Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/10—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/04—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

• the invention relates to impact-modified polyamide compositions and molded parts produced therefrom, which are particularly suitable for online painting, and to the molded parts painted online.
• DE-A 101 019 225 generally describes polymer compositions containing polyamide, graft polymer, nylon (co) polymer, non-intolerance mediator and very finely divided mineral particles with anisotropic particle geometry.
• the composition of the present invention is a selection in view of this disclosure.
• DE-A 101 019 225 also does not mention that the compositions described there can be painted online.
• EP 0 202 214 A discloses polymer blends made of a polyamide, a styrene / acrylonitrile copolymer and an excipient.
• a copolymer of a vinylaromatic monomer and acrylonitrile, methacrylonitrile, to C -alkyl methacrylate or C 1 to C 4 -alkyl acrylate in a weight ratio of 85:15 to 15:85 is used as a low-tolerance agent.
• Increased impact resistance is to be achieved through the use of nerve tolerance agents.
• a disadvantage of the polymer blends described in this publication is that they have too low a stiffness and a too high expansion coefficient 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 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.
• inorganic materials in certain polymer compositions, in particular in polycarbonate compositions, are also generally known.
• the inorganic materials are used, for example, as a reinforcing agent 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 blends which contain certain inorganic fillers to improve rigidity and linear thermal expansion resistance.
• DE 39 38 421 A1 also describes molding compositions composed of polyamides and special graft polymers containing tert-alkyl esters. These polymers have a high surface gloss and good dimensional stability. However, it would be desirable to further improve the impact strength required for thin-wall applications.
• Noryl® GTX from General Electric Plastics is known for some inline applications. 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, 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 methods, which differ at the time the plastic add-on parts are attached to the outer body part.
• plastic body parts Additional requirements placed on plastic body parts are good rigidity, low thermal expansion and shrinkage, good surface quality, good paintability, sufficient toughness and good chemical resistance.
• the molding compounds used to produce the exterior parts of the body must have good flowability in the melt.
• the object of the present invention was to provide polyamide molding compositions which have excellent heat resistance and low thermal expansion.
• the compositions according to the invention additionally have an increased tensile strength combined with good processing behavior.
• the object was achieved by a polymer composition containing
• the sum of the parts by weight of the components is 100.
• the composition may contain, as further components, a compatibilizer (component D) and / or vinyl (co) polymer (component E).
• a compatibilizer component D
• / or vinyl (co) polymer component E
• Graft polymers based on ethylene-propylene rubbers (EPR) or rubbers based on ethylene-propylene and non-conjugated diene (EPDM) according to JP 11 24 1016 A2 are preferably excluded from the graft polymers according to component B of the present invention as a graft base.
• the invention furthermore also relates to the online lacquered moldings obtainable from the compositions mentioned above.
• special mineral particles are used as component C of the composition. As explained in detail below, these are characterized by an anisotropic particle geometry. According to the invention, particles with anisotropic particle geometry are understood to mean those particles whose so-called aspect ratio, i.e. the ratio of the larger 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 the broadest
• 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. Polyamide-6, polyamide-6,6, mixtures and corresponding copolymers of these components are suitable as partially crystalline polyamides.
• Semi-crystalline polyamides are also suitable, the acid components of which are wholly or partly composed of terephthalic acid and / or isophthalic acid and / or Succic acid and / or sebacic acid and / or azelaic acid and / or adipic acid and / or cyclohexanedicarboxylic acid, the diamine component of which consists entirely or partly of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4-trimethylhexa-methylenediamine and / or 2,4,4-trimethylhexamethylene diamine and / or isophorone diamine 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-trimethylhexamethylenediamine, 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) norboman and / or 1,4-diaminomethylcyclohexane with dicarboxylic acids such as oxa
• Copolymers which are obtained by polycondensation of several monomers are also suitable, furthermore copolymers which are prepared with the addition of amino carboxylic acids such as e-aminocaproic acid, w-aminoundecanoic acid or w-aminolauric acid or their lactams.
• amino carboxylic 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-methylene diamine, 2,5- and / or 2,6-bis (aminomethy ⁇ ) norbornene; or from isophthalic acid, 4,4'-diamino-dicyclohexylmethane and ⁇ -caprolactam; or from isophthalic acid, 3,3'-dimethyl-4,4Xdiamino-dicyclohexylmethane and laurolactam; or from terephthalic acid and the isomer mixture of 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine.
• Positional isomers diamine dicyclohexalmethanes are used, 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.) of 2.0 to 5.0, particularly preferably of
• 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 B1, preferably according to B1 and B.1.2, and one grafted with vinyl monomers, preferably according to B1 and B1 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
• graft bases B.2 with glass transition temperatures ⁇ 10 ° C, preferably ⁇ -10 ° C.
• Preferred monomers B1 are styrene, .alpha.-methylstyrene, halogen- or alkyl nucleus-substituted styrenes such as p-methylstyrene, p-chlorostyrene, (methyl methacrylate CrCs alkyl esters such as methyl methacrylate, n-butyl acrylate and tert-butyl acrylate.
• Preferred monomers are B.1.2 unsaturated nitriles such as acrylonitrile, methacrylonitrile, (meth) - acrylic acid-CrCs-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.l.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 (for example based on butadiene, isoprene etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable vinyl monomers (for example in accordance with B1 and B1), with the proviso that the glass transition temperature of 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 of alkyl acrylates, 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-Cj-Cg-alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
• Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic esters, can optionally be used to prepare the graft base B.2 are, for. B. acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl - 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 are described in DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631 539.
• 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 LT, Georg Thieme-Verlag, Stuttgart 1977).
• the average particle size d 50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifugal 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 crosslinking 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, trivinyl cyanurate, triallyl cyanurate, allyl (meth) acrylate, diallyl maleate, diallyl fumarate, triallyphosphate and diallyl phthalate.
• alkylene diol di (meth) acrylates polyester di (meth) - acrylates
• divinylbenzene trivinylbenzene
• trivinyl cyanurate trivinyl cyanurate
• triallyl cyanurate triallyl cyanurate
• allyl (meth) acrylate diallyl maleate, diallyl fumarate, triallyphosphate
• Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least three ethylenically unsaturated groups.
• the rubber-modified graft polymer B is obtained in the case of production by bulk or solution or bulk suspension polymerization 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 preferably 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 B1 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 dso 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 dso of the resulting grafted rubber particles which can be obtained by means of bulk or solution or bulk suspension polymerization processes (determined by counting on electron micrographs), 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.
• Very finely divided mineral particles suitable according to the invention are those with anisotropic particle geometry.
• mineral particles with anisotropic particle geometry are understood to mean those particles whose so-called aspect ratio - ratio of the largest and smallest particle dimensions - 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 (alumino) silicates with a layer or Fiber geometry such as bentonite, wollastonite, mica (mica), kaolin, hydrotalcite, hectorite or montmorillonite.
• Inorganic materials with a flaky or flake-like character are preferably used, such as talc, mica / clay layer minerals,
• Montmorrilonite the latter also in an organophilic foi, kaolin and vermiculite modified by ion exchange.
• Talc is particularly preferred.
• Talc is understood to mean a naturally occurring or synthetically produced talc.
• Pure talc has the chemical composition 3MgO ' 4SiO 2 ' HO 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 a layer structure.
• Talktypes of high purity are preferred. These include, for example
• 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 talc types 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.
• talc in the form of finely ground types with an average particle size d 50 of ⁇ 10 ⁇ m, preferably ⁇ 5 ⁇ m, particularly preferably ⁇ 2.5 ⁇ m, very particularly preferably ⁇ 1.5 ⁇ m is also particularly advantageous.
• talc with an average particle size d5 Q of 350 nm to 1.5 ⁇ m is particularly preferred.
• Particle size and particle diameter in the sense of this invention means the average particle diameter d 50 , determined by ultracentrifuge measurements according to W. Scholtan et al., Kolloid-Z. and Z. Polymers 250 (1972), pp. 782-796.
• 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.
• Very particularly fine mineral particles with anisotropic particle geometry that are particularly suitable for use in the composition according to the invention are also the inorganic materials described in US Pat. Nos. 5,714,537 and 5,091,461.
• D / T average diameter to thickness
• compositions which contain particles which have an average diameter / thickness (D / T) ratio, measured in the manner described in US Pat. No. 5,714,537, of at least 4, preferably at least 6, more preferably at least 7 are highly preferred.
• D / T ratio it has been 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 am most preferably up to and including 10.
• Mineral particles to be used with preference are the known minerals talc and clay types.
• the non-calcined talc and clays, which have a very low content of free metal oxide, are particularly preferred.
• Types of talc and clay are well-known fillers for various polymeric resins. In US-A 5 091 461, US-A 3 424 703 and EP-A 391 413 generally describe these materials and their suitability as fillers for polymeric resins.
• the most suitable types of the mineral talc are hydrated magnesium silicates, as generally represented by the theoretical formula:
• compositions of the talc can vary somewhat with the location where they are mined. For example, talc varieties match
• the most suitable types of clay are hydrous compounds from
• Suitable clay materials are commercially available as Tex 10R clay from Anglo
• These mineral particles preferably have a number average particle size, measured by a Coulter Counter, of less than or equal to 10 micrometers ( ⁇ m), more preferably less than or equal to 2 ⁇ m, even more preferably less than or equal to 1.5 ⁇ m and most preferably less than or equal to 1.1 ⁇ m.
• a Coulter Counter 10 micrometers
• such fillers can have number average particle sizes of at least 0.05 ⁇ m, preferably at least 0.1 ⁇ m and more preferably at least 0.5 ⁇ m.
• these mineral particles generally have a maximum particle size of less than or equal to 50 ⁇ m, preferably less than or equal to 30 ⁇ m, more preferably less than or equal to 25 ⁇ m, even more preferably less than or equal to 20 ⁇ m and most preferably less than or equal to 15 ⁇ m.
• Another way of specifying the desired uniform small particle size and the particle size distribution of the mineral particles preferably used in the practice of the present invention is by stating that at least 98%, preferably at least 99%, by weight of the particles thereof have an equivalent spherical volume diameter of less than 44 ⁇ m, preferably less than 20 ⁇ m in the finished mixture.
• the weight percentage of the filler particles with such diameters can likewise be measured by particle size analysis using a Coulter Counter.
• the mineral particles can be present as powders, pastes, brine dispersions or suspensions. Precipitation can be used to obtain powders 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 methods are the production of a masterbatch, e.g. B. 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 very finely divided inorganic powders, e.g. by co-precipitation of an aqueous
• Emulsion and the finely divided inorganic powders optionally in the form of dispersions, suspensions, pastes or sols of the finely divided inorganic materials.
• the mineral particles of component C can, in the composition according to the invention, in an amount of preferably 0 to 30 parts by weight, particularly preferably 0 to 20 parts by weight, if present, in a most preferred manner 0.4 to 13 parts by weight . Parts.
• Thermoplastic polymers with polar groups are preferably used as compatibilizers.
• D.2 at least one monomer selected from the group C to C 12 alkyl methacrylates, C 2 to C 1 alkyl acrylates, methacrylonitriles and acrylonitriles and
• D.3 contain ⁇ , ⁇ -unsaturated components containing dicarboxylic anhydrides.
• Styrene is particularly preferred as vinyl aromatic monomer D.l.
• Acrylonitrile is particularly preferred for component D.2.
• Maleic anhydride is particularly preferred for ⁇ , ⁇ -unsaturated components containing dicarboxylic anhydrides D.3.
• Terpolymers of the monomers mentioned are preferably used as component D.l, D.2 and D.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. Particularly good mechanical properties with regard to tensile strength and elongation at break are achieved in this area.
• 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 D.l (vinyl aromatic monomer) and component D.2, e.g. the acrylonitrile monomer in the terpolymer is preferably between 80:20 and 50:50.
• an amount of vinyl aromatic monomer Dl is preferably selected which corresponds to the amount of the vinyl monomer B1 in the graft copolymer B.
• compatibilizers D which can be used according to the invention are described in 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.
• the compatibilizers can be contained in component D 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 D 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 E comprises one or more thermoplastic vinyl (co) polymerizates.
• Suitable vinyl (co) polymers for component E 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) of unsaturated carboxylic acids.
• (Co) polymers of are particularly suitable
• Nitriles such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid
• (-C ⁇ alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and / or imides of unsaturated carboxylic acids (e.g. N-phenylmaleimide).
• the (co) polymers E are resinous, thermoplastic and rubber-free.
• the copolymer of E.l styrene and E.2 acrylonitrile is particularly preferred.
• the (co) polymers E 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 E alone or in any mixture with one another.
• Component E is preferably in the polymer composition in an amount of 0 to 30 parts by weight, in particular 0 to 25 parts by weight and particularly preferably 0 to 20 parts by weight, in particular 0.5 to 10 parts by weight . Parts included.
• the polymer compositions according to the invention can contain conventional additives such as
• Flame retardants for anti-dripping agents, finely divided inorganic compounds, different from component D, lubricants and mold release agents, nucleating agents, Contain antistatic agents, stabilizers, fillers and ner starch substances as well as dyes and pigments.
• compositions according to the invention can generally contain 0.01 to 20% by weight, based on the total composition, of flame retardants.
• flame retardants examples include organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds such as Mg-Al hydroxide, inorganic compounds such as aluminum oxides, titanium dioxide, antimony oxides, barium metaborate, Hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, tin borate, ammonium borate and tin oxide and siloxane compounds.
• 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
• EP-A 363 608, EP-A 345 522 and / or EP-A 640 655 are used.
• filling and reinforcing materials that can be used are those that differ from component E).
• glass fibers optionally cut or ground, glass beads, glass balls, kaolins, talk, mica, silicates, quartz, talc, titanium dioxide, wollastonite, mica, carbon fibers or mixtures thereof are suitable. Cut or ground glass fibers are preferably used as the reinforcing material.
• Preferred fillers which can also have a reinforcing effect, are glass balls, mica, silicates, quartz, talc, titanium dioxide, wollastonite.
• compositions according to the invention are prepared by mixing the respective constituents in a known manner and at temperatures from 200 ° C. to 300 ° C. in conventional units such as internal kneaders, extruders and double wave screws melt-compounded and melt-extracted, 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 be produced by 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.
• polymer compositions according to the invention can be used, for example, to produce the following moldings:
• housings for electrical equipment containing small transformers, housings for devices for disseminating and transmitting information, flat wall elements, housings for safety devices, rear spoilers and other body parts for motor vehicles, heat-insulated transport containers, holding device or supply of small animals, cover grilles for ventilation openings, molded parts for garden and tool sheds, housings for garden tools.
• 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 the use of the compositions according to the invention for the production of molded parts of any Licher type, preferably the above, and the moldings from the compositions of the invention.
• the online-painted molded parts preferably online-painted automotive exterior parts, for example wheel arches,
• compositions are produced, processed into test specimens and tested in accordance with the information in Table 1.
• Polyamide 6.6 (Radipol® A45, Chimica SPA, Cologno Mouzese).
• 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.
• compositions are mixed on a 3-1 internal kneader.
• the moldings are produced on an Arburg 270 E injection molding machine at 260 ° C.
• the heat resistance HDT is determined in accordance with ISOR 75.
• the longitudinal expansion coefficient (10 -4 x K "1 ) was determined in accordance with ASTM E 831.
• a 60 x 60 x 2 mm plate is injection molded at a melt temperature of 260 ° C, a pressure of 500 bar and a mold temperature of 80 ° C. This plate is then immediately measured in the longitudinal and transverse directions, then annealed at 80 ° C. for 1 h and then measured again. The difference in length measurements is given in% as the length or width shrinkage. This procedure is repeated five times and the mean is given.

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• 2002
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