WO2000037551A1

WO2000037551A1 - X-ray contrasting moulded part with improved long-term stability

Info

Publication number: WO2000037551A1
Application number: PCT/EP1999/009558
Authority: WO
Inventors: Martin Döbler; Wolfgang Ebert; Siegfried Neumann; Walter Köhler
Original assignee: Bayer Aktiengesellschaft
Priority date: 1998-12-18
Filing date: 1999-12-07
Publication date: 2000-06-29
Also published as: AU1559600A; EP1141113A1; CA2355139A1; JP2002533509A; HK1042912A1; CN1330682A

Abstract

The invention relates to the use of a mixture of at least one brominated and/or iodinated oligocarbonate, polycarbonate and/or copolycarbonate and at least one stabilizer for the production of X-ray contrasting plastic moulded parts with improved long-term stability.

Description

X-ray contrastable molded parts with improved long-term stability

The present invention relates to the use of a mixture of at least one brominated and / or iodinated oligo-, poly- and / or copolycarbonates and at least one stabilizer for the production of X-ray-contrasting molded parts made of plastic.

Special molded parts in the sense of the present invention are in particular those for medical applications, such as probes or joint parts and toys for

Children, like building blocks.

For the medical field and also for children's toys, materials with good mechanics that are as transparent as possible are sought, which can be detected in the body during X-ray examinations. Commercially available molding compounds

Polycarbonate bases are unsuitable for this purpose because their contrast in the X-ray image is too low. A material used for this purpose is e.g. PVC, however, is not transparent. Known iodine-containing polymers also have inadequate mechanical properties and / or are difficult to produce.

The task was therefore to develop molding compositions which, with good mechanical properties and high transparency and a glass temperature well above 100 ° C., have a good contrast in X-ray examinations.

The great advantage of the molded parts according to the invention is that they have an improved X-ray contrast and are therefore easily recognizable, that is to say they can be used well in targeted operations on the one hand, and on the other hand for eliminating accidents which arise from swallowing or inhalation of toys in children. US Pat. No. 3,469,704 describes polycarbonates which have iodophenyls as the end group (column 2, lines 60 ff.).

Dipodyl carbonates containing iodine and their addition to polycarbonates are known from US Pat. No. 3,382,207.

According to DE-A 17 20 812, iodine-containing phenols are known as chain terminators for polycarbonates. See also the corresponding GB-PA 1 1 63 816.

According to US Pat. No. 3,535,300, iodine-containing compounds are known as additives to polycarbonates (column 4, line 64; column 5, line 43).

The use as an X-ray contrast medium is not described for these materials, nor is it used for the production of X-ray contrastable moldings. It has now been found that molded parts with at least one brominated and / or iodinated oligo-, poly- and / or copolycarbonate are excellent in X-ray contrast, but change color in daylight even in closed rooms. Surprisingly, this can be remedied by adding stabilizers from the benzotriazole series or benzophenone series.

The present application accordingly relates to the use of a mixture of at least one brominated and / or iodinated oligo-, poly- and / or copolycarbonates and at least one stabilizer for the production of X-ray-contrasting molded parts made of plastic.

Oligo-, poly- or copolycarbonates according to the invention have, for example, an M _w between 600 and 100,000, preferably between 1000 and 80,000, particularly preferably between 3,000 and 40,000 and have iodine or bromophenyl carbonate end groups, preferably end groups of the general formula (I) on

wherein

R 1 to R _{3 represent} H, C 1 -C _8, optionally branched alkyl, Cl, Br or J, with the proviso that at least one of the radicals R 1, R ₂ and R _{3 represents} J and / or Br.

Preferred end groups are 4-iodophenyl carbonate and 2,4,6-triiodophenyl carbonate end groups.

Examples of the iodophenols (Ia) which, in the customary processes for the production of polycarbonate, preferably the interfacial process, lead to the end groups according to the invention when used as chain terminators,

are 2- / 3- or 4-iodophenol, 2- / 3- or 4-iodo-6-methylphenol, 4- or 6-iodo-3-methylphenol, 2- or 6-iodo-4-methylphenol, 4,5 -Diiod-2-methylphenol, 4,6-diiodo-2-methylphenol, 4,5-diiodo-3-methylphenol, 4,6-diiodo-3-methylphenol, 2,4,6-triiodo-phenol, preferably 4- Iodophenol and 2,4,6-triiodophenol.

The iodophenols are compounds available in the chemical trade or are accessible in organic syntheses from aromatic intermediates, possibly via the detour via diazonium salts. You can individually, in combinations, possibly can also be used in combination with conventional chain terminators such as phenol, p-tert-butylphenol, hexylphenol, i-octylphenol or nonylphenol.

Diphenols such as, for example, come as diol components for the oligo-, poly- or copolycarbonates according to the invention with end groups of the general formula (I)

Hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis ( hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, α, α′-bis (hydroxyphenyl) diisopropylbenzenes, and also their ring-alkylated compounds in question.

Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4th -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, l, l-bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2- Bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-di-bromo-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) propane 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- (4th -hydroxyphenyl) -3,3,5-trimethylcyclohexane.

The oligo-, poly- or copolycarbonates according to the invention with end groups of the general formula (I) can be linear or branched in a known manner. Suitable branching agents are triphenols, trimesic acid (trichloride), cyanuric acid trichloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole. Also suitable as the oligo-, poly- or copolycarbonates according to the invention are those with iodinated and / or brominated diols, such as, for example, iodinated or brominated derivatives of hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes , Bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, ä, ä'-bis (hydroxyphenyl ) -diisopropylbenzenes, as well as their nuclear alkylated compounds, the iodine and / or bromine atoms preferably sitting on the aromatic nucleus of the diols.

Preferred iodinated and / or brominated diphenols are the single or multiple iodinated and / or brominated derivatives of 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, l, l-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 1,5-bis (4-hydroxyphenyl) -3 , 3,5-trimethylcyclohexane.

Particularly preferred iodinated and / or brominated diphenols are the single or multiple iodinated and / or brominated derivatives of 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 l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (tetrabromobisphenol) and / or and 2,2-bis (4-hydroxy) are preferred for the oligo-, poly- and / or copolycarbonates according to the invention -3,5-diiodophenyl) propane (tetraiodobisphenol), optionally in a mixture with one another or optionally with other diols. The oligo-, poly- and / or copolycarbonates according to the invention are preferred in amounts between 0.1 to 100% by weight, preferably 0.1 to 20% by weight, particularly preferably 1 to 10% by weight and very particularly preferably 2 to 7 wt .-% based on the molded part used.

In addition, the mixture contains a stabilizer from the benzotriazole series in amounts between 0.01 and 10% by weight, preferably in amounts between 0.1 and 1% by weight.

Preferred stabilizers are UV absorbers, as described, for example, in EP 0 839 623

AI or EP 0 500 496 AI are described. Benzotriazoles such as, for example, 2- (3 ^' , 5- ^' bis (1, 1-dimethylbenzyl) -2 ^' -hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5' - (tert -octyl) -phenyl) -benzotriazole, 2- (2'-hydroxy-3 '- (2-butyl) -5' - (tert-butyl) -phenyl) -benzotriazole, bis- (3- (2H-benzotriazolyl) -2-hydroxy-5-tert-octyl) methane.

But also 2- (4-hexoxy-2-hydroxyphenyl) -4,6-diphenyl-l, 3,5-triazine, as well as benzophenones, e.g. 2,4-Dihydroxy-benzophenone are preferably used.

In the molded parts there is preferably at least one transparent thermoplastic, preferably a non-halogenated polycarbonate or copolycarbonate in amounts of 85 to 99.9% by weight, preferably 90 to 99% by weight, particularly preferably 93 to 98% by weight, based on the molding included.

The polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds are particularly preferably used as transparent thermoplastics.

Particularly suitable transparent thermoplastics are polycarbonates or copolycarbonates based on diphenols. The oligomers according to the invention can, however also with poly- or copolyacrylates and poly- or copolymethacrylates such as poly- or copolymethyl methacrylate, but also as copolymers with styrene such as transparent polystyrene-acrylonitrile (SAN).

Furthermore, they can be used in transparent cycloolefins, poly- or copolycondensates

Terephthalic acid, e.g. Poly or copolyethylene terephthalate (PET or CoPET) or glycol-modified PET (PETG) can be mixed in.

The person skilled in the art achieves excellent results with polycarbonates and / or copolycarbonates, preferably non-halogenated polycarbonates and / or copolycarbonates.

Thermoplastic, aromatic polycarbonates in the sense of the present invention are both homopolycarbonates and copolycarbonates; the polycarbonates can be linear or branched in a known manner.

These polycarbonates are produced in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents.

Details of the production of polycarbonates have been laid down in many patents for about 40 years. Examples include Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, on D. Freitag, U. Grigo, P.R. Müller, H. Nouvertne ', BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering,

Volume 11, Second Edition, 1988, pages 648-718 and finally on Dres. U. Grigo, K. Kirchner and PR Müller "Polycarbonate" in Becker / Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, Cellulose ester, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299. 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, α, α′-bis (hydroxyphenyl) diisopropylbenzenes, and also their alkylated compounds.

The x-ray-opaque polymer compositions thus obtained can be prepared by the usual methods, e.g. Hot pressing, spinning, extruding or injection molding, can be converted into shaped objects, e.g. Toy parts, but also fibers,

Foils, tapes, plates, multi-wall sheets, vessels, pipes and other profiles. The polymer compositions can also be processed into cast films.

The use of multilayer systems is also of interest. Here, the composition of the invention with a relatively high content of iodine

Additives applied in a thin layer to a molded article made of a polymer that is X-ray transparent. The application can take place simultaneously or immediately afterwards with the shaping of the base body, for example by coextrusion or multi-component injection molding. However, it can also be applied to the fully formed base body, for example by lamination with a film or by coating with a solution. The molding compounds are particularly suitable for transparent children's toy parts or for medical applications. Such molded parts are particularly suitable for small parts of children's toys.

Examples:

In the following examples, η _{re [} measured in dichloromethane at 25 ° C. and a concentration of 0.5% by weight.

Production of the iodinated polycarbonates according to the invention

example 1

180 ml of dichloromethane and 25.3 ml of 6.5% sodium hydroxide solution are placed in a 1000 ml three-necked flask with stirrer, thermometer and reflux condenser. 22.83 g of 2,2-bis (4-hydroxyphenyl) propane are dissolved therein with stirring and then 15.8 g of phosgene are introduced within 5 minutes. Then 1.32 g of 4-iodophenol are added, the mixture is stirred at room temperature for 5 minutes and 0.137 ml of N-ethylpiperidine is added. The mixture is stirred at room temperature for 1 hour and then the organic phase is separated off and washed with dilute acid. It is then washed with demineralized water until the washing phases are almost free of electrolytes. The organic phase is concentrated and dried for 16 hours at 80 ° C. in a vacuum drying cabinet in a water jet vacuum. Yield: 26.3 g η _re _ = U99

Example 2

Like example 1, but instead of 4-iodophenol, 2.83 g of 2,4,6-triiodophenol are used as

Chain breaker used. Yield: 28.7 g η _rel = 1.174

For low molecular weight derivatives, the person skilled in the art can proceed as follows: Preparation of the iodinated oligocarbonates according to the invention

Example 3

450 ml of dichloromethane, 19.8 g of pyridine and 44.0 g of iodophenol are placed in a 1000 ml three-necked flask equipped with a stirrer, thermometer and reflux condenser. 35.3 g of bischlorocarbonic acid ester of 2,2-bis (4-hydroxy-phenyl) propane, dissolved in 200 ml of dichloromethane, are added dropwise with stirring over the course of 40 minutes. The mixture is stirred at room temperature for 1 hour and then the organic phase is washed with dilute acid. It is then washed with demineralized water until the washing phases are almost free of electrolytes. The organic phase is concentrated and dried for 16 hours at 50 ° C. in a vacuum drying cabinet in a water jet vacuum. Yield: 64.0 g

Example 4

900 ml of dichloromethane, 19.8 g of pyridine and 94.4 g of 2,4,6-triiodophenol are placed in a 2000 ml three-necked flask equipped with a stirrer, thermometer and reflux condenser. 35.3 g of bischlorocarbonic acid ester of 2,2-bis (4-hydroxyphenyl) propane, dissolved in 200 ml of dichloromethane, are added dropwise with stirring over the course of 65 min. The mixture is stirred at room temperature for 15 minutes and then the organic phase is washed with dilute acid. It is then washed with demineralized water until the washing phases are almost free of electrolytes. The organic phase is concentrated and dried for 16 hours at 50 ° C. in a vacuum drying cabinet in a water jet vacuum. Yield: 89.0 g Example 5

161.1 g (0.11 mol) of oligo- [2,2-bis (4-hydroxyphenyl) propane carbonate] chlorocarbonic acid ester (degree of polymerization approx. 5) (produced according to U. Grigo, K. Kirchner and PR Müller "Polycarbonate" in Becker / Braun, plastic manual, volume 3/1,

Polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna 1992, pages 143 formula (3.9)) are dissolved in 1000 g dichloromethane. A clear solution consisting of 89.1 g (0.189 mol) of 2,4,6-triiodophenol, 35.6 g (0.40 mol) of 45% sodium hydroxide solution and 800 g of water is added at 20-25 ° C. with stirring. After 5 minutes, 0.71 g of N-ethylpiperidine is added and the mixture is stirred intensively for 30 minutes. The dichloromethane phase is separated from the aqueous phase and washed free of electrolytes. The solvent is evaporated off and the concentrated solution is dried at 120 ° C. in a water jet vacuum. Yield: 202 g colorless solid. Analyzes: phenolic OH: 160 mg / kg, saponifiable Cl: <0.2 mg / kg

Iodine content: approx. 27%

Example 6

An oligocarbonate containing tetrabromobisphenol can be obtained commercially under the designation Great Lakes BC 52.

Example 7

The brominated and / or iodinated oligo-, poly- and / or copolycarbonates (9.5% by weight) obtained according to Examples 1 to 6 are mixed with polycarbonate based on bisphenol A (Makrolon 2808, Bayer AG) and 0.5% by weight .-% Tinuvin 234 (2- (3 ', 5-'-bis (l, l-dimethylbenzyl) -2 ^' -hydroxyphenyl) benzotriazole from Ciba Specialty Chemicals, Basel, Switzerland) as a stabilizer in the usual manner in Mixed methylene chloride. Then a film is made and 200 hours with one Xenon WOM 0.5 W / mm ² 102: 18 weathered. The yellowness index (YI) was measured before and after weathering.

In the following example, iodinated oligocarbonate according to Example 5 was used.

Unstabilized: Start (Y.I.): 0.86 200 h (Y.I.): 20.78

Stabilized: Start (Y.I.): 0.97 200 h (Y.I.): 6.20

This clearly shows the stabilization of the films by the mixture according to the invention.

The same observation can be made for toys and medical devices.

The x-ray contrast of these molded parts is so great that they can be discovered in children's bodies.

However, the mixtures can also be processed on an injection molding machine and, for example, molded into building blocks.

Claims

claims

1. Use of a mixture of at least one brominated and / or iodinated oligo-, poly- and / or copolycarbonates and at least one stabilizer selected from the group 2- (3 ', 5-'-bis (l, l-dimethylbenzyl) -2 '- hydroxy-phenyl) -benzotriazole, 2- (2' -hydroxy-5 '- (tert-octyl) -phenyl) -benzo-triazole, 2- (2'-hydroxy-3 ^' - (2-butyl) - 5 ^' - (tert-butyl) phenyl) benzotriazole, bis (3- (2H-benzotriazolyl) -2-hydroxy-5-tert-octyl) methane, 2- (4-hexoxy-2-hydroxyphenyl) -4,6-diphenyl-l, 3,5-triazine or another benzotriazole as well as benzophenones, such as 2,4-dihydroxy-benzophenone for the production of X-ray contrastable molded parts made of plastic.

2. Use according to claim 1, characterized in that the brominated and / or iodinated oligo-, poly- and / or copolycarbonates are selected from the group of those with an M _w between 600 and 100,000, preferably between 1000 and 80,000, particularly preferably between 3,000 and 40,000 and iodine or bromophenyl carbonate end groups, preferably end groups of the general formula (I),

wherein

R _j to R _{3 are} H, Cj-Cι ₈ optionally branched alkyl, Cl, Br or .1, with the proviso that at least one of the radicals R _{1 5} R ₂ and R _{3 is} J and or Br.

3. Use according to one of the preceding claims, characterized in that the end groups are 4-iodophenyl carbonate and 2,4,6-triiodophenyl carbonate end groups.

4. Use according to claim 1, characterized in that oligo-, poly- or copolycarbonates contain iodinated and / or brominated diols, preferably iodinated or brominated derivatives of hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis ( hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, ä, ä'- To-

(hydroxyphenyl) -diisopropylbenzenes, as well as their nuclear alkylated compounds, particularly preferably with iodine and / or bromine atoms on the aromatic nucleus of the diols.

5. Use according to claim 1 and / or 4, characterized in that the iodinated and / or brominated diphenols are selected from the group of one or more iodinated and / or brominated derivatives of 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- (4th -hydroxyphenyl) -

3, 3, 5-trimethylcyclohexane.

6. Use according to claim 1 and / or 4 and / or 5, characterized in that the iodinated and / or brominated diphenols are selected from the group of one or more iodinated and / or brominated derivatives of

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- (4th -hydroxyphenyl) -cyclohexane and l, l-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Use according to claim 1 and / or 4 and / or 5 and / or 6, characterized in that the iodinated and / or brominated diphenols are selected from the group tetrabromobisphenol and / or tetraiodobisphenol, preferably optionally in a mixture with one another and / or optionally in a mixture with other diols.

8. Use according to at least one of the preceding claims, characterized in that the stabilizer is selected from the group of benzotriazoles, preferably the group 2- (3 ', 5-' bis (l, l-dimethylbenzyl) -2'-hydroxy -phenyl) -benzotriazole, 2- (2 '-hydroxy-5 ^' - (tert-octyl) -phenyl) -benzo-triazole, 2- (2'-hydroxy-3 '- (2-butyl) -5'- (tert-butyl) phenyl) benzotriazole, bis

(3- (2H-benzotriazolyl) -2-hydroxy-5-tert-octyl) methane.

9. Use according to at least one of the preceding claims, characterized in that the stabilizer is contained in amounts of 0.01 to 10 wt .-%, preferably 0.1-1 wt .-%.

10. Use according to at least one of the preceding claims, characterized in that the brominated and / or iodinated oligo-, poly- and / or copolycarbonates in amounts between 0.1 to 50 wt .-%, preferably 0.1 to 15 wt. %, particularly preferably 1 to 10% by weight and very particularly preferably 2 to 7% by weight, based on the molding.

1 1. Use according to at least one of the preceding claims, characterized in that in addition at least one transparent thermoplastic, preferably a non-halogenated polycarbonate and / or copolycarbonate in Amounts of 85 to 99.9% by weight, preferably 90 to 99% by weight, particularly preferably 93 to 98% by weight, based on the molding, are present.

12. Shaped bodies, preferably toys and medical objects, particularly preferably toys, containing a mixture of at least one brominated and / or iodinated oligo-, poly- and / or copolycarbonates and at least one stabilizer selected from the group 2- (3 ', 5-' Bis- (l, l-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 ^' - (tert-octyl) phenyl) benzotriazole, 2- (2'-hydroxy- 3 '- (2-butyl) -5' - (tert-butyl) phenyl) benzotriazole, bis (3- (2H-benzotriazolyl) -2-hydroxy-5-tert-octyl) methane, 2- ( 4-hexoxy-2-hydroxyphenyl) -4,6-diphenyl-l, 3,5-triazine, and

Benzophenones, e.g. 2,4-Dihydroxy-benzophenone to increase the X-ray contrast.