EP1183309A2 - Matieres moulables a utiliser dans l'habitacle d'un vehicule automobile, composite contenant ces matieres moulables, et leurs produits de recyclage - Google Patents

Matieres moulables a utiliser dans l'habitacle d'un vehicule automobile, composite contenant ces matieres moulables, et leurs produits de recyclage

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Publication number
EP1183309A2
EP1183309A2 EP00926866A EP00926866A EP1183309A2 EP 1183309 A2 EP1183309 A2 EP 1183309A2 EP 00926866 A EP00926866 A EP 00926866A EP 00926866 A EP00926866 A EP 00926866A EP 1183309 A2 EP1183309 A2 EP 1183309A2
Authority
EP
European Patent Office
Prior art keywords
component
weight
molding composition
molding
graft
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
EP00926866A
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German (de)
English (en)
Inventor
Michael Fischer
Graham Edmund Mckee
Gerd Blinne
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1183309A2 publication Critical patent/EP1183309A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the invention relates to fiber-reinforced molding compositions, molded parts and composites thereof, their recyclates and the use of the molding compositions, molded parts, composites and their recyclates.
  • Molded parts made of polymer materials, particularly in the interior of
  • a material used is glass fiber reinforced ABS / PC (polymer blend made of acrylonitrile / butadiene / styrene copolymer and polycarbonate).
  • ABS / PC polymer blend made of acrylonitrile / butadiene / styrene copolymer and polycarbonate.
  • this material has insufficient UV resistance, poor fluidity, poor heat aging behavior (toughness and elongation at break after heat storage), unfavorable surface properties, poor foam adhesion and, in particular, poor odor behavior.
  • Odor behavior is understood to mean the tendency of materials to emit volatile components that have a perceptible odor after a fixed period of temperature and climate storage.
  • SMA polystyrene / maleic anhydride copolymer
  • SMA also has inadequate surface properties, poor heat aging resistance, and in particular low heat resistance and poor
  • PPE / ⁇ IPS GF a polymer blend made of polyphenylene ether and high-impact polystyrene as well as glass fibers. This material also has poor flowability, poor UV resistance, poor heat aging and, ultimately, poor odor behavior.
  • PP / Mineral / EPDM Another material that is suitable for automotive interior use is PP / Mineral / EPDM. This is a polymer blend consisting of polypropylene, a mineral filler and an ethylene-propylene diene polymer. This material also has low rigidity, poor foam adhesion and poor paintability.
  • the object of the invention is to provide suitable molding compositions for the production of moldings which are used in the interior of motor vehicles, which have a favorable property profile with regard to their mechanical, optical and sensory properties, and in particular good heat resistance, heat aging resistance and good emission behavior and / or have olfactory behavior. Furthermore, the molding compositions should have the lowest possible density. The low density is particularly advantageous in terms of fuel savings in motor vehicles. In addition, laser patterning, preferably labeling of the molding compound surface is desirable. This allows a technically simple and very precise surface design.
  • the object is achieved by a fiber-reinforced molding composition containing, based on the sum of components A to I, which gives a total of 100% by weight, a) as the remaining constituent up to a total of 100% by weight of the molding composition of at least one polycondensate as component A,
  • component C2 10 to 50% by weight of acrylonitrile and / or methacrylonitrile as component C2, in each case based on component C,
  • conventional additives such as UV stabilizers, pigments, oxidation retardants, lubricants and mold release agents as component I.
  • no component C is contained.
  • no component D is contained.
  • a further embodiment of the fiber-reinforced molding composition which is preferred according to the invention does not contain any component F.
  • Yet another embodiment of the fiber-reinforced molding composition which is preferred according to the invention does not contain any component H.
  • Components C, D, F and H are not present in another embodiment of the fiber-reinforced molding composition according to the invention.
  • Another preferred embodiment of the molding composition according to the invention contains at least C, but not D, F and H as components.
  • the molding composition according to the invention contains up to 100% by weight of the molding composition, preferably 20 to 75% by weight, particularly preferably 30 to 60% by weight, of a preferably meltable polycondensate, preferably a polyester and particularly preferably one, as the remaining constituent aromatic polyester.
  • a preferably meltable polycondensate preferably a polyester and particularly preferably one, as the remaining constituent aromatic polyester.
  • the polycondensates contained in the molding compositions according to the invention are known per se. It is preferred that the polycondensates have a viscosity number in the range from 40 to 135, preferably 70 to 130 and particularly preferably 80 to 110.
  • the polyesters can be prepared as polycondensate, preferably by reacting terephthalic acid, its esters or other ester-forming derivatives with 1,4-butanediol, 1,3-propanediol or 1,2-ethanediol in a manner known per se.
  • terephthalic acid can be replaced by other dicarboxylic acids.
  • examples include naphthalenedicarboxylic acids, isophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and cyclohexanedicarboxylic acids, mixtures of these carboxylic acids and ester-forming derivatives thereof.
  • dihydroxy compounds 1, 4-butanediol, 1,3-propanediol or 1, 2-ethanediol can be mixed with other dihydroxy compounds, for example 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-di (hydroxymethyl) cyclohexane, bisphenol A, neopentyl glycol Diols and ester-forming derivatives of the same can be replaced.
  • aromatic polyesters are polytrimethylene terephthalate (PTT) and in particular polybutylene terephthalate (PBT), which are formed exclusively from terephthalic acid and the corresponding diols 1, 2-ethanediol, 1,3-propanediol and 1,4-butanediol.
  • PTT polytrimethylene terephthalate
  • PBT polybutylene terephthalate
  • the aromatic polyesters can also be used in whole or in part in the form of polyester recyclates, such as PET regrind from bottle material (post-consumer) or from waste from bottle production (post-industrial).
  • component A consists of
  • polybutylene terephthalate (AI) and a2) 0 to 40% by weight, 0 to 20% by weight, particularly preferably 0.1 to 10% by weight of a further polycondensate.
  • AI has a viscosity number in the range from 60 to 135, preferably 70 to 130, particularly preferably 80 to 100 and particularly preferably 85 to 95.
  • the molding composition contains no PET.
  • molding compositions are preferred in which component A is PET-free.
  • the inventive molding composition contains, as component B, 1 to 15% by weight, preferably 4 to 10% by weight and particularly preferably 5 to 8% by weight of at least one particulate graft copolymer with a glass transition temperature of Soft phase below 0 ° C and an average particle size of 50 to 1000 nm.
  • Component B is preferably a graft copolymer
  • the particulate graft base B1 cannot contain from 70 to 100% by weight of a Ci-Cio-conjugated diene or both, preferably a Ci to Ciö-alkyl ester of acrylic acid, 0 to 30% by weight of a difunctional monomer with two olefinic conjugated double bonds exist.
  • graft bases are used, for example, as component B in ABS polymers or MBS polymers.
  • the graft base B1 consists of the monomers
  • bl2 0.1 to 10% by weight of at least one polyfunctional monomer with at least two olefinic, non-conjugated double bonds as component B12 and bl3) 0 to 24.9% by weight of one or more further copolymerizable monomers as component B13.
  • the graft base B1 is an elastomer, which is a
  • Glass transition temperature of preferably below -20 ° C, particularly preferably below -30 ° C.
  • preferred monomers B 11 are esters of acrylic acid with 1 to 10 C atoms, in particular 4 to 8 C atoms in the
  • Particularly preferred monomers B1 are iso- and n-butyl acrylate and 2-ethylhexyl acrylate, of which n-butyl acrylate is particularly preferred.
  • a polyfunctional monomer having at least two olefinic, non-conjugated double bonds examples are divinylbenzene, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricylodecenyl acrylate and dihydrodicyclopentadienyl acrylate, of which the latter two are particularly preferred.
  • the graft base B1 does not contain 1,3-butadiene; in particular, the graft base B1 consists exclusively of components B1 and B12.
  • graft base B1 On the graft base B1 is a graft B2 from the monomers b21) 50 to 90% by weight, preferably 60 to 90% by weight, particularly preferably 65 to 80% by weight, of a vinylaromatic monomer as component B21 and
  • component B22 10 to 50% by weight, preferably 10 to 40% by weight, particularly preferably 20 to 35% by weight, of acrylonitrile or methacrylonitrile or mixtures thereof as component B22
  • vinyl aromatic monomers are unsubstituted styrene and substituted styrenes such as ⁇ -methylstyrene, p-chlorostyrene and p-chloro- ⁇ -methylstyrene. Unsubstituted styrene and ⁇ -methylstyrene are preferred; unsubstituted styrene is particularly preferred.
  • the average particle size of component B is 50 to 200 nm, preferably 55 to 150 nm, and particularly preferably 90 to 10 nm.
  • the average is
  • Particle size of component B 200 to 1000 nm, preferably 400 to 550 nm.
  • the particle size distribution of component B is bimodal, component B being 10 to 90% by weight, preferably 30 to 90% by weight, particularly preferably 50 to
  • a small-sized graft copolymer with an average particle size of 50 to 200 nm, preferably 55 to 150 nm and 10 to 90% by weight, preferably 10 to 70% by weight, particularly preferably 25 to 50 Wt .-% consists of a large graft copolymer with an average particle size of 250 to 1000 nm, preferably about 400 to 550 nm.
  • the average particle size and particle size distribution are those from the integral mass distribution specified sizes.
  • the average particle sizes according to the invention are in all cases the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge according to the method of W Scholtan and H. Lange, Kolloid-Z. and Z. Polymer 250 (1972), pages 782-796.
  • the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
  • the mean particle diameter which is also referred to as the dso value of the integral mass distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the d 50 value.
  • the dio and d 0 values resulting from the integral mass distribution are used to characterize the width of the particle size distribution of the rubber particles.
  • the d ⁇ 0 - d or o-value of the integral mass distribution are the d 5 o-defined value, with the difference that they are based on 10 and 90 wt .-% of the particles. The quotient
  • Emulsion polymers A which can be used according to the invention as component A preferably have Q values less than 0.5, in particular less than 0.35.
  • the graft copolymer B is generally one or more stages, i.e. a polymer composed of a core and one or more shells.
  • the polymer consists of a basic stage (graft core) B1 and one or - preferably - several stages B2 (graft support) grafted thereon, the so-called graft stages or graft shells.
  • One or more can be obtained by simple grafting or multiple grafting Graft sleeves are applied to the rubber particles, wherein each graft sleeve can have a different composition.
  • polyfunctional, crosslinking or reactive group-containing monomers can also be grafted on (see, for example, EP-A 0 230 282, DE-A 36 01 419, EP-A 0 269 861).
  • crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. serve as the graft base B1.
  • the crosslinked acrylic acid ester polymers should preferably have a glass transition temperature below -20 ° C., in particular below -30 ° C.
  • a multi-layer structure of the graft copolymer is also possible, with at least one inner shell having a glass transition temperature of below 0 ° C. and the outermost shell having a glass transition temperature of more than 23 ° C.
  • the graft B2 consists of at least one graft shell, the outermost graft shell having a glass transition temperature of more than 30 ° C and wherein a polymer formed from the monomers of the graft B2 would have a glass transition temperature of more than 80 ° C.
  • Suitable preparation processes for graft copolymers B are emulsion, solution, bulk or suspension polymerization.
  • the graft copolymers B are preferably prepared by radical emulsion polymerization, at temperatures of 20 ° C.-90 ° C. using water-soluble and / or oil-soluble initiators such as peroxodisulfate or benzyl peroxide, or with the aid of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.
  • Suitable emulsion polymerization processes are described, for example, in DE-A-28 26 925, DE-A 31 49 358 and in DE-C-12 60 135.
  • the graft shells are preferably constructed in the emulsion polymerization process as described in DE-A-32 27 555, 31 49 357, 31 49 358, 34 14 118.
  • the defined particle sizes of 50-1000 nm according to the invention are preferably carried out after the processes described in DE-C-12 60 135 and DE-A-28 26 925, or Applied Polymer Science, Volume 9 (1965),
  • Page 2929 The use of polymers with different particle sizes is known for example from DE-A-28 26 925 and US 5,196,480.
  • the molding compositions according to the invention contain, as component C, 0 to 15% by weight, preferably 4 to 10% by weight and particularly preferably 5 to 8% by weight of one
  • cl 75 to 90% by weight, preferably 77 to 90% by weight, particularly preferably 81 to 80% by weight, of at least one vinylaromatic monomer as component Cl and
  • c2) 10 to 25% by weight, preferably 10 to 20% by weight, particularly preferably 10 to 19% by weight and in particular 17 to 19% by weight, acrylonitrile and / or methacrylonitrile as component C2.
  • Suitable vinyl aromatic monomers are the above-mentioned monomers Cl and the above-mentioned vinyl aromatic monomers as component B21.
  • Component C is preferably an amorphous polymer, as described above as graft B2. According to one embodiment of the invention, a copolymer of styrene and / or ⁇ -methylstyrene is also used as component C.
  • Component C also includes the free, non-grafted styrene-acrylonitrile copolymers formed in the graft copolymerization to produce component B.
  • component B the free, non-grafted styrene-acrylonitrile copolymers formed in the graft copolymerization to produce component B.
  • component C it may be possible that a sufficient proportion of component C has already been formed in the graft copolymerization. In general, however, it will be necessary to mix the products obtained in the graft copolymerization with additional, separately produced component C.
  • This additional, separately prepared component C can preferably be a styrene / acrylonitrile copolymer, an ⁇ -methylstyrene / acrylonitrile copolymer or an ⁇ -methylstyrene / styrene / acrylonitrile polymer. It is important that the acrylonitrile content in the copolymers C does not exceed 25% by weight, in particular 19% by weight.
  • the copolymers can be used individually or as a mixture for component C, so that the additional, separately produced component C of the molding compositions according to the invention is, for example, a mixture of a styrene / acrylonitrile copolymer (PSAN) and an ⁇ - Methyl styrene / acrylonitrile copolymer can be used.
  • PSAN styrene / acrylonitrile copolymer
  • ⁇ - Methyl styrene / acrylonitrile copolymer can be used.
  • the acrylonitrile content of the various copolymers of component C can also be different.
  • component C preferably consists only of one or more styrene / acrylonitrile copolymers, it being possible for the copolymers to have a different acrylonitrile content.
  • component C consists of only one styrene / acrylonitrile copolymer.
  • the molding compositions according to the invention contain 0 to 20% by weight, preferably 1 to 20% by weight, particularly preferably 5 to 17.5% by weight, in particular 10 to 15% by weight, of fibers. These are commercially available products.
  • these generally have an average length of 0.1 to 0.5 mm, preferably 0.1 to 0.4 mm and a diameter in the range of 6 to 20 ⁇ m.
  • the fibers can be coated with organosilanes, epoxisilanes or other polymer coatings.
  • the molding compositions according to the invention contain, as component E, 0.01 to 15, preferably 0.1 to 12 and particularly preferably 4 to 8% by weight of a polycarbonate, based on the molding composition. Suitable polycarbonates are all known to the person skilled in the art, the meltable ones being particularly suitable. In this connection, "Polymer Chemistry, A Introduction", 2 "Edition, Malcolm P.
  • polycarbonates have high flowability, preferably an MVR at 300 ° C and 1.2 kg of> 9, preferably> 15 and more preferably> 20, wherein component e is a preferred MVR of up to 100, preferably 90, particularly preferably 50 cm 3/10 min show.
  • component Lexan 121R from General Electric Plastics is preferred.
  • PC recyclate as both "post industrial” and “post consumer recyclate” has proven to be particularly suitable, since it can be processed particularly well.
  • the molding compositions according to the invention contain 0 to 2, preferably 0.01 to 2, particularly preferably 0.1 to 0.5 and furthermore preferably 0.1 to 0.3% by weight, based on the molding composition, of a carbon black as a component F.
  • a carbon black as a component F.
  • all carbon blacks known to the person skilled in the art are suitable for component F.
  • Particularly preferred are acetylene black or the natural gases or petroleum residues resulting from the combustion of tar, tar oils, naphthalene or hydrocarbon in the event of inadequate air supply or with rapid cooling of the combustion gases . Due to the soot content of the molding compositions according to the invention
  • the molding compositions according to the invention can contain from 0.01 to 15% by weight, preferably 0.1 to 10 and particularly preferably 3 to 8% by weight, different from B, preferably homogeneously miscible with components A and / or C. contained in these dispersible polymers.
  • Preferential as usual (grafted) rubbers are used, such as ethylene vinyl acetate rubbers, silicone rubbers, thermoplastic polyurethanes, polyether rubbers, polyether ester rubbers, hydrogenated diene rubbers, polyalkenamer rubbers, acrylate rubbers, ethylene propylene rubbers, ethylene propylene Diene rubbers and butyl rubbers, methyl methacrylate butadiene styrene
  • MBS methyl methacrylate-butyl acrylate-styrene rubbers, preferably insofar as they are miscible with or dispersible in the mixed phase formed from components A, B and C.
  • Acrylate rubbers ethylene-propylene (EP) rubbers, ethylene-propylene-diene (EPDM) rubbers, in particular as graft copolymers, are preferably used.
  • An EDPM-graft-PSAN rubber is particularly preferred, in particular that from GE Specialty Chemicals, Blendex WX 270.
  • Polymers or copolymers, such as polyacrylates, polymethacrylates, which are compatible or miscible with the mixed phase formed from components B and C, are also suitable.
  • Reactive rubbers which bind to the polyester (component A) via a covalent bond, such as with acid anhydrides, such as maleic anhydride, or epoxy compounds, such as glycidyl methacrylate, grafted polyolefin rubbers and / or particulate acrylate rubbers, are also suitable.
  • acid anhydrides such as maleic anhydride
  • epoxy compounds such as glycidyl methacrylate, grafted polyolefin rubbers and / or particulate acrylate rubbers, are also suitable.
  • polymers examples include graft copolymers of PBT and PSAN or segmented copolymers such as block copolymers or multiblock copolymers from at least one segment from PBT with M> 1000 and at least one segment from PSAN or a miscible segment with M w > 1000 compatible with PSAN.
  • the molding composition according to the invention contains 0 to 20, preferably 0 to 15 and particularly preferably 0 to 10% by weight, based on the total molding composition, of a polyester different from component A as component H.
  • the polyester of component H has at least 50, preferably at least 70 and especially preferably 100% by weight of polyethylene terephthalate (PET) based on component H.
  • PET polyethylene terephthalate
  • the aromatic polyesters already defined above are preferred as further polyesters of component H.
  • the PET can be used either directly from the synthesis or as a recyclate, preferably from regrind from PET bottles.
  • the use of recycled PET is advisable on the one hand for reasons of cost and on the other hand because of the effect of the recycled material on improving the toughness of the molding compound.
  • the PET used in component H according to the invention thus preferably consists of at least 50, preferably at least 80 and particularly preferably 100% of recycled PET.
  • the molding compositions according to the invention contain, as component I, 0 to 10, preferably 0.1 to 9,% by weight of conventional additives.
  • additives are: UV stabilizers, transesterification stabilizers, oxidation retarders, lubricants and mold release agents, dyes, pigments, colorants, nucleating agents, antistatic agents, antioxidants, stabilizers to improve
  • Heat stabilizers or oxidation retardants are usually metal halides (chlorides, bromides, iodides) which are derived from metals of group I of the periodic table of the elements (such as Li, Na, K, Cu).
  • Suitable stabilizers are the usual sterically hindered phenols, but also vitamin E or compounds with an analog structure.
  • HALS stabilizers modified amine light stabilizers
  • benzophenones modified amine light stabilizers
  • resorcinols resorcinols
  • salicylates benzotriazoles and other compounds are also suitable (for example Irganox®, Tinuvin®, such as
  • Tinuvin® 770 HALS absorber, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate
  • Tinuvin®P UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol
  • Topanol® UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol
  • Transesterification stabilizers include, for example, organic phosphonites such as tetrakis (2,4-di-tert-butylphenyl) bisphenylene diphosphonite (Irgaphos® PEPQ or
  • the transesterification stabilizers can be present, for example, in powder form or as PBT batches.
  • Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures with 12 to 30 carbon atoms.
  • the amounts of these additives are in the range from 0.05 to 1% by weight.
  • Silicone oils, oligomeric isobutylene or similar substances can also be used as additives; the usual amounts are 0.05 to 5% by weight.
  • Pigments, dyes, color brighteners, such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides or derivatives of perylene tetracarboxylic acid can also be used.
  • Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in amounts of 0.01-5% by weight, based on the total molding composition.
  • Nucleating agents such as talc, calcium fluoride, sodium phenylphosphinate, aluminum oxide or finely divided polytetrafluoroethylene can also be used in amounts, for example up to 5% by weight, based on the total molding composition.
  • Plasticizers such as dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N- (n-butyl) benzenesulfonamide, o- and p-toluenesulfonamide are advantageously added in amounts of up to about 5% by weight, based on the molding composition.
  • Colorants such as dyes and pigments, can be added in amounts of up to about 5% by weight, based on the molding composition.
  • the molding composition according to the invention has a component G with a copolymer which does not contain a butadiene or isoprene derivative or neither.
  • none of the graft copolymers used in the molding composition have a butadiene or isoprene derivative or neither.
  • Another molding composition preferred according to the invention has no butadiene or isoprene derivative or neither.
  • butadiene and isoprene are preferred as derivatives.
  • Components A to I can be mixed in any desired manner by all known methods.
  • the components can be used as such or in the form of mixtures of one component with one or more of the other components.
  • component B can be premixed with part or all of component C and then mixed with the other components.
  • components B and C have been prepared, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, then to precipitate the polymers together and to work up the polymer mixture.
  • components B and C are preferably mixed by extruding, kneading or rolling the components together, components B and C having, if necessary, been isolated beforehand from the solution or aqueous dispersion obtained in the polymerization.
  • thermoplastic molding compositions according to the invention can be produced, for example, by melting component A with components B and C or with a mixture of these, and optionally with the other components, in an extruder and feeding the fibers through an inlet on the extruder.
  • Component E can be mixed with the other components of the molding composition both in the “cold feed process”, ie at temperatures below the melting temperature of the components, before processing in a mixing device. However, it is preferred if component E is in the “hot Feed method ", ie in the melt the other components of the molding composition for incorporation into the
  • Molding compound is supplied.
  • a temperature range from 250 to 280 ° C. is preferred for the “hot feed method” and from 260 to 270 ° C. is particularly preferred.
  • component D in the “hot feed process” by adding it to the other components of the molding compositions.
  • components D and E are each independent of one another, i.e. without premixing them in the "hot feed"
  • the molding compositions according to the invention can be processed into molded parts by the known methods of thermoplastic processing.
  • they can be produced by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by injection molding.
  • the moldings which can be produced from the molding compositions according to the invention are also the subject of the present invention.
  • the molded parts produced from the molding compositions according to the invention have only low emissions of volatile constituents with a noticeable odor.
  • the odor behavior of polymer materials is assessed according to DIN 50011 / PV 3900 and applies to components of the vehicle interior.
  • the result of the odor test according to this standard is generally better than grade 5, preferably better than grade 4.5, particularly preferably better than grade 4 in the case of the molded parts according to the invention.
  • the carbon emission of the molded parts according to PV 3341 is im generally ⁇ 50 ⁇ g / g, preferably ⁇ 40 ⁇ g / g, particularly preferably ⁇ 35 ⁇ g / g.
  • the lower limit is preferably 5 ⁇ g / g.
  • the moldings according to the invention also have good heat resistance.
  • the Vicat B softening temperature is generally> 130 ° C, preferably> 135 ° C, particularly preferably> 138 ° C.
  • the upper limit of the Vicat B softening temperature is preferably 160 ° C.
  • the moldings according to the invention also have good heat aging behavior.
  • the impact strength of the moldings according to the invention according to ISO 179 / leU after 1000 hours of heat storage at 130 ° C. is generally> 25 kJ per m, preferably> 30 kJ per m.
  • the elongation at break of the moldings according to the invention is generally> 1.5%, preferably> 2% and particularly preferably> 2.5% after heat storage at 130 ° C. for 1000 hours.
  • the decrease in impact strength according to ISO 179 / leU after 1000 h of heat storage at 120 ° C. of ⁇ 30%, preferably ⁇ 20% compared to before heat storage is preferred.
  • the moldings according to the invention also have good mechanical properties.
  • its modulus of elasticity is generally> 3000, preferably> 4500 MPa, but preferably a maximum of 8000 MPa, its yield stress in general> 80, preferably> 85 MPa, but preferably a maximum of 120 MPa, its impact strength in accordance with ISO 179 / leU in general> 45, preferably> 48 kJ / m, their impact strength without prior heat storage according to ISO 179 / leA, generally> 5 kJ / m, but in each case below 75 kJ / m, and their HDT B (measured according to ISO 75, embodiment B) in general> 190 ° C, preferably> 200 ° C, but at a maximum at 230 ° C, and their flowability as MVR (melt volume ratio 275 ° C / 2.16 kp contact force according to ISO 1133)> 10, preferably> 14 cm 3 / 10min, but maximum at 30 cm / 10min.
  • MVR melt volume ratio
  • a compression hardness according to DIN53577 of 20 to 100 kPa at 20 to 60% compression is also preferred for the molding compositions according to the invention.
  • the molded parts according to the invention have no splintering behavior in the puncture test (2 and 3 mm plate diameter, in accordance with ISO 6603/2), even after 1000 hours of heat storage at 130 ° C., at -30 ° C.
  • the elongation at break according to DIN 53457 after 1000 h of heat treatment at 130 ° C is> 2.5%.
  • the molding compositions according to the invention are suitable for a large number of moldings which contain these molding compositions owing to their high heat resistance, their good heat aging resistance, their good mechanical properties and their good surface properties.
  • Examples include: camera housings, cell phone housings, sockets for binoculars, vapor duct for extractor hoods, parts for pressure cookers, housings for hot air grills and pump housings, safety side panels, in particular side skirts for trucks and buses.
  • the molded parts according to the invention are particularly suitable for applications in motor vehicles.
  • Molded parts according to the invention are therefore, in particular, parts made from the molding compositions according to the invention, such as light switch housings, lamp housings, housings for the central electrical system, plug strips, plug connectors, housings for ABS controllers, license plate holders and luggage rack roof strips.
  • the molded parts according to the invention are particularly suitable for applications in the motor vehicle interior. Molded parts according to the invention are therefore preferably covers, storage compartments, instrument panel supports, door parapets, parts for the center console and brackets for radio and air conditioning, covers for the center console, covers for radio, air conditioning and Ashtrays, extensions of the center console, storage pockets, storage for the driver and front passenger door, storage for the center console, components for the driver and front passenger seat, such as seat panels, defroster duct, interior mirror housings, sunroof elements such as sunroof frames, instrument panel and covers, instrument holders, top and Bottom shell for the steering column, air ducts, air outlets and intermediate pieces for inflow and defroster duct, door side panels, panels in the knee area, air outlet nozzles, defroster openings, switches and levers as well as air filters and fan ducts. These applications are only examples of conceivable automotive interior applications. It is particularly preferred that the molded parts according to the invention can be laser patterned.
  • the invention further relates to a composite which contains a molded part according to the invention and a polycondensate foam or a layer or both.
  • the molded part and the polycondensate foam or layer or all three are advantageously firmly connected to one another via their surfaces.
  • the composites with the polycondensate foam are distinguished by excellent foam adhesion of the foam to the surface of the molded part, without the need for pretreatment, for example by a primer.
  • foamable polycondensates known to the person skilled in the art can be used for the polycondensate foam.
  • the foam is applied to the molding surfaces without the use of a primer.
  • polyamides and polyurethanes are preferred and polyurethanes are particularly preferred.
  • semi-rigid and flexible foams are again particularly preferred; these can optionally contain adhesion promoters.
  • the product Elastoflex from Elastogran GmbH, Lemforde is used as the polyurethane foam.
  • a layer thickness between 0.0001 and 2 mm, preferably 0.001 and 1 mm and particularly preferably 0.001 and 0.5 mm is preferably used in the composite according to the invention, comprising a molded part according to the invention and a layer.
  • Such layers preferably also consist of polymeric material. Paints in particular have proven themselves as polymeric materials. Among these paints, two components of hydro soft feeling paints are particularly preferred. Hydro-soft feeling lacquers based on polyurethane are particularly suitable as layers. According to the invention, preference is given to a two-component hydro soft feeling varnish from W ⁇ RWAG GmbH & CoKG.
  • Composites according to the invention which contain a molded part according to the invention and a layer have particularly advantageous
  • the invention further relates to a recyclate which is obtainable from the molding compositions or molded parts or composites described above or from at least two of them.
  • the recyclate from the molding compositions or moldings or composites after their use i. that is, if they are waste.
  • the recyclate is obtained from generally known recycling processes. Crushing, such as shredding or grinding, and subsequent sintering or pressing are particularly preferred as recycling processes.
  • Molding compositions not or only slightly negatively influenced by the recycling process.
  • Material property changes between the molding composition and the recycled material of the molding composition preferably occur at a maximum of 25%, based on the material properties of the molding composition before the recycling process.
  • the material properties such as heat resistance and emission behavior, preferably the emission behavior, are not adversely affected by the recycling of the molding compositions.
  • the material obtained from the recycling of the molding compounds is particularly used partially or entirely for instrument panels and / or attachments.
  • molding compositions according to the invention with somewhat less toughness have proven useful for air ducts. Molding compositions from the recycling process with a toughness up to a maximum of 25% below the viscosity of the molding compositions prior to the recycling process are particularly preferred.
  • Molding materials, molded parts or composites containing the recyclate can be obtained from the recyclate. This is preferably done according to the methods described above. The above-defined molding compositions, molded parts and composites are particularly preferred.
  • the invention also relates to the use of the molding compositions according to the invention for the production of the moldings mentioned, in particular in the interior of a motor vehicle.
  • the invention relates to a method for adjusting at least one of the previously defined properties of a molding composition, preferably a molding composition according to one of claims 1 to 6, by varying the concentration of at least one of the components defined above in the weight% ranges defined above .
  • PBT1 is a polybutylene terephthalate with a viscosity number of 130 (determined in a 0.05 g / ml polymer solution of phenol and 1, 2-dichlorobenzene (1: 1)).
  • Pl is a small-sized ASA graft rubber with 25% by weight acrylonitrile in the SAN graft shell with an average particle size of approx. 100 nm (determined in a 0.05 g / ml polymer solution of phenol and 1, 2-dichlorobenzene (1: 1)).
  • PBT2 is a polybutylene terephthalate with a viscosity number of 107.
  • PC is the polycarbonate Lexan from General Electric Plastics AG.
  • Glass fibers standard glass (cut glass)
  • Small ASA is an ASA graft rubber with an average particle diameter of approx. 100 nm.
  • PSAN 2 (35) is a styrene / acrylonitrile copolymer with 35% by weight acrylonitrile.
  • PSAN 1 (19) is a styrene / acrylonitrile copolymer with 19% by weight acrylonitrile.
  • the mold release agent is Loxiol ® VPG 861 / 3.5 from Henkel KGaA.
  • Soot is Black Pearls ® ⁇ 880
  • the emission behavior was assessed according to PV 3341 and DIN 50011 / PV 3900 C3.
  • the odor emission was measured according to DIN 50011 / PV3900 C3 as follows:
  • a sample volume of 50 cm was tightly closed in a 1 liter container with an odorless seal and lid and placed in a preheated heating karnmer with air circulation stored at 80 ° C for 2 hours. After the test vessel was removed from the heat chamber, the test vessel was cooled to 60 ° C before the evaluation was carried out by at least 3 examiners.
  • the odor assessment is based on the rating scale with the grades 1 to 6, whereby half intermediate steps are possible.
  • Table 2 contains the results of the odor test and the results of the mechanical tests carried out in addition.
  • the laser marking was carried out by a Na-YAg laser with a lamp current of approx. 15 A.
  • the contrast strength was determined by looking at the labeling over the legibility and rated "good” and "bad".
  • VZ viscosity number

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matières moulables renforcées par fibres contenant, par rapport à la somme des composants A à I, laquelle correspond à 100 % en poids: a) comme constituant résiduel, jusqu'à un total de 100 % en poids, par rapport à la matière moulable, d'au moins un polycondensat, comme composant A; b) 1 à 15 % en poids d'au moins un copolymérisat greffé particulaire, dont la phase molle présente une température de transition vitreuse inférieure à 0 °C et dont la grandeur moyenne de particule est de 50-1000 nm, comme composant B; c) 0 à 15 % en poids d'au moins un copolymérisat, comme composant C, ce copolymérisat étant constitué de: c1) 50 à 90 % en poids d'au moins un monomère aromatique vinylique, comme composant C1, et c2) 10 à 50 % en poids d'acrylnitrile et/ou de méthacrylnitrile, comme composant C2, ces derniers pourcentages en poids se rapportant au composant C; d) 0 à 20 % en poids de fibres, comme composant D; e) 0,01 à 15 % en poids d'un poycarbonate, comme composant E; f) 0 à 2 % en poids d'une suie, comme composant F; g) 0,01 à 15 % en poids d'un polymère différent du composant B, comme composant G; h) 0 à 20 % en poids d'un polyester différent du composant A, comme composant H; i) 0 à 10 % en poids d'additifs habituels, tels que stabilisateurs anti U.V., retardateurs d'oxydation, lubrifiants et agents de démoulage, comme composant I. L'invention concerne également des pièces moulées et des composites constituées de ces matières, leurs produits de recyclage, ainsi que l'utilisation desdites matières moulables, desdites pièces moulées, desdits composites et de leurs produits de recyclage.
EP00926866A 1999-04-26 2000-04-11 Matieres moulables a utiliser dans l'habitacle d'un vehicule automobile, composite contenant ces matieres moulables, et leurs produits de recyclage Withdrawn EP1183309A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19918912 1999-04-26
DE19918912A DE19918912A1 (de) 1999-04-26 1999-04-26 Formmassen für Kraftfahrzeug-Innenanwendungen und diese beinhaltende Verbunde sowie deren Recyclate
PCT/EP2000/003209 WO2000064974A2 (fr) 1999-04-26 2000-04-11 Matieres moulables a utiliser dans l'habitacle d'un vehicule automobile, composite contenant ces matieres moulables, et leurs produits de recyclage

Publications (1)

Publication Number Publication Date
EP1183309A2 true EP1183309A2 (fr) 2002-03-06

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Country Status (9)

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US (1) US6479617B1 (fr)
EP (1) EP1183309A2 (fr)
CN (1) CN1349550A (fr)
AU (1) AU4547000A (fr)
BR (1) BR0010035A (fr)
CZ (1) CZ20013762A3 (fr)
DE (1) DE19918912A1 (fr)
MX (1) MXPA01010387A (fr)
WO (1) WO2000064974A2 (fr)

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Publication number Priority date Publication date Assignee Title
EP1678257A1 (fr) * 2003-10-10 2006-07-12 Basf Aktiengesellschaft Compositions a mouler thermoplastiques
US20060030659A1 (en) * 2004-08-09 2006-02-09 Destio Paul Low warp polybutylene terephthalate molding compositions
US20070231576A1 (en) * 2005-09-30 2007-10-04 Davis M S Multilayer films comprising tie layer compositions, articles prepared therefrom, and method of making

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DE643104C (de) * 1932-11-13 1937-03-25 Kali Forschungs Anstalt G M B Verfahren zur Nutzbarmachung des gebundenen Stickstoffes im Nitrosylchlorid
DE3339001A1 (de) * 1983-07-06 1985-01-17 Bayer Ag, 5090 Leverkusen Thermoplastische polyester-formmassen mit hoher zaehigkeit
DE3827568A1 (de) * 1988-08-13 1990-02-15 Basf Ag Kaelteschlagzaehe thermoplastische polyesterformmassen
DE4330490A1 (de) * 1993-09-09 1995-03-16 Basf Ag Thermoplastische Formmassen
JP3327652B2 (ja) * 1993-12-20 2002-09-24 ダイセル化学工業株式会社 熱可塑性樹脂組成物
DE19903073A1 (de) * 1999-01-27 2000-08-10 Basf Ag Formmassen für Kraftfahrzeug-Innenanwendungen
DE19905321A1 (de) * 1999-02-09 2000-08-10 Basf Ag Formmassen für Kraftfahrzeug-Anwendungen
DE19905341A1 (de) * 1999-02-09 2000-08-10 Basf Ag Polycarbonatarme Formmassen für Kraftfahrzeug-Anwendungen

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Title
See references of WO0064974A3 *

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Publication number Publication date
AU4547000A (en) 2000-11-10
BR0010035A (pt) 2002-01-15
MXPA01010387A (es) 2002-03-27
WO2000064974A3 (fr) 2001-03-29
CZ20013762A3 (cs) 2002-03-13
CN1349550A (zh) 2002-05-15
WO2000064974A2 (fr) 2000-11-02
DE19918912A1 (de) 2000-11-02
US6479617B1 (en) 2002-11-12

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