CA2374445A1 - Polycarbonate moulding materials with good demoulding properties and moulded bodies and semi-finished products produced with said materials, with good sliding properties - Google Patents
Polycarbonate moulding materials with good demoulding properties and moulded bodies and semi-finished products produced with said materials, with good sliding properties Download PDFInfo
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- CA2374445A1 CA2374445A1 CA002374445A CA2374445A CA2374445A1 CA 2374445 A1 CA2374445 A1 CA 2374445A1 CA 002374445 A CA002374445 A CA 002374445A CA 2374445 A CA2374445 A CA 2374445A CA 2374445 A1 CA2374445 A1 CA 2374445A1
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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
- C08K5/04—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
Abstract
The invention relates to polycarbonate moulding materials with good demoulding properties and to moulded bodies and semi-finished products produced with said polycarbonate moulding materials, with good sliding properties.
Description
t Polycarbonate moulding compositions having food demouldin~ and moulded bodies and semi-finished products having food surface slip characteristics produced therefrom The present invention provides polycarbonate moulding compositions which are adjusted to be readily demouldable having fatty acid esters based on 1,2-dihydroxypropane and C,-C,~ carboxylic acids as mould release agents, optionally in addition to other additives conventional in polycarbonates.
Patents and publications which describe the demoulding effect of additives in thermoplastics in general and polycarbonate in particular are known. The substances employed most frequently as mould release agents are esters prepared from long-chain aliphatic acids and alcohols. The use of esters prepared from fatty acid alcohols or polyols such as, for example, pentaerythritol with fatty acids might be named here by way of example, as described in DE 33 12 158, EP 100 918, EP 103 107, EP 561 629, EP 352 458, EP 436 117, or if Guerbet alcohols have been used, US 5 001 180, DE 33 12 157, US 5 744 626, and where montanic acids have been used as-the acid component, US 4 097 435.
A disadvantage is that the fatty acid esters show a clear demoulding effect only in quantities upwards of 0.5 wt.%. However, such concentrations are frequently sufficiently high to cause turbidity and/or the formation of a deposit on the mould.
Other mould release agents such as, for example, long-chain ketones, tend to form chromophores as a result of internal condensation and are not readily accessible (EP 100 918).
Siloxanes which are also used (US 4 536 590, US 4 390 651, US 3 751 519), while being sufficiently resistant to high and low temperatures, have very poor compatibility with polycarbonate and, at the concentrations which are required in order to be effective, lead to undesirable turbidity which greatly restricts the usability of a~ common material such as polycarbonate which is predominantly in transparent adjusted.
a-Olefin polymers, optionally having residual double bonds (DE-A-32 44 499) and S described, for example, in EP-A-561 630 and EP-A-230 015, are not stable as to colour. In the case of hydrogenated systems, as with the long-chain alkanes (US 4 415 696) compatibility with polycarbonate is a problem and leads to mouldings which are turbid and consequently not transparent. The wax-like or liquid-waxy consistency of these products is moreover inconvenient.
Because shorter cycle times and higher processing temperatures are required, distortion-free demoulding of polycarbonate mouldings poses an on-going challenge, if the very high-quality surface is to be retained irrespective of frequently very different moulding designs. It is often the case that problems are overcome only by a tailor-made mould release formulation. There is therefore a constant need for novel potential mould release agents.
There are two forces at work during the demoulding operation, static friction and kinetic friction. The mould release agent must be designed such as to minimise both forces without the formation of an undesirable deposit on the mould.
T'he object was therefore to find mould release agents which minimise both of the demoulding forces simultaneously, so that with one moulding composition any shape of finished part is able to be demoulded, without the formation of a deposit on the mould.
The object was furthermore to find mould release agents which do not have the tendency to transesterify with the polycarbonate and which, at the effective concentrations, give rise to neither turbidity nor discoloration.
WO 00/73377 CA 02374445 2001-11-23 PCT/EP00/0467"l A further object is to reduce problems arising from the adhesion of finished polycarbonate mouldings, such as occurs when, for example, beakers are pulled apart after storage.
A further object is to reduce problems arising from the adhesion of finished polycarbonate mouldings to metals, such as occurs when, for example sliding on inclined metallic surfaces.
A further object is to control the force of attachment which is important, for example, with toys. Here, however, precise matching of the components must be ensured, since an excessively low force of attachment is also undesirable in some applications.
The objects were achieved by the use of fatty acid esters based on 1,2-dihydroxypropane and C,-C4° carboxylic acids as mould release agents which have sufficient solubility and stability in polycarbonate.
The present invention provides polycarbonate moulding compositions containing from 0.005 to 5.0 wt.%, preferably 0.05 to 3.0 wt.%, most particularly preferably 0.1 S to 2.0 wt.%, fatty acid esters based on 1,2-dihydroxypropane and C,-C~
carboxylic acids as well as esters prepared from 1,2-dihydroxypropane with mixtures of different C,-C~ carboxylic acids wherein the alcohol may also be partially esterified as well as mixtures of partially esterified and fully esterified products and optionally with use of other additives which are conventional in polycarbonates, such as, for example, heat stabilisers, IJV stabilisers, other mould release agents, flame retardants, anti-drip agents, fillers, glass fibres and blend components such as ABS, ASA, SAN, EPDM or polyesters based on terephthalic acid and diols, which are characterised in that the moulding compositions have, on a demoulding force measuring device (coefficient of friction measuring device) coefficients of friction of preferably < 0.80, particularly preferably < 0.60 and most particularly preferably <
0.40 in respect of the static and kinetic friction, wherein the reference value of a polycarbonate of the same viscosity containing no mould release agent, measured on the coefficient of friction device, has a value of between 0.85 and 1.50.
The moulding compositions according to the invention may be contaminated with impurities which are contained in the individual constituents of the moulding composition arising from the synthesis, working-up, processing and storage thereof, as well as contaminants which originate during the preparation or processing of the moulding compositions according to the invention, The aim is, however, to work with products which are as clean as possible.
If the moulding compositions contain free OH groups, it is preferred that they contain less than 10 ppm ions, particularly preferably less than 5 ppm. This applies most particularly to ions of the elements Na, K, Mg, Ca, Sn, Ti, Fe, Ni and Cr.
If the fatty acid esters to be used according to the invention are partially esterified and contain free OH groups, it is preferred that they contain less than 10 ppm ions, particularly preferably less than 5 ppm. This applies most particularly to ions of the elements Na, K, Mg, Ca, Sn, Ti, Fe, Ni and Cr.
The adhesion of finished polycarbonate mouldings is preferably reduced by the 1.5 wt.% to 2.5 wt.% mould release agent content.
The fatty acid esters according to the invention are available commercially.
Thermoplastic aromatic polycarbonates within the meaning of the present invention are both homopolycarbonates and copolycarbonates; the polycarbonates may be linear or branched in known manner.
A portion, up to 80 mol%, preferably from 20 mol% to 50 mol%, of the carbonate groups in the polycarbonates which are suitable according to the invention may be replaced by aromatic dicarboxylic acid ester groups. Such polycarbonates, which contain, incorporated in the molecular chain, both acid residues of carbonic acid and also acid residues of aromatic dicarboxylic acids are, strictly speaking, aromatic polyester carbonates. For the sake of simplicity in the present Application they are to be subsumed in the generic term thermoplastic aromatic polycarbonates.
The polycarbonates to be used according to the invention are prepared in known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, wherein in order to prepare the polyester carbonates a portion of the carbonic acid derivatives is replaced by aromatic dicarboxylic acids or derivatives of the dicarboxylic acids, specifically according to those carbonate structural units in the aromatic polycarbonates which are to be replaced by aromatic dicarboxylic acid ester structural units.
Details relating to the preparation of polycarbonates have been recorded in hundreds of patent specifications over the course of some 40 years. Reference might be made here to the following few, by way of example:
~ Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964;
~ D.C. Prevorsek, B.T. Debona and Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Morristown, New Jersey 07960: "Synthesis of Polyester Carbonate) Copolymers" in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 19, 75-90 (1980)";
~ D. Freitag, U, Grigo, P.R. Miiller, N, Nouvertne', BAYER AG, "Polycarbonates"
in Encyclopedia of Polymer Science and Engineering, Volume 1 1, Second Edition, 1988, pp. 648-718, and finally ~ Dres. U. Grigo, K. Kircher and P.R. Miiller "Polycarbonate" [Polycarbonates) in BeckerlBraun, Kunststoff Handbuch [Manual of Plastics], Volume 3/1, Polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna 1992, pp. 117-299.
The thermoplastic polycarbonates including the thermoplastic aromatic polyester carbonates have average molecular weights MW (calculated by measuring the relative _6_ viscosity at 25°C in CHZCIZ and a concentration of 0.5 g per 100 ml CHZC12) of 12000 to 120000, preferably 15000 to 80000 and in particular 22000 to 60000.
Diphenols which are 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, a,a' bis(hydroxyphenyl)diisopropylbenzenes, as well as ring-alkylated and ring halogenated compounds thereof.
Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenyl propane, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)-m/p-diisopropylbenzene, 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, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-m/p-diisopropylbenzene, 2,2-and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, 1,1-bis(4-hydroxyphenyl)phenylethane, 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-trimethylcyclohexane.
These and further suitable diphenols are described, for example in US-PS-3 028 635, US-PS-2 999 835, US-PS-3 148 172, US-PS-2 991 273, US-PS-3 271 367, US-PS-4 982 014 and US-PS-2 999 846, German Offenlegungsschriften DE-A-1 570 703, DE-A-2 063 050, DE-A-2 036 052, DE-A-2 211 956 and DE-A-3 832 396, French patent specification FR-A-1 561 518, in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" and in Japanese Offenlegungsschriften 62039/1986, 62040/1986 and 105550/1986.
- '7 _ In the case of the homopolycarbonates only one diphenol is used, and in the case of the copolycarbonates a plurality of diphenols are used, naturally with the possibility that the bisphenols used, like all the other chemicals and auxiliary substances added to the synthesis, are contaminated with the impurities originating from their own synthesis, although it is desirable to work with raw materials which are as clean as possible.
Suitable chain terminators are both monophenols and also monocarboxylic acids.
Suitable monophenols are phenol, alkylphenols such as cresols, p-tert.butylphenol, 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, and mixtures thereof.
Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halobenzoic acids.
Preferred chain terminators are the phenols of the formula (I) R6--Ph--OH (I) in which R6 stands for H or a branched or unbranched C,-C,e alkyl radical.
The quantity of chain terminator to be used is from 0.5 mol% to 10 mol%, in relation to moles of diphenols used in each case. The chain terminators may be added before, during or after phosgenation.
Suitable branching agents are the trifunctional or higher-functional compounds known in polycarbonate chemistry, in particular those having three or more 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)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]
S propane, 2,4-bis(4-hydroxyphenyl isopropyl)phenol, 2,6-bis(2-hydroxy-5'-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, hexa-(4-(4-hydroxyphenyl isopropyl)phenyl) orthoterephthalic acid ester, tetra-(4-hydroxyphenyl)methane, tetra-(4-(4-hydroxyphenyl isopropyl)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-dihydroindol.
The quantity of the branching agent which is optionally to be used is from 0.05 mol% to 2.5 mol%, again in relation to moles of diphenols used in each case.
The branching agents may either be introduced in the aqueous alkaline phase with the diphenols and the chain terminators, or they may be added dissolved in an organic solvent before phosgenation.
The measures for preparing the polycarbonates are familiar to those skilled in the art.
Aromatic dicarboxylic acids which are suitable for the preparation of the polyester carbonates are, for example, phthalic acid, terephthalic acid, isophthalic acid, tert.butylisophthalic acid, 3,3'-diphenyl dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 4,4-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid.
Of the aromatic dicarboxylic acids, terephthalic acid and/or isophthalic acid are particularly preferably used.
Derivatives of the dicarboxylic acids are dicarboxylic acid dihalides and dicarboxylic acid dialkylesters, in particular dicarboxylic acid dichlorides and dicarboxylic acid dimethyl esters.
The replacement of the carbonate groups by the aromatic dicarboxylic acid ester groups takes place in substantially stoichiometric manner and also in quantitative manner, such that the molar ratio of the reagents reappears in the finished polyester carbonate. The aromatic dicarboxylic acid ester groups may be incorporated in both random and also block manner.
Preferred methods of preparing the polycarbonates, including the polyester carbonates, to be used according to the invention are the known interfacial process and the known melt transesterification process.
In the former case, phosgene preferably serves as the carbonic acid derivative, and in the latter case preferably diphenylcarbonate. The catalysts, solvents, working-up, reaction conditions etc. for the preparation of the polycarbonate have in both cases been described adequately and are known.
The moulding compositions according to the invention may be prepared by the addition of the alkanes according to the invention to the melt during the synthesis or, in the case of the interphacial process, to a working-up or concentration step, or also in solution, in that the alkanes according to the invention and optionally further additives are added in simultaneous or successive manner to the polycarbonates dissolved in a polycarbonate solvent, and the polycarbonate solvent is then evaporated.
The present invention consequently further provides a process for the preparation of the polycarbonate moulding compositions according to the invention, which is characterised in that polycarbonates are mixed with the esters according to the invention either in simultaneous or successive manner, either without solvent or in solution, and the mixtures are afterwards melt-compounded at temperatures of WO 00/73377 CA 02374445 2001-11-23 pCT/EP00/04677 between 260°C and 450°C, preferably 260°C to ~
420°C and most particularly preferably 260°C to 360°C, or are melt-extruded at temperatures of between 250°C
and 320°C, or the polycarbonate solutions are concentrated by evaporation, and the mixture obtained is granulated.
The polycarbonate moulding compositions according to the invention may also contain the conventional additives such as glass fibres, fillers, pigments, UV
stabilisers, heat stabilisers, antioxidants, flame retardants, toughening agents and optionally other mould release agents, in the quantities which are conventional for thermoplastic polycarbonates.
Suitable glass fibres are any commercially obtainable glass fibre products and grades, that is chopped strands and milled fibres, provided they are equipped with suitable sizing for compatibility with polycarbonate.
The glass fibres used for the preparation of the moulding compositions are prepared from E-glass. E-glass is understood to be an aluminium-boron-silicate glass having an alkali metal oxide content of less than 1 wt.%, to DIN 1259. Glass fibres having a diameter of from 8 to 20 ~,m and a length of from 3 to 6 mm (chopped strands) are conventionally used. Milled fibres may also be used, as may suitable glass spheres.
Flame retardants such as are used, for example, in polycarbonate and also such as may be used in the moulding compositions according to the invention are alkali metal salts of organic and inorganic acids, in particular sulfonic acids such as, for example, sodium or potassium perfluorobutane sulfonate, potassium hexafluoroaluminate, sodium hexalluoroaluminate, potassium diphenylsulfone sulfonate, sodium-2-formylbenzene sulfonate, sodium-(N-benzenesulfonyl) benzene sulfonamide, frequently combined with other flame retardants such as halogenated organic compounds such as, for example, tetrabromo oligocarbonate, cryolite and Teflon. Mixtures of the additives mentioned are likewise suitable.
These conventional additives may be added in known manner to the polycarbonates which are to be rendered flame-resistant, together with the components according to the invention or afterwards.
The polycarbonate moulding compositions according to the invention may be processed to form moulded bodies on conventional processing machines using known methods under the processing parameters which are conventional for polycarbonate.
Processing by injection moulding is preferred.
The invention therefore further provides the parts manufactured from the moulding compositions according to the invention, such as mouldings and semi-finished products.
The mouldings are used, for example, in the electrical, electronics, lighting, computer, construction, vehicle and/or aircraft sectors as well as the packaging, foods or toy industries.
The moulding compositions are suitable for injection moulded and extruded articles such as, for example, filins, beakers, sheets, twin-wall sheets, lamps, housings for electrical appliances, computers or vehicle fittings such as windows, instrument panel parts, headlight lenses, casings and the like, or playthings.
The demoulding properties of the polycarbonate moulding compositions according to the invention and of the Comparison Examples from the prior art were measured on a demoulding force measuring device (coefficient of friction measuring device).
The coefficients of friction for static and kinetic friction are determined, these representing a measure of the demoulding forces in respect of adhesion and sliding of the form from the injection mould.
W~ 00/73377 CA 02374445 2001-11-23 pCT/EP00/04677 A plate-shaped moulding having a melt temperature of 300°C and a mould temperature of 90°C is injection-moulded.
After cooling for 20 seconds in the closed mould the moulding is turned through an angle of 90°. A process data gathering system measures the breakaway moment of the plate and the force of the mould core acting against the plate. The coefficients are determined from the measuring parameter.
WO 00/73377 CA 02374445 2001-11-23 pCT/EP00/04677 Examples Quantities indicated in the Examples, expressed as wt.%, relate to the weight of the total mixture.
Examples 1 to 4 and Comparison Examples 1 to 4 An aromatic polycarbonate prepared from 2,2-bis(4-hydroxyphenyl) propane (melting index 10, measured to DIN 53 735) having phenol as the chain terminator was melted in a twin-sha$ extruder (ZSK 32/2) with vacuum venting. The quantity of ester according to the invention, as mentioned in accordance with the Examples, l0 was then dispensed directly into the polycarbonate melt. The polymer extrudate was cooled in a water bath and was then granulated. The granules were dried in a vacuum drying cabinet at 120°C for 8 hours and were injection moulded in an injection moulding machine having a melt temperature of 300°C and a mould temperature of 90°C, to form 60 x 40 x 4 mm test specimens.
is Optical properties such as transmission and turbidity were measured on these sample sheets.
The coefficients of friction were measured with the aid of a purpose-built measuring 20 device. In all the tests, the same plate-shaped moulding was in all cases injection moulded at a melt temperature of 300°C and at a mould temperature of 90°C on an Arburg Allrounder 320-210-850-D injection moulding machine. The moulding is turned through an angle of 90° after cooling for 20 seconds in the closed mould. A
process data gathering system measures the breakaway moment of the plate and the 25 force of the mould core acting on the plate. The coefficients are determined from the measuring parameters.
The coefficient for static and kinetic friction is used as a measure of the demoulding effect. Lower values are therefore advantageous compared with high values.
Table 1 30 shows Examples 1 and 2 and Comparison Examples 'l to 3. A polycarbonate containing no mould release agent and a product containing PETS =
pentaerythritol tetrastearate were shown as the control.
The moulding compositions according to the invention are distinguished by markedly lower coefficients of friction and even at smallish quantities are more effective than the standard mould release agent PETS conventionally used.
The moulding compositions according to the invention underwent a moulding-on-moulding slide test.
Beakers were produced by injection moulding for the test.
Two beakers were inserted without force in one another and were pulled apart after one hour. The beakers produced from the moulding compositions according to the invention (Examples 1 and 2) were able to be pulled apart without adhesion.
Adhesion effects occurred in the case of the beakers prepared from the moulding composition of Comparison Examples 1, 2 and 3.
Table 1 ComparisonComparison ComparisonExample Example Polycarbonate100.00 99.80 99.50 99.20 99.5 PETS 0 0.20 0.50 Grinsted 0.20 0.50 PGMS
SPV
Coeff. of 1.06 0.52 0.34 0.29 0.27 static friction Coeff. of 0.85 0.59 0.38 0.38 0.32 kinetic friction Slide - beaker- - + ++ +++
on beaker WD ~~/733T~ CA 02374445 2001-11-23 PCT/EP00/04677 - = high adhesion, poor slide, + = lower adhesion, moderate slide, ++ = virtually no adhesion, food slide, +++ = no adhesion, very food slide Even at higher mould release agent contents, the moulding compositions according to the invention show low turbidity and better transmission (Examples 3 and 4) than Comparison Example 4 (see Table 2).
Table 2 Comparison Example Example Polycarbonate 99.00 99.00 98.00 PETS 1.00 Grinsted PGMS 1.00 2.00 SPV
Turbidity 1.8% 0.9% 1.0%
Transmission 84.3% 86.1 % 86.2%
Patents and publications which describe the demoulding effect of additives in thermoplastics in general and polycarbonate in particular are known. The substances employed most frequently as mould release agents are esters prepared from long-chain aliphatic acids and alcohols. The use of esters prepared from fatty acid alcohols or polyols such as, for example, pentaerythritol with fatty acids might be named here by way of example, as described in DE 33 12 158, EP 100 918, EP 103 107, EP 561 629, EP 352 458, EP 436 117, or if Guerbet alcohols have been used, US 5 001 180, DE 33 12 157, US 5 744 626, and where montanic acids have been used as-the acid component, US 4 097 435.
A disadvantage is that the fatty acid esters show a clear demoulding effect only in quantities upwards of 0.5 wt.%. However, such concentrations are frequently sufficiently high to cause turbidity and/or the formation of a deposit on the mould.
Other mould release agents such as, for example, long-chain ketones, tend to form chromophores as a result of internal condensation and are not readily accessible (EP 100 918).
Siloxanes which are also used (US 4 536 590, US 4 390 651, US 3 751 519), while being sufficiently resistant to high and low temperatures, have very poor compatibility with polycarbonate and, at the concentrations which are required in order to be effective, lead to undesirable turbidity which greatly restricts the usability of a~ common material such as polycarbonate which is predominantly in transparent adjusted.
a-Olefin polymers, optionally having residual double bonds (DE-A-32 44 499) and S described, for example, in EP-A-561 630 and EP-A-230 015, are not stable as to colour. In the case of hydrogenated systems, as with the long-chain alkanes (US 4 415 696) compatibility with polycarbonate is a problem and leads to mouldings which are turbid and consequently not transparent. The wax-like or liquid-waxy consistency of these products is moreover inconvenient.
Because shorter cycle times and higher processing temperatures are required, distortion-free demoulding of polycarbonate mouldings poses an on-going challenge, if the very high-quality surface is to be retained irrespective of frequently very different moulding designs. It is often the case that problems are overcome only by a tailor-made mould release formulation. There is therefore a constant need for novel potential mould release agents.
There are two forces at work during the demoulding operation, static friction and kinetic friction. The mould release agent must be designed such as to minimise both forces without the formation of an undesirable deposit on the mould.
T'he object was therefore to find mould release agents which minimise both of the demoulding forces simultaneously, so that with one moulding composition any shape of finished part is able to be demoulded, without the formation of a deposit on the mould.
The object was furthermore to find mould release agents which do not have the tendency to transesterify with the polycarbonate and which, at the effective concentrations, give rise to neither turbidity nor discoloration.
WO 00/73377 CA 02374445 2001-11-23 PCT/EP00/0467"l A further object is to reduce problems arising from the adhesion of finished polycarbonate mouldings, such as occurs when, for example, beakers are pulled apart after storage.
A further object is to reduce problems arising from the adhesion of finished polycarbonate mouldings to metals, such as occurs when, for example sliding on inclined metallic surfaces.
A further object is to control the force of attachment which is important, for example, with toys. Here, however, precise matching of the components must be ensured, since an excessively low force of attachment is also undesirable in some applications.
The objects were achieved by the use of fatty acid esters based on 1,2-dihydroxypropane and C,-C4° carboxylic acids as mould release agents which have sufficient solubility and stability in polycarbonate.
The present invention provides polycarbonate moulding compositions containing from 0.005 to 5.0 wt.%, preferably 0.05 to 3.0 wt.%, most particularly preferably 0.1 S to 2.0 wt.%, fatty acid esters based on 1,2-dihydroxypropane and C,-C~
carboxylic acids as well as esters prepared from 1,2-dihydroxypropane with mixtures of different C,-C~ carboxylic acids wherein the alcohol may also be partially esterified as well as mixtures of partially esterified and fully esterified products and optionally with use of other additives which are conventional in polycarbonates, such as, for example, heat stabilisers, IJV stabilisers, other mould release agents, flame retardants, anti-drip agents, fillers, glass fibres and blend components such as ABS, ASA, SAN, EPDM or polyesters based on terephthalic acid and diols, which are characterised in that the moulding compositions have, on a demoulding force measuring device (coefficient of friction measuring device) coefficients of friction of preferably < 0.80, particularly preferably < 0.60 and most particularly preferably <
0.40 in respect of the static and kinetic friction, wherein the reference value of a polycarbonate of the same viscosity containing no mould release agent, measured on the coefficient of friction device, has a value of between 0.85 and 1.50.
The moulding compositions according to the invention may be contaminated with impurities which are contained in the individual constituents of the moulding composition arising from the synthesis, working-up, processing and storage thereof, as well as contaminants which originate during the preparation or processing of the moulding compositions according to the invention, The aim is, however, to work with products which are as clean as possible.
If the moulding compositions contain free OH groups, it is preferred that they contain less than 10 ppm ions, particularly preferably less than 5 ppm. This applies most particularly to ions of the elements Na, K, Mg, Ca, Sn, Ti, Fe, Ni and Cr.
If the fatty acid esters to be used according to the invention are partially esterified and contain free OH groups, it is preferred that they contain less than 10 ppm ions, particularly preferably less than 5 ppm. This applies most particularly to ions of the elements Na, K, Mg, Ca, Sn, Ti, Fe, Ni and Cr.
The adhesion of finished polycarbonate mouldings is preferably reduced by the 1.5 wt.% to 2.5 wt.% mould release agent content.
The fatty acid esters according to the invention are available commercially.
Thermoplastic aromatic polycarbonates within the meaning of the present invention are both homopolycarbonates and copolycarbonates; the polycarbonates may be linear or branched in known manner.
A portion, up to 80 mol%, preferably from 20 mol% to 50 mol%, of the carbonate groups in the polycarbonates which are suitable according to the invention may be replaced by aromatic dicarboxylic acid ester groups. Such polycarbonates, which contain, incorporated in the molecular chain, both acid residues of carbonic acid and also acid residues of aromatic dicarboxylic acids are, strictly speaking, aromatic polyester carbonates. For the sake of simplicity in the present Application they are to be subsumed in the generic term thermoplastic aromatic polycarbonates.
The polycarbonates to be used according to the invention are prepared in known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, wherein in order to prepare the polyester carbonates a portion of the carbonic acid derivatives is replaced by aromatic dicarboxylic acids or derivatives of the dicarboxylic acids, specifically according to those carbonate structural units in the aromatic polycarbonates which are to be replaced by aromatic dicarboxylic acid ester structural units.
Details relating to the preparation of polycarbonates have been recorded in hundreds of patent specifications over the course of some 40 years. Reference might be made here to the following few, by way of example:
~ Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964;
~ D.C. Prevorsek, B.T. Debona and Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Morristown, New Jersey 07960: "Synthesis of Polyester Carbonate) Copolymers" in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 19, 75-90 (1980)";
~ D. Freitag, U, Grigo, P.R. Miiller, N, Nouvertne', BAYER AG, "Polycarbonates"
in Encyclopedia of Polymer Science and Engineering, Volume 1 1, Second Edition, 1988, pp. 648-718, and finally ~ Dres. U. Grigo, K. Kircher and P.R. Miiller "Polycarbonate" [Polycarbonates) in BeckerlBraun, Kunststoff Handbuch [Manual of Plastics], Volume 3/1, Polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna 1992, pp. 117-299.
The thermoplastic polycarbonates including the thermoplastic aromatic polyester carbonates have average molecular weights MW (calculated by measuring the relative _6_ viscosity at 25°C in CHZCIZ and a concentration of 0.5 g per 100 ml CHZC12) of 12000 to 120000, preferably 15000 to 80000 and in particular 22000 to 60000.
Diphenols which are 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, a,a' bis(hydroxyphenyl)diisopropylbenzenes, as well as ring-alkylated and ring halogenated compounds thereof.
Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenyl propane, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)-m/p-diisopropylbenzene, 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, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-m/p-diisopropylbenzene, 2,2-and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, 1,1-bis(4-hydroxyphenyl)phenylethane, 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-trimethylcyclohexane.
These and further suitable diphenols are described, for example in US-PS-3 028 635, US-PS-2 999 835, US-PS-3 148 172, US-PS-2 991 273, US-PS-3 271 367, US-PS-4 982 014 and US-PS-2 999 846, German Offenlegungsschriften DE-A-1 570 703, DE-A-2 063 050, DE-A-2 036 052, DE-A-2 211 956 and DE-A-3 832 396, French patent specification FR-A-1 561 518, in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" and in Japanese Offenlegungsschriften 62039/1986, 62040/1986 and 105550/1986.
- '7 _ In the case of the homopolycarbonates only one diphenol is used, and in the case of the copolycarbonates a plurality of diphenols are used, naturally with the possibility that the bisphenols used, like all the other chemicals and auxiliary substances added to the synthesis, are contaminated with the impurities originating from their own synthesis, although it is desirable to work with raw materials which are as clean as possible.
Suitable chain terminators are both monophenols and also monocarboxylic acids.
Suitable monophenols are phenol, alkylphenols such as cresols, p-tert.butylphenol, 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, and mixtures thereof.
Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halobenzoic acids.
Preferred chain terminators are the phenols of the formula (I) R6--Ph--OH (I) in which R6 stands for H or a branched or unbranched C,-C,e alkyl radical.
The quantity of chain terminator to be used is from 0.5 mol% to 10 mol%, in relation to moles of diphenols used in each case. The chain terminators may be added before, during or after phosgenation.
Suitable branching agents are the trifunctional or higher-functional compounds known in polycarbonate chemistry, in particular those having three or more 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)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]
S propane, 2,4-bis(4-hydroxyphenyl isopropyl)phenol, 2,6-bis(2-hydroxy-5'-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, hexa-(4-(4-hydroxyphenyl isopropyl)phenyl) orthoterephthalic acid ester, tetra-(4-hydroxyphenyl)methane, tetra-(4-(4-hydroxyphenyl isopropyl)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-dihydroindol.
The quantity of the branching agent which is optionally to be used is from 0.05 mol% to 2.5 mol%, again in relation to moles of diphenols used in each case.
The branching agents may either be introduced in the aqueous alkaline phase with the diphenols and the chain terminators, or they may be added dissolved in an organic solvent before phosgenation.
The measures for preparing the polycarbonates are familiar to those skilled in the art.
Aromatic dicarboxylic acids which are suitable for the preparation of the polyester carbonates are, for example, phthalic acid, terephthalic acid, isophthalic acid, tert.butylisophthalic acid, 3,3'-diphenyl dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 4,4-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid.
Of the aromatic dicarboxylic acids, terephthalic acid and/or isophthalic acid are particularly preferably used.
Derivatives of the dicarboxylic acids are dicarboxylic acid dihalides and dicarboxylic acid dialkylesters, in particular dicarboxylic acid dichlorides and dicarboxylic acid dimethyl esters.
The replacement of the carbonate groups by the aromatic dicarboxylic acid ester groups takes place in substantially stoichiometric manner and also in quantitative manner, such that the molar ratio of the reagents reappears in the finished polyester carbonate. The aromatic dicarboxylic acid ester groups may be incorporated in both random and also block manner.
Preferred methods of preparing the polycarbonates, including the polyester carbonates, to be used according to the invention are the known interfacial process and the known melt transesterification process.
In the former case, phosgene preferably serves as the carbonic acid derivative, and in the latter case preferably diphenylcarbonate. The catalysts, solvents, working-up, reaction conditions etc. for the preparation of the polycarbonate have in both cases been described adequately and are known.
The moulding compositions according to the invention may be prepared by the addition of the alkanes according to the invention to the melt during the synthesis or, in the case of the interphacial process, to a working-up or concentration step, or also in solution, in that the alkanes according to the invention and optionally further additives are added in simultaneous or successive manner to the polycarbonates dissolved in a polycarbonate solvent, and the polycarbonate solvent is then evaporated.
The present invention consequently further provides a process for the preparation of the polycarbonate moulding compositions according to the invention, which is characterised in that polycarbonates are mixed with the esters according to the invention either in simultaneous or successive manner, either without solvent or in solution, and the mixtures are afterwards melt-compounded at temperatures of WO 00/73377 CA 02374445 2001-11-23 pCT/EP00/04677 between 260°C and 450°C, preferably 260°C to ~
420°C and most particularly preferably 260°C to 360°C, or are melt-extruded at temperatures of between 250°C
and 320°C, or the polycarbonate solutions are concentrated by evaporation, and the mixture obtained is granulated.
The polycarbonate moulding compositions according to the invention may also contain the conventional additives such as glass fibres, fillers, pigments, UV
stabilisers, heat stabilisers, antioxidants, flame retardants, toughening agents and optionally other mould release agents, in the quantities which are conventional for thermoplastic polycarbonates.
Suitable glass fibres are any commercially obtainable glass fibre products and grades, that is chopped strands and milled fibres, provided they are equipped with suitable sizing for compatibility with polycarbonate.
The glass fibres used for the preparation of the moulding compositions are prepared from E-glass. E-glass is understood to be an aluminium-boron-silicate glass having an alkali metal oxide content of less than 1 wt.%, to DIN 1259. Glass fibres having a diameter of from 8 to 20 ~,m and a length of from 3 to 6 mm (chopped strands) are conventionally used. Milled fibres may also be used, as may suitable glass spheres.
Flame retardants such as are used, for example, in polycarbonate and also such as may be used in the moulding compositions according to the invention are alkali metal salts of organic and inorganic acids, in particular sulfonic acids such as, for example, sodium or potassium perfluorobutane sulfonate, potassium hexafluoroaluminate, sodium hexalluoroaluminate, potassium diphenylsulfone sulfonate, sodium-2-formylbenzene sulfonate, sodium-(N-benzenesulfonyl) benzene sulfonamide, frequently combined with other flame retardants such as halogenated organic compounds such as, for example, tetrabromo oligocarbonate, cryolite and Teflon. Mixtures of the additives mentioned are likewise suitable.
These conventional additives may be added in known manner to the polycarbonates which are to be rendered flame-resistant, together with the components according to the invention or afterwards.
The polycarbonate moulding compositions according to the invention may be processed to form moulded bodies on conventional processing machines using known methods under the processing parameters which are conventional for polycarbonate.
Processing by injection moulding is preferred.
The invention therefore further provides the parts manufactured from the moulding compositions according to the invention, such as mouldings and semi-finished products.
The mouldings are used, for example, in the electrical, electronics, lighting, computer, construction, vehicle and/or aircraft sectors as well as the packaging, foods or toy industries.
The moulding compositions are suitable for injection moulded and extruded articles such as, for example, filins, beakers, sheets, twin-wall sheets, lamps, housings for electrical appliances, computers or vehicle fittings such as windows, instrument panel parts, headlight lenses, casings and the like, or playthings.
The demoulding properties of the polycarbonate moulding compositions according to the invention and of the Comparison Examples from the prior art were measured on a demoulding force measuring device (coefficient of friction measuring device).
The coefficients of friction for static and kinetic friction are determined, these representing a measure of the demoulding forces in respect of adhesion and sliding of the form from the injection mould.
W~ 00/73377 CA 02374445 2001-11-23 pCT/EP00/04677 A plate-shaped moulding having a melt temperature of 300°C and a mould temperature of 90°C is injection-moulded.
After cooling for 20 seconds in the closed mould the moulding is turned through an angle of 90°. A process data gathering system measures the breakaway moment of the plate and the force of the mould core acting against the plate. The coefficients are determined from the measuring parameter.
WO 00/73377 CA 02374445 2001-11-23 pCT/EP00/04677 Examples Quantities indicated in the Examples, expressed as wt.%, relate to the weight of the total mixture.
Examples 1 to 4 and Comparison Examples 1 to 4 An aromatic polycarbonate prepared from 2,2-bis(4-hydroxyphenyl) propane (melting index 10, measured to DIN 53 735) having phenol as the chain terminator was melted in a twin-sha$ extruder (ZSK 32/2) with vacuum venting. The quantity of ester according to the invention, as mentioned in accordance with the Examples, l0 was then dispensed directly into the polycarbonate melt. The polymer extrudate was cooled in a water bath and was then granulated. The granules were dried in a vacuum drying cabinet at 120°C for 8 hours and were injection moulded in an injection moulding machine having a melt temperature of 300°C and a mould temperature of 90°C, to form 60 x 40 x 4 mm test specimens.
is Optical properties such as transmission and turbidity were measured on these sample sheets.
The coefficients of friction were measured with the aid of a purpose-built measuring 20 device. In all the tests, the same plate-shaped moulding was in all cases injection moulded at a melt temperature of 300°C and at a mould temperature of 90°C on an Arburg Allrounder 320-210-850-D injection moulding machine. The moulding is turned through an angle of 90° after cooling for 20 seconds in the closed mould. A
process data gathering system measures the breakaway moment of the plate and the 25 force of the mould core acting on the plate. The coefficients are determined from the measuring parameters.
The coefficient for static and kinetic friction is used as a measure of the demoulding effect. Lower values are therefore advantageous compared with high values.
Table 1 30 shows Examples 1 and 2 and Comparison Examples 'l to 3. A polycarbonate containing no mould release agent and a product containing PETS =
pentaerythritol tetrastearate were shown as the control.
The moulding compositions according to the invention are distinguished by markedly lower coefficients of friction and even at smallish quantities are more effective than the standard mould release agent PETS conventionally used.
The moulding compositions according to the invention underwent a moulding-on-moulding slide test.
Beakers were produced by injection moulding for the test.
Two beakers were inserted without force in one another and were pulled apart after one hour. The beakers produced from the moulding compositions according to the invention (Examples 1 and 2) were able to be pulled apart without adhesion.
Adhesion effects occurred in the case of the beakers prepared from the moulding composition of Comparison Examples 1, 2 and 3.
Table 1 ComparisonComparison ComparisonExample Example Polycarbonate100.00 99.80 99.50 99.20 99.5 PETS 0 0.20 0.50 Grinsted 0.20 0.50 PGMS
SPV
Coeff. of 1.06 0.52 0.34 0.29 0.27 static friction Coeff. of 0.85 0.59 0.38 0.38 0.32 kinetic friction Slide - beaker- - + ++ +++
on beaker WD ~~/733T~ CA 02374445 2001-11-23 PCT/EP00/04677 - = high adhesion, poor slide, + = lower adhesion, moderate slide, ++ = virtually no adhesion, food slide, +++ = no adhesion, very food slide Even at higher mould release agent contents, the moulding compositions according to the invention show low turbidity and better transmission (Examples 3 and 4) than Comparison Example 4 (see Table 2).
Table 2 Comparison Example Example Polycarbonate 99.00 99.00 98.00 PETS 1.00 Grinsted PGMS 1.00 2.00 SPV
Turbidity 1.8% 0.9% 1.0%
Transmission 84.3% 86.1 % 86.2%
Claims (12)
1. Polycarbonate moulding compositions, characterised in that they contain as a mould release agent, in quantities of from 0.005 to 5.0 wt.%, preferably 0.01 to 3.0 wt.%, most particularly preferably 0.02 to 2.0 wt.%, an ester prepared from 1,2-dihydroxypropane and C1 to C40 carboxylic acids, preferably ester prepared from 1,2-dihydroxypropane with C10 to C40 carboxylic acids and most particularly preferably ester prepared from 1,2-dihydroxypropane with C10 to C25 carboxylic acids as well as ester prepared from 1,2-dihydroxypropane with mixtures of different carboxylic acids wherein the alcohol may also be partially esterified as well as mixtures of partially esterified and fully esterified products.
2. Polycarbonate moulding compositions according to Claim 1, characterised in that the moulding compositions have, on a demoulding force measuring device (coefficient of friction measuring device), coefficients of friction of preferably < 0.80, particularly preferably < 0.60 and most particularly preferably < 0.40 in respect of the static and kinetic friction, wherein the reference value of a polycarbonate of the same viscosity containing no mould release agent, measured on the coefficient of friction device, has a value of between 0.85 and 1.50.
3. Polycarbonate moulding compositions according to Claim 1, characterised in that the adhesion of finished mouldings prepared from the moulding compositions, to metals is reduced, such that the slide of the mouldings on inclined metallic planes is facilitated.
4. Polycarbonate moulding compositions according to Claim 1, characterised in that the adhesion and the slide of finished mouldings on one another is reduced, such that mouldings which are, for example, placed inside one another, such as, for example, beakers, can be readily separated from one another.
5. Polycarbonate moulding compositions according to Claim 1, characterised in that the force of attachment of finished parts can be adjusted in targeted manner, such that the mouldings can be separated using defined forces.
6. Polycarbonate moulding compositions according to at least one of the preceding claims, characterised in that further additives such as, for example, heat stabilisers, UV stabilisers, other mould release agents, flame retardants, anti-drip agents, fillers, pigments, glass fibres and blend components such as ABS, ASA, SAN, EPDM or polyesters based on terephthalic acid and diols are contained.
7. Polycarbonate moulding compositions according to at least one of the preceding claims, characterised in that the mould release agent is contained in quantities of from 1.5 wt.% to 2.5 wt.%.
8. Polycarbonate moulding compositions according to at least one of the preceding claims, characterised in that up to 80 mol%, preferably from 20 mol% to 50 mol%, of the carbonate groups in the polycarbonates which are suitable according to the invention may be replaced by aromatic dicarboxylic acid ester groups.
9. Process for the preparation of polycarbonate moulding compositions according to at least one of the preceding claims, characterised in that polycarbonates are mixed with esters either in simultaneous or successive manner, either as such or in solution, and the mixtures are afterwards melt-compounded at temperatures of between 260°C and 450°C, preferably 260°C to 420°C and most particularly preferably 260°C to 360°C, or are melt-extruded at temperatures of between 250°C and 320°C, or the polycarbonate solutions are concentrated by evaporation, and the mixture obtained is granulated.
10. Process according to Claim 6, characterised in that further additives such as glass fibres, fillers, pigments, UV stabilisers, heat stabilisers, antioxidants, flame retardants, toughening agents and optionally other mould release agents are added to the polycarbonate moulding compositions, together with the components according to the invention or subsequently.
11. Mouldings and semi-finished products containing one of the moulding compositions of the Claims 1 to 8, preferably for applications in the electrical, electronics, lighting, computer, toy, packaging, construction, vehicle and/or aircraft sectors.
12. Injection moulded and extruded articles containing one of the moulding compositions of the Claims 1 to 8, preferably films, sheets, twin-wall sheets, lamps, housings for electrical appliances, computers or vehicle fittings such as, for example, windows, instrument panel parts, headlight lenses, casings and the like.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19925116.9 | 1999-06-01 | ||
| DE19925116 | 1999-06-01 | ||
| PCT/EP2000/004677 WO2000073377A1 (en) | 1999-06-01 | 2000-05-23 | Polycarbonate moulding materials with good demoulding properties and moulded bodies and semi-finished products produced with said materials, with good sliding properties |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2374445A1 true CA2374445A1 (en) | 2000-12-07 |
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ID=7909904
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002374445A Abandoned CA2374445A1 (en) | 1999-06-01 | 2000-05-23 | Polycarbonate moulding materials with good demoulding properties and moulded bodies and semi-finished products produced with said materials, with good sliding properties |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1189982A1 (en) |
| JP (1) | JP2003501506A (en) |
| KR (1) | KR20020005766A (en) |
| CN (1) | CN1353737A (en) |
| AR (1) | AR024160A1 (en) |
| AU (1) | AU5215600A (en) |
| BR (1) | BR0011096A (en) |
| CA (1) | CA2374445A1 (en) |
| IL (1) | IL146256A0 (en) |
| MX (1) | MXPA01012389A (en) |
| WO (1) | WO2000073377A1 (en) |
Cited By (1)
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|---|---|---|---|---|
| US8425032B2 (en) | 2008-05-28 | 2013-04-23 | Teijin Chemicals, Ltd. | Spectacle lens |
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| US20090043053A1 (en) * | 2007-08-07 | 2009-02-12 | Rudiger Gorny | Aircraft window |
| WO2011078265A1 (en) * | 2009-12-24 | 2011-06-30 | 三菱レイヨン株式会社 | Method for evaluating performance of organic release agent, process for producing mold, and process for producing transparent film with finely roughened structure on surface |
| CN103351596A (en) * | 2013-08-08 | 2013-10-16 | 深圳市兴盛迪新材料有限公司 | Improved glass fiber reinforced PC/ASA composition |
| JP6340238B2 (en) * | 2014-04-17 | 2018-06-06 | 住化ポリカーボネート株式会社 | Movable production role for gaming machines |
| JP7253334B2 (en) * | 2018-07-03 | 2023-04-06 | 出光興産株式会社 | Polycarbonate resin composition and molded article thereof |
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| GB1489717A (en) * | 1975-05-07 | 1977-10-26 | Sapchim Fournier Cimag Sa | Synthetic plastics materials containing lubricating agent |
| WO1998017725A1 (en) * | 1996-10-21 | 1998-04-30 | Eastman Chemical Company | 1,4-cyclohexanedimethanol based polyester blends |
-
2000
- 2000-05-23 KR KR1020017015409A patent/KR20020005766A/en not_active Application Discontinuation
- 2000-05-23 EP EP00936785A patent/EP1189982A1/en not_active Withdrawn
- 2000-05-23 JP JP2001500701A patent/JP2003501506A/en active Pending
- 2000-05-23 BR BR0011096-5A patent/BR0011096A/en not_active Application Discontinuation
- 2000-05-23 WO PCT/EP2000/004677 patent/WO2000073377A1/en not_active Application Discontinuation
- 2000-05-23 MX MXPA01012389A patent/MXPA01012389A/en not_active Application Discontinuation
- 2000-05-23 CA CA002374445A patent/CA2374445A1/en not_active Abandoned
- 2000-05-23 CN CN00808397A patent/CN1353737A/en active Pending
- 2000-05-23 AU AU52156/00A patent/AU5215600A/en not_active Abandoned
- 2000-05-23 IL IL14625600A patent/IL146256A0/en unknown
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8425032B2 (en) | 2008-05-28 | 2013-04-23 | Teijin Chemicals, Ltd. | Spectacle lens |
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| Publication number | Publication date |
|---|---|
| WO2000073377A1 (en) | 2000-12-07 |
| MXPA01012389A (en) | 2002-09-02 |
| AR024160A1 (en) | 2002-09-04 |
| JP2003501506A (en) | 2003-01-14 |
| AU5215600A (en) | 2000-12-18 |
| IL146256A0 (en) | 2002-07-25 |
| CN1353737A (en) | 2002-06-12 |
| EP1189982A1 (en) | 2002-03-27 |
| BR0011096A (en) | 2002-06-11 |
| KR20020005766A (en) | 2002-01-17 |
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