WO2000037562A1 - Use of polycarbonates containing iodine and/or bromine for moulded parts with high x-ray contrast and moulded parts produced with same - Google Patents

Use of polycarbonates containing iodine and/or bromine for moulded parts with high x-ray contrast and moulded parts produced with same Download PDF

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Publication number
WO2000037562A1
WO2000037562A1 PCT/EP1999/009556 EP9909556W WO0037562A1 WO 2000037562 A1 WO2000037562 A1 WO 2000037562A1 EP 9909556 W EP9909556 W EP 9909556W WO 0037562 A1 WO0037562 A1 WO 0037562A1
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WIPO (PCT)
Prior art keywords
weight
iodine
brominated
polycarbonates
ray contrast
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PCT/EP1999/009556
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German (de)
French (fr)
Inventor
Martin Döbler
Siegfried Neumann
Axel Brenner
Walter Köhler
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Bayer Aktiengesellschaft
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Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to EP99963402A priority Critical patent/EP1141129A1/en
Priority to CA002355142A priority patent/CA2355142A1/en
Priority to AU19713/00A priority patent/AU1971300A/en
Priority to JP2000589625A priority patent/JP2002533515A/en
Publication of WO2000037562A1 publication Critical patent/WO2000037562A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/10—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B90/00—Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges
    • A61B90/39—Markers, e.g. radio-opaque or breast lesions markers
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
    • A63H33/00—Other toys
    • A63H33/001—Toy-moulding appliances; Toy moulding

Definitions

  • the invention relates to the use of iodine and / or bromine-containing thermoplastics for molded parts with high X-ray contrast and those produced therewith
  • Molded parts especially toys and medical devices.
  • Such molding materials can be made radiopaque by suitable additives.
  • X-ray detectable plastic molding compositions have also been described in Silberman-Hazony, Encycl. Polym. Be. Closely. (1988), 14, 1-8. Thermoplastics with various heavy metals have been described as X-ray contrast media. A halogen-containing terpolymer was also mentioned.
  • FR 2223403 describes PVC and other vinyl polymers with iodine-containing salicylic acids, benzoic acids and their esters, which are similar to those of US Pat. Nos. 3,361,700 and 3,645,955.
  • PVC is not suitable for applications where high transparency and good mechanical properties are required.
  • transparent plastic molding compositions made of polycarbonates with iodine-containing end groups have also been described. In this way, iodine is only introduced at the end groups. All other monomers remain unmodified, which is why the weight fraction of iodine remains limited.
  • the layer thickness at which the plastic can still be recognized should be as small as possible, but at most 1.2 mm.
  • the task was to develop molding compounds with good mechanics and
  • Transparency have sufficient contrast in X-ray examinations.
  • the addition of heavy metals should be avoided for toxicological reasons, since materials for children's toys were sought.
  • the subject of the present application is accordingly the use of iodine and / or bromine-containing transparent thermoplastics for molded parts with high X-ray contrast.
  • Polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds which contain bromine or iodine are suitable.
  • Particularly suitable plastics are polycarbonates or copolycarbonates based on diphenols.
  • oligomers according to the invention can, however, also be used with poly- or copolyacrylates and poly- or copolymer-methacrylates such as, for example, brominated and / or iodinated poly- or copolymethyl methacrylate, but also as copolymers with styrene, such as transparent brominated and / or iodinated polyurethane-acrylonitrile
  • SAN can be used.
  • poly- or copolycondensates of terephthalic acid e.g. Poly- or copolyethylene terephthalate (PET or CoPET) or glycol-modified PET (PETG) can be mixed in.
  • PET or CoPET Poly- or copolyethylene terephthalate
  • PETG glycol-modified PET
  • Brominated and / or iodinated polycarbonates are particularly preferred for moldings with high X-ray contrast, the polycarbonates having an iodine and / or brominated diol unit and a weight average molecular weight Mw
  • polycarbonates which, as a diol unit, between 0.1 and 100% by weight, preferably between 1 and 100% by weight, particularly preferably between 10 and 100% by weight, preferably 100% by weight, of brominated and / or iodinated 2,2-bis - (4-hydroxyphenyl) propane included.
  • diols are 2,2-bis
  • the molded parts can consist entirely of the iodine and / or bromine-containing polycarbonate.
  • the iodine and / or bromine content in the molded part is then between 0.2 to
  • the moldings then contain the iodine and / or bromine-containing polycarbonates in amounts between 0.1 to 100% by weight, preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight and very particularly preferably 2 to 10 % By weight based on the molded part.
  • the molded parts can optionally additionally contain at least one transparent thermoplastic, preferably a non-halogenated polycarbonate or copolycarbonate in amounts of 70 to 99% by weight, preferably 80 to 98% by weight, particularly preferably 90 to 98% by weight, based on the molded part his.
  • at least one transparent thermoplastic preferably a non-halogenated polycarbonate or copolycarbonate in amounts of 70 to 99% by weight, preferably 80 to 98% by weight, particularly preferably 90 to 98% by weight, based on the molded part his.
  • 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 also be mixed with poly- or copolyacrylates and poly- or copolymethacrylates such as e.g. Poly- or copolymethyl methacrylate, but also as copolymers with styrene such as transparent polystyrene acrylonitrile (SAN) can be used.
  • SAN transparent polystyrene acrylonitrile
  • PET or CoPET poly or copolyethylene terephthalate
  • PETG glycol-modified PET
  • 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.
  • Carbonic acid derivatives optionally chain terminators and optionally branching agents.
  • 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, ä, ä'-bis- (hydroxyphenyl) diisopropylbenzenes, and their alkylated compounds.
  • the iodinated and / or brominated derivatives of these diols are suitable for the preparation of the polycarbonates and / or copolycarbonates according to the invention.
  • Preferred for the polycarbonates and / or copolycarbonates according to the invention are tetrabromobisphenol and / or tetraiodobisphenol, optionally in a mixture with one another or optionally with other diols.
  • a preferred copolymer for the polycarbonates and / or copolycarbonates according to the invention is one of tetrabromobisphenol with bisphenol A as a comonomer.
  • a preferred mixture for the polycarbonates and / or copolycarbonates according to the invention is a mixture of polymers from tetrabromobisphenol with polymers with bisphenol A.
  • Preferred diphenols for the additional polycarbonates and / or copolycarbonates 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,
  • Particularly preferred diphenols for the additional polycarbonates and or copolycarbonates 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-hj-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl ) -cyclohexane and l, l-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.
  • Suitable chain terminators for the iodine and / or bromine-containing polycarbonates according to the invention, but also the additional polycarbonates and / or copolycarbonates are both monophenols and monocarboxylic acids.
  • Suitable monophenols are phenol itself, alkylphenols such as cresols, p-tert-butylphenol, p-n-octylphenol, p-iso-
  • halophenols such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol, especially 2,4,6-triiodophenol, p- Jodpbenol, as well as their mixtures.
  • the preferred chain terminator is p-tert-butylphenol.
  • Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halogenated benzoic acids.
  • Preferred chain terminators are the phenols of the formula (I)
  • R is hydrogen, tert-butyl or a branched or unbranched C 8 and / or C 9 alkyl radical.
  • the amount of chain terminator to be used is 0.1 mol% to 5 mol%, based on moles of diphenols used in each case.
  • the chain terminators can be added before, during or after phosgenation.
  • Suitable branching agents are the tri- or more than trifunctional compounds known in polycarbonate chemistry, in particular those with three or more than three phenolic OH groups.
  • Suitable branching agents are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl ) -heptane, l, 3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2- Bis- [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenyl isopropyl) phenol, 2,6-bis (2-hydroxy-5 '-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, hexa- (4- (4-hydroxyphenylisopropyl) phenyl) -orthotere
  • the amount of the branching agents to be used is from 0.05 mol% to
  • the branching agents can either be introduced with the diphenols and the chain terminators in the aqueous alkaline phase, or added dissolved in an organic solvent before the phosgenation. In the case of the transesterification process, the branching agents are used together with the diphenols.
  • thermoplastic polycarbonates All of these measures for producing the thermoplastic polycarbonates are familiar to the person skilled in the art.
  • the additional polycarbonates and / or copolycarbonates can be present in amounts between 0 and 99.9% by weight, preferably 70 and 99% by weight, particularly preferably between 80 and 98% by weight and very particularly preferably between 90 and 98% by weight. -% based on the molded part.
  • thermoplastics preferably poly- and copolycarbonates, such as e.g. Stabilizers (as described, for example, in EP 0 839 623 AI or EP 0 500 496 AI), in particular thermal stabilizers, in particular organic phosphites or phosphines, mold release agents, for example fatty acid esters of glycerol or tetramethanol methane, where unsaturated fatty acid can also be completely or partially epoxidized, in particular Glycerol monostearate or pentaerytetratetearate (PETS), flame retardants, antistatic agents, UV absorbers, for example triazoles, fillers, foaming agents, dyes, pigments, optical brighteners, and nucleating agents or the like, preferably in amounts of up to 5% by weight, preferably 0.01 up to 5% by weight based on the entire mixture, particularly preferably 0.01% by weight to 1% by weight based on the
  • transesterification catalysts known from the literature such as organic tin or titanium compounds, can also optionally be used in the amounts known from the literature, preferably between 10 and
  • UV stabilizers from the triazole series.
  • 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,
  • the polymer compositions can also be processed into cast films.
  • the invention therefore further relates to the use of the polymer compositions according to the invention for the production of a shaped article.
  • the use of multilayer systems is also of interest.
  • the invention is also of interest.
  • Polymer composition with a relatively high content of bromine- or iodine-containing additives in a thin layer applied to a molded article made of a polymer which is transparent to X-rays The application can take place at the same time 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 finished molded 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:

Abstract

The invention relates to the use of thermoplastic materials containing iodine and/or bromine for moulded parts with high X-ray contrast. The invention also relates to moulded parts produced therewith, notably toys and medical devices.

Description

VERWENDUNG VON JOD- UND/ODER BROMHALTIGEN POLYCARBONATEN FÜR FORMTEILE MIT HOHEM RÖNTGENKONTRAST SOWIE DAMITUSE OF IODINE AND / OR BROMIC POLYCARBONATES FOR MOLDED PARTS WITH HIGH X-RAY CONTRAST AND WITH IT
HERGESTELLTE FORMTEILEPRODUCED MOLDED PARTS
Gegenstand der Erfindung ist die Verwendung von jod- und/oder bromhaltigen Thermoplasten für Formteile mit hohem Röntgenkontrast und damit hergestellteThe invention relates to the use of iodine and / or bromine-containing thermoplastics for molded parts with high X-ray contrast and those produced therewith
Formteile, besonders Spielzeug und medizinische Geräte.Molded parts, especially toys and medical devices.
Für den medizinischen Bereich und auch für Kinderspielzeug werden Materialien mit möglichst hoher Transparenz und guter Mechanik gesucht, die bei Röntgenuntersu- chungen im Körper detektiert werden können. Im Gegensatz zu metallischen Gegenständen sind Gegenstände aus Kunststoff in der Regel nicht oder nur schlecht im Röntgenbild erkennbar. Durch geeignete Zusätze können solche Formmassen röntgenkontrastierbar gemacht werden.Materials with the highest possible transparency and good mechanics are sought for the medical field and also for children's toys, which can be detected in the body during X-ray examinations. In contrast to metallic objects, objects made of plastic are usually not or only poorly recognizable in the X-ray image. Such molding materials can be made radiopaque by suitable additives.
Durch geeignete Zusätze können solche Formmassen röntgenkontrastierbar gemacht werden.Such molding materials can be made radiopaque by suitable additives.
Solche Formmassen wurden zum Beispiel in der DE-A 195 45 289 beschrieben. In diesem Patent wurden röntgenkontrastierbare thermoplastische Formmassen aus ABS mit BaSO4 -Zusatz beschrieben.Such molding compositions have been described, for example, in DE-A 195 45 289. In this patent, X-ray contrastable thermoplastic molding compositions made of ABS with BaSO 4 additive have been described.
Röntgendetektierbare Kunststofformmassen wurden ferner in Silberman-Hazony, Encycl. Polym. Sei. Eng. (1988), 14, 1-8 beschrieben. Es wurden Thermoplaste mit verschiedenen Schwermetallen als Röntgenkontrastmittel beschrieben. Außerdem wurde ein halogenhaltiges Terpolymer erwähnt.X-ray detectable plastic molding compositions have also been described in Silberman-Hazony, Encycl. Polym. Be. Closely. (1988), 14, 1-8. Thermoplastics with various heavy metals have been described as X-ray contrast media. A halogen-containing terpolymer was also mentioned.
Schließlich beschreibt FR 2223403 PVC und andere Vinylpolymere mit iodhaltigen Salicylsäuren, Benzoesäuren und deren Estern, die denen der US 3,361.700 und 3,645,955 ähneln. PVC eignet sich jedoch nicht für Anwendungen, bei denen hohe Transparenz und gute mechanische Eigenschaften erwünscht sind. In US 3,469,704 und DE-A 17 20 812 wurden ferner transparente Kunst- stofformmassen aus Polycarbonaten mit jodhaltigen Endgruppen beschrieben. Auf diese Weise wird Jod aber nur an den Endgruppen eingeführt. Alle anderen Monomere bleiben unmodifiziert, weshalb der Gewichtsanteil an Jod beschränkt bleibt.Finally, FR 2223403 describes PVC and other vinyl polymers with iodine-containing salicylic acids, benzoic acids and their esters, which are similar to those of US Pat. Nos. 3,361,700 and 3,645,955. However, PVC is not suitable for applications where high transparency and good mechanical properties are required. In US 3,469,704 and DE-A 17 20 812, transparent plastic molding compositions made of polycarbonates with iodine-containing end groups have also been described. In this way, iodine is only introduced at the end groups. All other monomers remain unmodified, which is why the weight fraction of iodine remains limited.
Aus US 3,382,207 schließlich sind jodhaltige Diphenylcarbonate als Zusätze für Polycarbonate bekannt.Finally, US 3,382,207 iodine-containing diphenyl carbonates are known as additives for polycarbonates.
Für transparente Kunststoffteile steht im Stand der Technik bis jetzt also noch keine adäquate röntgenkontrastierbare Kunststoffmasse zur Verfügung. Aufgrund seiner hervorragenden mechanischen Eigenschaften wurde bislang Polycarbonat insbesondere für mechanisch hochbeanspruchte und transparente Spielzeugteile verwendet. Es soll nun ein Kunststofftyp entwickelt werden, der bei unverändert hoher Transparenz und möglichst nur geringfügig verschlechterten mechanischen Eigenschaften imSo far, there has not yet been an adequate X-ray-contrastable plastic mass available for transparent plastic parts in the prior art. Due to its excellent mechanical properties, polycarbonate has so far been used especially for mechanically highly stressed and transparent toy parts. A type of plastic is now to be developed which, while maintaining high transparency and, if possible, only slightly deteriorating mechanical properties in the
Rahmen einer herkömmlichen Röntgenaufnahme erkennbar ist. Die Schichtdicke bei der der Kunststoff noch erkennbar ist, sollte möglichst gering sein, höchstens jedoch 1.2 mm.Frame of a conventional x-ray is recognizable. The layer thickness at which the plastic can still be recognized should be as small as possible, but at most 1.2 mm.
Die Aufgabe bestand darin Formmassen zu entwickeln, die bei guter Mechanik undThe task was to develop molding compounds with good mechanics and
Transparenz einen ausreichenden Kontrast bei Röntgenuntersuchungen besitzen. Auf den Zusatz von Schwermetallen sollte aus toxikologischen Gründen verzichtet werden, da Materialien für Kinderspielzeug gesucht waren.Transparency have sufficient contrast in X-ray examinations. The addition of heavy metals should be avoided for toxicological reasons, since materials for children's toys were sought.
Gegenstand der vorliegenden Anmeldung ist demnach die Verwendung von jod- und/oder bromhaltigen transparenten Thermoplasten für Formteile mit hohem Röntgenkontrast. Geeignet sind dabei Polymerisate von ethylenisch ungesättigten Monomeren und/oder Polykondensate von bifunktionellen reaktiven Verbindungen, welche Brom oder Jod enthalten. Besonders geeignete Kunststoff sind Polycarbonate oder Copolycarbonate auf Basis von Diphenolen. Die erfindungsgemäßen Oligomere können aber auch mit Poly- oder Copolyacrylaten und Poly- oder Copolymefhacrylaten wie z.B. bromiertes und/oder jodiertes Poly- oder Copolymethylmethacrylat, aber auch als Copolymere mit Styrol wie z.B. transparentes bromiertes und/oder jodiertes PblystyrolacrylnitrilThe subject of the present application is accordingly the use of iodine and / or bromine-containing transparent thermoplastics for molded parts with high X-ray contrast. Polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds which contain bromine or iodine are suitable. Particularly suitable plastics are polycarbonates or copolycarbonates based on diphenols. The oligomers according to the invention can, however, also be used with poly- or copolyacrylates and poly- or copolymer-methacrylates such as, for example, brominated and / or iodinated poly- or copolymethyl methacrylate, but also as copolymers with styrene, such as transparent brominated and / or iodinated polyurethane-acrylonitrile
(SAN) verwendet werden.(SAN) can be used.
Ferner könne sie in transparente bromierte und/oder jodierte Cycloolefine, Poly- oder Copolykondensate der Terephthalsäure, wie z.B. Poly- oder Copolyethylentere- phthalat (PET oder CoPET) oder glycol-modifiziertes PET (PETG) eingemischt werden.They can also be converted into transparent brominated and / or iodinated cycloolefins, poly- or copolycondensates of terephthalic acid, e.g. Poly- or copolyethylene terephthalate (PET or CoPET) or glycol-modified PET (PETG) can be mixed in.
Besonders bevorzugt geeignet sind bromierte und/oder jodierte Polycarbonaten für Formteile mit hohem Röntgenkontrast, wobei die Polycarbonate eine jod- und/oder bromierte Dioleinheit aufweisen und ein Gewichtsmittel des Molekulargewichts MwBrominated and / or iodinated polycarbonates are particularly preferred for moldings with high X-ray contrast, the polycarbonates having an iodine and / or brominated diol unit and a weight average molecular weight Mw
500 bis 100.000, bevorzugt 1000 bis 40.000 und besonders bevorzugt 1000 bis 8.000 haben.500 to 100,000, preferably 1000 to 40,000 and particularly preferably 1000 to 8,000.
Es sind Mischungen aller oben aufgeführten jodhaltigen Verbindungen ebenso ge- eignet.Mixtures of all the iodine-containing compounds listed above are also suitable.
Besonders geeignet sind Polycarbonate, welche als Dioleinheit zwischen 0.1 und 100 Gew.%, bevorzugt zwischen 1 und 100 Gew.%, besonders bevorzugt zwischen 10 und 100 Gew.%, vorzugsweise 100 Gew.% bromiertes und/oder jodiertes 2,2-Bis-(4- hydroxyphenyl)-propan enthalten. Besonders bevorzugt geeignete Diole sind 2,2-Bis-Particularly suitable are polycarbonates which, as a diol unit, between 0.1 and 100% by weight, preferably between 1 and 100% by weight, particularly preferably between 10 and 100% by weight, preferably 100% by weight, of brominated and / or iodinated 2,2-bis - (4-hydroxyphenyl) propane included. Particularly preferred diols are 2,2-bis
(3,5-dibrom-4-hydroxyphenyl)-propan (Tetrabrombisphenol) und 2,2-Bis-(4-hydroxy- 3,5-diiodphenyl)-propan (Tetrajodbisphenol).(3,5-dibromo-4-hydroxyphenyl) propane (tetrabromobisphenol) and 2,2-bis (4-hydroxy-3,5-diiodophenyl) propane (tetraiodobisphenol).
Die Formteile können ganz aus dem jod- und/oder bromhaltigen Polycarbonat be- stehen. Der Jod- und/oder Bromgehalt im Formteil beträgt dann zwischen 0,2 bisThe molded parts can consist entirely of the iodine and / or bromine-containing polycarbonate. The iodine and / or bromine content in the molded part is then between 0.2 to
70 Gew.-%, bevorzugt 1 bis 25 Gew.-%, besonders bevorzugt 2 bis 15 Gew.-%. Aber auch andere Inlialtsstoffe können zugesetzt werden. Die Formteile enthalten dann die jod- und/oder bromhaltigen Polycarbonate in Mengen zwischen 0,1 bis 100 Gew.-%, bevorzugt 1 bis 30 Gew.-%, besonders bevorzugt 2 bis 20 Gew.-% und ganz besonders bevorzugt 2 bis 10 Gew.-% bezogen auf das Formteil.70% by weight, preferably 1 to 25% by weight, particularly preferably 2 to 15% by weight. However, other domestic substances can also be added. The moldings then contain the iodine and / or bromine-containing polycarbonates in amounts between 0.1 to 100% by weight, preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight and very particularly preferably 2 to 10 % By weight based on the molded part.
In den Formteilen kann optional zusätzlich mindestens ein transparenter Thermoplast, bevorzugt ein nichthalogeniertes Polycarbonat oder Copolycarbonat in Mengen von 70 bis 99Gew.-%, bevorzugt 80 bis 98 Gew.-%, besonders bevorzugt 90 bis 98 Gew.-% bezogen auf das Formteil enthalten sein.The molded parts can optionally additionally contain at least one transparent thermoplastic, preferably a non-halogenated polycarbonate or copolycarbonate in amounts of 70 to 99% by weight, preferably 80 to 98% by weight, particularly preferably 90 to 98% by weight, based on the molded part his.
Als transparente Thermoplaste werden besonders bevorzugt die Polymerisate von ethylenisch ungesättigten Monomeren und/oder Polykondensate von bifunktionellen reaktiven Verbindungen genutzt.The polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds are particularly preferably used as transparent thermoplastics.
Besonders geeignete transparente Thermoplaste sind Polycarbonate oder Copoly- carbonate auf Basis von Diphenolen. Die erfindungsgemäßen Oligomere können aber auch mit Poly- oder Copolyacrylaten und Poly- oder Copolymethacrylaten wie z.B. Poly- oder Copolymethylmethacrylat, aber auch als Copolymere mit Styrol wie z.B. transparentes Polystyrolacrylnitril (SAN) verwendet werden.Particularly suitable transparent thermoplastics are polycarbonates or copolycarbonates based on diphenols. However, the oligomers according to the invention can also be mixed with poly- or copolyacrylates and poly- or copolymethacrylates such as e.g. Poly- or copolymethyl methacrylate, but also as copolymers with styrene such as transparent polystyrene acrylonitrile (SAN) can be used.
Ferner könne sie in transparente Cycloo ϊfine, Poly- oder Copolykondensate der Terephthalsäure, wie z.B. Poly- oder Copolyethylenterephthalat (PET oder CoPET) oder glycol-modifiziertes PET (PETG) eingemischt werden.They can also be converted into transparent cyclo-fines, poly- or copolycondensates of terephthalic acid, e.g. Poly or copolyethylene terephthalate (PET or CoPET) or glycol-modified PET (PETG) can be mixed in.
Der Fachmann erzielt ausgezeichnete Resultate mit Polycarbonaten und/oder Copolycarbonaten, bevorzugt nicht halogenierten Polycarbonaten und/oder Copoly- carbonaten. Thermoplastische, aromatische Polycarbonate im Sinne der vorliegenden Erfindung sind sowohl Homopolycarbonate als auch Copolycarbonate; die Polycarbonate können in bekannter Weise linear oder verzweigt sein.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.
Die Herstellung dieser Polycarbonate erfolgt in bekannter Weise aus Diphenolen,These polycarbonates are produced in a known manner from diphenols,
Kohlensäurederivaten, gegebenenfalls Kettenabbrechern und gegebenenfalls Verzweigern.Carbonic acid derivatives, optionally chain terminators and optionally branching agents.
Einzelheiten der Herstellung von Polycarbonaten sind in vielen Patentschriften seit etwa 40 Jahren niedergelegt. Beispielhaft sei hier nur auf Schnell, "Chemistry andDetails of the production of polycarbonates have been laid down in many patents for about 40 years. One example here is Schnell, "Chemistry and
Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, auf D. Freitag, U. Grigo, P.R. Müller, H. Nouvertne', BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, Seiten 648-718 und schließlich auf Dres. U. Grigo, K. Kirchner und P.R. Müller "Polycarbonate" in Becker/Braun, Kunststoff-Handbuch,Physics of Polycarbonates ", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, on D. Freitag, U. Grigo, PR 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,
Band 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag München, Wien 1992, Seiten 117-299 verwiesen.Volume 3/1, polycarbonates, polyacetals, polyester, cellulose esters, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299.
Für die Herstellung der Polycarbonate geeignete Diphenole sind beispielsweise Hydro- chinon, Resorcin, Dihydroxydiphenyle, Bis-(hydroxyphenyl)-alkane, Bis(hydroxy- phenyl)-cycloalkane, Bis-(hydroxyphenyl)-sulfιde, Bis-(hydroxyphenyl)-ether, Bis-(hy- droxyphenyl)-ketone, Bis-(hydrc yphenyl)-sulfone, Bis-(hydroxyphenyl)-sulfoxide, ä,ä'-Bis-(hydroxyphenyl)-diisopropylbenzole, sowie deren kernalkylierte Verbindungen.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, ä, ä'-bis- (hydroxyphenyl) diisopropylbenzenes, and their alkylated compounds.
Für die Herstellung der erfindungsgemäßen Polycarbonate und/oder Copolycarbonate sind die jodierten und/oder bromierten Derivate dieser Diole geeignet.The iodinated and / or brominated derivatives of these diols are suitable for the preparation of the polycarbonates and / or copolycarbonates according to the invention.
Bevorzugt für die erfindungsgemäßen Polycarbonate und/oder Copolycarbonate sind Tetrabrombisphenol und/oder Tetrajodbisphenol, gegebenenfals im Gemisch miteinander oder gegebenenfalls mit anderen Diolen. Ein bevorzugtes Copolymer für die erfindungsgemäßen Polycarbonate und/oder Copolycarbonate ist eines aus Tetrabrombisphenol mit Bisphenol A als Comonomerem.Preferred for the polycarbonates and / or copolycarbonates according to the invention are tetrabromobisphenol and / or tetraiodobisphenol, optionally in a mixture with one another or optionally with other diols. A preferred copolymer for the polycarbonates and / or copolycarbonates according to the invention is one of tetrabromobisphenol with bisphenol A as a comonomer.
Ein bevorzugtes Gemisch für die erfindungsgemäßen Polycarbonate und/oder Copolycarbonate ist ein Gemisch aus Polymeren aus Tetrabrombisphenol mit Polymeren mit Bisphenol A.A preferred mixture for the polycarbonates and / or copolycarbonates according to the invention is a mixture of polymers from tetrabromobisphenol with polymers with bisphenol A.
Bevorzugte Diphenole für die zusätzlichen Polycarbonate und/oder Copolycarbonate sind 4,4'-Dihydroxydiphenyl, 2,2-Bis-(4-hydroxyphenyl)-propan, 2,4-Bis-(4-hydroxy- phenyl)-2-mefhylbutan, 1 , 1 -Bis-(4-hydroxyphenyl)-p-diisopropylbenzol, 2,2-Bis-(3- methyl-4-hydroxyphenyl)-propan, 2,2-Bis-(3-chlor-4-hydroxyphenyl)-propan, Bis- (3,5-dimethyl-4-hydroxyphenyl)-methan, 2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)- propan, Bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfon, 2,4-Bis-(3,5-dimefhyl-4-hydroxy- phenyl)-2-methylbutan, 1 , 1 -Bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzol,Preferred diphenols for the additional polycarbonates and / or copolycarbonates 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-dichlor-4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dibrom-4-hydroxyphenyl)- propan und l,l-Bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan.2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and l, l-bis (4-hydroxyphenyl ) -3,3,5-trimethylcyclohexane.
Besonders bevorzugte Diphenole für die zusätzlichen Polycarbonate und oder Copoly- carbonate sind 2,2-Bis-(4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dimethyl-4-hydroxy- phenyl)-propan, 2,2-Bis-(3,5-dichlor-4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dibrom-4- hj droxyphenyl)-propan, l,l-Bis-(4-hydroxyphenyl)-cyclohexan und l,l-Bis-(4-hy- droxyphenyl)-3,3,5-trimethylcyclohexan.Particularly preferred diphenols for the additional polycarbonates and or copolycarbonates 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-hj-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl ) -cyclohexane and l, l-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
Diese und weitere geeignete Diphenole sind z.B. in den US-PS 3 028 635, 2 999 835,These and other suitable diphenols are e.g. in U.S. Patents 3,028,635, 2,999,835,
3 148 172, 2 991 273, 3 271 367, 4 982 014 und 2 999 846, in den deutschen Offen- legungsschriften 1 570 703, 2 063 050, 2 036 052, 2 21 1 956 und 3 832 396, der französischen Patentschrift 1 561 518, in der Monographie "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" sowie in den japanischen Offenlegungsschriften 62039/1986, 62040/1986 und 105550/1986 beschrieben. Im Falle der Homopolycarbonate ist nur ein Diphenol eingesetzt, im Falle der Copolycarbonate sind mehrere Diphenole eingesetzt.3 148 172, 2 991 273, 3 271 367, 4 982 014 and 2 999 846, in the German patent applications 1 570 703, 2 063 050, 2 036 052, 2 21 1 956 and 3 832 396, the French patent specification 1,561,518, in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" and in Japanese Laid-Open Publications 62039/1986, 62040/1986 and 105550/1986. In the case of homopolycarbonates, only one diphenol is used; in the case of copolycarbonates, several diphenols are used.
Geeignete Kohlensäurederivate sind beispielsweise Phosgen oder Diphenylcarbonat.Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.
Geeignete Kettenabbrecher für die erfindungsgemäßen jod- und/oder bromhaltigen Polycarbonate, aber auch die zusätzlichen Polycarbonate und/oder Copolycarbonate sind sowohl Monophenole als auch Monocarbonsäuren. Geeignete Monophenole sind Phenol selbst, Alkylphenole wie Kresole, p-tert.-Butylphenol, p-n-Octylphenol, p-iso-Suitable chain terminators for the iodine and / or bromine-containing polycarbonates according to the invention, but also the additional polycarbonates and / or copolycarbonates are both monophenols and monocarboxylic acids. Suitable monophenols are phenol itself, alkylphenols such as cresols, p-tert-butylphenol, p-n-octylphenol, p-iso-
Octylphenol, p-n-Nonylphenol und p-iso-Nonylphenol, Halogenphenole wie p-Chlor- phenol, 2,4-Dichlorphenol, p-Bromphenol und 2,4,6-Tribromphenol, besonders auch 2,4,6-Trijodphenol, p-Jodpbenol, sowie deren Mischungen.Octylphenol, pn-nonylphenol and p-iso-nonylphenol, halophenols such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol, especially 2,4,6-triiodophenol, p- Jodpbenol, as well as their mixtures.
Bevorzugter Kettenabbrecher ist p-tert.-Butylphenol.The preferred chain terminator is p-tert-butylphenol.
Geeignete Monocarbonsäuren sind Benzoesäure, Alkylbenzoesäuren und Halogen- benzoesäuren.Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halogenated benzoic acids.
Bevorzugte Kettenabbrecher sind die Phenole der Formel (I)Preferred chain terminators are the phenols of the formula (I)
Figure imgf000009_0001
Figure imgf000009_0001
worinwherein
R Wasserstoff, tert.-Butyl oder ein verzweigter oder unverzweigter C8- und/oder C9-Alkylrest ist. Die Menge an einzusetzendem Kettenabbrecher beträgt 0,1 Mol-% bis 5 Mol-%, bezogen auf Mole an jeweils eingesetzten Diphenolen. Die Zugabe der Kettenabbrecher kann vor, während oder nach der Phosgenierung erfolgen.R is hydrogen, tert-butyl or a branched or unbranched C 8 and / or C 9 alkyl radical. The amount of chain terminator to be used is 0.1 mol% to 5 mol%, based on moles of diphenols used in each case. The chain terminators can be added before, during or after phosgenation.
Geeignete Verzweiger sind die in der Polycarbonatchemie bekannten tri- oder mehr als trifunktionellen Verbindungen, insbesondere solche mit drei oder mehr als drei phenolischen OH-Gruppen.Suitable branching agents are the tri- or more than trifunctional compounds known in polycarbonate chemistry, in particular those with three or more than three phenolic OH groups.
Geeignete Verzweiger sind beispielsweise Phloroglucin, 4,6-Dimethyl-2,4,6-tri-(4-hy- droxyphenyl)-hepten-2, 4,6-Dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptan, l,3,5-Tri-(4- hydroxyphenyl)-benzol, 1,1,1 -Tri-(4-hydroxyphenyl)-ethan, Tri-(4-hydroxyphenyl)- phenylmethan, 2,2-Bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propan, 2,4-Bis-(4-hy- droxyphenyl-isopropyl)-phenol, 2,6-Bis-(2-hydroxy-5'-methyl-benzyl)-4-methyl- phenol, 2-(4-Hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propan, Hexa-(4-(4-hydroxy- phenyl-isopropyl)-phenyl)-orthoterephthalsäureester, Tetra-(4-hydroxyphenyl)-methan,Suitable branching agents are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl ) -heptane, l, 3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2- Bis- [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenyl isopropyl) phenol, 2,6-bis (2-hydroxy-5 '-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, hexa- (4- (4-hydroxyphenylisopropyl) phenyl) -orthoterephthalic acid ester, tetra- (4-hydroxyphenyl) methane,
Tetra-(4-(4-hydroxyphenyl-isopropyl)-phenoxy)-methan und 1 ,4-Bis-(4',4"-dihydroxy- triphenyl)-methyl)-benzol sowie 2,4-Dihydroxybenzoesäure, Trimesinsäure, Cyanur- chlorid und 3,3-Bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindol.Tetra- (4- (4-hydroxyphenyl-isopropyl) phenoxy) methane and 1, 4-bis (4 ', 4 "-dihydroxy-triphenyl) methyl) benzene and 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid - chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
Die Menge der gegebenenfalls einzusetzenden Verzweiger beträgt 0,05 Mol-% bisThe amount of the branching agents to be used is from 0.05 mol% to
2 Mol-%, bezogen wiederum auf Mole an jeweils eingesetzten Diphenolen.2 mol%, based in turn on moles of diphenols used in each case.
Die Verzweiger können entweder mit den Diphenolen und den Kettenabbrechern in der wäßrig alkalischen Phase vorgelegt werden, oder in einem organischen Lösungsmittel gelöst vor der Phosgenierung zugegeben werden. Im Falle des Umesterungsverfahrens werden die Verzweiger zusammen mit den Diphenolen eingesetzt.The branching agents can either be introduced with the diphenols and the chain terminators in the aqueous alkaline phase, or added dissolved in an organic solvent before the phosgenation. In the case of the transesterification process, the branching agents are used together with the diphenols.
Alle diese Maßnahmen zur Herstellung der thermoplastischen Polycarbonate sind dem Fachmann geläufig. Die zusätzlichen Polycarbonate und/oder Copolycarbonate können in Mengen zwischen 0 und 99,9 Gew.-%, bevorzugt 70 und 99 Gew.-%, besonders bevorzugt zwischen 80 und 98 Gew.-% und ganz besonders bevorzugt zwischen 90 und 98 Gew.-% bezogen auf das Formteil vorhanden sein.All of these measures for producing the thermoplastic polycarbonates are familiar to the person skilled in the art. The additional polycarbonates and / or copolycarbonates can be present in amounts between 0 and 99.9% by weight, preferably 70 and 99% by weight, particularly preferably between 80 and 98% by weight and very particularly preferably between 90 and 98% by weight. -% based on the molded part.
Es ist zur Erreichung von verbesserten Zusammensetzungen möglich, daß zusätzlich noch mindestens ein weiterer in thermoplastischen Kunststoffen, bevorzugt Poly- und Copolycarbonaten, üblicherweise vorhandener Zusatzstoff wie z.B. Stabilisatoren (wie z.B. in EP 0 839 623 AI oder EP 0 500 496 AI beschrieben) besonders Thermostabilisatoren, insbesondere organische Phosphite oder Phosphine, Ent- formungsmittel, beispielsweise Fettsäureester des Glycerins oder Tetramethanolmethan, wobei ungesättigte Fettsäure auch ganz oder teilweise epoxidiert sein können, insbesondere Glycerinmonostearat oder Pentaerytrittetrastearat (PETS), Flammschutzmittel, Antistatika, UV-Absorber, beispielsweise Triazole, Füllmittel, Schaummittel, Farbstoffen, Pigmente, optische Aufheller, und Nukleierungsmittel o.a., bevorzugt in Mengen von jeweils bis zu 5 Gew.-%, bevorzugt 0,01 bis 5 Gew.-% bezogen auf die gesamte Mischung, besonders bevorzugt 0,01 Gew.-% bis 1 Gew.-% bezogen auf die Menge Kunststoff enthalten ist.To achieve improved compositions it is possible that at least one further additive usually present in thermoplastics, preferably poly- and copolycarbonates, such as e.g. Stabilizers (as described, for example, in EP 0 839 623 AI or EP 0 500 496 AI), in particular thermal stabilizers, in particular organic phosphites or phosphines, mold release agents, for example fatty acid esters of glycerol or tetramethanol methane, where unsaturated fatty acid can also be completely or partially epoxidized, in particular Glycerol monostearate or pentaerytetratetearate (PETS), flame retardants, antistatic agents, UV absorbers, for example triazoles, fillers, foaming agents, dyes, pigments, optical brighteners, and nucleating agents or the like, preferably in amounts of up to 5% by weight, preferably 0.01 up to 5% by weight based on the entire mixture, particularly preferably 0.01% by weight to 1% by weight based on the amount of plastic.
Auch Mischungen dieser Zusatzstoffe sind möglich.Mixtures of these additives are also possible.
Um bei Mischungen von mehreren Thermoplasten eine bessere Verträglichkeit der Bestandteile und damit eine bessere Transparenz zu erreichen, können zusätzlich optional auch literaturbekannte Umesterungskatalysatoren wie organische Zinn- oder Titanverbindungen in den literaturbekannten Mengen, bevorzugt zwischen 10 undIn order to achieve a better compatibility of the constituents and thus a better transparency in the case of mixtures of several thermoplastics, transesterification catalysts known from the literature, such as organic tin or titanium compounds, can also optionally be used in the amounts known from the literature, preferably between 10 and
1000 ppm verwendet werden.1000 ppm can be used.
Besonders gute Eigenschaften erzielt man mit UV-Stabilisatoren der Triazolreihe.Particularly good properties are achieved with UV stabilizers from the triazole series.
Hier sind besonders zu nennen 2-(3',5-'Bis-(l,l-dimethylbenzyl)-2'-hydroxy- phenyl)-benzotriazol, 2-(2'-Hydroxy-5'-(tert-octyl)-phenyl)-benzotriazol, 2-(2'-Hy- droxy-3 '-(2-butyl)-5 '-(tert-butyl)-phenyl)-benzotriazol, Bis-(3-(2H-benztriazolyl)-2- hydroxy-5-tert-octyl)methan, 2-(4-Hexoxy-2-hydroxyphenyl)-4,6-diphenyl-l,3,5- triazin, sowie Benzophenone, wie z.B. 2,4-Dihydroxy-benzophenon.Here are especially to be mentioned 2- (3 ', 5-'Bis- (l, l-dimethylbenzyl) -2' -hydroxy- phenyl) 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, such as 2,4-dihydroxy-benzophenone.
Dies ist um so überraschender, d bei Anwendungen in Häusern (wie z. B. bei Spielzeug und medizinischen Geräten im allgemeinen üblich) bisher davon ausgegangen wurde, daß kein UV-Schutz zuzusetzen ist.This is all the more surprising since it has hitherto been assumed that no UV protection has to be added in applications in houses (such as, for example, in general in toys and medical devices).
Die so erhaltenen röntgenopaken Polymerzusammensetzungen können nach den üblichen Methoden, wie z.B. Heißpressen, Spinnen, Extrudieren oder Spritzgießen, in geformte Gegenstände überführt werden, wie z.B. Spielzeugteile, aber auch Fasern,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,
Folien, Bändchen, Platten, Stegplatten, Gefäße, Rohre und sonstige Profile. Die Polymerzusammensetzungen können auch zu Gießfolien verarbeitet werden. Die Erfindung betrifft daher weiterhin die Verwendung der erfindungsgemäßen Polymerzusammensetzungen zur Herstellung eines geformten Gegenstandes. Von Interesse ist auch die Verwendung von Mehrschichtsystemen. Hierbei wird die erfindungsgemäßeFoils, tapes, plates, multi-wall sheets, vessels, pipes and other profiles. The polymer compositions can also be processed into cast films. The invention therefore further relates to the use of the polymer compositions according to the invention for the production of a shaped article. The use of multilayer systems is also of interest. Here, the invention
Polymerenzusammensetzung mit einem relativ hohen Gehalt an brom- oder jodhaltigen Zusätzen in dünner Schicht auf einen geformten Gegenstand aus einem Polymer, welches röntgentransparent ist, aufgebracht. Das Aufbringen kann zugleich oder unmittelbar danach mit der Formgebung des Grundkörpers geschehen, z.B. durch Coextrusion oder Mehrkomponentenspritzguß. Das Aufbringen kann aber auch auf den fertig geformten Grundkcrper geschehen, z.B. durch Lamination mit einem Film oder durch Beschichtung mit einer Lösung. Die Formmassen sind besonders für transparente Kinderspielzeugteile geeignet oder für medizinische Anwendungen. Ganz besonders geeignet sind solche Formteile hierbei für kleine Teile von Kinder- Spielzeug. Beispiele:Polymer composition with a relatively high content of bromine- or iodine-containing additives in a thin layer applied to a molded article made of a polymer which is transparent to X-rays. The application can take place at the same time 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 finished molded 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:
Beispiele 1-4:Examples 1-4:
92,5 Gewichtsteile Polycarbonat mit Bisphenol A (Makrolon 2808® Bayer AG) werden zusammen mit 5-20 Gewichtsteilen Tetrabrombisphenololigocarbonat (TBBOC) der Great Lakes Chemical Corp., Lafayette, IN, USA, bei 280°C mit einem Zweischneckenextruder kompoundiert und anschließend zu Prüfstäben mit unterschiedlicher Dicke verspritzt.92.5 parts by weight of polycarbonate with bisphenol A (Makrolon 2808 ®, Bayer AG) are compounded together with 5-20 parts by weight Tetrabrombisphenololigocarbonat (TBBOC) Great Lakes Chemical Corp., Lafayette, IN, USA, at 280 ° C with a twin-screw extruder and then Test bars sprayed with different thickness.
Figure imgf000013_0001
Figure imgf000013_0001
Bei einer Dicke von 4 mm waren Plättchen mit 5 oder 7.5 Gew.% TBBOC völlig transparent.With a thickness of 4 mm, platelets with 5 or 7.5% by weight TBBOC were completely transparent.
Der Röntgenkontrast dieser Plättchen ist ausgezeichnet. Selbst bei einer Dicke von nur 1 ,2 mm Dicke sind sie klar im Röntgenbild erkennbar. The x-ray contrast of these platelets is excellent. Even with a thickness of only 1.2 mm, they can be clearly recognized in the X-ray image.

Claims

Patentansprtiche Claims
1. Verwendung von jod- und/oder bromhaltigen Polycarbonaten für Formteile mit hohem Röntgenkontrast, dadurch gekennzeichnet, daß sie eine jod- und/oder bromierte Dioleinheit aufweisen und ein Gewichtsmittel des Molekulargewichts Mw 500 bis 100 000, bevorzugt 1 000 bis 40 000 und besonders bevorzugt 1 000 nie 8 000 haben.1. Use of iodine and / or bromine-containing polycarbonates for moldings with high X-ray contrast, characterized in that they have an iodine and / or brominated diol unit and a weight average molecular weight Mw 500 to 100,000, preferably 1,000 to 40,000 and particularly preferably 1,000 never 8,000.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß der Jod- und/oder Bromgehalt im Formteil zwischen 0,2 bis 70 Gew.-%, bevorzugt 1 bis 25 Gew.-%, besonders bevorzugt 2 bis 15 Gew.-% beträgt.2. Use according to claim 1, characterized in that the iodine and / or bromine content in the molded part is between 0.2 to 70% by weight, preferably 1 to 25% by weight, particularly preferably 2 to 15% by weight .
3. Verwendung nach mindestens einem der vorgenannten Ansprüche, dadurch gekennzeichnet, daß in den Formteilen zusätzlich mindestens ein trans- parenter Thermoplast, bevorzugt ein nichthalogeniertes Polycarbonat oder3. Use according to at least one of the preceding claims, characterized in that in the molded parts additionally at least one transparent thermoplastic, preferably a non-halogenated polycarbonate or
Copolycarbonat in Mengen von 70 bis 99 Gew.-%, bevorzugt 80 bis 98 Gew.-%, besonders bevorzugt 90 bis 98 Gew.-% bezogen auf das Formteil enthalten ist.Copolycarbonate is present in amounts of 70 to 99% by weight, preferably 80 to 98% by weight, particularly preferably 90 to 98% by weight, based on the molding.
4. Verwendung nach mindestens einem der vorgenannten Ansprüche, dadurch gekennzeichnet, daß zusätzlich noch mindestens ein weiterer in Poly- und Co- polycarbonaten, üblicherweise vorhandener Zusatzstoff wie z.B. Stabilisatoren besonders Thermostabilisatoren, insbesondere organische Phosphite oder Phosphine, Entformungsmittel, beispielsweise Fettsäureester des Glyce- rins oder Tetramethanolmethan, wobei ungesättigte Fettsäure auch ganz oder teilweise epoxidiert sein können, insbesondere Glycerinmonostearat oder Pentaerytrittetrastearat (PETS), Flammschutzmittel, Antistatika, UV -Absorber, beispielsweise Triazole, Füllmittel, Schaummittel, Farbstoffen, Pigmente, optische Aufheller, Umesterungskatalysatoren und Nukleierungsmittel o.a., bevorzugt in Mengen von jeweils bis zu 5 Gew.-%, bevorzugt 0,01 bis 5 Gew.-% bezogen auf die gesamte Mischung, besonders bevorzugt 0,01 Gew.-% bis 1 Gew.-% bezogen auf die Menge Kunststoff enthalten ist.4. Use according to at least one of the preceding claims, characterized in that additionally at least one further additive usually present in poly- and copolycarbonates, such as, for example, stabilizers, especially thermostabilizers, in particular organic phosphites or phosphines, mold release agents, for example fatty acid esters of glycerol or tetramethanol methane, where unsaturated fatty acid can also be completely or partially epoxidized, in particular glycerol monostearate or pentaerythretetrastearate (PETS), flame retardants, antistatic agents, UV absorbers, for example triazoles, fillers, foaming agents, dyes, pigments, optical brighteners, transesterification catalysts, and preferably nucleating agents in amounts of up to 5% by weight, preferably 0.01 to 5 wt .-% based on the entire mixture, particularly preferably 0.01 wt .-% to 1 wt .-% based on the amount of plastic is included.
5. Verwendung nach mindestens einem der vorgenannten Ansprüche, dadurch gekennzeichnet, daß der Stabilisator ein UV-Stabilisator, bevorzugt aus der5. Use according to at least one of the preceding claims, characterized in that the stabilizer is a UV stabilizer, preferably from the
Triazolreihe, besonders bevorzugt der Benzotriazolreihe istTriazole series, particularly preferred is the benzotriazole series
6. Spielzeug enthaltend jod- und/oder bromierte Polycarbonate, dadurch gekennzeichnet, daß sie eine jod- und/oder bromierte Dioleinheit aufweisen und ein Gewichtsmittel des Molekulargewichts Mw 500 bis 100 000, bevorzugt 1 000 bis 40 000 und besonders bevorzugt 1 000 bis 8 000 haben zur Verbesserung des Röntgenkontrastes.6. Toys containing iodine and / or brominated polycarbonates, characterized in that they have an iodine and / or brominated diol unit and a weight average molecular weight Mw 500 to 100,000, preferably 1,000 to 40,000 and particularly preferably 1,000 to 8th 000 have to improve the x-ray contrast.
7. Medizinische Geräte wie Sonden oder Gelenkteile enthaltend jod- und/oder bromierte Polycarbonate, dadurch gekennzeichnet, daß sie eine jod- und/oder bromierte Dioleinheit aufweisen und ein Gewichtsmittel des Molekulargewichts Mw 500 bis 100 000, bevorzugt 1 000 bis 40 000 und besonders bevorzugt 1 000 bis 8 000 haben zur Verbesserung des Röntgenkontrastes.7. Medical devices such as probes or joint parts containing iodine and / or brominated polycarbonates, characterized in that they have an iodine and / or brominated diol unit and a weight average molecular weight Mw 500 to 100,000, preferably 1,000 to 40,000 and particularly preferably have 1,000 to 8,000 to improve the x-ray contrast.
8. Spielzeug enthaltend jod- und/oder bromierte transparente Thermoplaste, dadurch gekennzeichnet, daß sie mindestens eine jod- und oder bromierte Monomereinheit aufweisen und ein Gewichtsmittel des Molekulargewichts Mw 500 bis 1 000 000, bevorzugt 10 000 bis 40 000 haben zur Verbesserung des Röntgenkontrastes.8. Toys containing iodine and / or brominated transparent thermoplastics, characterized in that they have at least one iodine and or brominated monomer unit and have a weight average molecular weight Mw 500 to 1,000,000, preferably 10,000 to 40,000 to improve the X-ray contrast .
9. Medizinische Geräte wie Sonden oder Gelenkteile enthaltend jod- und/oder bromierte transparente Thermoplaste, dadurch gekennzeichnet, daß sie mindestens eine jod- und/oder bromierte Monomereinheit aufweisen und ein Gewichtsmittel des Molekulargewichts Mw 500 bis 1 000 000, bevorzugt 10 000 bis 40 000 haben zur Verbesserung des Röntgenkontrastes. 9. Medical devices such as probes or joint parts containing iodine and / or brominated transparent thermoplastics, characterized in that they have at least one iodine and / or brominated monomer unit and a weight average molecular weight Mw 500 to 1,000,000, preferably 10,000 to 40 000 have to improve the x-ray contrast.
PCT/EP1999/009556 1998-12-18 1999-12-07 Use of polycarbonates containing iodine and/or bromine for moulded parts with high x-ray contrast and moulded parts produced with same WO2000037562A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP99963402A EP1141129A1 (en) 1998-12-18 1999-12-07 Use of polycarbonates containing iodine and/or bromine for moulded parts with high x-ray contrast and moulded parts produced with same
CA002355142A CA2355142A1 (en) 1998-12-18 1999-12-07 Use of polycarbonates containing iodine and/or bromine for moulded parts with high x-ray contrast and moulded parts produced with same
AU19713/00A AU1971300A (en) 1998-12-18 1999-12-07 Use of polycarbonates containing iodine and/or bromine for moulded parts with high x-ray contrast and moulded parts produced with same
JP2000589625A JP2002533515A (en) 1998-12-18 1999-12-07 Use of polycarbonate containing iodine and / or bromine for molded parts exhibiting high X-ray contrast, and molded parts produced therefrom

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DE19858788 1998-12-18
DE19858788.0 1998-12-18

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JP2005325319A (en) * 2004-04-15 2005-11-24 Teijin Chem Ltd Polycarbonate resin composition
EP1778761B1 (en) * 2004-08-13 2021-09-29 Reva Medical, Inc. Inherently radiopaque bioresorbable polymers for multiple uses
JP5347244B2 (en) * 2006-08-04 2013-11-20 三菱化学株式会社 Method for producing halogen-containing polycarbonate resin
AU2015370426B2 (en) * 2014-12-23 2019-09-12 Rutgers, The State University Of New Jersey Biocompatible iodinated diphenol monomers and polymers
EP3930770A1 (en) 2019-02-28 2022-01-05 Speed Care Mineral GmbH Paste for marking textile fabrics and/or other products incapable of x-ray contrast

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JPH0641416A (en) * 1992-07-24 1994-02-15 Nippon Steel Chem Co Ltd Flame-retardant polycarbonate resin composition and molded object thereof
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JPH0857033A (en) * 1994-08-25 1996-03-05 Terumo Corp X-ray contrasting medical molding
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JPH0641416A (en) * 1992-07-24 1994-02-15 Nippon Steel Chem Co Ltd Flame-retardant polycarbonate resin composition and molded object thereof
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