WO1998004624A1 - Gehäuse und verkleidungen für medizinische geräte - Google Patents
Gehäuse und verkleidungen für medizinische geräte Download PDFInfo
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- WO1998004624A1 WO1998004624A1 PCT/EP1997/004033 EP9704033W WO9804624A1 WO 1998004624 A1 WO1998004624 A1 WO 1998004624A1 EP 9704033 W EP9704033 W EP 9704033W WO 9804624 A1 WO9804624 A1 WO 9804624A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- the invention relates to housings and linings for medical devices.
- the invention relates to housings and linings for medical devices which are stable and at the same time resistant to chemicals and free from yellowing.
- ABS acrylonitrile / butadiene / styrene
- ABS has the disadvantage of not always being sufficiently resistant to yellowing, with yellowing sometimes also occurring indoors when exposed to light for a long time.
- ABS is not always sufficiently resistant to cleaning agents, disinfectants and chemicals.
- the object of the present invention is to provide housings and claddings for medical devices which are stable and are resistant to cleaning agents and disinfectants and other chemicals.
- Another object of the invention is to provide housings and linings for medical devices which avoid the disadvantages of the housings and linings of the prior art.
- thermoplastic molding composition other than ABS containing, based on the Sum of the amounts of components A and B, and if appropriate C and / or D, which gives a total of 100% by weight,
- A 1-99% by weight of a particulate emulsion polymer with a glass transition temperature below 0 ° C. and an average particle size of 50-1000 nm as component A,
- b 1-99% by weight of at least one amorphous or partially crystalline polymer as component B,
- component D 0 - 50% by weight of fibrous or particulate fillers or mixtures thereof as component D.
- the described housings and claddings for medical devices are stable and resistant to cleaning agents and disinfectants, as well as chemicals. They also have very good dimensional stability and are scratch-resistant.
- thermoplastic molding compositions used according to the invention for producing the housings and cladding according to the invention are known per se.
- DE-A-12 60 135, DE-C-19 11 882, DE-A-28 26 925, DE-A-31 49 358, DE-A-32 27 555 and DE-A-40 11 162 Molding compositions which can be used according to the invention are described.
- the molding compositions other than ABS used to manufacture the housings and cladding according to the invention contain components A and B and, if appropriate, C and / or D, as defined below. They contain, based on the sum of the amounts of components A and B, and possibly C and / or D, which gives a total of 100% by weight,
- b 1-99% by weight, preferably 40-85% by weight, in particular 50-75% by weight, of at least one amorphous or partially crystalline polymer as component B,
- d 0 - 50% by weight of fibrous or particulate fillers or their mixtures as component D.
- Component A is a particulate emulsion polymer with a glass transition temperature below 0 ° C and an average particle size of 50-1000 nm.
- Component A is preferably a graft copolymer
- a2 1-99% by weight, preferably 20-45% by weight, in particular 35-45% by weight, of a graft A2 composed of the monomers, based on A2,
- a22 up to 60% by weight, preferably 15-35% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile, in particular acrylonitrile as component A22.
- the graft pad A2 consists of at least one graft shell, the graft copolymer A overall having an average particle size of 50-1000 nm.
- component AI consists of the monomers
- al l 80-99.99% by weight, preferably 95-99.9% by weight, of a C 1-6 alkyl ester of acrylic acid, preferably n-butyl acrylate and / or ethylhexyl acrylate as component All,
- al2 0.01-20% by weight, preferably 0.1-5.0% by weight, of at least one polyfunctional crosslinking monomer, preferably diallyl phthalate and / or DCPA as component A12.
- the average particle size of component A is 50-800 nm, preferably 50-600 nm.
- the particle size distribution of component A is bimodal, 60-90% by weight having an average particle size of 50-200 nm and 10-40% by weight having an average particle size of 50-400 nm on the total weight of component A.
- the sizes determined from the integral mass distribution are given as the average particle size or particle size distribution.
- the mean particle sizes according to the invention are in all cases the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 25Q (1972), pages 782-796. the.
- the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
- the average particle diameter which is also referred to as the d 50 value of the integral mass distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the d 50 value. Likewise, 50% by weight of the particles then have a larger diameter than the d 50 value.
- the d 10 and d Q values resulting from the integral mass distribution are used.
- the d 10 or d ⁇ value of the integral mass distribution is defined in accordance with the d 50 value with the difference that they are based on 10 or 90% by weight of the particles. The quotient
- Emulsion polymers A which can be used according to the invention as component A preferably have Q values less than 0.5, in particular less than 0.35.
- the glass transition temperature of the emulsion polymer A and also of the other components used according to the invention is determined by means of DSC (differential scanning calorimetry) according to ASTM 3418 (mid point temperature).
- customary rubbers can be used as emulsion polymer A, such as epichlorohydrate according to one embodiment of the invention.
- rubbers ethylene-vinyl acetate rubbers, polyethylene chlorosulfone rubbers, silicone rubbers, polyether rubbers, hydrogenated diene rubbers, polyalkename rubbers, acrylate rubbers, ethylene-propylene rubbers, ethylene-propylene-diene rubbers and fluorinated rubbers, butyl rubbers.
- Acrylate rubber, ethylene-propylene (EP) rubber, ethylene-propylene-diene (EPDM) rubber, in particular acrylate rubber are preferably used.
- the diene basic building block content in the emulsion polymer A is kept so low that as few unreacted double bonds remain in the polymer. According to one embodiment, there are no basic diene building blocks in the emulsion polymer A.
- the acrylate rubbers are preferably alkyl acrylate rubbers composed of one or more C 1 -g alkyl acrylates, preferably C. g - alkyl acrylates, butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n-butyl and 2-ethylhexyl acrylate, preferably being used at least in part.
- These alkyl acrylate rubbers can contain up to 30% by weight of hard polymer-forming monomers, such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate or vinyl ether, in copolymerized form.
- the acrylate rubbers further contain 0.01-20% by weight, preferably 0.1-5% by weight, of cross-linking polyfunctional monomers (cross-linking monomers).
- cross-linking monomers are monomers which enabled 2 or more of them to copolymerize Contain double bonds, which are preferably not conjugated in the 1,3 positions.
- Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, triallyl phosphate, allyl acrylate.
- Dicyclopentadienyl acrylate (DCPA) has proven to be a particularly favorable crosslinking monomer (cf. DE-C-12 60 135).
- Suitable silicone rubbers can be, for example, crosslinked silicone rubbers composed of units of the general formulas R 2 SiO, RSiO 3/2 , R 3 SiO 1/2 and SiO 2 4 , the radical R representing a monovalent radical.
- the amount of the individual siloxane units is such that for 100 units of the formula R 2 SiO 0 to 10 mol units of the formula RSiC ⁇ , 0 to 1.5 mol units R 3 SiO 1 2 and 0 to 3 mol units SiO 2 are present.
- R can be either a monovalent saturated hydrocarbon radical having 1 to 18 carbon atoms, the phenyl radical or the alkoxy radical or a radical which is easily attackable by free radicals, such as the vinyl or mercaptopropyl radical. It is preferred that at least 80% of all residues R are methyl residues; combinations of methyl and ethyl or phenyl radicals are particularly preferred.
- Preferred silicone rubbers contain built-in units of groups which can be attacked by free radicals, in particular vinyl, allyl, halogen, mercapto groups, preferably in amounts of 2-10 mol%, based on all radicals R. They can be prepared, for example, as in EP-A-0 260 558.
- an emulsion polymer A made from uncrosslinked polymer As monomers for production these polymers can serve all of the monomers mentioned above.
- Preferred uncrosslinked emulsion polymers A are, for example, homopolymers and copolymers of acrylic esters, in particular n-butyl and ethylhexyl acrylate, and homopolymers and copolymers of ethylene, propylene, butylene, isobutylene, and also poly (organosiloxanes), all with provided that they can be linear or branched.
- the emulsion polymer A can also be a multi-stage polymer (so-called “core / shell structure", “core-shell morphology”).
- core / shell structure a multi-stage polymer
- core-shell morphology a rubber-elastic core (T g ⁇ 0 ° C) can be encased by a “hard” shell (polymers with T g > 0 ° C) or vice versa.
- component A is a graft copolymer.
- the graft copolymers A of the molding compositions according to the invention have an average particle size d 50 of 50-1000 nm, preferably 50-600 nm and particularly preferably 50-400 nm. These particle sizes can be achieved if A1 of this component A is used as the graft base Particle sizes of 50-350 nm, preferably 50-300 nm and particularly preferably 50-250 nm are used.
- the graft copolymer A is generally one or more stages, ie a polymer composed of a core and one or more shells.
- the polymer consists of a basic stage (graft core) Al and one or - preferably - several stages A2 grafted thereon, the so-called graft stages or graft shells.
- One or more graft shells can be applied to the rubber particles by simple grafting or multiple step-wise grafting, each graft sheath having a different composition.
- polyfunctional crosslinking or reactive group-containing monomers can also be grafted on (see, for example, EP-A-0 230 282, DE-A-36 01 419, EP-A-0 269 861).
- component A consists of a multi-stage graft copolymer, the graft stages being generally made from resin-forming monomers and having a glass transition temperature T g above 30 ° C., preferably above 50 ° C.
- the multi-stage structure serves, inter alia, to achieve (partial) compatibility of the rubber particles A with the thermoplastic B.
- Graft copolymers A are prepared, for example, by grafting at least one of the monomers A2 listed below onto at least one of the graft bases or graft core materials AI listed above.
- Suitable graft bases AI for the molding compositions according to the invention are all polymers which are described above under emulsion polymers A.
- the graft base AI is composed of 15-99% by weight of acrylate rubber, 0.1-5% by weight of crosslinking agent and 0-49.9% by weight of one of the further monomers or rubbers indicated.
- Suitable monomers for forming the graft A2 can be selected, for example, from the monomers listed below and their mixtures: Vinylaromatic monomers, such as styrene and its substituted derivatives, such as ⁇ -methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, p-tert-butylstyrene, o- and p-divinylbenzene and p-methyl- ⁇ -methylstyrene or C j - Cg-Alky met acrylate such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate; styrene, ⁇ -methylstyrene, methyl methacrylate, in particular styrene and / or ⁇ -methylstyrene, and ethylenically
- (co) monomers styrene, vinyl, acrylic or methacrylic compounds (eg, styrene optionally substituted with C j ⁇ - alkyl radicals, halogen atoms, halomethyl groups;.
- component A comprises 50-90% by weight of the above-described graft base AI and 10-50% by weight of the above-described graft base A2, based on the total weight of component A.
- crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. serve as the graft base.
- the crosslinked acrylic ester polymers should preferably have a glass transition temperature below -20 ° C., in particular below -30 ° C.
- the graft A2 consists of at least one graft shell and the outermost graft shell thereof has a glass transition temperature of more than 30 ° C, a polymer formed from the monomers of the graft A2 would have a glass transition temperature of more than 80 ° C.
- the graft copolymers A can also be prepared by grafting pre-formed polymers onto suitable graft homopolymers. Examples of this are the reaction products of copolymers containing maleic anhydride or acid groups with base-containing rubbers.
- Suitable preparation processes for graft copolymers A are emulsion, solution, bulk or suspension polymerization.
- the graft copolymers A are preferably prepared by free-radical emulsion polymerization, in particular in the presence of latices of component AI at temperatures from 20 ° C. to 90 ° C. using water-soluble or oil-soluble initiators such as peroxodisulfate or benzyl peroxide, or with the aid of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.
- Suitable emulsion polymerization processes are described in DE-A-28 26 925, 31 49 358 and in DE-C-12 60 135.
- the graft casings are preferably constructed in the emulsion polymerization process, as described in DE-A-32 27 555, 31 49 357, 31 49 358, 34 14 118.
- the defined particle sizes of 50-1000 nm according to the invention are preferably carried out after the processes that are described in DE-C-12 60 135 and DE-A-28 26 925, or Applied Polymer Science, Volume 9 (1965), page 2929.
- the use of polymers with different particle sizes is known, for example, from DE-A-28 26 925 and US 5,196,480.
- the graft base AI is first prepared by adding the acrylic acid ester (s) used according to one embodiment of the invention and the multifunctional monomers which bring about crosslinking, if appropriate together with the others Comonomers, in aqueous emulsion in a conventional manner at temperatures between 20 and 100 ° C, preferably between 50 and 80 ° C, polymerized.
- the usual emulsifiers such as alkali salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms or resin soaps can be used.
- the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are preferably used.
- the emulsifiers are used in amounts of 0.5-5% by weight, in particular 1-2% by weight, based on the monomers used in the preparation of the graft base AI.
- the weight ratio of water to monomers is from 2: 1 to 0.7: 1.
- the usual persulfates, such as potassium persulfate, are used in particular as polymerization initiators. However, redox systems can also be used.
- the initiators are in generally used in amounts of 0.1-1% by weight, based on the monomers used in the preparation of the graft base AI.
- buffer substances by means of which pH values of preferably 6-9, such as sodium bicarbonate and sodium pyrophosphate, and 0-3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric ⁇ -methylstyrene, can be added as further polymerization auxiliaries the polymerization can be used.
- pH values of preferably 6-9 such as sodium bicarbonate and sodium pyrophosphate
- a molecular weight regulator such as mercaptans, terpinols or dimeric ⁇ -methylstyrene
- the precise polymerization conditions in particular the type, dosage and amount of the emulsifier, are determined in detail within the ranges given above such that the latex of the crosslinked acrylic ester polymer obtained ad 50 value in the range from about 50-1000 nm, preferably 50- 150 nm, particularly preferably in the range of 80-100 nm.
- the particle size distribution of the latex should preferably be narrow. The quotient
- a monomer mixture of styrene and acrylonitrile is then polymerized in a next step in the presence of the latex of the crosslinked acrylic acid ester polymer thus obtained, the weight ratio of styrene to acrylonitrile in the monomer mixture according to an Aus -
- the embodiment of the invention should be in the range from 100: 0 to 40:60, preferably in the range from 65: 35 to 85: 15. It is advantageous to re-graft copolymerize styrene and acrylonitrile onto the crosslinked polyacrylic acid ester polymer used as the graft base in aqueous ger emulsion under the usual conditions described above.
- the graft copolymerization can expediently take place in the same system as the emulsion polymerization for the preparation of the graft base A1, it being possible, if necessary, to add further emulsifier and initiator.
- the monomer mixture of styrene and acrylonitrile to be grafted on according to one embodiment of the invention can be added to the reaction mixture all at once, batchwise in several stages or preferably continuously during the polymerization.
- the graft copolymerization of the mixture of styrene and acrylonitrile in the presence of the crosslinking acrylic ester polymer is carried out in such a way that a degree of grafting of 1-99% by weight, preferably 20-45% by weight, in particular 35-45% by weight, based on the Total weight of component A, resulting in graft copolymer A. Since the graft yield in the graft copolymerization is not 100%, a somewhat larger amount of the monomer mixture of styrene and acrylmtril must be used in the graft copolymerization than corresponds to the desired degree of grafting.
- the control of the graft yield in the graft copolymerization and thus the degree of grafting of the finished graft copolymer A is known to the person skilled in the art and can be carried out, for example, by the metering rate of the monomers or by adding a regulator (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329 ff.) .
- the emulsion graft copolymerization generally gives rise to about 5 to 15% by weight, based on the graft copolymer, of free, non-grafted styrene / acrylonitrile copolymer.
- the proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method given above.
- graft copolymers A In the production of the graft copolymers A by the emulsion process, in addition to the given process engineering advantages, reproducible particle size changes are also possible, for example by at least partially agglomerating the particles into larger particles. This is indicates that polymers with different particle sizes may also be present in the graft copolymers A.
- Component A in particular, consisting of the graft base and graft shell (s) can be optimally adapted for the particular application, in particular with regard to the particle size.
- the graft copolymers A generally contain 1-99% by weight, preferably 55-80 and particularly preferably 55-65% by weight of graft base AI and 1-99% by weight, preferably 20-45, particularly preferably 35-45% by weight .-% of the graft A2, each based on the entire graft copolymer.
- Component B is an amorphous or partially crystalline polymer.
- Component B is preferably a copolymer of
- bl 40-100% by weight, preferably 60-70% by weight, units of a vinylaromatic monomer, preferably styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof, in particular styrene and / or ⁇ -methylstyrene as component Bl,
- b2 up to 60% by weight, preferably 30-40% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile, in particular acrylonitrile as component B2.
- the viscosity number of component B is 50-90, preferably 60-80.
- the amorphous or partially crystalline polymers of component B of the molding composition used according to the invention for producing the housings and cladding according to the invention are preferably composed of at least one polymer from partially crystalline polyamides, partially aromatic copolyamides, polyolefins, ionomers, polyesters, polyether ketones, polyoxyalkylenes, polyarylene sulfides and polymers selected from vinyl aromatic monomers and / or ethylenically unsaturated monomers. Polymer mixtures can also be used.
- Component B of the molding composition used according to the invention for the production of the housings and cladding according to the invention is made from partially crystalline, preferably linear polyamides such as polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 6, 12 and partially crystalline copolyamides based on these components .
- partially crystalline polyamides can be used, the acid component of which consists entirely or partly of adipic acid and / or terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / orginaic acid and / or dodecanedicarboxylic acid and / or a cyclohexanedicarboxylic acid, and whose diamine component consists wholly or partly in particular of m- and / or p-xylylenediamine and / or hexamethylene diamine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine and / or isophoronediamine, and their compositions are known in principle from the prior art (cf. Encyclopedia of Polymers, Vol. 11, p. 315 ff.).
- housing and cladding molding compositions used according to the invention are partially crystalline polyolefins, preferably Homopolymers and copolymers of olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, 3-methylbutene-1, 4-methylbutene-1, 4-methylpentene-1 and octene-1 .
- Suitable polyolefins are polyethylene, polypropylene, polybutene-1 or poly-4-methylpentene-1. In general, a distinction is made between s polyethylene (PE) and high-density PE (HDPE), low-density PE (LDPE) and linear-low-density PE (LLDPE).
- component B is an ionomer.
- These are generally polyolefins as they are
- polyethylene which contain monomers co-condensed with acid groups, for example acrylic acid, methacrylic acid and optionally other copolymerizable monomers.
- the acid groups are generally converted into ionic, optionally ionically crosslinked polyolefins with the aid of metal ions such as Na + , Ca 2+ , Mg 2+ and Al 3+ , but these can still be processed thermoplastically (see, for example, US Pat. No. 3,264,272; 3,404,134; 3,355,319; 4,321,337).
- metal ions such as Na + , Ca 2+ , Mg 2+ and Al 3+
- Component B according to the invention is also suitable for polyolefins containing free acid groups, which then generally have a rubber-like character and in some cases also contain further copolymerizable monomers, for example (meth) acrylates.
- component B can also be polyester, preferably aromatic-aliphatic polyester.
- polyester preferably aromatic-aliphatic polyester.
- polyalkylene terephthalate e.g. based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis-hydroxymethyl-cyclohexane, as well as polyalkylene naphthalates.
- Aromatic polyether ketones can also be used as component B, as described, for example, in documents GB 1 078 234, US 4,010,147, EP-A-0 135 938, EP-A-0 292 211, EP-A-0 275 035, EP-A-0 270 998, EP-A-0 165 406, and in the publication by CK Sham et. al. , Polymer 29/6, 1016-1020 (1988).
- component B of the molding compositions used according to the invention for the production of the housings and cladding according to the invention e.g. Polyoxymethylene, and oxymethylene polymers are used.
- suitable components B are the polyarylene sulfides, in particular the polyphenylene sulfide.
- it is composed of 50-99% by weight of vinyl aromatic monomers and 1-50% by weight of at least one of the other specified monomers.
- Component B is preferably an amorphous polymer, as described above as graft A2.
- a copolymer of styrene and / or ⁇ -methylstyrene with acrylonitrile is used as component B.
- the acrylonitrile content in these copolymers of component B is 0-60% by weight, preferably 30-40% by weight, based on the total weight of component B.
- Component B also includes those formed in the graft copolymerization to produce component A. free, non-grafted styrene / acrylonitrile copolymers.
- component B can preferably be a styrene / acrylonitrile copolymer, an ⁇ -methylstyrene / acrylonitrile copolymer or an ⁇ -methylstyrene / styrene / acrylonitrile terpolymer.
- copolymers can be used individually or as a mixture for component B, so that the additional, separately produced component B of the molding compositions used according to the invention is, for example, a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / Acrylonitrile copolymer can act.
- component B of the molding compositions used according to the invention consists of a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile copolymer
- the acrylonitrile content of the two copolymers should preferably be no more than 10 % By weight, preferably not more than 5% by weight, based on the total weight of the copolymer, differ from one another.
- Component B of the molding compositions used according to the invention can, however, also consist of only a single styrene / acrylonitrile copolymer if, in the graft copolymerizations for the production of component A and also in the production of the additional, separately produced component B, the same monomer mixture of styrene and acrylonitrile is assumed.
- the additional, separately manufactured component B can be obtained by the conventional methods.
- the copolymerization of the styrene and / or ⁇ -methylstyrene with the acrylonitrile can be carried out in bulk, solution, suspension or aqueous emulsion.
- Component B preferably has a viscosity number of 40 to 100, preferably 50 to 90, in particular 60 to 80. The viscosity number is determined in accordance with DIN 53 726, 0.5 g of material being dissolved in 100 ml of dimethylformamide.
- Components A and B and optionally C, D can be mixed in any desired manner by all known methods.
- components A and B have been prepared, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, to precipitate the polymers together thereupon and to work up the polymer mixture.
- components A and B are preferably mixed by extruding, kneading or rolling the components together, the components having, if necessary, been isolated beforehand from the solution or aqueous dispersion obtained in the polymerization.
- the products of the graft copolymerization (component A) obtained in aqueous dispersion can also only be partially dewatered and mixed as a moist crumb with component B, the complete drying of the graft copolymers then taking place during the mixing.
- the molding compositions used according to the invention for producing the housings and cladding according to the invention contain, in addition to components A and B, additional components C and / or D and, if appropriate, further additives, as described below.
- Suitable polycarbonates C are known per se. They preferably have a molecular weight (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range from 10,000 to 60,000 g / mol. They can be obtained, for example, in accordance with the processes of DE-B-1 300 266 by interfacial polycondensation or in accordance with the process of DE-A-1 495 730 by reacting diphenyl carbonate with bisphenols.
- Preferred bisphenol is 2,2-di (4-hydroxyphe- nyl) propane, generally - as in the following - referred to as bisphenol A.
- aromatic dihydroxy compounds can also be used, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4 , 4'-dihydroxydiphenyl sulfite, 4,4'-dihydroxydiphenylmethane, l, l-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkanes, preferably dihydroxydiphenylcyclohexanes or dihydroxylcyclopentanes, especially l, l-bis (4- hydroxyphenyl) -3,3,5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds.
- Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the aromatic dihydroxy compounds mentioned above.
- Copolycarbonates according to US Pat. No. 3,737,409 can also be used; Of particular interest are copolycarbonates based on bisphenol A and di (3,5-dimemyl-dihydroxyphenyl) sulfone, which are characterized by a high heat resistance. It is also possible to use mixtures of different polycarbonates.
- the average molecular weights (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) of the polycarbonates C are in the range from 10,000 to 64,000 g / mol. They are preferably in the range from 15,000 to 63,000, in particular in the range from 15,000 to 60,000 g / mol. This means that the polycarbonates C have relative solution viscosities in the range from 1.1 to 1.3, measured in 0.5% strength by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to 1.33, to have.
- the polycarbonates C can be used both as regrind and in granular form. They are present as component C in amounts of 0-50% by weight, preferably 10-40% by weight, based in each case on the total molding composition.
- the addition of polycarbonates leads, inter alia, to higher thermal stability and improved crack resistance of the molding compositions used to produce the housings and cladding according to the invention.
- the preferred thermoplastic molding compositions used according to the invention for the production of the housings and cladding according to the invention contain 0 to 50% by weight, preferably 0 to 40% by weight, in particular 0 to 30% by weight of fibrous or particulate fillers or mixtures thereof , each based on the entire molding compound. These are preferably commercially available products.
- Reinforcing agents such as carbon fibers and glass fibers are usually used in amounts of 5-50% by weight, based on the total molding composition.
- the glass fibers used can be made of E, A or C glass and are preferably equipped with a size and an adhesion promoter. Their diameter is generally between 6 and 20 ⁇ m. It can continuous fibers (rovings) as well as chopped glass fibers (staple) with a length of 1 - 10 ⁇ m, preferably 3 - 6 ⁇ , can be used.
- fillers or reinforcing materials such as glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite can be added.
- metal flakes e.g. aluminum flakes from Transmet Corp.
- metal powder e.g. aluminum flakes from Transmet Corp.
- metal fibers e.g. nickel-coated glass fibers
- metal-coated fillers e.g. nickel-coated glass fibers and other additives that shield electromagnetic waves
- Aluminum flakes K 102 from Transmet
- EMI purposes electro-magnetic interference
- the compositions can also be mixed with additional carbon fibers, carbon black, in particular conductivity carbon black, or nickel-coated carbon fibers.
- the molding compositions used according to the invention for the production of the housings and cladding according to the invention may also contain further additives which are typical and customary for polycarbonates, SAN polymers and graft copolymers or mixtures thereof.
- additives are: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers for improving the thermostability, for increasing the light stability, for increasing the resistance to hydrolysis and the resistance to chemicals, agents against heat decomposition and in particular the lubricants / lubricants, which are useful for the production of moldings or moldings.
- War Mestabilizers or oxidation retardants are usually metal halides (chlorides, bromides, iodides) which are derived from metals of group I of the periodic table of the elements (such as Li, Na, K, Cu).
- Suitable stabilizers are the usual hindered phenols, but also vitamin E or compounds with an analog structure.
- HALS stabilizers hindered amine light stabilizers
- benzophenones hindered amine light stabilizers
- resorcinols salicylates
- benzotriazoles and other compounds are also suitable (for example Irganox *, Tinuvin *, such as Tinuvin * 770 (HAI ⁇ S absorber, bis (2.2, 6,6-tetramethyl-4-piperidyl) sebazate) or Tinuvin P (UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol), topanol).
- Tinuvin * such as Tinuvin * 770 (HAI ⁇ S absorber, bis (2.2, 6,6-tetramethyl-4-piperidyl) sebazate
- Tinuvin P UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol
- Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures with 12-30 carbon atoms.
- the amounts of these additives are in the range of 0.05-1% by weight.
- Silicone oils, oligomeric isobutylene or similar substances are also suitable as additives, the usual amounts being 0.05-5% by weight.
- Pigments, dyes, color brighteners such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylene tetracarboxylic acid can also be used.
- Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in amounts of 0.01 - 5% by weight, based on the total molding compound.
- thermoplastic molding compositions used according to the invention for producing the housings and cladding according to the invention can be carried out according to methods known per se by mixing the components. It can be advantageous to premix individual components. Mixing the components in solution and removing the solvents is also possible.
- Suitable organic solvents are, for example, chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene or aromatic hydrocarbons, e.g. Toluene.
- the solvent mixtures can be evaporated, for example, in evaporation extruders.
- Mixing the e.g. dry components can be made by all known methods. However, the mixing is preferably carried out by extruding, kneading or rolling the components together, preferably at temperatures of 180-400 ° C., the components having, if necessary, been isolated beforehand from the solution obtained in the polymerization or from the thermal dispersion.
- the components can be metered in together or separately / one after the other.
- the housings and linings and fastening parts therefor according to the invention can be produced from the thermoplastic molding compositions used according to the known methods of thermoplastic processing.
- the production can be carried out by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by extrusion blowing or injection molding.
- the thermoplastic molding compositions can be used for a large number of housings and linings for medical devices. They can also be used to manufacture parts of these housings and panels.
- medical devices are suitable for the treatment, measurement, control, support or replacement of human or animal body functions, in particular the functions of the internal organs.
- the medical devices can, for example, replace internal organs that are not or no longer fully functional. You can also replace the internal organs as long as they are not functional during a surgical procedure.
- the housing and cladding according to the invention can also belong to medical devices which serve to feed substances into the human or animal body or to remove substances from the human or animal body.
- the devices are used in medical or therapeutic treatment and in the human or animal body.
- Measuring devices with which body functions or parameters of the body are measured can also be provided with the housings and linings according to the invention.
- both the metering devices and the infusion vessels and lines can consist of the thermoplastic molding compositions according to the invention.
- Other medical devices that are used in the medical or therapeutic field are known to the person skilled in the art.
- the housings and linings are used for diagnostic devices or measuring devices. These devices are usually installed in an open housing (rack) in which a variable combination of devices can be attached.
- the medical devices can be provided with covers according to the invention, which cover the front of the rack.
- the measuring devices can contain, for example, oscillographs, and also information output media, such as screens, printers, recorders, plotters, etc.
- the medical devices are those which are set up in the immediate vicinity of the patient or those which are in contact with the patient, for example, via lines, hoses or cables. These devices must be kept clean and sterile and must therefore be treated with appropriate cleaning agents and disinfectants.
- the housing and cladding should have a surface that is both scratch-resistant and very resistant to cleaning agents, disinfectants and chemicals.
- the housing and cladding according to the invention have a very good dimensional stability even when exposed to moisture and chemicals. They are therefore also suitable for use in environments where they are exposed to moisture.
- the housings and panels of the invention can also be used in environments where they are exposed to continued thermal stress.
- housings and cladding made of molding compounds that contain C polycarbonates as components are very heat-resistant and resistant to resistant to persistent heat.
- the heat resistance and impact resistance of the housing and cladding are further improved.
- These housings and claddings also have a balanced ratio of toughness and rigidity and good dimensional stability, as well as excellent resistance to heat aging and high resistance to yellowing under thermal stress and exposure to UV radiation.
- Housings and cladding made of molding compounds that contain components A and B have excellent surface properties, which can be obtained without further surface treatment.
- the appearance of the finished surfaces of the housings and claddings can be modified by suitable modification of the rubber morphology, for example in order to achieve glossy or matt surface designs.
- the housing and cladding show very little graying or yellowing effect when exposed to weather and UV radiation, so that the surface properties are retained.
- Further advantageous properties of the housings and cladding are the high weather stability, good thermal resistance, high yellowing resistance under UV radiation and thermal stress, good stress crack resistance, especially when exposed to chemicals, and good anti-electrostatic behavior. In addition, they have high color stability, for example due to their excellent resistance to yellowing and embrittlement.
- the housings and claddings made of the thermoplastic molding compositions used according to the invention do not show any significant loss of toughness or impact strength at low temperatures or after prolonged exposure to heat, which loss is retained even when exposed to UV rays. The tensile strength is also retained. They also show a balanced relationship between rigidity and toughness. It is possible to recycle thermoplastic molding compositions which have already been used to produce the housings and linings according to the present invention. Because of the high color stability, weather resistance and aging resistance, the molding compositions used according to the invention are very suitable for reuse. The proportion of reused (recycled) molding compound can be high.
- Butyl acrylate polymers had a solids content of 40%.
- the mean particle size (weight average) of the latex was found to be 410 nm.
- Allocate emulsifier After adding 1 part of potassium persulfate in 40 parts of water, a mixture of 196 parts of butyl acrylate, 4 parts of tricyclodecenyl acrylate and 1.52 parts of the emulsifier was finally added dropwise over the course of 2 hours. The polymer mixture was then polymerized at 65 ° C. for a further 2 hours. An approximately 40% dispersion with an average particle diameter of approximately 500 nm was obtained. If only 100 parts were added instead of a total of 300 parts of monomers, a latex with an average particle diameter of about 300 nm was obtained.
- a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
- the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number of 80 ml / g.
- a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
- the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number of 60 ml / g.
- a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
- the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 27% by weight, based on the copolymer, and a viscosity number of 80 ml / g.
- the graft rubber content was 29% by weight, based on the total weight of the finished polymer.
- the Charpy impact strength was determined from the molding compounds given in the table. It can be seen from the values given in Table 1 that the molding compositions according to the invention, in particular molding compositions II and m, have a significantly higher impact strength than the comparative compositions.
- the ASA molding composition according to the invention is clearly superior to ABS.
- Meliseptol ® contains in 100 g: 50 g 1-PropanoI
- Lysoformin ® contains in 100 g: 16.8 g formaldehyde DAB 8 3.5 g glutaraldehyde From Table 2 above it can be seen that the molding composition I according to the invention has better resistance to disinfectants and chemicals than comparison molding composition I.
- molding compound I and comparative compound I were subjected to the xenon test 450 in accordance with DIN 53387, method 2.
- Ultra-Scan from the manufacturer Hunter LAB was used as the light source.
- Test specimens were injection molded at 250 ° C plastic temperature and 60 ° C mold temperature. The following results were obtained:
- the molding composition additionally contained 4% by weight of TiO 2
- the molding composition additionally contained 4% by weight of TiO 2 , based on the total weight of components A and B.
- the molding composition additionally contained 4% by weight of TiO 2 , 0.5% by weight of a HALS stabilizer (Tinuvin * 770, sold by CIBA AG) and 0.5% by weight of a UV absorber (Tinuvin * P CIBA AG)
- the yellowness index from Table 3 shows that the molding compositions according to the invention are considerably more resistant to yellowing than the comparative composition I.
- the housings and linings for medical devices according to the invention have a far superior chemical resistance and a far superior resistance to yellowing and graying (light resistance) compared to known housings and linings for medical devices have a far superior chemical resistance and a far superior Resistance to yellowing and graying (lightfastness) compared to known housings and claddings for medical devices.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97936654A EP0914375A1 (de) | 1996-07-25 | 1997-07-24 | Gehäuse und verkleidungen für medizinische geräte |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19630143.2 | 1996-07-25 | ||
DE19630143A DE19630143A1 (de) | 1996-07-25 | 1996-07-25 | Gehäuse und Verkleidungen für medizinische Zwecke |
Publications (1)
Publication Number | Publication Date |
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WO1998004624A1 true WO1998004624A1 (de) | 1998-02-05 |
Family
ID=7800888
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP1997/004033 WO1998004624A1 (de) | 1996-07-25 | 1997-07-24 | Gehäuse und verkleidungen für medizinische geräte |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0914375A1 (de) |
KR (1) | KR20000029501A (de) |
DE (1) | DE19630143A1 (de) |
WO (1) | WO1998004624A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000020084A1 (de) * | 1998-10-07 | 2000-04-13 | Basf Aktiengesellschaft | Spielgeräte für den aussenbereich |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19846203A1 (de) * | 1998-10-07 | 2000-04-13 | Basf Ag | Gehäuse und Abdeckungen für Filter, Pumpen und Motoren |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3691260A (en) * | 1969-03-08 | 1972-09-12 | Hans Mittnacht | Impact resistant thermoplastic composition |
DE3301161A1 (de) * | 1983-01-15 | 1984-07-19 | Bayer Ag, 5090 Leverkusen | Thermoplastische formmassen |
US4975487A (en) * | 1988-01-06 | 1990-12-04 | The Dow Chemical Company | Polymeric polyblend composition |
US5196480A (en) * | 1990-04-06 | 1993-03-23 | Basf Aktiengesellschaft | Thermoplastic molding material based on graft copolymers with bimodal particle size distribution and a two-step graft shell |
DE4442168A1 (de) * | 1994-11-26 | 1996-05-30 | Basf Ag | Witterungsbeständige thermoplastische Formmassen |
-
1996
- 1996-07-25 DE DE19630143A patent/DE19630143A1/de not_active Withdrawn
-
1997
- 1997-07-24 EP EP97936654A patent/EP0914375A1/de not_active Withdrawn
- 1997-07-24 WO PCT/EP1997/004033 patent/WO1998004624A1/de not_active Application Discontinuation
- 1997-07-24 KR KR1019997000535A patent/KR20000029501A/ko not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3691260A (en) * | 1969-03-08 | 1972-09-12 | Hans Mittnacht | Impact resistant thermoplastic composition |
DE3301161A1 (de) * | 1983-01-15 | 1984-07-19 | Bayer Ag, 5090 Leverkusen | Thermoplastische formmassen |
US4975487A (en) * | 1988-01-06 | 1990-12-04 | The Dow Chemical Company | Polymeric polyblend composition |
US5196480A (en) * | 1990-04-06 | 1993-03-23 | Basf Aktiengesellschaft | Thermoplastic molding material based on graft copolymers with bimodal particle size distribution and a two-step graft shell |
DE4442168A1 (de) * | 1994-11-26 | 1996-05-30 | Basf Ag | Witterungsbeständige thermoplastische Formmassen |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000020084A1 (de) * | 1998-10-07 | 2000-04-13 | Basf Aktiengesellschaft | Spielgeräte für den aussenbereich |
Also Published As
Publication number | Publication date |
---|---|
DE19630143A1 (de) | 1998-01-29 |
EP0914375A1 (de) | 1999-05-12 |
KR20000029501A (ko) | 2000-05-25 |
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