DE102009058462A1 - Producing polycarbonate injection molded body comprises introducing injection molded bodies containing polycarbonate in reactor, inerting atmosphere of reactor, introducing fluorine-inert gas mixture and evacuating and flushing the reactor - Google Patents

Abstract

Producing polycarbonate injection molded body or extrudate, comprises (a) introducing one or more injection molded bodies and/or extrudates consisting of polycarbonate in a reactor, (b) inerting the atmosphere of the reactor until an oxygen content of 10 ppm by volume or less is reached, (c) introducing a fluorine-inert gas mixture that contains 0.5-20% of fluorine, (d) repeatedly evacuating and flushing the reactor with inert gas and then with air after fluorination and (e) flushing the injection-molded body or extrudate with surfactant-containing distilled water and pure distilled water. Producing polycarbonate injection molded body or extrudate, comprises (a) introducing one or more injection molded bodies and/or extrudates consisting of polycarbonate in a reactor, (b) inerting the atmosphere of the reactor until an oxygen content of 10 ppm by volume or less is reached, (c) introducing a fluorine-inert gas mixture that contains 0.5-20% of fluorine, where the total pressure in the reactor during fluorination lies at 0.3-0.7 bar and the temperature in the fluorination lies at 10-50[deg] C, and the process time is 10-60 minutes, (d) repeatedly evacuating and flushing the reactor with inert gas and then with air after fluorination, and (e) flushing the injection-molded body or extrudate with surfactant-containing distilled water and then with pure distilled water.

Description

The present invention relates to specially treated polycarbonates and specially treated moldings or injection molded parts and extrudates obtainable from polycarbonate and to processes for the surface treatment of these polycarbonates, molded articles or injection-molded parts and extrudates with bactericidal activity.

These specially treated polymers also have improved optical properties, such. As an increased transmission and lower reflection. The combination of these properties leads to a unique property picture and thus to special application areas.

Thus, these polycarbonates, especially for the production of transparent injection molded body for the optical sector such. As lenses or lenses or for products from the extrusion sector such. B. use plates or foils.

These products are often exposed to the external environment and thus weather conditions. As biomaterials such as bacteria and / or algae accumulate on these products, they can reduce the optical transmission. The present invention makes it possible to protect the optical properties of injection-molded articles or extrudates from the influence of microorganisms and at the same time to improve the polycarbonate with regard to the transmission. Even with polycarbonate foils z. B. in telecommunications such. As mobile phone shells and cell phone keyboards antibacterial polycarbonate can be beneficial. In light collection systems z. As in photovoltaic systems, these polycarbonates may also be beneficial. Likewise for high-quality housing and display and lamp covers.

This process is suitable for both polycarbonates prepared by the interfacial process and polycarbonates prepared in the melt transesterification process.

The gas-phase fluorination of thermoplastics is known in principle and is based on the exchange of hydrogen atoms in the material by fluorine. Comprehensive representations can be found in the monograph of Kharitonov, AP; Direct Fluorination of Polymers, Nova Science Publishers Inc., New York 2007 and and at AP Kharitonov, R. Taege, G. Ferrier, VV Teplyakov, DA Syrtsova, G.-H. Koogs Journal of Fluorine Chemistry, Volume 126, Issue 2, February 2005, pages 251-263 , just like A. Tressaud, E. Durand, C. Labrugère, AP Kharitonov, LN Kharitonova, Journal of Fluorine Chemistry, Volume 128, Issue 4, April 2007, pages 378-391 , In particular, barrier properties, membrane properties, adhesion, frictional resistance and chemical resistance of polymer materials are to be improved by gas phase fluorination. However, fundamental studies on the fluorination of polycarbonates are not known.

In U.S. 5,275,882 describes the metal coating process of a polycarbonate or polycarbonate blend, which comprises a fluorination of the material surface. In contrast to the present invention, however, there is no direct fluorination in the gas phase.

In US-3,413,266 A For example, a method of improving the chemical resistance of polycarbonate is described. Fluorine gas is used in this process. However, the method differs from the process according to the invention described here. In a multi-stage process, a long-term fluorination (up to 5 hours) takes place under exclusion of oxygen with subsequent heat treatment. The method of the present invention has the advantage of shorter cycle times.

In DE 102 16 263 A1 a method for the production of plastic containers will be described. A process component is the contact of the container with fluorine gas. The goal of the fluorine treatment of the containers, which can also be made of polycarbonate, with a fluorine-inert gas mixture is to achieve an improved barrier effect against paraffin-based latent heat storage material. The method described here is not suitable for the production of biocidal polycarbonate materials with good optical properties.

In US-20050245693 A1 It is intended to replace a high proportion of hydrogen in the entire polymer body (including polycarbonate) by fluorine. It is therefore fluorinated in polymer melt or in polymer solution. Such a procedure changes the overall properties of the polymer matrix and is technically complicated.

An improvement in optical or bactericidal properties is not intended in the aforementioned publications and can not be achieved in the ways described.

In the DE 10 2006 041 835 A1 Double chamber cartridges (including polycarbonate) are treated for the storage of dental materials by means of the gas phase fluoridation in order to significantly reduce the gas and liquid permeability of the inner wall of the cartridge and thus to increase the storage stability of the sensitive dental materials. The improvement of optical or bactericidal properties is not targeted. The chosen fluorination conditions are to achieve higher Transmission unfavorable. Also, the method described here is not suitable for the production of biocidal polycarbonate materials with good optical properties.

In order to decisively improve the optical properties of transparent polymer substrates and to reduce the interfacial reflection, in the DE 102 41 708 A1 the polymer surface by plasma treatment in the argon / oxygen stream and then coated with a protective layer of diethylene glycol bisallyl carbonate (CR39) coated. Although this method is very effective in terms of improving the optical properties, but very expensive compared to the gas phase fluorination. In addition, an antibacterial effect can not be achieved with it.

To antibacterial polycarbonates also a prior art is documented.

EP 491 279 A1 describes a fluorination process wherein finished cross-linked polyethylene moldings are chemically modified by treatment with gaseous fluorine at the surface. Such moldings then have germ-growth-inhibiting properties. The chosen fluorination conditions would result in the case of fluorination of polycarbonate under the same conditions to a thermally oxidative degradation with degraded optical properties and are therefore not suitable.

In order to curb or completely prevent the growth of bacteria, spores or fungi on surfaces of industrial materials, germ-growth-inhibiting equipment of the corresponding materials is becoming increasingly important. There are a variety of biocidal agents, such as beta-lactam antibiotics or fluoroquinolones, antiseptics and disinfectants, such as chlorhexidine, trichlosan, octenidine or quaternary ammonium salts and metallic agents, such as silver or silver ions available that either applied to the surface (coated ) or, for example, in the case of plastics, be homogeneously distributed over the entire material (bulk) via compounding processes. For example. describes WO 2007/075643 a compounding method wherein silver-containing antibacterial agents are compounded into aromatic polycarbonate resins. The corresponding plastic granules can then be further processed into antibacterial plastic molded parts. This method has, besides the good biocidal activity, two significant disadvantages. On the one hand, relatively high amounts of active ingredient (silver in an inorganic matrix) are required, whereby only the active substance located on the plastic surface can be utilized. This is particularly true for materials, eg. For glassy plastics with low polymer chain mobility, such as polymethylmethacrylate (Plexiglas ^®) or Poycarbonat (Makrolon ^®). Because of the relatively high amounts of active substance required in the corresponding compounding processes, inevitably relatively high costs arise. In addition, the beneficial properties of the base material are often adversely affected by the compounded drug components. For example, at the in WO 2007/075643 Compounds described which significantly reduces intrinsic transparency of the polycarbonate material.

Against this background, the relatively expensive active ingredients are increasingly applied by coating to the corresponding surface. For example, describes EP 169 606 A1 Such a coating process wherein a biocide layer is provided with a transport control layer (porous membrane layer). In the case of coatings of this type, although smaller amounts of active ingredient are required, the corresponding processes are associated with considerable technical complexity. In addition, the uniform coating of hard-to-reach surfaces, for example, inner walls of fine tubes, is extremely critical. Finally, the mechanical and optical properties of the base material are also changed by the coating in this case.

It was therefore an object to provide moldings, injection molded articles or extrusions made of polycarbonate, which on the one hand permanently outstanding optical properties, such as. B. have high transmission and at the same time have an antibacterial effect. It was a further object of the present invention to develop a process which is as simple and cost-effective as possible for the biocidal, in particular antibacterial, finishing of finished components, in particular polycarbonate molded parts.

Surprisingly, it has been found that these properties can be achieved by a special treatment method. In this method, the substrate material or the injection molded body or the extrudate is brought into contact with fluorine gas in the absence of oxygen and in the presence of inert gases. A polycarbonate surface treated by the process of the invention has bactericidal effects in conjunction with good optical properties. In addition, these layers have a high mechanical stability.

As inert gases are preferably nitrogen, argon, helium, carbon dioxide, more preferably nitrogen.

• a) Einbringen eines oder mehrerer Spritzgusskörper und/oder Extrudate bestehend aus Polycarbonat in einen Reaktor,
• b) Inertisierung der Atmosphäre des Reaktors bis ein Sauerstoffgehalt unter 10 Vol-ppm erreicht ist,
• c) Einleiten einer Fluor-Inertgasmischung welche aus etwa 0,5–20% Fluor enthält, wobei der Gesamtdruck im Reaktor während der Fluorierung bei 0,3–0,7 bar und die Temperatur bei der Fluorierung bei 1–50°C liegt, und die Verfahrensdauer 10–60 Minuten beträgt
• d) Nach der Fluorierung mehrfache Evakuierung und Spülung des Reaktors mit Inertgas und anschließend mit Luft
• e) Spülung der Spritzgusskörper bzw. Extrudate mit tensidhaltigen destilliertem Wasser und anschliessend mit reinem destillierten Wasser.

The object is achieved by the method comprising at least the following steps:

• a) introducing one or more injection-molded bodies and / or extrudates consisting of polycarbonate into a reactor,
• b) inerting the atmosphere of the reactor until an oxygen content of less than 10 ppm by volume is reached,
• c) introducing a fluorine-inert gas mixture which contains about 0.5-20% fluorine, wherein the total pressure in the reactor during fluorination at 0.3-0.7 bar and the temperature during the fluorination at 1-50 ° C, and the process time is 10-60 minutes
• d) After fluorination multiple evacuation and flushing of the reactor with inert gas and then with air
• e) rinsing the injection-molded body or extrudates with surfactant-containing distilled water and then with pure distilled water.

• 1. Bereitstellung des Spritzgusskörpers oder Extrudats bestehend aus Polycarbonat. Treten oberflächliche Verunreinigungen des Polymerkörpers auf, so muss eine Reinigung mit geeigneten Medien wie z. B. mit Wasser oder mit Isopropanol und nachfolgender Trocknung erfolgen.
• 2. Der nach Schritt 1 gefertigte und vorbereitete Spritzgusskörper bzw. das Extrudat wird in einen Reaktor eingebracht. Die Atmosphäre des Reaktors wird solange inertisiert, d. h solange evakuiert und mit Inertgas gespült, bis der Sauerstoffgehalt unter 10 Vol-ppm, bevorzugt unter 3 Vol-ppm gesunken ist. In den Reaktor wird nun eine Fluor-Inertgasmischung eingeleitet. welche aus etwa 0,5–20% Fluor, bevorzugt 1–15% Fluor und insbesondere bevorzugt 8–10% Fluor enthält. Bevorzugt enthält das Gasgemisch Inertgas in einer Konzentration von 99,5–80, bevorzugt 99–85 und insbesondere bevorzugt 92–90%. Der Gesamtdruck im Reaktor liegt während der Fluorierung bei 0,3–0,7 bar. Die Temperatur bei der Fluorierung liegt bei 1–50°C. bevorzugt bei 5–40°C und insbesondere bevorzugt bei 15–30°C. Die Verfahrensdauer beträgt 10–60 Minuten, bevorzugt 15–25 Minuten. Die zur Fluorierung kommende Polycarbonatoberfläche im einzelnen Batch muss dabei so bemessen sein, dass die für die Fluorierung zur Verfügung stehende Fluormenge mindestens 0,5 g/m² Oberfläche des Polymermaterials, bevorzugt 1,5–8 g/m² Oberfläche des Polymermaterials beträgt. Um dies zu erreichen, kann die obige Prozedur auch mehrfach durchgeführt werden. Es ist ebenfalls möglich, Fluor mehrfach nachzuspeisen und darüber hinaus von Fluorierung zu Fluorierung einen steigenden Gradienten der Fluorkonzentration zu verwenden. Der Reaktor wird nach der Reaktion evakuiert, mit Inertgas gespült und danach mehrfach evakuiert und belüftet oder mit Inertgas gespült, um verbliebenes Fluor und Fluorwasserstoff zu entfernen.

The method according to the invention is divided into the following steps in a preferred embodiment:

• 1. Provision of the injection-molded body or extrudate consisting of polycarbonate. Occur superficial impurities of the polymer body, so must be cleaned with suitable media such. B. with water or with isopropanol and subsequent drying.
• 2. The prepared and prepared after step 1 injection molding or extrudate is introduced into a reactor. The atmosphere of the reactor is inertized, d. h evacuated and purged with inert gas until the oxygen content has fallen below 10 ppm by volume, preferably below 3 ppm by volume. A fluorine-inert gas mixture is now introduced into the reactor. which contains from about 0.5-20% fluorine, preferably 1-15% fluorine and more preferably 8-10% fluorine. Preferably, the gas mixture contains inert gas in a concentration of 99.5-80, preferably 99-85 and particularly preferably 92-90%. The total pressure in the reactor during the fluorination is 0.3-0.7 bar. The temperature during fluorination is 1-50 ° C. preferably at 5-40 ° C, and more preferably at 15-30 ° C. The process time is 10-60 minutes, preferably 15-25 minutes. The polycarbonate surface for the fluorination in the individual batch must be such that the amount of fluorine available for the fluorination is at least 0.5 g / m ² surface area of the polymer material, preferably 1.5-8 g / m ² surface area of the polymer material. To accomplish this, the above procedure can also be performed multiple times. It is also possible to replenish fluorine several times and, moreover, to use an increasing gradient of the fluorine concentration from fluorination to fluorination. The reactor is evacuated after the reaction, purged with inert gas, and then repeatedly evacuated and vented or purged with inert gas to remove residual fluorine and hydrogen fluoride.

The injection-molded bodies or extrudates are removed and rinsed with distilled water, which per liter of water contains 50-70 mg of a surfactant mixture, preferably 7-11% by weight of Na-C ₁₄ -C ₁₇ alkanesulfonate and 6-9% by weight. of the Na salt of alkyl (C ₁₂ -C ₁₃ ) polyethylene glycol (2 EO) sulfate. It is then rinsed with running distilled water. Both cleaning operations can be assisted by the use of microfibre cloths. In order to obtain surfaces of high optical quality, drying is also supported by the use of microfibre cloths.

Further subject of the invention are injection molded articles or extrudates made of polycarbonate, which are obtained by the method described above and are characterized in that they have a layer which has a constant over the layer thickness refractive index. This refractive index is lower than the underlying base material (polycarbonate).

For the production of polycarbonates for the compositions according to the invention is by way of example "Fast", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964 , on DC PREVORSEK, BT DEBONA and Y. KESTEN, Corporate Research Center, Allied Chemical Corporation, Moristown, New Jersey 07960, "Synthesis of Poly (ester) Carbonate Copolymer" in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 19, 75- 90 (1980) , on D. Freitag, U. Grigo, PR Müller, N. Nouvertne, BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Vol. 11, Second Edition, 1988, pages 648-718 and finally up Dres. U. Grigo, K. Kircher and PR Müller "Polycarbonates" in Becker / Braun, Plastics Handbook, Volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299 directed. The preparation preferably takes place by the phase boundary process or the melt transesterification process and will initially be described by way of example using the phase boundary process.

Diphenols 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 isatin or phenolphthalein derivatives and their nuclear alkylated and nuclear halogenated compounds.

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-hydroxyphenyl) -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 other suitable diphenols are z. In US 3,028,635 A . US 2,999,825 A . US-A-3,148,172 . US 2,991,273 A . US-A-3,271,367 . US 4,982,014 A and US 2,999,846 A , in DE 1 570 703 A . DE 2 063 050 A . DE 2 036 052 A . DE 2 211 956 A and DE 3 832 396 A , in FR 1 561 518 A , in the Monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 as in JP 62039/1986 A . JP 62040/1986 A and JP 105550/1986 A described.

In the case of homopolycarbonates, only one diphenol is used; in the case of copolycarbonates, several diphenols are used.

A suitable carbonic acid derivative is, for example, phosgene.

Suitable chain terminators which can be used in the preparation of the polycarbonates are both monophenols and monocarboxylic acids. Suitable monophenols are phenol itself, alkylphenols such as cresols, p-tert-butylphenol, pn-octylphenol, p-iso-octylphenol, pn-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.

In the case of the interfacial polycondensation process, monofunctional chain terminators, such as phenol or p-tert-butylphenol, iso-octylphenol, cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators are required for controlling the molecular weight. These are either added to the reaction with the bisphenolate or the bisphenolates or added to the synthesis at any time, as long as phosgene or chlorocarbonic acid end groups are present in the reaction mixture or in the case of the acid chlorides and chloroformates as chain terminators as long as sufficient phenolic end groups of the forming polymer be available. Preferably, however, the chain terminator (s) are added after phosgenation at one point or at a time when phosgene is no longer present but the catalyst has not yet been metered, or before the catalyst, with the catalyst together or in parallel.

The amount of chain terminator to be used is preferably from 0.1 to 5 mol%, based on mols of diphenols used in each case. The addition of the chain terminators can be done before, during or after the phosgenation.

Suitable branching agents are the trifunctional or more than trifunctional compounds known in polycarbonate chemistry, especially those having three or more than three phenolic OH groups.

Suitable branching agents include, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane , 1,3,5-tri (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis- [4 , 4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5'-methyl-benzene) -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 and 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3- bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

The amount of optionally used branching agent is preferably from 0.05 to 2 mol%, based in turn on moles of diphenols used in each case.

The branching agents can be presented either with the diphenols and the chain terminators in the aqueous alkaline phase, or dissolved in an organic solvent before the Phosgenation can be added. In the case of the transesterification process, the branching agents are used together with the diphenols.

The preparation of the polycarbonates according to the invention is also possible from diaryl carbonates and diphenols according to the known polycarbonate process in the melt, the so-called melt transesterification process, the z. In WO 01/05866 A and WO 01/05867 A is described. In addition, transesterification (acetate and Phenylesterverfahren), for example, in the US-3,494,885 A . US-A-4,386,186 . US 4,661,580 A . US 4,680,371 A and US 4,680,372 A , in the EP 26 120 A1 . EP 26 121 A1 . EP 26 684 A1 . EP 28 030 A1 . EP 39 845 A1 . EP 39 845 A1 . EP 91 602 A1 . EP 97 970 A1 . EP 79 075 A1 . EP 146 887 A1 . EP 156 103 A1 . EP 234 913 A1 and EP 240 301 A1 as well as in the DE 14 95 626 A1 and DE 22 32 977 A1 described.

und Formel (VII),

wobei R, R' und R'' unabhängig voneinander H, gegebenenfalls verzweigte C₁-C₃₄-Alkyl/Cycloalkyl, C₇-C₃₄-Alkaryl oder C₆-C₃₄-Aryl bzw. C₆-C₃₄-Aryl-oxy darstellen können, beispielsweise Diphenylcarbonat, Butylphenyl-phenylcarbonat, Di-butylphenylcarbonat, Isobutylphenyl-phenylcarbonat, Di-isobutylphenylcarbonat, tert-Butylphenyl-phenylcarbonat, Di-tert-butylphenylcarbonat, n-Pentylphenyl-phenylcarbonat, Di-(n-pentylphenyl)carbonat, n-Hexylphenyl-phenylcarbonat, Di-(n-hexylphenyl)carbonat, Cyclohexylphenyl-phenylcarbonat, Di-cyclohexylphenylcarbonat, Phenylphenol-phenylcarbonat, Di-phenylphenolcarbonat, Isooctylphenyl-phenylcarbonat, Di-isooctylphenylcarbonat, n-Nonylphenyl-phenylcarbonat, Di-(n-nonylphenyl)carbonat, Cumylphenyl-phenylcarbonat, Di-cumylphenylcarbonat, Naphthylphenyl-phenylcarbonat, Di-naphthylphenylcarbonat, Di-tert-butylphenyl-phenylcarbonat, Di-(di-tert-butylphenyl)carbonat, Dicumylphenyl-phenylcarbonat, Di-(dicumylphenyl)carbonat, 4-Phenoxyphenyl-phenylcarbonat, Di-(4-phenoxyphenyl)carbonat, 3-Pentadecylphenyl-phenylcarbonat, Di-(3-pentadecylphenyl)-carbonat, Tritylphenyl-phenylcarbonat, Di-tritylphenylcarbonat, bevorzugt Diphenylcarbonat, tert-Butylphenyl-phenylcarbonat, Di-tert-butylphenylcarbonat, Phenylphenol-phenylcarbonat, Di-phenylphenolcarbonat, Cumylphenyl-phenylcarbonat, Di-cumylphenylcarbonat, besonders bevorzugt Diphenylcarbonat.Diaryl carbonates are those carbonic diesters of the formula (2)

and formula (VII),

where R, R 'and R "independently of one another are H, optionally branched C ₁ -C ₃₄ -alkyl / cycloalkyl, C ₇ -C ₃₄ -alkaryl or C ₆ -C ₃₄ -aryl or C ₆ -C ₃₄ -aryl for example, diphenyl carbonate, butylphenyl phenyl carbonate, di-butylphenyl carbonate, isobutylphenyl phenyl carbonate, di-isobutylphenyl carbonate, tert-butylphenyl phenyl carbonate, di-tert-butylphenyl carbonate, n-pentylphenyl phenyl carbonate, di (n-pentylphenyl) carbonate, n-hexylphenyl-phenylcarbonate, di- (n-hexylphenyl) carbonate, cyclohexylphenyl-phenylcarbonate, di-cyclohexylphenylcarbonate, phenylphenol-phenylcarbonate, diphenylphenolcarbonate, isooctylphenyl-phenylcarbonate, diisooctylphenylcarbonate, n-nonylphenyl-phenylcarbonate, di- (n- nonylphenyl) carbonate, cumylphenyl phenylcarbonate, di-cumylphenylcarbonate, naphthylphenylphenylcarbonate, di-naphthylphenylcarbonate, di-tert-butylphenyl-phenylcarbonate, di- (di-tert-butylphenyl) carbonate, dicumylphenyl-phenylcarbonate, di (dicumylphenyl) carbonate, 4-phenoxyphenyl-phen yl carbonate, di- (4-phenoxyphenyl) carbonate, 3-pentadecylphenyl phenyl carbonate, di- (3-pentadecylphenyl) carbonate, tritylphenyl phenyl carbonate, di-tritylphenyl carbonate, preferably diphenyl carbonate, tert-butylphenyl phenyl carbonate, di-tert-butylphenyl carbonate, Phenylphenol-phenylcarbonate, di-phenylphenolcarbonate, cumylphenyl-phenylcarbonate, di-cumylphenylcarbonate, more preferably diphenylcarbonate.

Diphenols for the preparation of the polycarbonates or copolycarbonates according to the invention can also be polymers or condensates with phenolic end groups, so that according to the invention polycarbonates or copolycarbonates with block structures are also included.

The polycarbonate compositions according to the invention can be worked up in a known manner and processed to give any shaped bodies, for example by extrusion or injection molding.

The compositions according to the invention may also contain other aromatic polycarbonates and / or other aromatic polyester carbonates and / or others.

In addition, the polycarbonates may be added further below mentioned additives in conventional mixing devices such as screw extruders (for example twin-screw extruder, ZSK), kneaders, Brabender or Banbury mills and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.

The compositions according to the invention can be worked up in a known manner and processed to give any shaped bodies, for example by extrusion, injection molding or extrusion blow molding.

The compositions according to the invention may also be admixed with the customary additives for these thermoplastics, such as fillers, UV stabilizers, IR stabilizers, heat stabilizers, antistatic agents and pigments, colorants; if appropriate, the demolding behavior, the flow behavior, and / or the flame retardancy can be improved by adding external mold release agents, flow agents, and / or flame retardants (eg, alkyl and aryl phosphites, phosphates, phosphanes, low molecular weight carboxylic acid esters, halogen compounds, salts , Chalk, quartz powder, glass and carbon fibers, pigments and their combination. Such compounds be z. In WO 99/55772 A1 , Pp. 15-25, and in "Plastics Additives", R. Gächter and H. Müller, Hanser Publishers 1983 as in " Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999 ", in the " Plastics Additives Handbook, Hans Zweifel, Hanser, Munich 2001 "Described).

Suitable antioxidants or thermal stabilizers are, for example:
Alkylated monophenols, alkylthiomethylphenols, hydroquinones and alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, O-, N- and S-benzyl compounds, hydroxybenzylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, acylaminophenols, esters of β- (3,5-di-tert-butyl) butyl-4-hydroxyphenyl) propionic acid, esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid, esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid, esters of 3, 5-di-tert-butyl-4-hydroxyphenylacetic acid, amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, suitable thiosynergists, secondary antioxidants, phosphites, phosphines and phosphonites, benzofuranones and indolinones.

Preference is given to organic phosphites, phosphines, phosphonates and phosphanes, usually those in which the organic radicals consist entirely or partially of optionally substituted aromatic radicals.

Suitable complexing agents for heavy metals and for the neutralization of alkali traces are o / m phosphoric acids, fully or partially esterified phosphates or phosphites.

In a preferred embodiment, the composition according to the invention contains an ultraviolet absorber. Ultraviolet absorbers suitable for use in the composition according to the invention are compounds which have the lowest possible transmission below 400 nm and the highest possible transmission above 400 nm. Such compounds and their preparation are known from the literature and are for example in the EP 839 623 A1 . WO 96/15102 A and EP 500 496 A1 described. Particularly suitable ultraviolet absorbers for use in the composition according to the invention are benzotriazoles, triazines, benzophenones and / or arylated cyanoacrylates.

Particularly useful ultraviolet absorbers are hydroxy-benzotriazoles, such as 2- (3 ', 5'-bis (1,1-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole (Tinuvin ^® TM 234, Ciba Specialty Chemicals, Basel) , 2- (2'-hydroxy-5 '- (tert-octyl) phenyl) benzotriazole (Tinuvin ^® TM 329, Ciba specialty Chemicals, Basel), 2- (2'-hydroxy-3' - (2-butyl ) -5 '- (tert-butyl) phenyl) benzotriazole (Tinuvin ^® TM 350, Ciba specialty Chemicals, Basel), bis (3- (2H-benzotriazolyl) -2-hydroxy-5-tert-octyl) methane (Tinuvin ^® TM 360, Ciba specialty Chemicals, Basel), 2- (hydroxy-2-hydroxyphenyl) -4,6-diphenyl-1,3,5-triazine (Tinuvin ^® TM 1577, Ciba specialty Chemicals, Basel) and the benzophenones 2,4-dihydroxybenzophenone (Chimasorb22 ^® TM, Ciba specialty Chemicals, Basel) and 2-hydroxy-4- (octyloxy) benzophenone (Chimassorb ^® 81, Ciba, Basel), 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 (9Cl) (Uvinul ^® TM Uvinul 3030, BASF AG Ludwigshafen), CGX UVA 006 (Ciba Specialty Chemicals, Basel) or Hostavin B-Cap (Clariant AG). It is also possible to use mixtures of these ultraviolet absorbers.

With respect to the amount of the ultraviolet absorber contained in the composition, there are no particular limitations as long as the desired absorption of ultraviolet rays and sufficient transparency of the molded article produced from the composition are ensured. According to a preferred embodiment of the invention, the composition contains ultraviolet absorber in an amount of 0.05 to 20 wt .-%, in particular from 0.07 to 10 wt .-% and most preferably 0.1 to 1 wt .-% ,

Further UV absorbers and additives are z. In WO 2009/059901 A1 described.

Polypropylene glycols alone or in combination with z. As sulfones or sulfonamides as stabilizers can be used against damage by gamma rays.

These and other stabilizers may be used singly or in combinations and added to the polymer in the above-mentioned forms.

In addition, processing aids such as mold release agents, usually derivatives of long-chain fatty acids, can be added. Preferably z. Pentaerythritol tetrastearate and glycerol monostearate. They are used alone or in admixture, preferably in an amount of from 0.01 to 1% by weight, based on the weight of the composition.

Suitable flame-retardant additives are phosphate esters, ie triphenyl phosphate, resorcinol diphosphoric acid esters, oligophosphates, bromine-containing compounds such as brominated phosphoric acid esters, brominated oligocarbonates and polycarbonates, and preferably salts of fluorinated organic sulfonic acids. In particular, the additives are suitable as flame retardants, which in WO 2008125203 are listed.

Suitable impact modifiers are butadiene rubber grafted with styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubbers grafted with maleic anhydride, ethyl and Butylacrylatkautschuke grafted with methyl methacrylate or styrene-acrylonitrile, interpenetrating siloxane and acrylate networks grafted with methyl methacrylate or Styro1-acrylonitrile.

Furthermore, colorants, such as organic dyes or pigments or inorganic pigments, IR absorbers, individually, in admixture or in combination with stabilizers, glass fibers, glass (hollow) balls, inorganic fillers may be added. However, the fluorination of filler-containing polycarbonate is not preferred since this can lead to complications such as clouding and pore formation.

The polycarbonates and copolycarbonates according to the invention, optionally in admixture with other thermoplastics and / or customary additives, can be used to form any molded articles / extrudates used wherever already known polycarbonates and copolycarbonates are used. Due to their property profile, they are suitable as construction materials for glazings and other structural elements of solar thermal systems. They can also be used as material for solar collectors (eg parabolic and flat reflectors and Fresnel-based concentrators). In photovoltaic systems, they are suitable as a protective glazing or as a support for photoelectric layers. Here, the bactericidal effect of the material plays a crucial role in terms of the lifetime of the applications.

The polycarbonates and copolycarbonates according to the invention, optionally in admixture with other thermoplastics and / or customary additives, can be used to form any molded articles / extrudates used wherever already known polycarbonates and copolycarbonates are used. Due to their property profile, they are suitable as substrate materials for lenses, eg. As Fresnel lenses, plates, multi-wall sheets, glazings, diffusers, lamp covers or optical data storage, such as audio CD, CD-R (W), DVD, DVD-R (W), etc., but are also, for example, as films in the electrical sector can be used as molded parts in vehicle construction and as panels for covers in the security sector. Further possible applications of the polycarbonates according to the invention are:
Safety discs, which are known to be required in many areas of buildings, vehicles and aircraft, as well as shields of helmets.
Production of films, in particular ski films.
Production of Blask bodies (see for example U.S. Patent 2,964,794 ), for example 1 to 5 gallons of water bottles.
Production of translucent panels, in particular of hollow panel panels, for example for covering buildings such as railway stations, greenhouses and lighting installations.
Production of optical data storage.
For the production of traffic light housings or traffic signs.
For the production of foams (see for example DE-B 1 031 507 ).
For the production of threads and wires (see for example DE 1 137 167 B and DE 1 785 137 A ).
As translucent plastics containing glass fibers for lighting purposes (see for example DE 1 554 020 A ).
As translucent plastics containing barium sulfate, titanium dioxide and / or zirconium oxide or organic polymeric acrylate rubbers ( EP 634 445 A . EP 269 324 A ) for the production of translucent and light-scattering molded parts.
For the production of precision injection molded parts, such as lens holders. For this purpose, one uses polycarbonates with a content of glass fibers, which optionally additionally about 1-10 wt .-% MoS2, based on total weight.
For the production of optical device parts, in particular lenses for photo and film cameras (see, for example DE 2 701 173 A ).
As a light transmission carrier, in particular as a fiber optic cable (see, for example EP 89 801 A1 ).
As electrical insulating materials for electrical conductors and for connector housings and connectors.
Manufacture of mobile phone cases with improved resistance to perfume, aftershave and skin sweat.
Network interface devices
As carrier material for organic photoconductors.
For the production of lights, z. As headlight lamps, as so-called "head-lamps", scattered light lenses or inner lenses.
For medical applications, eg. As oxygenators, dialyzers.
For food applications, such. As bottles, dishes and chocolate molds.
For applications in the automotive sector, where contact with fuels and lubricants may occur, such as bumpers possibly in the form of suitable blends with ABS or suitable rubbers.
For sporting goods, such. Slalom poles or ski boot buckles.
For household items, such. B. kitchen sinks and letterbox housing.
For housing, such. B. Electric distribution cabinets.
Housing for electric toothbrushes and hair dryer housing
Transparent washing machine portholes with improved resistance to washing.
Goggles, optical corrective goggles.
Lamp covers for kitchen equipment with improved resistance to kitchen fumes, especially oil vapors.
Packaging films for pharmaceuticals.
Chip boxes and chip carriers
For other applications, such. As stable mast doors or animal cages.

The moldings and extrudates obtainable from the polymers according to the invention are likewise the subject of this application.

Examples

Optical examinations

The transmission and reflection measurements are reproduced on a Perkin Elmer Lamda 900 spectrophotometer with photometer sphere (determination of the total transmission) ASTM E1348 and ASTM D1003 as far as the transmission is concerned and after ASTM E1331 as far as the reflection is concerned.

The transmission spectra are in the pictures 1 - 13 shown. The respective underlying fluorination method is described in the corresponding examples. The term oxifluorination used in the figures serves to denote the fluorination process which is not according to the invention.

Used material:

• Apec DP1-9379 from Bayer MaterialScience AG (copolymer of bisphenol A and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane) with a melt volume rate (MVR) of 7 cm ³ / (10 min ) measured at 330 ° C and 2.16 kg ISO 1133 ).
• Makrolon 2808 from Bayer MaterialScience AG (homopolymer of bisphenol A with a melt volume rate (MVR) of 9.5 cm ³ / (10 min) measured at 300 ° C. and a weight of 1.2 kg after ISO 1133 )

injection:

The granules are dried at 120 ° C for 3 hours in a vacuum and then on an injection molding machine Arburg 370 with a 25 injection unit at a melt temperature of 300 ° C and a mold temperature of 90 ° C to color sample plates with the dimensions 60 mm × 40 mm × 4 mm processed. The plates are shrink-wrapped in foil after injection molding to avoid superficial contamination. The film is removed just before the respective fluorination step. Cleaning the plates before fluorination is therefore not necessary.

Example 1 (comparative example)

60x40x4 mm color optical chips are made from Apec DP1-9379 and Makrolon 2808. The optical color sample plates are measured without further treatment. The transmission spectra are in 1 shown.
The optical transmission Ty [%] (D6510 °) of the sample of Apec DP1-9379 was 89.92%.
The optical transmission Ty [%] (D6510 °) of the sample of Makrolon 2808 was 89.56%.

Example 2 (comparative example)

It will opt. Color sample plates 60 × 40 × 4 mm made of Apec DP1-9379. The plates are subjected to fluorination without pretreatment under the following conditions: no inerting of the reactor before fluorination, reaction gas 10% fluorine in nitrogen 5.0, pressure in the reactor during the reaction 175 mbar, reaction temperature 24 ° C, reactor volume 62 l, reaction time 20 min

The transmission spectrum is in 2 shown:
The transmittance (Ty [%] (D6510 °) of the fluorinated sample is 92.0%, an improvement of 2.1% over the unfluorinated control, and the uniform profile of the transmittance curve indicates that the refractive index does not exceed the applied layer thickness is constant.

To test the strength of the fluorine layer formed, the sample was triturated with lukewarm distilled detergent containing water for 10 minutes, rinsed with distilled water and then rubbed wet and dry with a microfiber cloth. The result (transmission spectrum) is in 3 shown.

The transmission (Ty [%] (D6510 °) of the fluorinated sample of 92.0% was reduced by the after-treatment to the initial level of 90.0% Thus, no mechanically stable layers could be achieved by the method described here (in Example 2) become.

Example 3 (comparative example)

It will opt. Color sample plates 60 × 40 × 4 mm made from Makrolon 2808. The plates are subjected to fluorination without pretreatment under the following conditions: no inerting of the reactor before fluorination, reaction gas 10% fluorine in nitrogen 5.0, pressure in the reactor during the reaction 175 mbar, reaction temperature 24 ° C, reactor volume 62 l, reaction time 20 min. The result in 4 shown.

The transmission (Ty [%] (D6510 °) of the fluorinated sample is 91.1%, which is an improvement of 1.5% over the unfluorinated comparative sample is constant.

To test the strength of the fluorine layer formed, the sample was triturated with lukewarm distilled detergent containing water for 10 minutes, rinsed with distilled water and then rubbed wet and dry with a microfiber cloth. The transmission spectrum is in 5 shown.

The transmission Ty [%] (D6510 °) of the fluorinated sample of 91.1% was reduced by the post-treatment to 89.7%, ie the initial level of the non-fluorinated sample. By the method described here (in Example 3) thus no mechanically stable layers could be achieved.

Example 4 (according to the invention)

It will opt. Color sample plates 60 × 40 × 4 mm made of Apec DP1-9379. The plates are subjected to fluorination without pretreatment under the following conditions: double inerting of the reactor before fluorination with nitrogen 5.0, reaction gas 10% fluorine in nitrogen 5.0, pressure in the reactor during the reaction 546 mbar, reaction temperature 24 ° C, reactor volume 62 1, reaction time 20 min.

The corresponding transmission spectrum is in 6 shown. The transmission (Ty [%] (D6510 °) of the fluorinated sample is 92.6% ( ). This is an improvement of 2.7% over the non-fluorinated control. The wave-shaped course of the transmission curve (interference waves) characterizes a layer which has a refractive index which is constant over the layer thickness.

To test the strength of the fluorine layer formed, the sample was triturated with lukewarm distilled detergent containing water for 10 minutes, rinsed with distilled water and then rubbed wet and dry with a microfiber cloth. The result is in 7 shown.

The transmission (Ty [%] (D6510 °) of the fluorinated sample of 92.6% was not reduced by the aftertreatment The process according to the invention leads to the desired mechanical stability The good optical properties are retained even after mechanical stress.

Example 5 (according to the invention)

It will opt. Color sample plates 60 × 40 × 4 mm made of Apec DP1-9379. The plates are subjected to fluorination without pretreatment under the following conditions: double inerting of the reactor before fluorination with nitrogen 5.0, reaction gas 10% fluorine in nitrogen 5.0, pressure in the reactor during the reaction 546 mbar, reaction temperature 24 ° C, reactor volume 62 1, reaction time 60 min. the result is in 8th shown.

The transmission (Ty [%] (D6510 °) of the fluorinated sample is 93.5%, which is an improvement of 3.6% compared to the unfluorinated comparative sample The wavy curve of the transmission curve (interference waves) indicates a layer which exceeds the Layer thickness constant refractive index has.

To test the strength of the fluorine layer formed, the sample was triturated with lukewarm distilled detergent containing water for 10 minutes, rinsed with distilled water and then rubbed wet and dry with a microfiber cloth.

After washing, a transmission spectrum was also recorded; the result is in 9 shown. The transmission (Ty [%] (D6510 °) of the fluorinated sample of 93.5% was reduced (93.3%) within the scope of the measurement accuracy The method according to the invention leads to the desired mechanical stability The good optical properties also remain received mechanical stress.

Example 6 (according to the invention)

It will opt. Color sample plates 60 × 40 × 4 mm made of Makrolon 2808. The plates are subjected to fluorination without pretreatment under the following conditions: double inerting of the reactor before fluorination with nitrogen 5.0, reaction gas 10% fluorine in nitrogen 5.0, pressure in the reactor during the reaction 546 mbar, reaction temperature 24 ° C, reactor volume 62 1, reaction time 20 min.

The transmission spectrum is in 10 shown. The transmission (Ty [%] (D6510 °) of the fluorinated sample is 94.5%, which is an improvement of 4.9% compared to the unfluorinated comparative sample The wavy curve of the transmission curve (interference waves) indicates a layer which exceeds the Layer thickness constant refractive index has.

To test the strength of the fluorine layer formed, the sample was triturated with lukewarm distilled detergent containing water for 10 minutes, rinsed with distilled water and then rubbed wet and dry with a microfiber cloth.

The transmission (Ty [%] (D6510 °) of the fluorinated sample of 94.5% was only marginally reduced to 94.1% by the aftertreatment (s. 11 ). The process according to the invention leads to the desired mechanical stability. The good optical properties are retained even after mechanical stress.

Example 7 (according to the invention)

It will opt. Color sample plates 60 × 40 × 4 mm made of Makrolon 2808. The plates are subjected to fluorination without pretreatment under the following conditions: double inerting of the reactor before fluorination with nitrogen 5.0, reaction gas 10% fluorine in nitrogen 5.0, pressure in the reactor during the reaction 546 mbar, reaction temperature 24 ° C, reactor volume 62 1, reaction time 60 min

The corresponding transmission spectrum is in 12 shown. The transmission (Ty [%] (D6510 °) of the fluorinated sample is 93.9%, which is an improvement of 4.3% compared to the unfluorinated comparative sample The wavy curve of the transmission curve (interference waves) indicates a layer which exceeds the Layer thickness constant refractive index has.

To test the strength of the fluorine layer formed, the sample was triturated with lukewarm distilled detergent containing water for 10 minutes, rinsed with distilled water and then rubbed wet and dry with a microfiber cloth. The result is in 13 shown.

The transmission (Ty [%] (D6510 °) of the fluorinated sample of 93.9% remains constant within the measurement accuracy (93.7%) (s. 13 ). The process according to the invention leads to the desired mechanical stability. The good optical properties are retained even after mechanical stress.

Test of biocidal activity

As antibacterial are effective after JIS Z 2801 (Japanese Industrial Standard) to declare such surfaces that achieve at least one log-stage reduction (≥ 90% reduction of the number of bacteria) compared to the respective control. To JIS Z 2801 the bacterial strain Staphylokoccus aureus is used to determine the bacterial count. For a better understanding, the biological test protocol is described in more detail below.

Plates from Examples 2-7 are examined in this test.

The test procedure takes place after JIS (Japanese Industrial Standard) Z 2801

Test bacterium S. aureus ATCC 29213 is cultured in an overnight culture on Columbia agar at 37 ° C. Subsequently, some colonies are suspended in PBS (phosphate buffered saline, pH 7.4) with 50% Muller Hinton medium and a cell count of about 1 × 10 5 germs / ml is set.

Each 100 .mu.l of this suspension are distributed with the aid of a 20 × 20 mm parafilm on the test material (fluorinated PC platelets from Example 4), so that the surface is evenly wetted with cell suspension. Subsequently, the test material is incubated with the bacterial suspension for 24 h at 37 ° C in a humid chamber.

After 24 h, 20 μl of the cell suspension are removed for growth control. The cell count is determined by serial dilution and plating of the dilution steps on agar plates. Only living cells are determined. The cell number is given as colony forming units (CFU) / ml.

The parafilm is then removed from the test material and the test material is washed 3 times with 4 ml PBS each time to remove free-floating cells. Thereafter, the test material is transferred to 15 ml of PBS and sonicated for 120 seconds in an ultrasonic bath to detach the adherent cells. From the PBS solution containing the detached cells, cell number determination is also performed by dilution series and plating on agar plates. Again, only living cells are detected. Cells that are killed by the ultrasound process are not detected, so it can be assumed that the actual number of cells attaching to bacteria is slightly larger.

No living bacteria could be found in any of the test solutions (CFU / ml: 0)

Thus, fluorination leads to the desired bactericidal effect in all examples, but only the plates obtained according to Examples 4-7 according to the invention show the desired stability of the optical layers.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

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Claims (15)

Process for the production of polycarbonate injection molded articles or extrudates comprising at least the following steps: a) introducing one or more injection-molded bodies and / or extrudates consisting of polycarbonate into a reactor, b) inerting the atmosphere of the reactor until an oxygen content of 10 ppm by volume or less is reached, c) introducing a fluorine-inert gas mixture containing 0.5-20% fluorine, wherein the total pressure in the reactor during the fluorination at 0.3-0.7 bar and the temperature during the fluorination at 1-50 ° C, and the process time is 10-60 minutes, d) after the fluorination multiple evacuation and flushing of the reactor with inert gas and then with air, e) rinsing the injection-molded body or extrudates with surfactant-containing distilled water and then with pure distilled water. A method according to claim 1, characterized in that the polymer body is freed in step a) by cleaning with suitable media and subsequent drying of superficial impurities. A method according to claim 2, characterized in that the cleaning of the polymer body in step a) is carried out with water or with isopropanol and subsequent drying. Method according to one of the preceding claims, characterized in that in step b) the inerting of the atmosphere is carried out with nitrogen. Method according to one of the preceding claims, characterized in that the oxygen content in the inertized atmosphere in the reactor in step b) is 3 vol-ppm or less. Method according to one of the preceding claims, characterized in that in step c) the fluorine-inert gas mixture contains 1-15% fluorine. Method according to one of the preceding claims, characterized in that in step c) the fluorine-inert gas mixture contains 8-10% fluorine. Method according to one of the preceding claims, characterized in that in step c) the temperature in the reactor at 5-40 ° C. Method according to one of the preceding claims, characterized in that in step c) the temperature in the reactor is 15-30 ° C. Method according to one of the preceding claims, characterized in that in step c) the process duration is 15-25 minutes. Method according to one of the preceding claims, characterized in that in step c) the amount of fluorine available for the fluorination is at least 0.5 g / m2 surface of the polymer material. A method according to claim 11, characterized in that in step c) the amount of fluorine available for the fluorination 1.5-8 g / m2 surface of the polymer material. Method according to one of the preceding claims, characterized in that in step e) the rinse water per liter of water contains 50-70 mg of a surfactant mixture and then the injection-molded body or extrudates are rinsed with running distilled water. Method according to one of the preceding claims, characterized in that in step e) the cleaning operations and / or drying are supported by the use of microfiber cloths. Use of the polycarbonate according to any one of the preceding claims as antibacterial material.

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