Medical product consisting of polycarbonate material with high infelicit stability

Abstract

The use of functionalized siloxane polymers for improving the infelride resistance of aromatic polycarbonates is described, in particular relating to medical devices comprising elements intended to be in contact with infelride during the intended use of the medical device.

Description

[0001] The present invention relates to a medical device comprising an element made of a thermoplastic plastic, which is intended to come into contact with Intralipid during the intended use of the medical device.

[0002] Aromatic polycarbonates are an attractive material and are also used in some areas of medical technology. However, depending on the required performance profile, a polycarbonate-based composition suitable for all desired application areas has so far not been determined. However, in the context of the circular economy, it is desirable to be able to use polycarbonates also in products other than the hitherto known products, for example in autoinjectors, injection aids and dialyzers, in order to use as few different materials as possible and thus to be able to recycle them together.

[0003] For medical products such as three-way cocks for enteral or parenteral nutrition, Intralipid tolerance is very important. Intralipid is a soybean oil-based fat emulsion. In artificial nutrition administered intravenously, it serves as a source of fat. It also has other advantageous properties, such as improving the bioavailability of platinum-based anticancer drugs. It also seems to support the treatment of autoimmune diseases by reducing the activity of natural killer cells and also promotes the treatment of recurrent miscarriages.

[0004] A suitable material for such medical products that are intended to come into contact with Intralipid during their intended use is POM (polyoxymethylene). In contrast, polycarbonates have so far not been an attractive material for such applications. The chemical resistance of aromatic polycarbonates per se is limited, and even conventional specialty polycarbonates that are considered chemically resistant are not suitable for the corresponding applications if the material is to come into contact with Intralipid.

[0005] In order to increase the chemical resistance of polycarbonates, the molecular weight is usually increased. However, this is only possible to a certain extent, up to a molecular weight M of approximately 31,000 to 34,000 g / mol determined by GPC calibrated against a bisphenol A polycarbonate standard with dichloromethane as the eluent w . As the molecular weight increases, the melt flowability and thus the processability continuously decrease.

[0006] Therefore, the object of the present invention is to provide a polycarbonate material that is tolerant to Intralipid and that obtains Intralipid tolerance by means other than increasing the molecular weight, for use correspondingly in medical products that are intended to come into direct contact with Intralipid.

[0007] It has surprisingly been found that when aromatic polycarbonate-based compositions contain a functionalized silicone polymer consisting of silicone units, in particular polydimethylsiloxane, they have significantly improved Intralipid tolerance. This positive effect is also clearly visible at relatively low molecular weights of the polycarbonate which would otherwise classify the material as unsuitable for the corresponding medical products, i.e. polycarbonates having a melt volume flow rate MVR of 15 to 35 cm 3 / (10 min) determined at a test temperature of 300 °C and a load of 1.2 kg according to ISO 1133:2012-03. Corresponding embodiments using polycarbonates with a relatively low molecular weight are particularly attractive since very easily processable compositions can be used without the need to improve the flow with further additives which would otherwise be necessary.

[0008] The subject matter of the invention is thus

[0009] a medical device or part of a medical device,

[0010] wherein the medical device or part of the medical device comprises an element consisting of a thermoplastic composition containing the following components:

[0011] A) at least 75 wt% of an aromatic polycarbonate, and

[0012] B) 0.2 wt% to 1.5 wt% of a functionalized silicone polymer consisting only of silicone units as monomer units,

[0013] where the quantitative data are based on the total weight of the thermoplastic composition, and

[0014] wherein the element is intended to come into contact with Intralipid during the intended use of the medical device.

[0015] The subject matter of the invention is also the use of a functionalized silicone polymer consisting only of silicone units as monomer units for improving the Intralipid tolerance of aromatic polycarbonate-based compositions.

[0016] It should be recognized that a "medical device comprising an element consisting of a specific composition" or "a part of a medical device comprising an element consisting of a specific composition" also includes a medical device or a part of a medical device "consisting only" of the specific composition. It should also be recognized that the "element" is in particular a molded part made of a thermoplastic composition, and "consisting of" does not exclude here the attachment of other layers or connecting elements to the element. It is conceivable that an element consisting of a thermoplastic composition comprises, for example, one or more coatings, however, the coatings do not extend over their entire surface. The "element" can also be merely a sub-region of a molded part obtained, for example, by multi-component injection molding, where exactly this element, this sub-region, is in direct contact with Intralipid during the intended use of the medical device. The element can equally be a coating or a co-extruded layer of a molded part made of another thermoplastic material, which is present at least in the region of the molded part where it comes into contact with Intralipid during its intended use.

[0017] For cost-saving reasons and since the thermoplastic composition used according to the invention already has a very high Intralipid tolerance, the molded part made of this thermoplastic composition preferably does not have other layers.

[0018] The Intralipid that is in immediate contact, i.e., direct contact, with the element made of a thermoplastic composition during the intended use of the medical device is preferably of the type intended for parenteral nutrition, preferably of the type containing medium-chain triglycerides, where "medium-chain" preferably means C6 to C 12 . The corresponding Intralipid typically contains a mixture of soybean oil, glycerol, and phospholipids from eggs. Such a typical Intralipid is, for example, a mixture containing amino acids such as alanine, arginine, glycine, histidine, isoleucine, leucine, lysine acetate, methionine, phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine, valine, as well as refined soybean oil, medium-chain triglycerides, refined olive oil, fish oil rich in ω-3 acids, glucose (carbohydrates), nitrogen, acetate (part from the amino acid solution), phosphate (part from the fat emulsion), glycerol, lecithin, α-tocopherol (Ph.Eur.), sodium hydroxide, sodium oleate, acetic acid 99%, hydrochloric acid 10%, water. The Intralipid is preferably the SmofKabiven electrolyte-free emulsion from Fresenius Kabi AG.

[0019] Preferably, the medical device or the part of the medical device is a tube connector, a three-way stopcock, a Luer connector, a manifold, a drip chamber, an IV catheter.

[0020] Component A

[0021] Component A of the composition according to the invention is an aromatic polycarbonate.

[0022] The aromatic polycarbonates in the present invention include not only homopolycarbonates, but also copolycarbonates and / or polyester carbonates; the polycarbonates can be linear or branched in a known manner. Mixtures of polycarbonates can also be used according to the present invention.

[0023] The melt volume flow rate MVR of the aromatic polycarbonate used, measured according to ISO 1133:2012-03 at a test temperature of 300 °C and a load of 1.2 kg, is preferably 6 to 35 cm 3 / (10 min), more preferably 15 cm 3 / (10 min) to 35 cm 3 / (10 min), even more preferably 16 to 30 cm 3 / (10 min), particularly preferably 16 to 20 cm 3 / (10 min), very particularly preferably 18 to 20 cm 3 / (10 min). If the thermoplastic composition used according to the present invention contains a mixture of different aromatic polycarbonates, any preferred range is understood to be data for the overall mixture of aromatic polycarbonates.

[0024] Up to 80 mol%, preferably 20 mol% to 50 mol%, of the carbonate groups in the polycarbonate used according to the present invention can be replaced by aromatic dicarboxylate groups. Such polycarbonates containing the acid groups of carbonic acid incorporated into the molecular chain and the acid groups of aromatic dicarboxylic acids are called aromatic polyester carbonates. In the present invention, they are covered by the encompassing term "thermoplastic aromatic polycarbonate".

[0025] Details of polycarbonate production have been disclosed in many patent documents over the past approximately 40 years. Reference can be made here, for example, to Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, to D. Freitag, U. Grigo, P. R. Müller, H. Nouvertné, BAYER AG, "Polycarbonates", Encyclopedia of Polymer Science and Engineering, Volume 11, 2nd Edition, 1988, pages 648 - 718, and finally to U. Grigo, K. Kirchner and P. R. Müller "Polycarbonate", Becker / Braun, Kunststoff-Handbuch, Volume 3 / 1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag München, Wien 1992, pages 117 to 299.

[0026] Aromatic polycarbonates are produced, for example, by the reaction of dihydroxyaryl compounds with carbonyl halides, preferably phosgene, and / or with aromatic dicarbonyl dihalides, preferably benzene dicarbonyl dihalides, by the interfacial method, where a chain terminator is optionally used and a trifunctional or higher-functional branching agent is optionally used. It is also possible to produce them by melt polycondensation by reacting dihydroxyaryl compounds with, for example, diphenyl carbonate.

[0027] For the production of polyester carbonates, a part of the carbonic acid derivatives is replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, and depending on the carbonate structural units to be replaced by aromatic dicarboxylate structural units in the aromatic polycarbonate.

[0028] Dihydroxyaryl compounds suitable for the production of polycarbonates are those of formula (1)

[0029] HO-Z-OH(1),

[0030] where

[0031] Z is an aromatic group having 6 to 30 carbon atoms and may contain one or more aromatic rings, may be substituted and may contain aliphatic or cycloaliphatic groups or alkylaryl or heteroatoms as bridging elements.

[0032] Preferably, Z in formula (1) is a group of formula (2)

[0033]

[0034] wherein

[0035] R 6 and R 7 are each independently H, C1- to C 18 -alkyl, C1- to C 18 -alkoxy, a halogen such as Cl or Br or, in each case optionally substituted, aryl or aralkyl, preferably H or C1- to C 12 -alkyl, particularly preferably H or C1- to C8-alkyl, very particularly preferably H or methyl, and

[0036] X is a single bond, -SO2-, -CO-, -O-, -S-, C1- to C6-alkylene, C2- to C5-alkylidene or C5- to C6-cycloalkylidene, which may be substituted by C1- to C6-alkyl, preferably methyl or ethyl, or is C6- to C 12 -arylene which may optionally be fused with another heteroatom-containing aromatic ring.

[0037] X is preferably a single bond, C1- to C5-alkylene, C2- to C5-alkylidene, C5- to C6-cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-

[0038] or a group of formula (3)

[0039]

[0040] Examples of dihydroxyaryl compounds are: dihydroxybenzene, dihydroxybiphenyl, bis(hydroxyphenyl)alkane, bis(hydroxyphenyl)cycloalkane, bis(hydroxyphenyl)arene, bis(hydroxyphenyl)ether, bis(hydroxyphenyl)ketone, bis(hydroxyphenyl)sulfide, bis(hydroxyphenyl)sulfone, bis(hydroxyphenyl)sulfoxide, 1,1'-bis(hydroxyphenyl)diisopropylbenzene, and their compounds alkylated on the ring and halogenated on the ring.

[0041] Dihydroxyaryl compounds suitable for the production of polycarbonates include, for example, hydroquinone, resorcinol, dihydroxybiphenyl, bis(hydroxyphenyl)alkane, bis(hydroxyphenyl)cycloalkane, bis(hydroxyphenyl)sulfide, bis(hydroxyphenyl)ether, bis(hydroxyphenyl)ketone, bis(hydroxyphenyl)sulfone, bis(hydroxyphenyl)sulfoxide, α,α'-bis(hydroxyphenyl)diisopropylbenzene, benzopyrrolones derived from isatin or phenolphthalein derivatives, and their compounds alkylated on the ring, arylated on the ring and halogenated on the ring.

[0042] Preferred dihydroxyaryl compounds are 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, dimethyl bisphenol A, 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 and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and dihydroxyaryl compounds (I) to (III).

[0043]

[0044] wherein each R' is a C1- to C4-alkyl, aralkyl or aryl group, preferably a methyl or phenyl group, very particularly preferably a methyl group.

[0045] Particularly preferred dihydroxyaryl compounds are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxybiphenyl and dimethyl bisphenol A, and bisphenols of the formula (I), (II) and (III).

[0046] These and other suitable dihydroxyaryl compounds are described, for example, in US 3 028 635 A, US 2 999 835 A, US 3 148 172 A, US 2 991 273 A, US 3 271 367 A, US 4 982 014 A and US 2 999 846 A, DE 1 570 703 A, DE 2063 050 A, DE 2036 052 A, DE 2 211 956 A and DE 3 832 396 A, FR 1 561 518 A, the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" and JP 62039 / 1986 A, JP 62040 / 1986 A and JP 105550 / 1986 A.

[0047] In the case of homopolycarbonates, only one dihydroxyaryl compound is used; in the case of copolycarbonates, two or more dihydroxyaryl compounds are used.

[0048] Examples of suitable carbonic acid derivatives include phosgene or diphenyl carbonate.

[0049] Suitable chain terminators for the production of polycarbonates include monophenols. Examples of suitable monophenols include phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol and mixtures thereof.

[0050] Preferred chain terminators are straight-chain or branched, preferably unsubstituted C1- to C 30 -alkyl or phenols mono- or polysubstituted by tert-butyl. Particularly preferred chain terminators are phenol, cumylphenol and / or p-tert-butylphenol.

[0051] Based on the number of moles of the dihydroxyaryl compound used in each case, the amount of chain terminator used is preferably 0.1 to 5 mol%. The chain terminator can be added before, during or after the reaction with the carbonic acid derivative.

[0052] Suitable branching agents are trifunctional or higher-functional compounds known in polycarbonate chemistry, especially those having three or more phenolic OH groups.

[0053] Examples of suitable branching agents include 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)phenylmethane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, 2,6-bis(2-hydroxy-5'-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetrakis(4-hydroxyphenyl)methane, tetrakis(4-(4-hydroxyphenylisopropyl)phenoxy)methane and 1,4-bis((4',4"-dihydroxytriphenyl)methyl)benzene and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.

[0054] Based on the number of moles of the dihydroxyaryl compound used in each case, the amount of branching agent used optionally is preferably 0.05 mol% to 2.00 mol%.

[0055] The branching agent can be pre-loaded with the dihydroxyaryl compound and the chain terminator in an alkaline aqueous phase, or added in dissolved form in an organic solvent before phosgenation. In the case of the transesterification process, the branching agent is used together with the dihydroxyaryl compound.

[0056] Particularly preferred polycarbonates are bisphenol A-based homopolycarbonates, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane-based homopolycarbonates, and copolycarbonates based on the two monomers bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane or the two monomers bisphenol A and 4,4'-dihydroxybiphenyl, and homopolycarbonates or copolycarbonates derived from dihydroxyaryl compounds of formula (I), (II), and / or (III), in particular copolycarbonates with bisphenol A.

[0057]

[0058] wherein each R' is a C1- to C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, very particularly preferably methyl. Very particularly preferably, the aromatic polycarbonate comprises a bisphenol A-based homopolycarbonate. Extraordinarily preferably, the aromatic polycarbonate is a bisphenol A-based homopolycarbonate.

[0059] The total proportion of monomer units based on formula (I), (II), (III), 4,4'-dihydroxybiphenyl and / or bisphenol TMC in the copolycarbonate is preferably 0.1 - 88 mol%, particularly preferably 1 - 86 mol%, very particularly preferably 5 - 84 mol%, especially 10 - 82 mol% (based on the total number of moles of the dihydroxyaryl compounds used).

[0060] The relative solution viscosity of the copolycarbonate measured according to ISO 1628-4:1999 is preferably in the range of = 1.15–1.35.

[0061] The dihydroxyaryl compounds used, as well as all other chemicals and auxiliaries added to the synthesis, may be contaminated with impurities originating from their own synthesis, handling and storage. However, it is desirable to operate with raw materials that are as pure as possible.

[0062] Also preferred are copolycarbonates produced using a diphenol of general formula (4a):

[0063]

[0064] wherein

[0065] R 5 is hydrogen or a C1- to C4-alkyl, C1- to C3-alkoxy, preferably hydrogen, methoxy or methyl,

[0066] R 6 、R 7 、R 8 and R 9 are each independently of one another a C1- to C4-alkyl or a C6- to C 12 -aryl, preferably methyl or phenyl,

[0067] Y is a single bond, SO2-, -S-, -CO-, -O-, C1-C6-alkylene, C2-C5-alkylidene, C6-C arylene optionally fused with other heteroatom-containing aromatic rings 12 -arylene, or C5-C6-cycloalkylidene which may be mono- or polysubstituted by C1-C4-alkyl, preferably a single bond, -O-, isopropylidene or C5-C6-cycloalkylidene which may be mono- or polysubstituted by C1-C4-alkyl,

[0068] V is oxygen, C2-C6-alkylene or C3-C6-alkylidene, preferably oxygen or C3-alkylene, p, q and r are each independently 0 or 1,

[0069] When q = 0, W is a single bond, when q = 1 and r = 0, W is oxygen, C2-C6-alkylene or C3-C6-alkylidene, preferably oxygen or C3-alkylene,

[0070] When q = 1 and r = 1, W and V are each independently C2-C6-alkylene or C3-C6-alkylidene, preferably C3-alkylene,

[0071] Z is C1-C6-alkylene, preferably C2-alkylene,

[0072] o is the average number of repeating units from 10 to 500, preferably from 10 to 100, and

[0073] m is the average number of repeating units from 1 to 10, preferably from 1 to 6, more preferably from 1.5 to 5. It is also possible to use diphenols in which two or more siloxane blocks of general formula (4a) are interconnected via terephthalic acid and / or isophthalic acid to form ester groups.

[0074] Particularly preferred are the (poly)siloxanes of formulas (5) and (6)

[0075]

[0076] wherein R1 is hydrogen, C1-C4-alkyl, preferably hydrogen or methyl, particularly preferably hydrogen,

[0077] R2 are each independently aryl or alkyl, preferably methyl,

[0078] X is a single bond, -SO2-, -CO-, -O-, -S-, C1-C6-alkylene, C2-C5-alkylidene or C6-C arylene optionally fused with other heteroatom-containing aromatic rings 12 -arylene,

[0079] X is preferably a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C 12Cycloalkanediyl, -O-, -SO-, -CO-, -S-, -SO2-, X is particularly preferably a single bond, isopropylidene, C5 to C 12 cycloalkanediyl or oxygen, very particularly preferably isopropylidene,

[0080] n is an average number from 10 to 400, preferably from 10 to 100, particularly preferably from 15 to 50, and

[0081] m is an average number from 1 to 10, preferably from 1 to 6, particularly preferably from 1.5 to 5.

[0082] The siloxane block can equally preferably be derived from the following structures

[0083]

[0084] Preferably (Va)

[0085]

[0086]

[0087] wherein a in formulas (IV), (V) and (VI) is an average number from 10 to 400, preferably from 10 to 100, particularly preferably from 15 to 50.

[0088] Equally preferably, at least two identical or different siloxane blocks of the general formula (IV), (V) or (VI) are linked to one another via terephthalic acid and / or isophthalic acid to form ester groups.

[0089] Equally preferably, in formula (4a), p = 0, V is C3-alkylene, r = 1, Z is C2-alkylene, R 8 and R 9 are methyl, q = 1, W is C3-alkylene, m = 1, R 5 is hydrogen or C1- to C4-alkyl, preferably hydrogen or methyl, R 6 and R 7 are each independently of one another C1- to C4-alkyl, preferably methyl, and o is from 10 to 500.

[0090] The copolycarbonate having monomer units of formula (4a), in particular its production, is described in WO 2015 / 052106A2.

[0091] The copolycarbonate having monomer units of formula (IV), in particular its production, is described in WO 2015 / 052106A2.

[0092] Examples of aromatic dicarboxylic acids suitable for the production of polyester carbonates include phthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4-benzophenonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid.

[0093] Among the aromatic dicarboxylic acids, terephthalic acid and / or isophthalic acid are particularly preferably used.

[0094] Derivatives of the dicarboxylic acid are dicarbonyl dihalides and dialkyl dicarboxylates, especially dicarbonyl dichloride and dimethyl dicarboxylate.

[0095] The replacement of the carbonate group by the aromatic dicarboxylate group is substantially stoichiometric and quantitative, and thus the molar ratio of the reactants is also maintained in the final polyester carbonate. The aromatic dicarboxylate groups can be incorporated randomly or in blocks.

[0096] The composition according to the invention contains at least 75% by weight, preferably at least 85% by weight, more preferably at least 90% by weight, particularly preferably at least 95% by weight, and extremely preferably at least 97.5% by weight of aromatic polycarbonate, and thus is based on aromatic polycarbonate.

[0097] Component B

[0098] Component B is a functionalized silicone polymer consisting only of silicone units as monomer units, and its monomer unit group thus consists of silicone units. Component B can be a single silicone polymer or a mixture of two or more silicone polymers. Preferably, the silicone polymer - if it is a mixture of different silicone polymers - has a weight-average molecular weight M determined by GPC calibrated against polystyrene standards in tetrahydrofuran (THF) of >500000 g / mol, more preferably >750000 g / mol, particularly preferably >1000000 g / mol w , and thus is a UHMW (ultra-high molecular weight) silicone polymer.

[0099] In this case, "consisting only of" means that these polymers are not based on other monomer units. They are linear or branched polymers or copolymers, in which the organic groups of the siloxane units are preferably independently selected from methyl or phenyl groups from each other. Suitable siloxane polymers for component B include polydimethylsiloxane homopolymers and copolymers composed of dimethylsiloxane and methylphenylsiloxane units, copolymers composed of dimethylsiloxane and diphenylsiloxane units, copolymers composed of diphenylsiloxane units and methylphenylsiloxane units, and homopolymers of methylphenylsiloxane units. Mixtures of two or more of these polymers or copolymers can also be used in the blends of the above-mentioned higher and / or lower molecular weight siloxane polymers. Particularly preferably, component B is at least one polymer selected from polydimethylsiloxane homopolymers and copolymers composed of dimethylsiloxane and methylphenylsiloxane units, copolymers composed of dimethylsiloxane and diphenylsiloxane units, copolymers composed of diphenylsiloxane units and methylphenylsiloxane units, homopolymers of methylphenylsiloxane units, or mixtures of the above polymers.

[0100] The siloxane polymer of component B is a functionalized siloxane polymer. "Functionalized" as used herein means that the siloxane polymer as a whole contains one or more reactive groups. According to the present invention, "reactive group" is understood herein to mean a group that fundamentally determines the physical properties and reaction behavior of the compound. Such reactive groups include, for example, groups containing hydroxyl, methyl, fluorine, carboxyl, nitrogen-containing groups such as amine groups or alkenyl groups. Particularly preferably, the siloxane polymer contains hydroxyl groups. "As a whole" herein means that not every siloxane polymer must contain groups corresponding to the mixture, but there must be siloxane polymers containing reactive groups. Preferably, the overall siloxane polymer according to component B contains representatives of one or more reactive groups, especially at least hydroxyl groups.

[0101] The reactive groups are arranged at the molecular ends and / or along the polymer chain, and are preferably arranged at the chain ends. Very particularly preferably, hydroxyl groups are present as reactive groups arranged at the chain ends, particularly preferably in the form of diorganohydroxysilyloxy groups, such as dimethylhydroxysilyloxy groups, diphenylhydroxysilyloxy groups, and / or methylphenylhydroxysilyloxy groups.

[0102] If the reactive groups are only arranged along the polymer chain, the end groups of the siloxane polymer are not reactive and are generally of the diorganosilyloxy or triorganosilyloxy type, such as dimethylethenylsilyloxy or trimethylsilyloxy.

[0103] Particularly preferably, component B contains hydroxyl-terminated polydimethylsiloxane, and component B is very particularly preferably hydroxyl-terminated polydimethylsiloxane.

[0104] The siloxane polymer of component B is particularly preferably a functionalized linear polydimethylsiloxane containing at most 50 mol% of methyl groups, and the siloxane polymer is preferably here a polydimethylsiloxane homopolymer having dimethylhydroxysilyloxy end groups.

[0105] Component C

[0106] The thermoplastic composition used according to the invention may also contain one or more additives, herein referred to as component C. "May" means that it is not necessary to contain additional additives, and the amount of component C can thus also be 0% by weight. The amount of additional additives is preferably at most 15% by weight, more preferably at most 10% by weight, particularly preferably at most 5% by weight, and very particularly preferably at most 1.0% by weight.

[0107] Such additional additives as are customarily added to polycarbonates particularly include heat stabilizers, radiation stabilizers, flame retardants, antioxidants, release agents, anti-dripping agents such as polytetrafluoroethylene (Teflon) or PTFE encapsulated in SAN (e.g., Blendex 449), UV absorbers, IR absorbers, impact modifiers, fluorescent brighteners, fillers (such as talc, silicates or quartz), light scattering agents, hydrolysis stabilizers, transesterification stabilizers, compatibilizers, organic colorants, organic pigments, inorganic pigments and / or additives for laser marking, in particular in amounts customary for polycarbonate-based compositions. Such additives are described, for example, in EP-A 0839623, WO-A 96 / 15102, EP-A 0 500 496 or "Plastics Additives Handbook", Hans Zweifel, 5th edition 2000, Hanser Verlag, München. These additives can be added individually or in admixture.

[0108] It is to be recognized that only additives whose nature and amount do not have a significant adverse effect on the effect of improving Intralipid tolerance according to the invention are permitted.

[0109] Preferably, the thermoplastic composition contains at least one or more release agents, one or more heat stabilizers and / or antioxidants and optionally a colorant as additional additives.

[0110] Suitable release agents particularly include those based on fatty acid esters, more preferably based on stearic acid esters, and particularly preferably those based on pentaerythritol. Pentaerythritol tetrastearate (PETS) and / or glycerol monostearate (GMS) are particularly preferably used. When using one or more release agents, the amount thereof is preferably at most 1.0% by weight (including the endpoints), more preferably 0.01% to 0.7% by weight, particularly preferably 0.02% to 0.60% by weight, in each case based on the total composition.

[0111] If a heat stabilizer is used, the amount thereof is preferably at most 0.20% by weight, more preferably from 0.01% to 0.10% by weight, still more preferably from 0.01% to 0.05% by weight, and particularly preferably from 0.015% to 0.040% by weight, based on the total composition.

[0112] Suitable heat stabilizers are in particular phosphorus-based stabilizers selected from phosphates, phosphites, phosphonites, phosphines and mixtures thereof. Examples include triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, tris(octadecyl) phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite ( 168), diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite ( S-9228), bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecoxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, bis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin, 2,2',2"-nitrilo[triethyl tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl-2-(2,4,6-tris-tert-butylphenoxy)-1,3,2-dioxaphospholane, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, triphenylphosphine (TPP), trialkylphenylphosphine, bis(diphenylphosphino)ethane or trinaphthylphosphine. They may be used alone or in admixture, for example B900( 168 and a 4:1 ratio mixture of 1076) or S-9228 with B900 or 1076. Particular preference is given to using triphenylphosphine (TPP), 168 or tris(nonylphenyl) phosphite or a mixture thereof.

[0113] Phenolic antioxidants such as alkylated monophenols, alkylated thioalkylphenols, hydroquinones and alkylated hydroquinones can also be used. It is particularly preferred to use 1010 (pentaerythritol 3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate; CAS: 6683-19-8) and Irganox (octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), preferably in an amount of 0.05% to 0.5% by weight.

[0114] Sulfonic esters or alkyl phosphates such as monohexyl phosphate, dihexyl phosphate and / or trihexyl phosphate, triisooctyl phosphate and / or trinonyl phosphate can also be added as transesterification inhibitors. If a transesterification stabilizer is present, the alkyl phosphate used is preferably triisooctyl phosphate (tri-2-ethylhexyl phosphate). Mixtures of various monoalkyl phosphates, dialkyl phosphates and trialkyl phosphates can also be used. Triisooctyl phosphate is preferably used in an amount of 0.003% to 0.05% by weight, more preferably 0.005% to 0.04% by weight, and particularly preferably 0.01% to 0.03% by weight based on the total composition.

[0115] The composition for the medical device according to the present invention is generally produced as follows:

[0116] In order to incorporate the additives, the aromatic polycarbonate of component A on which the thermoplastic composition is based is optionally used as a thermoplastic mixture, preferably in the form of powder, pellets or a mixture of powder and pellets.

[0117] Different from the additives, the composition used according to the present invention may optionally contain one or more blending partners in addition to the additives. Suitable blending partners include ABS, polyesters such as PBT or PET, PMMA or mixtures thereof.

[0118] By common incorporation methods, component B and additional components, namely especially additional additives, are converted into the corresponding composition by combining, mixing and homogenizing the components, wherein homogenization is particularly preferably carried out in the melt by applying shear force. Optionally, a powder premix is used to carry out the combination and mixing before melt homogenization.

[0119] A pellet premix of the individual components, or a premix of pellets and powder, can also be used.

[0120] A premix made from a solution of the mixture components in a suitable solvent can also be used, wherein homogenization is optionally carried out in the solution and the solvent is subsequently removed.

[0121] The components of the composition can in particular be introduced into the thermoplastic polymer, especially into an aromatic polycarbonate, optionally into an aromatic polycarbonate having a blending partner, by known methods or as masterbatches. Preferably, at least component B is introduced as a masterbatch in an aromatic polycarbonate, more preferably in a homopolycarbonate based on bisphenol A, into the thermoplastic composition.

[0122] For the individual or combined introduction of the components, preference is given to using masterbatches based on aromatic polycarbonates in the present case. This also applies in particular to component B, the silicone polymer. When introduced by means of a masterbatch, the component preferably contains 0.5% to 60% by weight, more preferably 20% to 55% by weight, particularly preferably 45% to 52% by weight of the silicone polymer, based on the total weight of the masterbatch. By introduction as a masterbatch, a uniform distribution of the additives can generally be achieved.

[0123] The composition used according to the invention can be combined, mixed, homogenized and subsequently extruded in conventional apparatuses such as screw extruders (e.g. ZSK twin-screw extruders), kneaders or Brabender or Banbury mills. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix the individual components and then add them individually and / or also mixed to the remaining starting materials.

[0124] The combination and mixing of the premix in the melt can also be carried out in the plastifying unit of an injection molding machine. Here, the melt is directly converted into a molded article in a subsequent step.

[0125] The composition can be processed in a conventional manner in conventional machines, for example in an extruder or an injection molding machine, into any desired molded article.

[0126] Preference is given according to the invention

[0127] to medical devices or parts of medical devices,

[0128] wherein the medical device or part of the medical device comprises an element consisting of a thermoplastic composition containing the following components:

[0129] A) at least 90% by weight of an aromatic polycarbonate,

[0130] B) 0.2% to 1.5% by weight of a functionalized silicone polymer consisting only of silicone units as monomer units, wherein the functionalized silicone polymer has a weight-average molecular weight M determined by GPC calibrated against polystyrene standards in tetrahydrofuran (THF) of > 500000 g / mol w and contains dimethylsiloxane units and hydroxyl groups,

[0131] where the quantitative data are based on the total weight of the thermoplastic composition, and

[0132] wherein the element is intended to come into contact with Intralipid during the intended use of the medical device.

[0133] Further preferably according to the present invention

[0134] a medical device or a part of a medical device,

[0135] wherein the medical device or the part of the medical device comprises an element made of a thermoplastic composition, the thermoplastic composition consisting of the following components:

[0136] A) at least 90% by weight of an aromatic polycarbonate, and

[0137] B) 0.2% to 1.5% by weight of a functionalized silicone polymer consisting only of siloxane units as monomer units,

[0138] wherein the functionalized silicone polymer preferably has a weight-average molecular weight M determined by GPC calibrated against polystyrene standards in tetrahydrofuran (THF) of > 500000 g / mol w and contains dimethylsiloxane units and hydroxyl groups,

[0139] C) optionally one or more additional additives selected from heat stabilizers, flame retardants, antioxidants, release agents, anti-dripping agents, UV absorbers, IR absorbers, impact modifiers, optical brighteners, fillers, light scattering agents, hydrolysis stabilizers, transesterification stabilizers, compatibilizers, organic colorants, organic pigments, inorganic pigments and / or additives for laser marking,

[0140] where the dosage data is based on the total weight of the thermoplastic composition, and

[0141] wherein the element is intended to come into contact with Intralipid during the intended use of the medical device.

[0142] Particularly preferably according to the present invention

[0143] a medical device or a part of a medical device,

[0144] wherein the medical device or the part of the medical device comprises an element made of a thermoplastic composition, the thermoplastic composition consisting of the following components:

[0145] A) at least 90% by weight of an aromatic polycarbonate, and

[0146] B) 0.2% to 1.5% by weight of a functionalized silicone polymer consisting only of siloxane units as monomer units,

[0147] Wherein the functionalized silicone polymer preferably has a weight-average molecular weight M determined by GPC calibrated against polystyrene standards in tetrahydrofuran (THF) of >500,000 g / mol w and contains dimethylsiloxane units and hydroxyl groups,

[0148] C) Optionally one or more additional additives selected from mold release agents, heat stabilizers, antioxidants, colorants, pigments,

[0149] where the dosage data is based on the total weight of the thermoplastic composition, and

[0150] wherein the component is intended to come into contact with Intralipid during the intended use of the medical device.

[0151] Highly preferably according to the present invention is

[0152] a medical device or part of a medical device,

[0153] wherein the medical device or part of the medical device comprises a component consisting of a thermoplastic composition, the thermoplastic composition consisting of the following components:

[0154] A) At least 90% by weight of an aromatic polycarbonate, wherein the aromatic polycarbonate preferably contains bisphenol A-homopolycarbonate, particularly preferably bisphenol A-homopolycarbonate, and

[0155] B) 0.2% to 1.5% by weight, particularly 0.5% to 1% by weight of a functionalized silicone polymer consisting only of silicone units as monomer units,

[0156] Wherein the functionalized silicone polymer preferably has a weight-average molecular weight M determined by GPC calibrated against polystyrene standards in tetrahydrofuran (THF) of >500,000 g / mol w and contains dimethylsiloxane units and hydroxyl groups,

[0157] C) Optionally one or more additional additives selected from mold release agents, heat stabilizers, antioxidants, colorants, pigments,

[0158] where the dosage data is based on the total weight of the thermoplastic composition, and

[0159] wherein the component is intended to come into contact with Intralipid during the intended use of the medical device.

[0160] Highly preferably is

[0161] a medical device or part of a medical device,

[0162] Wherein the medical device or part of the medical device comprises an element composed of a thermoplastic composition, and the thermoplastic composition is composed of the following components:

[0163] A) At least 90% by weight of an aromatic polycarbonate, wherein the aromatic polycarbonate is a bisphenol A-homopolycarbonate and has a melt volume flow rate MVR of 16 to 20 cm 3 / (10 min) measured at a test temperature of 300 °C and a load of 1.2 kg according to ISO 1133:2012-03, and

[0164] B) 0.2% to 1.5% by weight, in particular 0.5% to 1% by weight, of a functionalized silicone polymer consisting only of siloxane units as monomer units,

[0165] wherein the functionalized silicone polymer has a weight average molecular weight M determined by GPC calibrated against polystyrene standards in tetrahydrofuran (THF) of >500000 g / mol w and contains dimethylsiloxane units and hydroxyl groups,

[0166] C) Optionally one or more additional additives selected from release agents, heat stabilizers, antioxidants, colorants, pigments,

[0167] wherein the dosage data is based on the total weight of the thermoplastic composition, and

[0168] wherein the element is intended to come into contact with Intralipid during the intended use of the medical device.

[0169] In the above preferred, more preferred and other embodiments, the functionalized silicone polymer is particularly preferably at least hydroxyl-functionalized, and very particularly preferably a dimethylsiloxane homopolymer functionalized only with hydroxyl groups.

[0170] The above-described embodiments which are described as preferred, more preferred and other embodiments for the medical device or part of the medical device according to the invention - where applicable - also apply to the use according to the invention of component B, i.e. for improving the Intralipid tolerance of an aromatic polycarbonate-based composition preferably comprising at least 75% by weight of an aromatic polycarbonate, more preferably at least 90% by weight of an aromatic polycarbonate.

[0171] The following examples are intended to illustrate the invention but not to limit the invention. Examples

[0172] 1. Components

[0173] Component A-1: Having 19 cm 3Bisphenol A-based linear homopolycarbonate with a melt volume flow rate (MVR) of / (10 min) (test temperature: 300 °C, test load: 1.2 kg, according to ISO 1133:2012-03)

[0174] Component A-2: having 6 cm 3 Bisphenol A-based linear homopolycarbonate with a melt volume flow rate (MVR) of / (10 min) (test temperature: 300 °C, test load: 1.2 kg, according to ISO 1133:2012-03)

[0175] Component A-3: having 5 cm 3 Bisphenol A-based linear homopolycarbonate with a melt volume flow rate (MVR) of / (10 min) (test temperature: 300 °C, test load: 1.2 kg, according to ISO 1133:2012-03)

[0176] Component B*-1: A pelletized composition containing 50 wt% of a hydroxy-terminated functionalized UHMW silicone polymer (polydimethylsiloxane) dispersed in an aromatic polycarbonate. Component B, the functionalized silicone polymer, is thus included in Examples 2 and 3 in amounts of 0.5 wt% and 1 wt%, respectively, based on the total composition.

[0177] Component C-1: A mold release agent, pentaerythritol tetrastearate from Emery Oleochemicals

[0178] Component C-2: Multranol 3600DHP (α,ω-bis(tetrahydro-2H-pyran-2-yl)poly[oxy(methyl-1,2-ethanediyl)], polyether polyol. M n = 2000 g / mol) and an additive set of two anthraquinone colorants

[0179] Intralipid used: SmofKabiven electrolyte-free emulsion from Fresenius Kabi AG. Active ingredients: 1000 ml contains: refined soybean oil (Ph.Eur.) 11.4 g, medium-chain triglycerides 11.4 g, refined olive oil 9.5 g, fish oil rich in ω-3 acids 5.7 g, glucose (as glucose monohydrate (Ph.Eur.)) 127 g, alanine 7.1 g, arginine 6.1 g, glycine 5.6 g, histidine 1.5 g, isoleucine 2.5 g, leucine 3.8 g, lysine acetate 3.4 g, methionine 2.2 g, phenylalanine 2.6 g, proline 5.7 g, serine 3.3 g, taurine 0.5 g, threonine 2.2 g, tryptophan 1.0 g, tyrosine 0.20 g, valine 3.1 g, corresponding to 51 g of amino acids, 8 g of nitrogen, 127 g of carbohydrates (anhydrous glucose), 38 g of lipids, 74.5 mmol of acetate (from the amino acid solution), 2.8 mmol of phosphate (from the fat emulsion). Total energy is approximately 1100 kcal (4.6 MJ), non-protein energy is approximately 900 kcal (3.8 MJ). Weight osmotic concentration Approximately 1600 mosm / kg water, volume osmotic concentration Approximately 1300 mosm / l, pH value (after mixing) is approximately 5.6. Other ingredients: glycerol, lecithin, α-tocopherol (Ph.Eur.), sodium hydroxide, sodium oleate, acetic acid 99%, hydrochloric acid 10%, water for injection. For intravenous infusion to provide parenteral nutrition.

[0180] Implementation

[0181] The polycarbonate composition described in the following examples is produced by compounding on a Berstorff ZE 25 extruder at a throughput of 10 kg / h. The melt temperature is 275 °C.

[0182] Environmental stress cracking (ESC) is used as a measure of chemical resistance. ESC is determined by the bent strip method at room temperature. A specimen with dimensions of 80 mm x 10 mm x 4 mm injection-molded at a melt temperature of 280 °C and a mold temperature of 80 °C is subjected to an outer edge fiber stress (Rfd.) of 1.4% using a bending fixture. Immediately after clamping the specimen, it is brought into contact with the test medium (SmofKabiven electrolyte-free emulsion). For this purpose, the test medium is applied dropwise to a fabric-like paper and then placed on the specimen (centered in the tensile zone of the specimen). The clamped specimen is stored with the test medium for one or four days. Then the specimen is removed from the bending fixture and visually inspected to determine the surface condition of the specimen according to the criteria described in Table 1:

[0183] Table 1: Criteria for evaluating chemical resistance

[0184]

[0185] Table 2: Tests Conducted and Results

[0186]

[0187]

[0188] As is evident from Table 1, only the compositions of the present invention in Examples 2 and 3 achieved the basic objective, while the composition of Comparative Example 1, which is a conventional polycarbonate having a generally high molecular weight and high chemical resistance, did not. That is, only the compositions of the present invention in Examples 2 and 3 exhibited good Intralipid tolerance even after long-term exposure, and thus did not show any changes on their surfaces.

Claims

1. A medical device or part of a medical device, wherein the medical device or part of the medical device comprises an element made of a thermoplastic composition containing the following components: A) at least 75% by weight of an aromatic polycarbonate, and B) 0.2 to 1.5% by weight of a functionalized silicone polymer consisting only of silicone units as monomer units, wherein the dosage data is based on the total weight of the thermoplastic composition, and wherein the element is intended to come into contact with Intralipid during the intended use of the medical device.

2. The medical device or part of the medical device according to claim 1, wherein the medical device is intended for parenteral nutrition.

3. The medical device or part of the medical device according to claim 1 or 2, wherein the medical device or part of the medical device is a tube connector, a three-way stopcock, a manifold, a drip chamber, a Luer connector, an IV catheter.

4. The medical device or part of the medical device according to any one of the preceding claims, wherein the aromatic polycarbonate is a homopolycarbonate based on bisphenol A.

5. A medical device or part of a medical device according to any one of the preceding claims, wherein the aromatic polycarbonate has a melt volume flow rate MVR of 15 to 35 cm3 / (10 min) measured according to ISO 1133:2012-03 at a test temperature of 300 °C and a load of 1.2 kg. 3 / (10 min).

6. The medical device or part of the medical device according to any one of the preceding claims, wherein the thermoplastic composition consists of the following components: A) at least 90% by weight of an aromatic polycarbonate, B) 0.2% to 1.5% by weight of a functionalized silicone polymer consisting only of silicone units as monomer units, and C) optionally one or more additional additives selected from heat stabilizers, flame retardants, antioxidants, radiation stabilizers, release agents, anti-dripping agents, ultraviolet absorbers, infrared absorbers, impact modifiers, fluorescent brighteners, fillers, light scattering agents, hydrolysis stabilizers, transesterification stabilizers, compatibilizers, organic colorants, organic pigments, inorganic pigments and / or additives for laser marking, wherein the dosage data is based on the total weight of the thermoplastic composition.

7. A medical device or part of a medical device, wherein the thermoplastic composition contains at least 95% by weight of an aromatic polycarbonate.

8. The medical device or part of the medical device according to any one of the preceding claims, wherein the thermoplastic composition consists of the following components: A) at least 95% by weight of an aromatic polycarbonate, B) 0.2% to 1.5% by weight of a functionalized silicone polymer consisting only of silicone units as monomer units, and C) optionally one or more additional additives selected from release agents, heat stabilizers, antioxidants, colorants, pigments.

9. The medical device or part of the medical device according to any one of the preceding claims, wherein 0.5% to 1% by weight of component B is used.

10. The medical device or part of a medical device according to any one of the preceding claims, wherein the aromatic polycarbonate has a melt volume flow rate of 16 to 20 cm 3 / (10 min) measured according to ISO 1133:2012-03 at a test temperature of 300 °C and a load of 1.2 kg. 3 / (10 min).

11. A medical device or part of a medical device according to any one of the preceding claims, wherein the functionalized siloxane polymer has a weight average molecular weight M determined by GPC calibrated against polystyrene standards in tetrahydrofuran (THF) of > 500,000 g / mol w .

12. The medical device or part of the medical device according to any one of the preceding claims, wherein the functionalized silicone polymer contains dimethylsiloxane units.

13. The medical device or part of the medical device according to any one of the preceding claims, wherein the functionalized silicone polymer contains hydroxyl groups.

14. Use of a functionalized silicone polymer for improving the Intralipid tolerance of an aromatic polycarbonate-based composition.

15. The use according to claim 14, wherein the functionalized siloxane polymer has a weight average molecular weight M determined by GPC calibrated against polystyrene standards in tetrahydrofuran (THF) of > 500,000 g / mol w and comprises dimethylsiloxane units and hydroxyl groups.

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