EP2188333A1 - Pièces moulées présentant des surfaces de qualité améliorée - Google Patents

Pièces moulées présentant des surfaces de qualité améliorée

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Publication number
EP2188333A1
EP2188333A1 EP08785612A EP08785612A EP2188333A1 EP 2188333 A1 EP2188333 A1 EP 2188333A1 EP 08785612 A EP08785612 A EP 08785612A EP 08785612 A EP08785612 A EP 08785612A EP 2188333 A1 EP2188333 A1 EP 2188333A1
Authority
EP
European Patent Office
Prior art keywords
hydroxyphenyl
gloss
bis
tert
butyl
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.)
Withdrawn
Application number
EP08785612A
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German (de)
English (en)
Inventor
Rolf Wehrmann
Michael Erkelenz
Gesa Dern
Berit Krauter
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.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP2188333A1 publication Critical patent/EP2188333A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • 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
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/06—Multi-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins

Definitions

  • Polycarbonates belong to the group of engineering thermoplastics.
  • Technical thermoplastics find versatile applications in the electrical and electronics sector, as housing material of luminaires and in applications where special mechanical properties are required. These applications almost always require good thermal and mechanical properties such as Vicat temperature, glass transition temperature and impact strength. This u. a. Blacks used for dark or opaque coloring.
  • a disadvantage of such compositions is often the shiny surface of the articles / moldings made therefrom. To prevent this disadvantage, the tool surfaces must be roughened
  • MWCNT Multi Wall Carbon Nanotubes
  • EP-A 1770126 describes polycarbonate compositions containing a fluorine-containing organic metal salt, at least one further component selected from the group consisting of a flame retardant, a fatty acid ester, a UV absorber, PTFE fibers, a filler, a silicate mineral and a titanium dioxide pigment.
  • a flame retardant e.g., a flame retardant, a fatty acid ester, a UV absorber, PTFE fibers, a filler, a silicate mineral and a titanium dioxide pigment.
  • MWCNT mulitwall carbon nanotubes
  • JP 2006-291081 A, JP 2006-193649 A, JP 2006-016553A and WO 2008/078850 A describe the use of MWCNT in polycarbonate.
  • the cited patent applications do not describe molded parts made of polycarbonate and MWCNT with a certain degree of gloss.
  • the invention therefore relates to moldings obtainable from compositions containing
  • thermoplastic %, very particularly preferably 99.70 to 93% by weight, in particular 98 to 94% by weight, of thermoplastic and
  • wt .-% preferably 0.1 to 12 wt .-%, particularly preferably 0.12 to 7 wt .-%, most preferably 0.3 to 7 wt.%, In particular 2 to 6 wt.% Multi Wall Carbon Nanotubes, a degree of gloss 20 ° of 104 to 20, preferably 100 to 20, particularly preferably 40 to 22 and a gloss level 60 ° of 103 to 50, preferably 100 to 50, particularly preferably 80 to 55, measured according to ISO 2813 with a Byk-Gardner Haze gloss exhibit.
  • molded parts which have a degree of gloss 20 ° of 104 to 20, preferably 100 to 20, particularly preferably 40 to 22 and a degree of gloss 60 ° of 103 to 50, preferably 100 to 50, particularly preferably 80 to 55, measured according to ISO 2813 with a Byk-Gardner haze gloss.
  • thermoplastics are particularly transparent thermoplastics such as polycarbonate, polyester, z.
  • polyethylene terephthalate and Polybutylenterephtalat polysulfones, polyethers, polyolefins, cycloolefin copolymers, polystyrenes and polyacrylates.
  • Preferred thermoplastic is polycarbonate.
  • opaque compositions such as polycarbonate-based blends such. B. with polyesters, SAN, ABS and / or polylactate are suitable.
  • Multiwall carbon nanotubes are preferably understood as meaning cylindrical carbon tubes with a carbon content of> 95%, which contain no amorphous carbon.
  • the carbon nanotubes preferably have an outer diameter between 3 and 80 nm, more preferably 5 to 20 nm.
  • the mean value of the outer diameter is preferably 13 to 16 nm.
  • the length of the cylindrical carbon nanotubes is preferably 0.1 to 20 .mu.m, more preferably 1 to 10 .mu.m.
  • the carbon nanotubes preferably consist of 2 to 50, more preferably 3 to 15 graphitic layers (also referred to as "layers" or "walls”) having a minimum inside diameter of 2 to 6 nm.
  • These carbon nanotubes are also referred to as “carbon fibrils” or “hollow carbon fibers", for example.
  • the preparation of the MWNT used according to the invention is generally known (cf., for example, US Pat. No. 5,643,502 and DE 10 2006 017 695 A1, preferably the preparation is carried out according to the method described in DE 10 2006 017 695 Al, particularly preferably according to the method disclosed in Example 3 of DE 10 2006 017 695 A1).
  • Thermoplastic, aromatic polycarbonates in the context of the present invention are both homopolycarbonates and copolycarbonates;
  • the polycarbonates may be linear or branched in a known manner.
  • thermoplastic polycarbonates including the thermoplastic, aromatic polyester carbonates, have average molecular weights M w (determined by gel permeation chromatography with polycarbonate calibration) of 12,000 to 120,000, preferably of 15,000 to 80,000, in particular of 18,000 to 60,000. most preferably from 18,000 to 40,000 g / mol.
  • a part, up to 80 mol%, preferably from 20 mol% up to 50 mol% of the carbonate groups in the polycarbonates suitable according to the invention may be replaced by aromatic dicarboxylic acid ester groups.
  • aromatic polyester carbonates Such polycarbonates, which contain both acid residues of carbonic acid and acid residues of aromatic dicarboxylic acids incorporated into the molecular chain, are referred to as aromatic polyester carbonates. They are subsumed for simplicity in the present application under the generic term of the thermoplastic, aromatic polycarbonates.
  • the preparation of the polycarbonates is carried out in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, wherein for the production of polyester carbonates, a part of the carbonic acid derivatives is replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, depending on the extent to be replaced in the aromatic polycarbonates Carbonate structural units by aromatic dicarboxylic ester structural units.
  • Dihydroxyaryl compounds suitable for the preparation of polycarbonates are those of the formula (2)
  • Z is an aromatic radical having 6 to 30 C atoms which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridge members.
  • Z in formula (2) preferably represents a radical of the formula (3)
  • R 6 and R 7 independently of one another are H, C 1 -C 6 -alkyl-, C 1 -C 6 -alkoxy, halogen, such as Cl or Br, or each optionally substituted aryl or aralkyl, preferably H or C 1 -C 2 -alkyl, particularly preferably H or Q-Cg-alkyl and very particularly preferably H or methyl, and
  • X is a single bond, -SO 2 -, -CO-, -O-, -S-, C r to C ⁇ -alkylene, C 2 - to C 5 -alkylidene or
  • C 5 - to C (, - cycloalkylidene which may be substituted by Q- to C ⁇ -alkyl, preferably methyl or ethyl, furthermore C 6 - to C ⁇ -arylene which optionally condenses with further heteroatome-containing aromatic rings can be, stands.
  • X is preferably a single bond, C 1 to C 5 -alkylene, C 2 to C 5 -alkylidene, C 5 to C 6 -cycloalkylidene, -O-, -SO-, -CO-, -S-, - SO 2 -,
  • R 8 and R 9 are individually selectable for each X 1 , independently of one another are hydrogen or C 1 -C 4 -alkyl, preferably hydrogen, methyl or ethyl, and
  • X 1 carbon and n is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X 1 , R 8 and R 9 are simultaneously alkyl
  • dihydroxyaryl compounds examples include dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) -aryls, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, l, r-bis (hydroxyphenyl) -dnsopropylbenzenes, and their ring-alkylated and ring-halogenated compounds
  • Diphenols suitable for the preparation of the polycarbonates to be used according to the invention are, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers , Bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, ⁇ , ⁇ '-bis (hydroxyphenyl) -dnsopropylbenzenes, and their alkylated, nuclear alkylated and nuclear halogenated compounds
  • Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -1-phenyl-propane, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2, 2-bis- (3-methyl-4-hydroxyphenyl) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) - propane, bis- (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,3-bis- [2- (2- 3,5-dimethyl-4-hydroxyphenyl)
  • diphenols are 4,4'-dihydroxydiphenyl, 1, 1-bis (4-hydroxyphenyl) phenyl ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5 -dimethyl-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-t-methylcyclohexane (Bisphenol TMC)
  • the monofunctional chain terminators needed to control the molecular weight such as phenol or alkylphenols, in particular phenol, p-tert. Butylphenol, iso-octylphenol, cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators are fed either with the bisphenolate or the bisphenolates of the reaction or added at any time during the synthesis, as long as phosgene or Chlorkohlenquipreend phenomenon in the reaction mixture are present or in the case of acid chlorides and chloroformate as chain terminators as long as enough phenolic end groups of the forming polymer are available.
  • the chain terminator (s) are added after phosgenation at one point or at a time when phosgene is no longer present but the catalyst has not yet been metered, or before the catalyst, with the catalyst together or in parallel.
  • any branching or debranching compounds to be used are added to the synthesis, but usually before the chain terminators.
  • trisphenols, quarterphenols or acid chlorides of tri- or tetracarboxylic acids are used, or mixtures of polyphenols or acid chlorides.
  • branching compounds having three or more than three phenolic hydroxyl groups include, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2, 4,6-tri- (4-hydroxyphenyl) -heptane, 1, 3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4 -hydroxyphenyl) -phenylmethane, 2,2-bis (4,4-bis (4-hydroxyphenyl) cyclohexyl] -propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4 hydroxyphenyl) methane.
  • trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • Preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri- (4-hydroxyphenyl) -ethane.
  • the amount of optionally used branching agent is 0.05 mol% to 2 mol%, based in turn on moles of diphenols used in each case.
  • the branching agents can be presented either with the diphenols and the chain terminators in the aqueous alkaline phase, or dissolved in an organic solvent prior to phosgenation be added.
  • aromatic dicarboxylic acids are, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyl dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,2-bis- (4-carboxyphenyl) -propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid.
  • aromatic dicarboxylic acids terephthalic acid and / or isophthalic acid are particularly preferably used.
  • dicarboxylic acids are the dicarboxylic acid dihalides and the dicarboxylic acid dialkyl esters, in particular the dicarboxylic acid dichlorides and the dimethyl dicarboxylates.
  • Substitution of the carbonate groups by the aromatic dicarboxylic ester groups is essentially stoichiometric and also quantitative, so that the molar ratio of the reactants is also found in the finished polyester carbonate.
  • the incorporation of the aromatic dicarboxylic acid ester groups can be carried out both statistically and in blocks.
  • Preferred methods of preparation of the polycarbonates to be used according to the invention, including the polyester carbonates, are the known interfacial process and the known melt remover process (cf., for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US Pat. No. 5,340,905, US 5,097,002, US-A 5,717,057).
  • the acid derivatives used are preferably phosgene and optionally dicarboxylic acid dichlorides, in the latter case preferably diphenyl carbonate and optionally dicarboxylic acid diester.
  • Catalysts, solvents, workup, reaction conditions, etc., for polycarbonate production or polyester carbonate production are sufficiently described and known in both cases.
  • the polycarbonates, polyester carbonates and polyesters can be worked up in a known manner and processed to form any shaped articles, for example by extrusion or injection molding.
  • the polycarbonate compositions may be added to the conventional additives for the thermoplastics mentioned additives such as fillers, UV stabilizers, heat stabilizers, antistatic agents, dyes and pigments, mold release agents, ER absorbers and flame retardants in the usual amounts become. It is particularly preferred to use only those that do not affect the transparency of the material.
  • Suitable additives are described, for example, in “Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999", in the “Plastics Additives Handbook, Hans Zweifel, Hanser, Kunststoff 2001”.
  • Suitable antioxidants or thermal stabilizers are, for example:
  • organic phosphites, phosphonates and phosphanes usually those in which the organic radicals completely or partially consist of optionally substituted aromatic radicals.
  • thermostabilizer is very particularly preferred (2,4,6-tri-t-butylphenyl) - (2-butyl-2-ethyl-propane-1, 3-diyl) phosphite:
  • the phosphites can be used alone, but also in combination with other phosphorus compounds, wherein the other phosphorus compounds can also be those which have a different oxidation number of the phosphorus. Accordingly, for example, combinations of the phosphites according to the invention with other phosphites, with phosphines, for example triphenylphosphine, with phosphonites, with phosphates, with phosphonates, etc. can be used. Phosphines can also be used alone, for example triphenylphosphine or tritoluylphosphine.
  • the phosphites used are generally known or prepared analogously to known phosphites, (2,4,6-tri-t-butylphenyl) - (2-butyl-2-ethyl-propane-l, 3-diyl) phosphite is described for example in the EP-A 702 018 and EP 635 514.
  • the polymer mixtures generally contain the phosphorus compound in a proportion of 10 to 5000 ppm, preferably 10 to 1000 ppm, particularly preferably 20 to 700 ppm, very particularly preferably between 50 and 500 ppm.
  • thermoplastic molding compositions The addition of the mold release agents, the phosphorus compound and the formals to the thermoplastic molding compositions is carried out by way of example and preferably by adding them after the preparation and during the work-up of the polycarbonates, e.g. added by addition to the polycarbonate polymer solution, or a melt of the thermoplastic molding compositions. Furthermore, it is also possible to meter in the components independently of one another in different work steps, e.g. one of the components during the processing of the polymer solution and the other (s) component (s) in the melt, as long as it is ensured that all components in the production of the end products (moldings) are included.
  • IRGANOX 1076 ®
  • Tinuvins the group of benzotriazoles 2.1 (so-called. Tinuvins), in particular in mixture with one another as well as triphenylphosphine (TPP).
  • Suitable flame retardants C) are: alkali metal or alkaline earth metal salts of aliphatic or aromatic sulfonic acid sulfonamide and sulfonimide derivatives, e.g. Potassium perfluorobutanesulfonate, potassium diphenyl sulfone sulfonate, N- (p-tolylsulfonyl) -p-toluenesulfimide potassium salt, N- (N'-benzylamino-cabonyl) -sulfanylimide potassium salt.
  • alkali metal or alkaline earth metal salts of aliphatic or aromatic sulfonic acid sulfonamide and sulfonimide derivatives e.g. Potassium perfluorobutanesulfonate, potassium diphenyl sulfone sulfonate, N- (p-tolylsulfonyl) -p-toluenesul
  • Salts which can optionally be used in the molding compositions are, for example:
  • organic flame retardant salts are preferably used in amounts of from 0.01 to 0.1 part by weight, preferably from 0.01 to 0.08 part by weight, more preferably from 0.01 to 0.06 part by weight, and more preferably 0.01 to 0.03 parts by weight (based on the polymer composition) used in the molding compositions.
  • compositions may contain suitable PTFE blends.
  • suitable PTFE blends are all physical mixtures of PTFE (polytetrafluoroethylene) with a layer substance which is compatible with polycarbonate or polyester carbonate and PTFE and obtains the fibril structure of the PTFE chains.
  • Suitable substances are, for example, styrene-acrylonitrile copolymers (SAN) and polyacrylates.
  • SAN styrene-acrylonitrile copolymers
  • PTFE is present in proportions of 20-80% by weight, preferably 20-70% by weight and most preferably 30-60% by weight.
  • Such blends are commercially available for example under the trade name Blendex ® B449 of GE Specialty Chemicals or Metablen A ® series from Mitsubishi Rayon.
  • the blends are prepared by mixing a PTFE emulsion with an emulsion of the suitable blend partner. From the resulting mixture, the blend is recovered by a suitable method such as coagulation, freeze
  • Alkali or alkaline earth salts for the production of flame-retardant polycarbonate are known, see, for example: US Pat. Nos. 3,775,367, 3,836,490, 3,933,734, 3,940,366, 3,953,399, 3,926,908, 4,104,246, 4,469,833 , 4,626,563, 4,254,015, 4,626,563 and 4,649,168.
  • Suitable antioxidants are, for example:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl 4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- ( ⁇ -methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6- Di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chain, for example, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1 '- methylundec-r-yl) phenol, 2,4-
  • esters of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols very particular preference is given to the ester with octadecanol (IRGANOX 1076® from Ciba Spec.)
  • Suitable thiosynergists are, for example, dilauryl thiodipropionate and / or distearyl thiodipropionate.
  • UV absorbers and light stabilizers can be used in the compositions according to the invention in amounts of from 0.1 to 15% by weight, preferably from 3 to 8% by weight, based on the mass of the composition. Suitable UV absorbers and light stabilizers are, for example:
  • Suitable metal deactivators are, for example, N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl 4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, iso-sophoyldihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-bis (salicyl - oyl) oxalyldihydrazide, N, N'-bis (salicyloyl) thiopropionyldi
  • Suitable peroxide scavengers are, for example, esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (dodecylmercapto) propionate. It is possible to use individual ones of these compounds or mixtures thereof.
  • Suitable basic costabilizers are, for example, melamine, polyvinyl pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatechol. lat or zinc pyrocatecholate. It is possible to use individual ones of these compounds or mixtures thereof.
  • Suitable nucleating agents are, for example, inorganic substances, such as talc, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably of alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and their salts, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talc, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably of alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and their salts, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (
  • Suitable fillers and reinforcing agents are, for example, calcium carbonate, silicates, glass fibers, glass balloons, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, Graphite, wollastonite, wood flour and flours or fibers of other natural products, synthetic fibers. It is possible to use individual ones of these compounds or mixtures thereof.
  • Suitable other additives are, for example, plasticizers, lubricants, emulsifiers, pigments, viscosity modifiers, catalysts, leveling agents, optical brighteners, flame retardants, antistatic agents and blowing agents.
  • Suitable benzofuranones and indolinones are, for example, those described in U.S. Pat. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S.
  • These compounds act as antioxidants. It is possible to use individual ones of these compounds or mixtures thereof.
  • Suitable fluorescent plasticizers are those listed in "Plastics Additives Handbook", ed. R. Gumbleter and H. Müller, Hanser Verlag, 3rd ed., 1990, pages 775-789.
  • Suitable flame retardant additives are Phosphatester, ie triphenyl phosphate, resorcinol diphosphoric acid esters, gocarbonate bromine-containing compounds such as brominated organophosphate, brominated olive and polycarbonates, as well as salts such as C 4 F 9 SG ⁇ -Na +.
  • Suitable tougheners are butadiene rubber grafted with styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubbers grafted with maleic anhydride, ethyl and butyl acrylate rubbers grafted with methyl methacrylate or styrene-acrylonitrile, interpenetrable rubber. siloxane and acrylate networks with grafted methyl methacrylate or styrene-acrylonitrile.
  • Suitable antistatic agents are sulfonate salts, for example tetraethylammonium salts or phosphonium salts of C 12 H 25 SO 3 " or C 8 Fi 7 SO 3" .
  • Suitable colorants are pigments as well as organic and inorganic dyes.
  • anhydride groups such as maleic anhydride, succinic anhydride, benzoic anhydride and phthalic anhydride.
  • Suitable phosphites and phosphonites as stabilizers It is possible to use some of these compounds or mixtures thereof.
  • tris (2,4-di-tert-butylphenyl) phosphite Irgafos® 168, Ciba-Geigy
  • triphenylphosphine especially preferred are tris (2,4-di-tert-butylphenyl) phosphite (Irgafos® 168, Ciba-Geigy), or triphenylphosphine.
  • the moldings according to the invention can be processed from the compositions on conventional machines, for example on extruders or injection molding machines, to any desired shaped bodies or shaped parts, to films or sheets, in the usual way.
  • Possible molded parts are safety discs, which are known to be required in many areas of buildings, vehicles and aircraft, as well as shields of helmets. Production of extrusion and dissolution films for displays, blister packs or electric motors, blown bodies (see, for example, US Pat. No. 2,964,794), translucent panels, in particular hollow panel panels, for example for covering buildings such as railway stations, greenhouses and lighting installations, traffic light housings, traffic signs, molded parts for lighting purposes ( see, for example, DE-A 1 554 020), goggles.
  • electrical insulating materials for electrical conductors and for connector housings and connectors.
  • As carrier material for organic photoconductors, luminaires or diffusers or lamp covers housing parts, such as electrical distribution cabinets, electrical appliances, household appliances. Components of household articles, electrical and electronic equipment, motorcycle and protective helmets, automotive parts, such as glazings, sunroofs, dashboards, body parts, transport racks and storage containers for electronic components.
  • Particularly preferred moldings are:
  • Safety windows, translucent panels or moldings for the building sector in particular hollow panel panels, safety windows, diffused light panels and lamp covers, sun roofs, automotive parts, housing parts and packaging materials for the electrical industry.
  • MWNT multi-wall carbon nanotubes
  • Baytubes ® DP HP Bayer MaterialScience AG, 51368 Leverkusen, Germany, is used. They consist of 3-15 graphitic layers, which have a smallest inner diameter of 2-6 nm, the lengths of the tubes are 1 to 10 microns and their outer diameter is between 5 and 20 nm (mean 13-16 nm).
  • the carbon blacks used were from Degussa AG (Dusseldorf, Germany) (Flammruß 101) and the Cabot Corp. (Boston MA, USA) (Black Pearls 800).
  • Bisphenol A-based polycarbonate (Makrolon ® 2805 Bayer Material Science AG, 51368 Leverkusen, Germany) having an MVR of 9.5 cm 3 / (10 min.) (Measured according to ISO 1133 (300 0 C, 1, 2 kg) ) was provided by compounding with a ZSK 25 (Paul Beier KG, Kassel, Germany) with different levels of the MWNTs and carbon blacks described above.
  • the compositions are listed in Tables 1 and 2 together with the values for the degree of gloss of the test specimens.
  • test specimens 60 x 40 x 4 mm were produced by injection molding in an Allrounder 370C 800-250 (Arburg GmbH & Co. KG, Lossburg, Germany) using a tool with polished surfaces.
  • the gloss values were measured on a Byk-Gardner Haze-Gloss according to ISO 2813 (ASTM D 523) in the angles 20 ° and 60 °.
  • Table 1 clearly shows a decrease in the degree of gloss (ie an increasingly matte surface) with increasing filling level of Baytubes DP-HP. Compared to the data from Table 2 (Example 4) it is clear that the addition of Black Pearls 800 leads to a much lower decrease in the gloss value.

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Abstract

La présente invention concerne des pièces moulées qui peuvent être obtenues à partir de compositions contenant A) 99,91 à 85 % en poids de matière thermoplastique et B) 0,09 à 15 % en poids de nanotubes de carbone multiparois qui ont une brillance à 20° de 104 à 20 et une brillance à 60° de 103 à 50, mesurée selon ISO 2813 à l'aide d'un appareil Byk-Gardner Haze-Gloss, ainsi que l'utilisation des compositions pour la réalisation de pièces moulées ayant les brillances mentionnées.
EP08785612A 2007-08-30 2008-08-19 Pièces moulées présentant des surfaces de qualité améliorée Withdrawn EP2188333A1 (fr)

Applications Claiming Priority (2)

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DE102007040926 2007-08-30
PCT/EP2008/006794 WO2009030357A1 (fr) 2007-08-30 2008-08-19 Pièces moulées présentant des surfaces de qualité améliorée

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WO (1) WO2009030357A1 (fr)

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WO2013079478A1 (fr) 2011-11-30 2013-06-06 Bayer Intellectual Property Gmbh Corps multicouches en polycarbonate à effet brillant profond
ES2639197T3 (es) 2011-11-30 2017-10-25 Covestro Deutschland Ag Cuerpo multicapa de policarbonato con efecto de brillo profundo
DE102012022482A1 (de) * 2012-11-19 2014-05-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Polymerzusammensetzung mit verbesserter Langzeitstabilität, hieraus hergestellte Formteile sowie Verwendungszwecke
ITRM20120656A1 (it) 2012-12-20 2014-06-21 Bayer Materialscience Ag Articolo multistrato a base di policarbonato con forte resistenza agli agenti atmosferici.
EP3700872B1 (fr) 2017-10-27 2024-02-07 Owens Corning Intellectual Capital, LLC Compositions d'encollage comprenant des sels d'anions faiblement coordinants et leurs utilisations
JP7144155B2 (ja) * 2018-03-01 2022-09-29 旭ファイバーグラス株式会社 サンルーフ用外装部品及びサンルーフ用複合部品

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US4663230A (en) * 1984-12-06 1987-05-05 Hyperion Catalysis International, Inc. Carbon fibrils, method for producing same and compositions containing same
US6608133B2 (en) * 2000-08-09 2003-08-19 Mitsubishi Engineering-Plastics Corp. Thermoplastic resin composition, molded product using the same and transport member for electric and electronic parts using the same
DE102004010455A1 (de) * 2004-03-01 2005-09-22 Basf Ag Thermoplastische Polyurethane enthaltend Kohlenstoffnanoröhren
JP4541078B2 (ja) * 2004-09-14 2010-09-08 出光興産株式会社 芳香族ポリカーボネート樹脂組成物、該樹脂組成物の製造方法及び該樹脂組成物の成形体

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JP2010537012A (ja) 2010-12-02
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WO2009030357A1 (fr) 2009-03-12
CN101784600A (zh) 2010-07-21

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