US20150011689A1 - Uv-stabilized, glass-fiber reinforced, flame-retardant polycarbonates for the ee and it sector - Google Patents
Uv-stabilized, glass-fiber reinforced, flame-retardant polycarbonates for the ee and it sector Download PDFInfo
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- US20150011689A1 US20150011689A1 US14/361,011 US201214361011A US2015011689A1 US 20150011689 A1 US20150011689 A1 US 20150011689A1 US 201214361011 A US201214361011 A US 201214361011A US 2015011689 A1 US2015011689 A1 US 2015011689A1
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- 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
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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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- 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
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
Definitions
- the present invention relates to glass fibre-reinforced polycarbonate compositions of high rigidity and improved thermal and rheological properties in combination with improved flameproofing properties and a significantly increased Vicat temperature.
- the present invention furthermore relates to the use of the compositions according to the invention for the production of thin-walled housing parts or switch boxes in the EE (electrical/electronics) and IT (information technology) sector.
- moulding compositions are suitable in particular for components which meet fire protection classification UL94 V0 at a wall thickness of from 1.2 mm to 1.5 mm.
- the object of the present invention was thus to provide glass fibre-reinforced polycarbonate compositions having a combination of high rigidity and toughness in axial and biaxial behaviour, good thermal and rheological properties and a flame resistance of UL94 V0 at 1.2 mm and 1.5 mm wall thickness and increased Vicat temperature which do not have the disadvantages of the compositions known from the prior art.
- the compositions are suitable for the production of frames for LCD screens and housing parts for the EE market.
- the compositions moreover should have an HDT-A edgewise and flatwise of >135° C.
- the moulding compositions of such composition are distinguished by good mechanical properties and a good toughness and good rheological and thermal properties coupled with improved flame resistance and high Vicat temperature.
- the present invention provides flame-resistant, thermoplastic moulding compositions comprising
- the composition consists of components A)-G).
- Preferred embodiments mentioned in the present invention can furthermore be combined with one another and are not to be regarded exclusively as an independent modification.
- Polycarbonates in the context of the present invention are both homopolycarbonates and copolycarbonates; the polycarbonates can be linear or branched in a known manner.
- the preparation of the polycarbonates is carried out in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and branching agents.
- Diphenols which are suitable for the preparation of the polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyls, bis-(hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl) sulfides, bis-(hydroxyphenyl)ethers, bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl) sulfones, bis-(hydroxyphenyl) sulfoxides, alpha,alpha′-bis-(hydroxyphenyl)-diisopropylbenzenes, phthalimidines derived from derivatives of isatin or of phenolphthalein, and nucleus-alkylated, nucleus-arylated and nucleus-halogenated compounds thereof.
- Preferred diphenols are 4,4′-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-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, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3,
- diphenols are 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
- Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.
- Suitable chain terminators which can be employed in the preparation of the polycarbonates which can be used according to the invention are monophenols according to formula (I)
- R1 and R2 independently of each other represent hydrogen, C1-C18-alkyl, C6-C12-aryl, phenyl-C1-C6-alkyl or naphthyl-C1-C6-alkyl, but wherein preferably R1 and R2 are not simultaneously hydrogen.
- R1 and R2 independently of each other further preferably represent hydrogen or alkyl having 1 to 8, particularly preferably having 1 to 4 carbon atoms, with the proviso that R1 and R2 are not simultaneously hydrogen.
- tert-Butylphenol or n-butylphenol is very particularly preferred, in particular p-tert-butylphenol.
- Suitable monophenols are, for example, phenol itself, alkylphenols, such as cresols, p-tert-butylphenol, cumylphenol, p-n-octylphenol, p-iso-octylphenol, p-n-nonylphenol and p-iso-nonylphenol, halophenols, such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol, 2,4,6-triiodophenol, p-iodophenol, and mixtures thereof.
- alkylphenols such as cresols, p-tert-butylphenol, cumylphenol, p-n-octylphenol, p-iso-octylphenol, p-n-nonylphenol and p-iso-nonylphenol
- halophenols such as p-chlorophenol, 2,4-
- Preferred chain terminators are furthermore the phenols which are substituted once or several times by C1 to C30-alkyl radicals, linear or branched, e.g. stearyl radicals, preferably unsubstituted or substituted by tert-butyl.
- p-tert-Butylphenol is particularly preferred as the chain terminator.
- mixtures of chain terminators according to the invention can also be employed, e.g. p-tert-butyl and phenol in the molar ratio of 9:1 to 1:9, preferably 9:1.
- the amount of chain terminator to be employed is preferably 0.1 to 5 mol %, based on the moles of the particular diphenols employed.
- the chain terminators can be added before, during or after the reaction with a carbonic acid derivative.
- Suitable branching agents are the tri- or more than trifunctional compounds known in polycarbonate chemistry, in particular those having three or more than three phenolic OH groups.
- Suitable branching agents are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 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)-phenyl-methane, 2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol, 2,6-bis-(2-hydroxy-5′-methyl-benzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, hexa-(4-(4-hydroxyphenylisopropyl
- the amount of branching agents optionally to be employed is preferably 0.05 mol % to 2.00 mol %, based in turn on the moles of the particular diphenols employed.
- the branching agents either can be initially introduced with the diphenols and the chain terminators in the aqueous alkaline phase, or can be added as a solution in an organic solvent before the phosgenation. In the case of the transesterification process, the branching agents are employed together with the diphenols.
- the aromatic polycarbonates of the present invention have weight-average molecular weights Mw (determined by gel permeation chromatography and calibration with a polycarbonate standard) of between 5,000 and 200,000 g/mol, preferably between 18,000-36,000 g/mol, further preferably between 22,000-34,000 g/mol, still further preferably between 24,000-32,000 g/mol, and particularly preferably between 26,000-32,000 g/mol.
- Mw weight-average molecular weights Mw (determined by gel permeation chromatography and calibration with a polycarbonate standard) of between 5,000 and 200,000 g/mol, preferably between 18,000-36,000 g/mol, further preferably between 22,000-34,000 g/mol, still further preferably between 24,000-32,000 g/mol, and particularly preferably between 26,000-32,000 g/mol.
- Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1,3-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, in each case with p-tert-butylphenol end groups (BUP).
- BUP p-tert-butylphenol end groups
- Suitable flameproofing agents in the context of the present invention are, inter alia, alkali metal and 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 and N—(N′-benzylaminocarbonyl)-sulfanylimide potassium salt.
- alkali metal and 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-toluen
- Salts which can optionally be used in the moulding compositions according to the invention are, for example: sodium or potassium perfluorobutane-sulfate, sodium or potassium perfluoromethanesulfonate, sodium or potassium perfluorooctane-sulfate, sodium or potassium 2,5-dichlorobenzene-sulfate, sodium or potassium 2,4,5-trichlorobenzene-sulfate, sodium or potassium methyl-phosphonate, sodium or potassium (2-phenylethylene)-phosphonate, sodium or potassium pentachlorobenzoate, sodium or potassium 2,4,6-trichlorobenzoate, sodium or potassium 2,4-dichlorobenzoate, lithium phenyl-phosphonate, sodium or potassium diphenyl sulfone-sulfonate, sodium or potassium 2-formylbenzenesulfonate, sodium or potassium (N-benzenesulfonyl)-benzenesulfonamide, trisodium or tripo
- Potassium nonafluoro-1-butanesulfonate is commercially obtainable inter alia as Bayowet®C4 (Lanxess, Leverkusen, Germany, CAS no. 29420-49-3), RM64 (Miteni, Italy) or as 3MTM Perfluorobutanesulfonyl Fluoride FC-51 (3M, USA). Mixtures of the salts mentioned are likewise suitable. Potassium nonafluoro-1-butanesulfonate is particularly preferably employed.
- UV (ultraviolet) stabilizers in the context of the present invention have the lowest possible transmission below 400 nm and the highest possible transmission above 400 nm.
- Ultraviolet absorbers which are particularly suitable for use in the composition according to the invention are benzotriazoles, triazines, benzophenones and/or arylated cyanoacrylates.
- Particularly suitable ultraviolet absorbers are hydroxy-benzotriazoles, such as 2-(3′,5′-bis-(1,1-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole (Tinuvin® 234, BASF, Ludwigshafen), 2-(2′-hydroxy-5′-(tert-octyl)-phenyl)-benzotriazole (Tinuvin® 329, BASF, Ludwigshafen), 2-(2′-hydroxy-3′-(2-butyl)-5′-(tert-butyl)-phenyl)-benzotriazole (Tinuvin® 350, BASF, Ludwigshafen), bis-(3-(2H-benzotriazolyl)-2-hydroxy-5-tert-octyl)methane, (Tinuvid® 360, BASF, Ludwigshafen), (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)-phenol (Tinuvin
- Tinuvin® 312 is particularly preferred as the UV stabilizer.
- Fillers in the context of the present invention are glass fibres.
- cut glass fibres which are produced from M-, E-, A-, S-, R- or C-glass are used, E- or C-glass being further preferred.
- the diameter of the fibres is preferably 5 to 25 ⁇ m, further preferably 6 to 20 ⁇ m, particularly preferably 7 to 17 ⁇ m.
- the cut glass fibres preferably have a length before the compounding of from 3 mm to 6 mm.
- the glass fibres used are distinguished in that the choice of the fibres is not limited by the interaction characteristics of the fibres with the polycarbonate matrix.
- compositions are shown both for a strong binding to the polymer matrix and in the case of a non-binding fibre.
- a strong binding of the glass fibres to the polymer matrix is to be seen from the low temperature fracture surfaces in scanning electron microscopy photographs, the highest number of broken glass fibres being broken at the same level as the matrix and only isolated glass fibres protruding out of the matrix.
- scanning electron microscopy photographs show that under low temperature fracture the glass fibres protrude markedly from the matrix or have slid out completely.
- the mould release agents E) used are esters of aliphatic long-chain carboxylic acids with mono- or polyfunctional aliphatic and/or aromatic hydroxy compounds.
- Aliphatic carboxylic acid esters which are particularly preferably used are compounds of the general formula (III):
- R 4 is an aliphatic saturated or unsaturated, linear, cyclic or branched alkyl radical and R 5 is an alkylene radical of a 1- to 4-functional aliphatic alcohol R 5 —(OH) o+p .
- C1-C18 alkyl radicals are particularly preferred for R 4 .
- C1-C18-alkyl represents, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl
- Alkylene represents a straight-chain, cyclic, branched or unbranched C1-C18 alkylene radical.
- C1-C18-alkylene represents, for example, methylene, ethylene, n-propylene, iso-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-hexadecylene or n-octadecylene.
- Free, non-esterified OH groups can also be present in esters of polyfunctional alcohols.
- Aliphatic carboxylic acid esters which are suitable according to the invention are e.g.: glycerol monostearate, palmityl palmitate and stearyl stearate. Mixtures of various carboxylic acid esters of the formula (III) can also be employed.
- Carboxylic acid esters which are preferably used are esters of pentaerythritol, glycerol, trimethylolpropane, propanediol, stearyl alcohol, cetyl alcohol or myristyl alcohol with myristic, palmitic, stearic or montanic acid and mixtures thereof. Pentaerythritol tetrastearate, stearyl stearate and propanediol distearate or mixtures thereof are particularly preferred and pentaerythritol tetrastearate is most preferred.
- Polytetrafluoroethylene can additionally be added to the moulding compositions as the antidripping agent of component (F).
- PTFE polytetrafluoroethylene
- additives such as Hostaflon® TF2021 or PTFE blends, such as Metablen® A-3800 (approx. 40% PTFE CAS 9002-84-0 and approx. 60% methyl methacrylate/butyl acrylate copolymer CAS 25852-37-3 from Misubishi-Rayon) or Blendex® B449 (approx. 50% PTFE and approx. 50% SAN [of 80% styrene and 20% acrylonitrile]) from Chemtura. Blendex® B449 is preferably used.
- PTFE can optionally be employed in amounts of from 0.05 wt. % to 5 wt. %, preferably 0.1 wt. % to 1.0 wt. %, particularly preferably 0.1 wt. % to 0.5 wt. %, in each case based on the total composition calculated for pure PTFE.
- the polymer compositions according to the invention can optionally also comprise further conventional polymer additives as component G), such as e.g. the antioxidants, heat stabilizers, flameproofing agents which differ from B), optical brighteners and light-scattering agents described in EP-A 0 839 623, WO-A 96/15102, EP-A 0 500 496 or “Plastics Additives Handbook”, Hans Zweifel, 5th edition 2000, Hanser Verlag, Kunststoff), in the conventional amounts for the particular thermoplastics.
- further conventional polymer additives as component G), such as e.g. the antioxidants, heat stabilizers, flameproofing agents which differ from B), optical brighteners and light-scattering agents described in EP-A 0 839 623, WO-A 96/15102, EP-A 0 500 496 or “Plastics Additives Handbook”, Hans Zweifel, 5th edition 2000, Hanser Verlag, Kunststoff), in the conventional amounts for the particular thermoplastics.
- the polymer compositions according to the invention can furthermore comprise pigments and/or dyestuffs in the conventional amounts as component G).
- Compounds which are preferably suitable as heat stabilizers according to component (G) are triphenylphosphine, tris-(2,4-di-tert-butylphenyl) phosphite (Irgafos 168), tetrakis-(2,4-di-tert-butylphenyl)-[1,1-biphenyl]-4,4′-diyl-bisphosphonite, trisoctyl phosphate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate (Irganox 1076), bis-(2,4-dicumylphenyl)-pentaerythritol diphosphite (Doverphos S-9228) and bis-(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite (ADK STAB PEP-
- Irganox B900 mixture of Irganox 168 and Irganox 1076 in the ratio of 1:3 or Doverphos S-92228 with Irganox B900 or Irganox 1076.
- the preparation of the polymer compositions according to the invention comprising components A) to G) is carried out with the usual processes of incorporation by bringing together, mixing and homogenizing the individual constituents, the homogenizing in particular preferably taking place in the melt under the action of shearing forces.
- the bringing together and mixing are optionally carried out before the melt homogenization, using powder premixes.
- Premixes of granules or granules and powders with the additives according to the invention can also be used.
- Premixes which have been prepared from solutions of the mixing components in suitable solvents, homogenization optionally being carried out in solution and the solvent then being removed, can also be used.
- additives of the composition according to the invention can be introduced here by known processes or as a masterbatch.
- masterbatches is preferred in particular for introduction of the additives, masterbatches based on the particular polymer matrix being used in particular.
- the composition can be brought together, mixed, homogenized and then extruded in conventional devices, such as screw extruders (for example twin-screw extruders, TSE), kneaders or Brabender or Banbury mills. After the extrusion, the extrudate can be cooled and comminuted. Individual components can also be premixed and the remaining starting substances can then be added individually and/or likewise as a mixture.
- the bringing together and thorough mixing of a premix in the melt can also be carried out in the plasticizing unit of an injection moulding machine. In this procedure, the melt is converted directly into a shaped body in the subsequent step.
- the production of the shaped parts of plastic can preferably be carried out by injection moulding.
- the plastics compositions according to the invention is applied in one or more layer(s) to a shaped object made of a plastic.
- the application can be effected at the same time as or immediately after the shaping of the shaped body, for example by insert moulding of a film, coextrusion or multi-component injection moulding.
- the application can also be effected on the ready-formed base body, e.g. by lamination with a film, injection moulding around an existing shaped body or by coating from a solution.
- the present invention furthermore relates to the use of compositions according to the invention for the production of thin-walled, rigid components, in particular frame components for LCD/LED equipment, in the EE and IT sector.
- Linear polycarbonate based on bisphenol A having an MVR of 8 (according to ISO 1133, at 300° C. under a 1.2 kg load).
- Potassium perfluoro-1-butanesulfonate commercially obtainable as Bayowet® C4 from Lanxess, Leverkusen, Germany, CAS no. 29420-49-3.
- Pentaerythritol tetrastearate as a lubricant/mould release agent
- the Charpy impact strength was measured in accordance with ISO 179/1 eU on test bars, injection moulded on one side, of dimensions 80 ⁇ 10 ⁇ 4 mm at RT and ⁇ 40° C.
- the Vicat B/50 as a measure of the heat distortion point, is determined in accordance with ISO 306 on test specimens of dimensions 80 ⁇ 10 ⁇ 4 mm with a plunger load of 50 N and a heating up rate of 50° C./h.
- the average particle size d 50 is the diameter above and below which in each case 50 wt. % of the particles lie.
- the maximum particle size d 95 is the diameter below which 95 wt. % of the particles lie.
- the corresponding diameters were determined by air separation.
- the burning properties are measured in accordance with UL 94V on bars of dimensions 127 mm ⁇ 12.7 mm ⁇ 1.0 mm, 127 ⁇ 12.7 ⁇ 1.2 mm, 127 ⁇ 12.7 ⁇ 1.5 mm.
- the burning properties are measured in accordance with UL 94 5V on bars of dimensions 127 mm ⁇ 12.7 mm ⁇ 3.0 mm and sheets of dimensions 105 mm ⁇ 105 mm ⁇ 3.0 mm
- Not passed means failed in the bar and sheet testing
- class A passed means bar and sheet testing passed.
- Class B passed means bar testing passed and sheet testing failed.
- the E modulus and the elongation at break were measured in accordance with ISO 527 on shoulder bars injection moulded on one side and having a core of dimensions 80 ⁇ 10 ⁇ 4 mm.
- melt volume rate is determined in accordance with ISO 1133 (at 300° C.; 1.2 kg).
- the characteristic values of the penetration experiment are determined at ⁇ 20° C. in accordance with ISO 6603-2 on test sheets of 60 mm ⁇ 60 mm ⁇ 2 mm.
- the HDT-A edgewise was determined in accordance with ISO 75 with a bearing force of 1.80 MPa on a test specimen of dimensions 120 mm ⁇ 10 mm ⁇ 4 mm on the 4 mm edge with a bearing span of 100 mm.
- the HDT-A flatwise was determined in accordance with ISO 75 with a bearing force of 1.80 MPa on a test specimen of dimensions 80 mm ⁇ 10 mm ⁇ 4 mm on the 10 mm edge with a bearing span of 64 mm.
- Example 1 2 3 4 5 6 A-1 wt. % 88.750 86.750 84.750 88.750 86.750 84.750 A-2 wt. % B wt. % 0.2 0.2 0.2 0.2 0.2 0.2 C wt. % 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 D-1 wt. % 10 12 14 D-2 wt. % 10 12 14 E wt. % 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
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Abstract
Description
- The present invention relates to glass fibre-reinforced polycarbonate compositions of high rigidity and improved thermal and rheological properties in combination with improved flameproofing properties and a significantly increased Vicat temperature. The present invention furthermore relates to the use of the compositions according to the invention for the production of thin-walled housing parts or switch boxes in the EE (electrical/electronics) and IT (information technology) sector.
- These moulding compositions are suitable in particular for components which meet fire protection classification UL94 V0 at a wall thickness of from 1.2 mm to 1.5 mm.
- The object of the present invention was thus to provide glass fibre-reinforced polycarbonate compositions having a combination of high rigidity and toughness in axial and biaxial behaviour, good thermal and rheological properties and a flame resistance of UL94 V0 at 1.2 mm and 1.5 mm wall thickness and increased Vicat temperature which do not have the disadvantages of the compositions known from the prior art. In particular, the compositions are suitable for the production of frames for LCD screens and housing parts for the EE market. The compositions moreover should have an HDT-A edgewise and flatwise of >135° C.
- It has now been found, surprisingly, that the abovementioned properties are obtained when polycarbonate compositions according to claim 1 of the present invention are employed.
- The moulding compositions of such composition are distinguished by good mechanical properties and a good toughness and good rheological and thermal properties coupled with improved flame resistance and high Vicat temperature.
- The present invention provides flame-resistant, thermoplastic moulding compositions comprising
- A) 41.500 to 94.899 parts by wt., preferably 60.000 to 93.000 parts by wt., particularly preferably 74.000 to 90.000 parts by wt. of at least one aromatic polycarbonate capped with phenols,
- B) 0.001 to 1.000 part by wt., preferably 0.050 to 0.800 part by wt., further preferably 0.100 to 0.600 part by wt., particularly preferably 0.100 to 0.300 part by wt. of at least one flameproofing agent,
- C) 0.05 to 1.50 parts by wt., preferably 0.10 to 1.00 part by wt., further preferably 0.15 to 0.90 part by wt., further preferably from 0.15 to 0.50 part by wt. of at least one UV absorber, preferably Tinuvin 312, Tinuvin 360 and Tinuvin 329, particularly preferably Tinuvin 312,
- D) 5.0 to 40.0 parts by wt., preferably 6.0 to 30.0 parts by wt., further preferably 7.0 to 20.0 parts by wt. of at least one glass fibre,
- E) 0.00 part by wt. to 1.00 part by wt., further preferably 0.10 part by wt. to 0.75 part by wt., particularly preferably 0.15 part by wt. to 0.60 part by wt., and very particularly preferably 0.20 part by weight to 0.50 part by wt. of at least one mould release agent,
- F) 0.05 wt. % to 5.00 wt. %, preferably 0.10 wt. % to 1.00 wt. %, particularly preferably 0.10 wt. % to 0.80 wt. % of at least one antidripping agent,
- G) 0 to 10.00 parts by wt., preferably 0.10 to 8.00 parts by wt., particularly preferably 0.20 to 3.00 parts by wt. of further conventional additives,
wherein the sum of the parts by weight of components A) to G) adds up to 100 parts by weight. - In a preferred embodiment, the composition consists of components A)-G).
- Preferred embodiments mentioned in the present invention can furthermore be combined with one another and are not to be regarded exclusively as an independent modification.
- Component A)
- Polycarbonates in the context of the present invention are both homopolycarbonates and copolycarbonates; the polycarbonates can be linear or branched in a known manner.
- The preparation of the polycarbonates is carried out in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and branching agents.
- Details of the preparation of polycarbonates have been laid down in many patent specifications for about 40 years. Reference may be made here by way of example to Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, volume 9, Interscience Publishers, New York, London, Sydney 1964, to D. Freitag, U. Grigo, P. R. Müller, H. Nouvertné, BAYER AG, “Polycarbonates” in Encyclopedia of Polymer Science and Engineering, volume 11, second edition, 1988, pages 648-718 and finally to Dres. U. Grigo, K. Kirchner and P. R. Müller “Polycarbonate” in Becker/Braun, Kunststoff-Handbuch, volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299.
- Diphenols which are suitable for the preparation of the polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyls, bis-(hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl) sulfides, bis-(hydroxyphenyl)ethers, bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl) sulfones, bis-(hydroxyphenyl) sulfoxides, alpha,alpha′-bis-(hydroxyphenyl)-diisopropylbenzenes, phthalimidines derived from derivatives of isatin or of phenolphthalein, and nucleus-alkylated, nucleus-arylated and nucleus-halogenated compounds thereof.
- Preferred diphenols are 4,4′-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-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, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3,5-dichloro-4-hydroxy-phenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
- Particularly preferred diphenols are 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
- These and further suitable diphenols are described e.g. in U.S. Pat. No. 3,028,635, U.S. Pat. No. 2,999,825, U.S. Pat. No. 3,148,172, U.S. Pat. No. 2,991,273, U.S. Pat. No. 3,271,367, U.S. Pat. No. 4,982,014 and U.S. Pat. No. 2,999,846, in DE-A 1 570 703, DE-A 2063 050, DE-A 2 036 052, DE-A 2 211 956 and DE-A 3 832 396, in FR-A 1 561 518, in the monograph “H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964” and in JP-A 62039/1986, JP-A 62040/1986 and JP-A 105550/1986.
- In the case of homopolycarbonates, only one diphenol is employed, and in the case of copolycarbonates several diphenols are employed.
- Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.
- Suitable chain terminators which can be employed in the preparation of the polycarbonates which can be used according to the invention are monophenols according to formula (I)
- in which
- R1 and R2 independently of each other represent hydrogen, C1-C18-alkyl, C6-C12-aryl, phenyl-C1-C6-alkyl or naphthyl-C1-C6-alkyl, but wherein preferably R1 and R2 are not simultaneously hydrogen.
- In formula 1, R1 and R2 independently of each other further preferably represent hydrogen or alkyl having 1 to 8, particularly preferably having 1 to 4 carbon atoms, with the proviso that R1 and R2 are not simultaneously hydrogen. tert-Butylphenol or n-butylphenol is very particularly preferred, in particular p-tert-butylphenol.
- Suitable monophenols are, for example, phenol itself, alkylphenols, such as cresols, p-tert-butylphenol, cumylphenol, p-n-octylphenol, p-iso-octylphenol, p-n-nonylphenol and p-iso-nonylphenol, halophenols, such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol, 2,4,6-triiodophenol, p-iodophenol, and mixtures thereof.
- Preferred chain terminators are furthermore the phenols which are substituted once or several times by C1 to C30-alkyl radicals, linear or branched, e.g. stearyl radicals, preferably unsubstituted or substituted by tert-butyl. p-tert-Butylphenol is particularly preferred as the chain terminator.
- In an alternative embodiment, mixtures of chain terminators according to the invention can also be employed, e.g. p-tert-butyl and phenol in the molar ratio of 9:1 to 1:9, preferably 9:1.
- The amount of chain terminator to be employed is preferably 0.1 to 5 mol %, based on the moles of the particular diphenols employed. The chain terminators can be added before, during or after the reaction with a carbonic acid derivative.
- Suitable branching agents are the tri- or more than trifunctional compounds known in polycarbonate chemistry, in particular those having three or more than three phenolic OH groups.
- Suitable branching agents are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 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)-phenyl-methane, 2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol, 2,6-bis-(2-hydroxy-5′-methyl-benzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, hexa-(4-(4-hydroxyphenylisopropyl)-phenyl)-orthoterephthalic acid ester, tetra-(4-hydroxyphenyl)-methane, tetra-(4-(4-hydroxyphenylisopropyl)-phenoxy)-methane and 1,4-bis-((4′,4″-dihydroxytriphenyl)-methyl)-benzene as well as 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.
- The amount of branching agents optionally to be employed is preferably 0.05 mol % to 2.00 mol %, based in turn on the moles of the particular diphenols employed.
- The branching agents either can be initially introduced with the diphenols and the chain terminators in the aqueous alkaline phase, or can be added as a solution in an organic solvent before the phosgenation. In the case of the transesterification process, the branching agents are employed together with the diphenols.
- The aromatic polycarbonates of the present invention have weight-average molecular weights Mw (determined by gel permeation chromatography and calibration with a polycarbonate standard) of between 5,000 and 200,000 g/mol, preferably between 18,000-36,000 g/mol, further preferably between 22,000-34,000 g/mol, still further preferably between 24,000-32,000 g/mol, and particularly preferably between 26,000-32,000 g/mol.
- Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1,3-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, in each case with p-tert-butylphenol end groups (BUP).
- Component B)
- Suitable flameproofing agents in the context of the present invention are, inter alia, alkali metal and 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 and N—(N′-benzylaminocarbonyl)-sulfanylimide potassium salt.
- Salts which can optionally be used in the moulding compositions according to the invention are, for example: sodium or potassium perfluorobutane-sulfate, sodium or potassium perfluoromethanesulfonate, sodium or potassium perfluorooctane-sulfate, sodium or potassium 2,5-dichlorobenzene-sulfate, sodium or potassium 2,4,5-trichlorobenzene-sulfate, sodium or potassium methyl-phosphonate, sodium or potassium (2-phenylethylene)-phosphonate, sodium or potassium pentachlorobenzoate, sodium or potassium 2,4,6-trichlorobenzoate, sodium or potassium 2,4-dichlorobenzoate, lithium phenyl-phosphonate, sodium or potassium diphenyl sulfone-sulfonate, sodium or potassium 2-formylbenzenesulfonate, sodium or potassium (N-benzenesulfonyl)-benzenesulfonamide, trisodium or tripotassium hexafluoroaluminate, disodium or dipotassium hexafluorotitanate, disodium or dipotassium hexafluorosilicate, disodium or dipotassium hexafluorozirconate, sodium or potassium pyrophosphate, sodium or potassium metaphosphate, sodium or potassium tetrafluoroborate, sodium or potassium hexafluorophosphate, sodium or potassium or lithium phosphate, N-(p-tolylsulfonyl)-p-toluenesulfimide potassium salt and N—(N′-benzylaminocarbonyl)-sulfanylimide potassium salt.
- Sodium or potassium perfluorobutane-sulfate, sodium or potassium perfluorooctane-sulfate, sodium or potassium diphenyl sulfone-sulfonate and sodium or potassium 2,4,6-trichlorobenzoate, N-(p-tolylsulfonyl)-p-toluenesulfimide potassium salt and N—(N′-benzylaminocarbonyl)-sulfanylimide potassium salt are preferred. Potassium nonafluoro-1-butanesulfonate and sodium or potassium diphenyl sulfone-sulfonate are very particularly preferred. Potassium nonafluoro-1-butanesulfonate is commercially obtainable inter alia as Bayowet®C4 (Lanxess, Leverkusen, Germany, CAS no. 29420-49-3), RM64 (Miteni, Italy) or as 3M™ Perfluorobutanesulfonyl Fluoride FC-51 (3M, USA). Mixtures of the salts mentioned are likewise suitable. Potassium nonafluoro-1-butanesulfonate is particularly preferably employed.
- Component C)
- UV (ultraviolet) stabilizers in the context of the present invention have the lowest possible transmission below 400 nm and the highest possible transmission above 400 nm. Ultraviolet absorbers which are particularly suitable for use in the composition according to the invention are benzotriazoles, triazines, benzophenones and/or arylated cyanoacrylates.
- Particularly suitable ultraviolet absorbers are hydroxy-benzotriazoles, such as 2-(3′,5′-bis-(1,1-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole (Tinuvin® 234, BASF, Ludwigshafen), 2-(2′-hydroxy-5′-(tert-octyl)-phenyl)-benzotriazole (Tinuvin® 329, BASF, Ludwigshafen), 2-(2′-hydroxy-3′-(2-butyl)-5′-(tert-butyl)-phenyl)-benzotriazole (Tinuvin® 350, BASF, Ludwigshafen), bis-(3-(2H-benzotriazolyl)-2-hydroxy-5-tert-octyl)methane, (Tinuvid® 360, BASF, Ludwigshafen), (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)-phenol (Tinuvin® 1577, BASF, Ludwigshafen), and the benzophenones 2,4-dihydroxybenzophenone (Chimassorb® 22, BASF, Ludwigshafen) and 2-hydroxy-4-(octyloxy)-benzophenone (Chimassorb® 81, BASF, Ludwigshafen), 2-propenoic acid, 2-cyano-3,3-diphenyl-, 2,2-bis[[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]-methyl]-1,3-propanediyl ester (9CI) (Uvinul® 3030, BASF AG Ludwigshafen), 2-[2-hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6-di(4-phenyl)phenyl-1,3,5-triazine (CGX UVA 006, BASF, Ludwigshafen), tetraethyl 2,2′-(1,4-phenylenedimethylidene)-bismalonate (Hostavin® B-Cap, Clariant AG) or N-(2-ethoxyphenyl)-N′-(2-ethylphenyl)-ethanediamide (Tinuvin® 312, CAS no. 23949-66-8, BASF, Ludwigshafen).
- Tinuvin® 312 is particularly preferred as the UV stabilizer.
- Mixtures of these ultraviolet absorbers can also be employed.
- Component D)
- Fillers in the context of the present invention are glass fibres.
- Preferably, cut glass fibres which are produced from M-, E-, A-, S-, R- or C-glass are used, E- or C-glass being further preferred.
- The diameter of the fibres is preferably 5 to 25 μm, further preferably 6 to 20 μm, particularly preferably 7 to 17 μm.
- The cut glass fibres preferably have a length before the compounding of from 3 mm to 6 mm.
- The glass fibres used are distinguished in that the choice of the fibres is not limited by the interaction characteristics of the fibres with the polycarbonate matrix.
- An improvement in the properties according to the invention of the compositions is shown both for a strong binding to the polymer matrix and in the case of a non-binding fibre.
- A strong binding of the glass fibres to the polymer matrix is to be seen from the low temperature fracture surfaces in scanning electron microscopy photographs, the highest number of broken glass fibres being broken at the same level as the matrix and only isolated glass fibres protruding out of the matrix. For the converse case of non-binding characteristics, scanning electron microscopy photographs show that under low temperature fracture the glass fibres protrude markedly from the matrix or have slid out completely.
- Component E)
- The mould release agents E) used are esters of aliphatic long-chain carboxylic acids with mono- or polyfunctional aliphatic and/or aromatic hydroxy compounds. Aliphatic carboxylic acid esters which are particularly preferably used are compounds of the general formula (III):
-
(R4—CO—O)o—R5—(OH)p where o=1 to 4 and p=3 to 0 (III) - wherein R4 is an aliphatic saturated or unsaturated, linear, cyclic or branched alkyl radical and R5 is an alkylene radical of a 1- to 4-functional aliphatic alcohol R5—(OH)o+p.
- C1-C18 alkyl radicals are particularly preferred for R4. C1-C18-alkyl represents, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, n-heptyl and n-Octyl, pinacyl, Adamantyl, the isomeric menthyls, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
- Alkylene represents a straight-chain, cyclic, branched or unbranched C1-C18 alkylene radical. C1-C18-alkylene represents, for example, methylene, ethylene, n-propylene, iso-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-hexadecylene or n-octadecylene.
- Free, non-esterified OH groups can also be present in esters of polyfunctional alcohols. Aliphatic carboxylic acid esters which are suitable according to the invention are e.g.: glycerol monostearate, palmityl palmitate and stearyl stearate. Mixtures of various carboxylic acid esters of the formula (III) can also be employed. Carboxylic acid esters which are preferably used are esters of pentaerythritol, glycerol, trimethylolpropane, propanediol, stearyl alcohol, cetyl alcohol or myristyl alcohol with myristic, palmitic, stearic or montanic acid and mixtures thereof. Pentaerythritol tetrastearate, stearyl stearate and propanediol distearate or mixtures thereof are particularly preferred and pentaerythritol tetrastearate is most preferred.
- Polytetrafluoroethylene (PTFE) can additionally be added to the moulding compositions as the antidripping agent of component (F). This is commercially available in various product qualities. These include additives such as Hostaflon® TF2021 or PTFE blends, such as Metablen® A-3800 (approx. 40% PTFE CAS 9002-84-0 and approx. 60% methyl methacrylate/butyl acrylate copolymer CAS 25852-37-3 from Misubishi-Rayon) or Blendex® B449 (approx. 50% PTFE and approx. 50% SAN [of 80% styrene and 20% acrylonitrile]) from Chemtura. Blendex® B449 is preferably used.
- In the context of the present invention, PTFE can optionally be employed in amounts of from 0.05 wt. % to 5 wt. %, preferably 0.1 wt. % to 1.0 wt. %, particularly preferably 0.1 wt. % to 0.5 wt. %, in each case based on the total composition calculated for pure PTFE.
- In addition to the stabilizers according to the invention, the polymer compositions according to the invention can optionally also comprise further conventional polymer additives as component G), such as e.g. the antioxidants, heat stabilizers, flameproofing agents which differ from B), optical brighteners and light-scattering agents described in EP-A 0 839 623, WO-A 96/15102, EP-A 0 500 496 or “Plastics Additives Handbook”, Hans Zweifel, 5th edition 2000, Hanser Verlag, Munich), in the conventional amounts for the particular thermoplastics.
- The polymer compositions according to the invention can furthermore comprise pigments and/or dyestuffs in the conventional amounts as component G).
- Compounds which are preferably suitable as heat stabilizers according to component (G) are triphenylphosphine, tris-(2,4-di-tert-butylphenyl) phosphite (Irgafos 168), tetrakis-(2,4-di-tert-butylphenyl)-[1,1-biphenyl]-4,4′-diyl-bisphosphonite, trisoctyl phosphate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate (Irganox 1076), bis-(2,4-dicumylphenyl)-pentaerythritol diphosphite (Doverphos S-9228) and bis-(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite (ADK STAB PEP-36). They are employed by themselves or in a mixture (e.g. Irganox B900 (mixture of Irganox 168 and Irganox 1076 in the ratio of 1:3) or Doverphos S-92228 with Irganox B900 or Irganox 1076).
- The preparation of the polymer compositions according to the invention comprising components A) to G) is carried out with the usual processes of incorporation by bringing together, mixing and homogenizing the individual constituents, the homogenizing in particular preferably taking place in the melt under the action of shearing forces. The bringing together and mixing are optionally carried out before the melt homogenization, using powder premixes.
- Premixes of granules or granules and powders with the additives according to the invention can also be used.
- Premixes which have been prepared from solutions of the mixing components in suitable solvents, homogenization optionally being carried out in solution and the solvent then being removed, can also be used.
- In particular, the additives of the composition according to the invention can be introduced here by known processes or as a masterbatch.
- The use of masterbatches is preferred in particular for introduction of the additives, masterbatches based on the particular polymer matrix being used in particular.
- In this connection, the composition can be brought together, mixed, homogenized and then extruded in conventional devices, such as screw extruders (for example twin-screw extruders, TSE), kneaders or Brabender or Banbury mills. After the extrusion, the extrudate can be cooled and comminuted. Individual components can also be premixed and the remaining starting substances can then be added individually and/or likewise as a mixture.
- The bringing together and thorough mixing of a premix in the melt can also be carried out in the plasticizing unit of an injection moulding machine. In this procedure, the melt is converted directly into a shaped body in the subsequent step.
- The production of the shaped parts of plastic can preferably be carried out by injection moulding.
- The use of the plastics compositions according to the invention for the production of multi-layer systems is also of interest. In this, the plastics composition according to the invention is applied in one or more layer(s) to a shaped object made of a plastic. The application can be effected at the same time as or immediately after the shaping of the shaped body, for example by insert moulding of a film, coextrusion or multi-component injection moulding. However, the application can also be effected on the ready-formed base body, e.g. by lamination with a film, injection moulding around an existing shaped body or by coating from a solution.
- The present invention furthermore relates to the use of compositions according to the invention for the production of thin-walled, rigid components, in particular frame components for LCD/LED equipment, in the EE and IT sector.
- BUP-capped linear polycarbonate based on bisphenol A having an MVR of 10 (according to ISO 1133, at 300° C. under a 1.2 kg load).
- Linear polycarbonate based on bisphenol A having an MVR of 8 (according to ISO 1133, at 300° C. under a 1.2 kg load).
- Potassium perfluoro-1-butanesulfonate commercially obtainable as Bayowet® C4 from Lanxess, Leverkusen, Germany, CAS no. 29420-49-3.
- N-(2-Ethoxyphenyl)-N′-(2-ethylphenyl)-ethanediamide (Tinuvin® 312, CAS no. 23949-66-8, BASF, Ludwigshafen)
- CS 7968, cut short glass fibres (binding) from Lanxess AG having an average fibre diameter of 11 μm and an average fibre length of 4.5 mm
- CS108F-14P, cut short glass fibres (non-binding) from 3B having an average fibre diameter of 14 μm and an average fibre length of 4.0 mm
- Pentaerythritol tetrastearate as a lubricant/mould release agent
- Polytetrafluoroethylene (Blendex® B449 (approx. 50% PTFE and approx. 50% SAN [of 80% styrene and 20% acrylonitrile] from Chemtura).
- The Charpy impact strength was measured in accordance with ISO 179/1 eU on test bars, injection moulded on one side, of dimensions 80×10×4 mm at RT and −40° C.
- The Vicat B/50, as a measure of the heat distortion point, is determined in accordance with ISO 306 on test specimens of dimensions 80×10×4 mm with a plunger load of 50 N and a heating up rate of 50° C./h.
- The average particle size d50 is the diameter above and below which in each case 50 wt. % of the particles lie.
- The maximum particle size d95 is the diameter below which 95 wt. % of the particles lie.
- The corresponding diameters were determined by air separation.
- The burning properties are measured in accordance with UL 94V on bars of dimensions 127 mm×12.7 mm×1.0 mm, 127×12.7×1.2 mm, 127×12.7×1.5 mm.
- The burning properties are measured in accordance with UL 94 5V on bars of dimensions 127 mm×12.7 mm×3.0 mm and sheets of dimensions 105 mm×105 mm×3.0 mm Not passed means failed in the bar and sheet testing, class A passed means bar and sheet testing passed. Class B passed means bar testing passed and sheet testing failed.
- The E modulus and the elongation at break were measured in accordance with ISO 527 on shoulder bars injection moulded on one side and having a core of dimensions 80×10×4 mm.
- The melt volume rate (MVR) is determined in accordance with ISO 1133 (at 300° C.; 1.2 kg).
- The characteristic values of the penetration experiment are determined at −20° C. in accordance with ISO 6603-2 on test sheets of 60 mm×60 mm×2 mm.
- The HDT-A edgewise was determined in accordance with ISO 75 with a bearing force of 1.80 MPa on a test specimen of dimensions 120 mm×10 mm×4 mm on the 4 mm edge with a bearing span of 100 mm.
- The HDT-A flatwise was determined in accordance with ISO 75 with a bearing force of 1.80 MPa on a test specimen of dimensions 80 mm×10 mm×4 mm on the 10 mm edge with a bearing span of 64 mm.
-
TABLE 1 Example 1 2 3 4 5 6 A-1 wt. % 88.750 86.750 84.750 88.750 86.750 84.750 A-2 wt. % B wt. % 0.2 0.2 0.2 0.2 0.2 0.2 C wt. % 0.25 0.25 0.25 0.25 0.25 0.25 D-1 wt. % 10 12 14 D-2 wt. % 10 12 14 E wt. % 0.3 0.3 0.3 0.3 0.3 0.3 F wt. % 0.3 0.3 0.3 0.3 0.3 0.3 MVR [cm3/10 min] 7.0 6.7 6.7 7.0 6.3 6.5 VICAT 145.9 146.1 146.0 144.2 144.0 144.5 HDT-A edgewise 135.2 136.1 137.0 132.6 134.2 135.0 HDT-A flatwise 135.8 137.4 137.9 135.1 135.9 136.8 Charpy 78 66 55 174 151 135 impact strength RT kJ/mm2 E modulus [N/mm2] 3,651 4,102 4,463 3,750 4,158 4,445 UL94 5 V 3.0 mm class A class A class A class A class A class A UL 94 V 1.2 mm V0 V0 V0 V0 V0 V0 UL 94 V 1.5 mm V0 V0 V0 V0 V0 V0 Example 7 8 9 10 11 12 A-1 wt. % A-2 wt. % 88.750 86.750 84.750 88.750 86.750 84.750 B wt. % 0.2 0.2 0.2 0.2 0.2 0.2 C wt. % 0.25 0.25 0.25 0.25 0.25 0.25 D-1 wt. % 10 12 14 D-2 wt. % 10 12 14 E wt. % 0.3 0.3 0.3 0.3 0.3 0.3 F wt. % 0.3 0.3 0.3 0.3 0.3 0.3 MVR [cm3/10 min] 5.9 5.9 5.5 6.0 5.7 5.3 VICAT 143.3 143.8 143.4 141.9 141.5 142.4 HDT-A edgewise 130.9 133.1 133.3 130.6 129.7 132.6 HDT-A flatwise 133.9 134.9 135.4 133.1 133.4 134.6 Charpy 78 74 64 161 156 136 impact strength RT kJ/mm2 E modulus [N/mm2] 3,739 4,115 4,397 3,843 4,162 4,601 UL94 5 V 3.0 mm class A class A class A class A class A class A UL 94 V 1.2 mm V0 V0 V0 V0 V0 V1 UL 94 V 1.5 mm V0 V0 V0 V0 V0 V0
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US14/361,011 Abandoned US20150011689A1 (en) | 2011-11-30 | 2012-11-30 | Uv-stabilized, glass-fiber reinforced, flame-retardant polycarbonates for the ee and it sector |
US14/922,513 Abandoned US20160040010A1 (en) | 2011-11-30 | 2015-10-26 | Uv-stabilized, glass-fiber reinforced, flame-retardant polycarbonates for the ee and it sector |
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TWI557179B (en) | 2016-11-11 |
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KR20140105492A (en) | 2014-09-01 |
CN103958585A (en) | 2014-07-30 |
TW201343780A (en) | 2013-11-01 |
WO2013079630A1 (en) | 2013-06-06 |
KR20140097230A (en) | 2014-08-06 |
US9296893B2 (en) | 2016-03-29 |
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WO2013079633A1 (en) | 2013-06-06 |
WO2013079634A1 (en) | 2013-06-06 |
CN104039881A (en) | 2014-09-10 |
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