenfalls geschnitten oder gemahlen, Glasperlen und Glaskugeln in Frage.Glass fibers, optionally cut or ground, glass beads and glass balls are suitable as further filling and reinforcing materials.
Alle Gewichtsteil-Angäben in dieser Anmeldung sind so zu normieren, dass die Summe der Gewichtsteile aller Komponenten gleich 100 gesetzt wird.All parts by weight in this application are to be standardized so that the sum of the parts by weight of all components is set to 100.
Die erfindungsgemäßen Zusammensetzungen werden hergestellt, indem man die jeweiligen Bestandteile in bekannter Weise vermischt und bei Temperaturen von 200°C bis 300°C in übhchen Aggregaten wie hrnenknetern, Extrudern und Doppelwellenschnecken schmelzcompoundiert und schmelzextrudiert, wobei das Entfor- mungsmittel in Form einer koagulierten Mischung eingesetzt wird.The compositions according to the invention are prepared by mixing the respective constituents in a known manner and at temperatures of 200 ° C to 300 ° C in conventional units such as kneaders, extruders and twin-screw extruders, melt-compounded and melt-extruded, the mold release agent being used in the form of a coagulated mixture.
Die Vermischung der einzelnen Bestandteile kann in bekannter Weise sowohl sukzessive als auch simultan erfolgen, und zwar sowohl bei etwa 20°C (Raumtemperatur) als auch bei höherer Temperatur.The individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
Die erfindungsgemäßen Polymer-Zusammensetzungen können zur Herstellung von Formteilen jeder Art verwendet werden. Insbesondere können Formteile durchThe polymer compositions according to the invention can be used for the production of moldings of any kind. In particular, molded parts can by
Spritzguss hergestellt werden. Beispiele für Formteile sind: Gehäuseteile jeder Art, beispielsweise für Haushaltsgeräte wie Elektrorasierapparate, Flatscreens, Monitore, Drucker, Kopierer oder Abdeckplatten für den Bausektor und Teile für den Kfz- und Schienenfahrzeuge. Sie sind außerdem auf dem Gebiet der Elektrotechnik einsetzbar, weil sie sehr gute elektrische Eigenschaften haben.Injection molding. Examples of molded parts are: Housing parts of all kinds, for example for household appliances such as electric shavers, flat screens, monitors, printers, copiers or cover plates for the construction sector and parts for motor vehicles and rail vehicles. They can also be used in the field of electrical engineering because they have very good electrical properties.
Weiterhin können die erfindungsgemäßen Polymer-Zusammensetzungen beispielsweise zur Herstellung von folgenden Formteilen verwendet werden:Furthermore, the polymer compositions according to the invention can be used, for example, to produce the following moldings:
Innenausbauteile für Schienenfahrzeuge, Schiffe, Busse, andere Kraftfahrzeuge undInterior components for rail vehicles, ships, buses, other motor vehicles and
Luftfahrzeuge, Radkappen, Gehäuse von Kleintransformatoren enthaltenden Elektrogeräten, Gehäuse für Geräte zur Ihformationsverbreitung und -Übermittlung, Flächige Wandelemente, Gehäuse für Sicherheitseinrichtungen, Heckspoiler und andere Karosserieteile für KFZ, Wärmeisolierte Transportbehältnisse, Vorrichtung zur Haltung oder Versorgung von Kleintieren, Abdeckgitter für Lüfteröffhungen,Aircraft, hubcaps, housings of electrical transformers containing small transformers, housings for devices for information distribution and transmission, flat wall elements, housings for safety devices, rear spoilers and other body parts for motor vehicles, heat-insulated transport containers, devices for holding or supplying small animals, cover grilles for ventilation openings,
Formteile für Garten- und Gerätehäuser, Gehäuse für Gartengeräte.Molded parts for garden and tool sheds, housings for garden tools.
Eine weitere Form der Verarbeitung ist die Herstellung von Formteilen durch Tiefziehen aus vorher hergestellten Platten oder Folien. Ein weiterer Gegenstand der vorliegenden Erfindung ist daher auch die Verwendung der erfindungsgemäßen Zusammensetzungen zur Herstellung von Formteilen jeglicher Art, vorzugsweise der oben genannten, sowie die Formteile aus den erfindungsgemäßen Zusammensetzungen.Another form of processing is the production of molded parts by deep drawing from previously produced sheets or foils. Another object of the present invention is therefore also the use of the compositions according to the invention for the production of moldings of any kind, preferably those mentioned above, and the moldings from the compositions according to the invention.
Aufgrund der ausgezeichneten Online-Lackierbarkeit sind die online-lackierten Formteile, vorzugsweise online-lackierte Kfz-Außenteile, beispielsweise Radkästen, Kotflügel, Spiegelaußengehäuse etc., ebenfalls Gegenstand der vorliegenden Erfindung.Because of the excellent online paintability, the online-painted molded parts, preferably online-painted automotive exterior parts, for example wheel arches, fenders, outer mirror housings, etc., are also the subject of the present invention.
Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung. The following examples serve to further explain the invention.
BeispieleExamples
Entsprechend den Angaben der Tabelle 1 werden die Zusammensetzungen hergestellt, zu Prüfkörpern weiterverarbeitet und geprüft.The compositions are prepared, processed into test specimens and tested in accordance with the information in Table 1.
Komponente AIComponent AI
Polyamid 6.6 (Ultramid® A 3, BASF, Ludwigshafen).Polyamide 6.6 (Ultramid ® A 3, BASF, Ludwigshafen, Germany).
Komponente A2Component A2
Noryl® GTX 974, General Electric Plastics, Bergen op Zoomen, Niederlande.Noryl ® GTX 974, General Electric Plastics, Bergen op Zoomen, The Netherlands.
Komponente BComponent B
Pfropfpolymerisat von 40 Gew.-Teilen eines Copolymerisats aus Styrol und Acrylnitril im Verhältnis von 73:27 auf 60 Gew.-Teile teilchenförmig vernetzten Poly- butadienkautschuk (mittlerer Teilchendurchmesser d50 = 0,28 μm), hergestellt durch Emulsionspolymerisation.Graft polymer of 40 parts by weight of a copolymer of styrene and acrylonitrile in a ratio of 73:27 to 60 parts by weight of particulate crosslinked polybutadiene rubber (average particle diameter d 50 = 0.28 μm), produced by emulsion polymerization.
Komponente CIComponent CI
Naintsch A3 (Naintsch Mineralwerke GmbH, Graz, Österreich)Naintsch A3 (Naintsch Mineralwerke GmbH, Graz, Austria)
Talk mit einem mittleren Partikeldurchmesser ^Q) lt. Herstellerangabe von 1,2 μm.Talc with an average particle diameter ^ Q ) according to the manufacturer's specification of 1.2 μm.
Komponente C2Component C2
Nyglos® 4-10013 (silanisierter Wollastonit mit einer Partikelgröße lt. Herstellerangäbe von 4,8 μm) NYCO Minerals Inc. Willsboro, N.Y. USA. Komponente DNyglos ® 4-10013 (silanized wollastonite with a particle size according to manufacturer's specifications of 4.8 μm) NYCO Minerals Inc. Willsboro, NY USA. Component D
Ketjenblack® EC 600 (Akzo Nobel, Verkaufsbüro Düren, 52349 Düren, Deutschland (elektrisch leitf higer Ruß)Ketjenblack ® EC 600 (Akzo Nobel, Düren sales office, 52349 Düren, Germany (electrically conductive carbon black)
Komponente EComponent E
Irgastat® P 22, Ciba Speciality Chemicals, Schweiz.Irgastat ® P 22, Ciba Specialty Chemicals, Switzerland.
Komponente F Component F
Terpolymer von Styrol und Acrylnitril mit einem Gewichtsverhältnis von 2,1:1 enthaltend 1 Mol% Maleinsäureanhydrid.Terpolymer of styrene and acrylonitrile with a weight ratio of 2.1: 1 containing 1 mol% of maleic anhydride.
Komponente GComponent G
Styrol/Acrylnitril-Copolymerisat mit einem Slyrol/AcryMtril-Gewichtsverhältnis von 72:28 und einer Grenzviskosität von 0,55 dl/g (Messung in Dimethylformamid bei 20°C).Styrene / acrylonitrile copolymer with a Slyrol / AcryMtril weight ratio of 72:28 and an intrinsic viscosity of 0.55 dl / g (measurement in dimethylformamide at 20 ° C).
Komponente HComponent H
Rhenosin® RB (Phenol-Formaldehyd-Harz), Rhein Chemie Rheinau GmbH, MannheimRhenosin ® RB (phenol-formaldehyde resin), Rhein Chemie Rheinau GmbH, Mannheim
Komponente JComponent J
Additive s. Tabelle 1 Herstellung und Prüfung der erfindungsgemäßen FormmassenAdditives see Table 1 Production and testing of the molding compositions according to the invention
Das Mischen der Komponenten der Zusammensetzungen erfolgt auf einem 3-1- Innenkneter. Die Formkörper werden auf einer Spritzgießmaschine Typ Arburg 270 E bei 280°C hergestellt.The components of the compositions are mixed on a 3-1 internal kneader. The moldings are produced on an Arburg 270 E injection molding machine at 280 ° C.
Die Bestimmung der Wärmeformbeständigkeit Vicat B erfolgt nach ISO 306 an Stäben der Abmessung 80 x 10 x 4 mm.Vicat B's dimensional stability under heat is determined in accordance with ISO 306 on rods measuring 80 x 10 x 4 mm.
Die Schlagzähigkeit a^ wird gemäß ISO 180/1 U bestimmt.The impact strength a ^ is determined in accordance with ISO 180/1 U.
Der MVR (Melt Volume Rate) wird gemäß ISO 1133 bei 280°C unter Verwendung einer Stempellast von 5 kg bestimmt.The MVR (Melt Volume Rate) is determined according to ISO 1133 at 280 ° C using a stamp load of 5 kg.
Der Oberflächenwiderstand wird nach DL IEC 60167 bestimmt.The surface resistance is determined according to DL IEC 60167.
Die Reißdehnung wird im Zugversuch nach ISO 527 bestimmt.The elongation at break is determined in a tensile test according to ISO 527.
Die Ergebnisse der einzelnen Tests sind in Tabelle 1 zusammengefasst. The results of the individual tests are summarized in Table 1.
Tabelle 1 Zusammensetzung und Eigenschaften (Angaben in Gew.-Teilen)Table 1 Composition and properties (data in parts by weight)
1) n.m.: nicht messbar Der Einsatz der Komponente E zeigt positive Eigenschaften in Bezug auf die Zähigkeit der Formmasse sowie auf das Fließverhalten. In Beispiel 1 wirkt sich die Kombination von E und D positiv aus. Beim Einsatz von vergleichbaren Mengen an Ruß (Vergleichsbeispiel 1) zu Komponente E in Beispiel 1 wird zwar ein sehr guter Oberflächenwiderstand erreicht, allerdings sinkt der MVR- Wert so stark ab, dass man ihn unter den gegebenen Bedingungen nicht mehr bestimmen kann. Bei einem Einsatz von weniger Ruß (Vergleichsbeispiel 2) ist der Oberflächenwiderstand sehr hoch und zusätzlich ist der MVR- Wert im Gegensatz zu den erfindungsgemäßen Beispielen 1 und 2 deutlich niedriger.1) nm: not measurable The use of component E shows positive properties with regard to the toughness of the molding composition and the flow behavior. In example 1, the combination of E and D has a positive effect. When using comparable amounts of carbon black (comparative example 1) to component E in example 1, a very good surface resistance is achieved, but the MVR value drops so much that it can no longer be determined under the given conditions. When less carbon black is used (comparative example 2), the surface resistance is very high and, in contrast to examples 1 and 2 according to the invention, the MVR value is significantly lower.
Die vorteilhaften Eigenschaften wie in Beispiel 1 zeigen sich auch mit Wollastonit als Füllstoff (Beispiel 3)The advantageous properties as in Example 1 are also evident with wollastonite as filler (Example 3)
Der Wert des Oberflächenwiderstandes in den Beispielen 1, 2 und 3 ist für eine elektrostatische Lackierung eines Formteiles ohne vorherige Behandlung mit einemThe value of the surface resistance in Examples 1, 2 and 3 is for electrostatic painting of a molded part without prior treatment with a
Leitprimer ausreichend. Leading primer sufficient.

Claims

Patentansprfiche Patentansprfiche
1. Polymer-Zusammensetzung enthaltend1. Containing polymer composition
A) 40 bis 99 Gew.-Teile Polyamid,A) 40 to 99 parts by weight of polyamide,
B) 0,5 bis 50 Gew.-Teile Pfropfpolymerisat,B) 0.5 to 50 parts by weight of graft polymer,
C) 0,1 bis 30 Gew.-Teile mineralische Partikel,C) 0.1 to 30 parts by weight of mineral particles,
D) 0 bis 1,5 Gew.-Teile elektrisch leitfahige KohlenstoffpartikelD) 0 to 1.5 parts by weight of electrically conductive carbon particles
E) 0,1 bis 15 _ Gew.-Teile mindestens ein Polymer ausgewählt aus der Gruppe der Polyesteretheramide, Polyester-ether-Blockcopolymere und Polyamid-Polyester-Blockpolymere.E) 0.1 to 15 parts by weight of at least one polymer selected from the group of polyester ether amides, polyester ether block copolymers and polyamide-polyester block polymers.
2. Zusammensetzung gemäß Ansprach 1, enthaltend als weitere Komponenten mindestens eine ausgewählt aus der Gruppe der Verträglichkeitsvermittler, Vinyl(Co)polymerisate, Phenol-Formaldehyd-Harze und Polymer- Additive.2. Composition according spoke 1, containing as further components at least one selected from the group of compatibilizers, vinyl (co) polymers, phenol-formaldehyde resins and polymer additives.
3. Zusammensetzung gemäß Ansprach 1,. enthaltend 50 bis 85 Gew.-Teile Polyamid A), 1 bis 30 Gew.-Teile Pfropfpolymerisat B), 1 bis 20 Gew.-Teile mineralische Partikel C) und 1 bis 12 Gew.-Teile mindestens ein Polymer ausgewählt aus der Gruppe der Polyesteretheramide, Polyether-Ester-Block- copolymere und Polyamid-Polyester-Blockpolymere.3. Composition according to spoke 1. containing 50 to 85 parts by weight of polyamide A), 1 to 30 parts by weight of graft polymer B), 1 to 20 parts by weight of mineral particles C) and 1 to 12 parts by weight of at least one polymer selected from the group of Polyester ether amides, polyether ester block copolymers and polyamide polyester block polymers.
4. Zusammensetzung gemäß Ansprach 1 enthaltend bis zu 30 Gew.-Teilen Vinyl(co)polymere aus4. Composition according spoke 1 containing up to 30 parts by weight of vinyl (co) polymers
F.1 ein vinylaromatisches Monomer,F.1 a vinyl aromatic monomer,
F.2 wenigstens ein Monomer ausgewählt aus der Gruppe C2 bis C12- Alkylmethacrylate, C2 bis C12-Alkylacrylate, Methacrylnitrile und Acrylnitrile und F.3 α,ß-ungesättigte Komponenten enthaltend Dicarbonsäureanhydride.F.2 at least one monomer selected from the group C 2 to C 12 alkyl methacrylates, C 2 to C 12 alkyl acrylates, methacrylonitriles and acrylonitriles and F.3 α, β-unsaturated components containing dicarboxylic anhydrides.
5. Zusammensetzung gemäß Ansprach 1, enthaltend Pfropfpolymerisat von wenigstens einem Monomer ausgewählt aus5. Composition according spoke 1, containing graft polymer selected from at least one monomer
B.l.l Styrol, α-Methylstyrol, halogen- oder alkylkemsubstituierte Styrole (Meth)Acrylsäure-Cι-Cg-Alkylester undB.l.l styrene, α-methylstyrene, halogen or alkyl nucleus-substituted styrenes (meth) acrylic acid -C-Cg-alkyl esters and
B.l.2 ungesättigten Nitrilen, (Meth)Acrylsäure-Cι-Cg-alkylester und Derivaten ungesättigter Carbonsäuren aufB.l.2 unsaturated nitriles, (meth) acrylic acid -C-Cg-alkyl esters and derivatives of unsaturated carboxylic acids
eine Pfropfgrundlage mit einer Glasübergangstemperatur <10°C.a graft base with a glass transition temperature <10 ° C.
6. Zusammensetzung gemäß Ansprach 5, wobei die Pfropfgrandlage ausgewählt ist aus mindestens einem Kautschuk der Gruppe der Dienkautschuke, Copoly- merisate von Dienkautschuken Acrylatkautschuke, Polyurethansilikon-, Chloropren- und Ethylen/Vinylacetat-Kautschuke.6. Composition according spoke 5, wherein the graft base is selected from at least one rubber from the group of diene rubbers, copolymers of diene rubbers, acrylate rubbers, polyurethane silicone, chloroprene and ethylene / vinyl acetate rubbers.
7. Zusammensetzung gemäß Ansprach 5, wobei die Pfropfgrundlage ausgewählt ist aus mindestens einem Kautschuk bestehend aus Dienkautschuken, Copoly- merisaten von Dienkautschuken und Acrylatkautschuken, wobei Ethylen/Pro- pylen-Kautschuke ausgenommen sind.7. Composition according to spoke 5, wherein the graft base is selected from at least one rubber consisting of diene rubbers, copolymers of diene rubbers and acrylate rubbers, with the exception of ethylene / propylene rubbers.
8. Zusammensetzung gemäß Ansprach 7, wobei die Pfropfgrundlage Poly- butadien ist.8. Composition according spoke 7, wherein the graft base is poly butadiene.
9. Zusammensetzung gemäß Ansprach 1, wobei elektrisch leitfähige Kohlenstoffpartikel ausgewählt sind aus mindestens einem aus der Gruppe der Ruße, Graphite und Kohlenstoff-Nanofibrillen. 9. Composition according spoke 1, wherein electrically conductive carbon particles are selected from at least one from the group of carbon blacks, graphites and carbon nanofibrils.
10. Zusammensetzung gemäß Ansprach 1, wobei mineralische Partikel ausgewählt sind aus mindestens einem aus Talk, Glimmer, Tonschichtaiineralien, Montmorrilonit, Kaolin, Vermiculit, Wollastonit.10. Composition according spoke 1, wherein mineral particles are selected from at least one of talc, mica, clay layer minerals, montmorrilonite, kaolin, vermiculite, wollastonite.
11. Zusammensetzung gemäß Ansprach 10, enthaltend Talk oder Wollastonit11. Composition according spoke 10, containing talc or wollastonite
12. Zusammensetzung gemäß Anspruch 1, enthaltend 1 bis 12 Gew.-Teile Phenol-Formaldehyd-Harz.12. The composition according to claim 1, containing 1 to 12 parts by weight of phenol-formaldehyde resin.
13. Verwendung der Zusammensetzung gemäß Anspruch 1, zur Herstellung von13. Use of the composition according to claim 1, for the production of
Formteilen.Moldings.
14. Formteile enthaltend eine Zusammensetzung gemäß Ansprach 1.14. Molded parts containing a composition according to spoke 1.
15. Online-lackierte Formteile enthaltend eine Zusammensetzung gemäß15. Online-painted molded parts containing a composition according to
Ansprach 1. Speech 1.
EP03772333A 2002-11-25 2003-11-13 Polymer compositions with a modified impact-resistance Withdrawn EP1567581A1 (en)

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DE10254877 2002-11-25
DE2002154877 DE10254877A1 (en) 2002-11-25 2002-11-25 Impact-modified polyamide composition useful for making shaped products, especially automobile bodywork parts, contains electrically conductive carbon particles and a graft copolymer
DE10257077 2002-12-06
DE2002157077 DE10257077A1 (en) 2002-12-06 2002-12-06 Polyamide composition, used for making molding, preferably for on-line lacquering, e.g. vehicle body component, contains graft polymer, mineral particles and polyester-ether-amide or block polymer, preferably as antistatic formulation
PCT/EP2003/012691 WO2004048452A1 (en) 2002-11-25 2003-11-13 Polymer compositions with a modified impact-resistance

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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006507402A (en) * 2002-11-25 2006-03-02 ランクセス ドイチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング Polymer composition with improved impact resistance
DE10259498A1 (en) * 2002-12-19 2004-07-01 Bayer Ag Conductive thermoplastics with soot and carbon nanofibrils
US7666477B2 (en) * 2004-03-30 2010-02-23 E.I. Du Pont De Nemours And Company Process for coating vehicle exterior parts comprising polyamide resins and parts and articles coated thereby
EP1773924A1 (en) * 2004-06-18 2007-04-18 E.I.Du pont de nemours and company Electrically conductive polyetherester composition comprising carbon black and product made therefrom
KR100539065B1 (en) * 2004-12-02 2005-12-26 제일모직주식회사 Abs resin composition with low coefficient of linear thermal expansion
BRPI0720406B1 (en) 2006-12-19 2018-10-16 Basf Se thermoplastic molding composition, and use thereof
US20080153959A1 (en) * 2006-12-20 2008-06-26 General Electric Company Thermally Conducting and Electrically Insulating Moldable Compositions and Methods of Manufacture Thereof
KR100810966B1 (en) 2006-12-29 2008-03-10 제일모직주식회사 Composite of nylon polymer
US20090187246A1 (en) * 2008-01-22 2009-07-23 Foley Kevin T Interbody implants for spinal alignment procedures
US20100310851A1 (en) * 2009-05-18 2010-12-09 Xiaoyun Lai Conductive Fiber Glass Strands, Methods Of Making The Same, And Composites Comprising The Same
US20110178205A1 (en) * 2010-01-18 2011-07-21 Martin Weber Process for producing thermoplastic molding compositions based on styrene copolymers and polyamide with improved toughness
US20110237693A1 (en) * 2010-03-23 2011-09-29 Basf Se Blends made of polyarylene ethers and of polyarylene sulfides
EP2598576B1 (en) * 2010-07-26 2018-04-04 DSM IP Assets B.V. Fuel part and process for preparation of a fuel part
DE102010043472A1 (en) * 2010-11-05 2012-05-10 Evonik Goldschmidt Gmbh Composition of polymers and electrically conductive carbon
US9721695B2 (en) * 2010-12-21 2017-08-01 Basf Se Thermoplastic molding composition
US20120153232A1 (en) * 2010-12-21 2012-06-21 Basf Se Thermoplastic molding composition
US8552101B2 (en) 2011-02-25 2013-10-08 Sabic Innovative Plastics Ip B.V. Thermally conductive and electrically insulative polymer compositions containing a low thermally conductive filler and uses thereof
US8741998B2 (en) * 2011-02-25 2014-06-03 Sabic Innovative Plastics Ip B.V. Thermally conductive and electrically insulative polymer compositions containing a thermally insulative filler and uses thereof
JP5810619B2 (en) * 2011-05-11 2015-11-11 株式会社カネカ Thermoplastic resin composition and molded article thereof
EP2762527B1 (en) * 2011-09-28 2018-03-21 Sumitomo Bakelite Company Limited Molding material
US9882082B2 (en) 2012-11-14 2018-01-30 Sun Chemical Corporation Compositions and processes for fabrication of rear passivated solar cells
US20140275366A1 (en) * 2013-03-13 2014-09-18 Bayer Materialscience Llc Filled polycarbonate compositions
EP3237166B1 (en) * 2014-12-24 2019-10-23 Momentive Performance Materials Inc. Thermally conductive plastic compositions
EP3256516B1 (en) * 2015-02-13 2019-12-25 EMS-Patent AG Polyamide moulding composition and moulded article made from this moulding composition
US20180086269A1 (en) * 2016-09-29 2018-03-29 Magna Mirrors Of America, Inc. Interior mirror stay formed by gas assist molding process
CN108239367A (en) * 2016-12-27 2018-07-03 上海邦中高分子材料有限公司 A kind of ABS material for 3D printing
KR102125262B1 (en) * 2019-01-11 2020-06-22 주식회사 엘지화학 Thermoplastic resin composition having excellent heat resistance and electromagnetic wave shielding property, method for preparing the same and injection-molded article prepared therefrom
TWI736210B (en) * 2020-04-08 2021-08-11 遠東新世紀股份有限公司 Polyester composition and polyester sheet

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3899462A (en) * 1974-03-29 1975-08-12 Gen Motors Corp Reinforced polyamide molding composition
US4713415A (en) * 1985-05-10 1987-12-15 Monsanto Company Rubber modified nylon composition
US5227428A (en) * 1985-05-10 1993-07-13 Monsanto Company Rubber modified nylon composition
US4974307A (en) * 1988-06-20 1990-12-04 Mazda Motor Corporation Method of making an automobile body
DE3827669A1 (en) 1988-08-16 1990-02-22 Bayer Ag THERMOPLASTIC INTERPOLYMERS AND THEIR USE IN MIXTURES OF POLYAMIDE AND STYRENE CO- AND / OR GRAFT POLYMERISAT
US5652326A (en) * 1993-03-03 1997-07-29 Sanyo Chemical Industries, Ltd. Polyetheresteramide and antistatic resin composition
JPH0776634A (en) * 1993-09-08 1995-03-20 Yokohama Rubber Co Ltd:The Rubber composition for tire tread
EP0685527B1 (en) * 1994-06-01 1997-03-05 General Electric Company Thermoplastic composition comprising a compatibilized polyphenylene ether- polyamide base resin and electroconductive carbon black
WO1996006136A1 (en) * 1994-08-22 1996-02-29 The Dow Chemical Company Filled carbonate polymer blend compositions
US5484838A (en) * 1994-12-22 1996-01-16 Ford Motor Company Thermoplastic compositions with modified electrical conductivity
BE1009903A3 (en) 1995-12-29 1997-10-07 Dsm Nv Rubber-modified polymer composition.
EP0829520B1 (en) * 1996-09-16 2004-10-13 Ciba SC Holding AG Antistatic composition
AU9340898A (en) * 1998-03-05 1999-09-20 Basf Aktiengesellschaft Polyamide/polyphenylene ether moulding materials with mineral filling materials
US6140405A (en) * 1998-09-21 2000-10-31 The B. F. Goodrich Company Salt-modified electrostatic dissipative polymers
AT407989B (en) * 1999-10-15 2001-07-25 Solutia Austria Gmbh EMULGATORS FOR ALKYD RESIN EMULSIONS WITH A HIGH SOLID CONTENT
US6469093B1 (en) * 1999-11-12 2002-10-22 General Electric Company Conductive polyphenylene ether-polyamide blend
AR033368A1 (en) * 2000-05-19 2003-12-17 Bayer Ag MIXTURES OF POLYMERS CONTAINING POLYAMIDE, AND POLYMERS MODIFIED WITH RUBBER, USE OF POLYMER MIXTURES IN THE PRODUCTION OF MOLDED BODIES, AND MOLDED BODIES, CABINET PARTS, COVER PLATES AND PARTS FOR THE AUTOMOTIVE BODY SECTOR POLYMERS
KR100384014B1 (en) 2000-11-30 2003-05-14 현대자동차주식회사 A polyamide resin composition excellent low temperature gasoline and perspiration-resistant impact
FR2824329B1 (en) * 2001-05-03 2003-06-13 Atofina ANTISTATIC POLYMER COMPOSITIONS
DE10233170A1 (en) * 2002-07-22 2004-02-12 Bayer Ag Polymer blends based on polyamide
JP2006507402A (en) * 2002-11-25 2006-03-02 ランクセス ドイチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング Polymer composition with improved impact resistance

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004048452A1 *

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AU2003279385A1 (en) 2004-06-18
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US20040167268A1 (en) 2004-08-26
WO2004048474A1 (en) 2004-06-10
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WO2004048452A1 (en) 2004-06-10
JP2006507402A (en) 2006-03-02
EP1567591A1 (en) 2005-08-31
EP1567591B2 (en) 2015-10-21
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US20040167264A1 (en) 2004-08-26

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