WO2014058003A1 - Procédé de fabrication d'article moulé - Google Patents

Procédé de fabrication d'article moulé Download PDF

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Publication number
WO2014058003A1
WO2014058003A1 PCT/JP2013/077554 JP2013077554W WO2014058003A1 WO 2014058003 A1 WO2014058003 A1 WO 2014058003A1 JP 2013077554 W JP2013077554 W JP 2013077554W WO 2014058003 A1 WO2014058003 A1 WO 2014058003A1
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Prior art keywords
vitamin
irradiation
radicals
sample
electron beam
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PCT/JP2013/077554
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English (en)
Japanese (ja)
Inventor
田嶋　邦彦
直秀 富田
啓太 植月
川崎　亮
尚 岩出
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国立大学法人京都工芸繊維大学
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Priority to JP2014540883A priority Critical patent/JP6215834B2/ja
Publication of WO2014058003A1 publication Critical patent/WO2014058003A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/505—Stabilizers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene

Definitions

  • the present invention relates to a method for producing a molded product containing ultra high molecular weight polyethylene and vitamin E.
  • UHMWPE ultra high molecular weight polyethylene
  • Sliding members made of ultra-high molecular weight polyethylene have excellent wear resistance, impact resistance, self-lubrication and chemical resistance, but their durability is still inadequate and improvements are required. Yes.
  • wear resistance is important when used over a long period of time.
  • a sliding member made of ultra high molecular weight polyethylene is embedded in the joint, it is inevitable that abrasion powder is generated due to long-term use.
  • this wear powder is said to be phagocytosed by macrophages in vivo to cause production of inflammatory cytokines.
  • osteoclasts activated by such cytokines promoting bone resorption there is a problem that the implant loosens.
  • Patent Documents 1 and 2 and Non-Patent Documents 1 and 2 describe a sliding member for an artificial joint containing ultra high molecular weight polyethylene and vitamin E.
  • vitamin E By blending vitamin E with ultrahigh molecular weight polyethylene, the oxidation resistance of the molded article is improved and the wear resistance is also improved, and as a result, the bioreactivity of the molded article is suppressed.
  • the presence of vitamin E in the grain boundaries of polyethylene crystals improves moldability and suppresses delamination destruction.
  • These documents describe that ultra-high molecular weight polyethylene blended with vitamin E is irradiated with radiation such as gamma rays or electron beams to crosslink polyethylene or sterilize it. Has been.
  • the mechanical properties of the molded article are improved, such as an increase in hardness and a reduction in the amount of creep. And it is supposed that the sliding member for artificial joints which is further improved in abrasion resistance and excellent in long-term durability can be obtained.
  • vitamin E radicals hydrogen radicals of hydroxyl groups of vitamin E are extracted and vitamin E radicals (radicals of tocopherol or derivatives thereof) are generated. And it is known that a vitamin E radical will change to a dimer, a trimer, a quinone body, etc. by subsequent reaction. Since the by-product produced in this way does not have the effect inherent in vitamin E, the antioxidant effect and bioreactivity suppression effect, which are the addition effects thereof, are reduced. Furthermore, the radiation energy is consumed for the radicalization of vitamin E, or the radical generated in the polyethylene chain reacts with the vitamin E radical and is consumed, so that the crosslinking reaction between the polyethylene chains is difficult to proceed. there were.
  • quinone form of ⁇ -tocopherol is known to have biotoxicity, and it is not desirable to include it in a molded article.
  • ⁇ -tocopherol quinone and its hydroquinone are still unclear about the physiological action in the joint, and there is still a concern about safety.
  • Such tocopherol quinone is produced by rearrangement of vitamin E radicals in the molecule.
  • Patent Document 3 describes a method of diffusing vitamin E in a pre-crosslinked ultra-high molecular weight polyethylene molded product.
  • vitamin E radicals are generated and changed into a dimer, trimer, quinone or the like by the subsequent reaction.
  • the present invention has been made in order to solve the above-described problems, and is excellent in oxidation resistance by controlling radicals generated when radiation is applied to a molded product containing ultrahigh molecular weight polyethylene and vitamin E. And it aims at providing the molded article excellent also in the safety
  • the above-mentioned problem is solved by providing a method for producing a molded product characterized by irradiating a molded product containing ultrahigh molecular weight polyethylene and vitamin E with radiation at a temperature of 0 ° C. or lower. At this time, it is preferable to irradiate radiation while cooling with dry ice. Moreover, it is also preferable to preserve
  • the above-mentioned problems can be solved by providing a method for producing a molded product that is stored for 1 day or longer at a temperature of 0 ° C. or lower after irradiating a molded product containing ultrahigh molecular weight polyethylene and vitamin E with radiation. .
  • a molded product containing 97 to 99.99% by mass of ultrahigh molecular weight polyethylene and 0.01 to 3% by mass of vitamin E. It is also preferable that the radiation to be irradiated is an electron beam, or the radiation dose is 2 to 1000 kGy. It is also preferable that the molded product is a medical implant.
  • the production method of the present invention it is possible to control radicals generated when a molded article containing ultra high molecular weight polyethylene and vitamin E is irradiated with radiation.
  • the vitamin E radicals contained in the molded article can be reduced immediately after irradiation, so that the amount of tocopherol quinone produced by rearrangement in the molecule can be reduced.
  • Safety for living bodies can be improved. That is, it is possible to provide a molded article having excellent oxidation resistance and excellent safety to living bodies.
  • a molded product containing ultra high molecular weight polyethylene (UHMWPE) and vitamin E is irradiated with radiation.
  • UHMWPE ultra high molecular weight polyethylene
  • the weight average molecular weight of the ultrahigh molecular weight polyethylene used in the production method of the present invention is 1 million or more, preferably 2 million or more.
  • the weight average molecular weight is usually 10 million or less.
  • polyethylene having such a high molecular weight a molded product excellent in wear resistance and fatigue resistance of the molded product can be obtained.
  • the form of the raw ultra high molecular weight polyethylene is not particularly limited, but is preferably in the form of a powder because uniform mixing with vitamin E is easy. When used as a raw material for producing a medical implant, it is desirable to use a medical brand.
  • Vitamin E used in the production method of the present invention is ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol or a derivative thereof, which is d-form, l-form, dl-form It does not matter. Mixtures of these can also be used.
  • the method for producing a molded product containing ultra high molecular weight polyethylene and vitamin E is not particularly limited, but a method of heating and compressing after mixing ultra high molecular weight polyethylene powder and vitamin E is preferably employed.
  • vitamin E may be mixed as it is with ultrahigh molecular weight polyethylene powder, or may be mixed after dissolving in a solvent such as alcohol.
  • a solvent such as alcohol.
  • the temperature during molding by heating and compression is preferably 200 to 250 ° C.
  • the temperature is preferably 200 ° C. or higher, while in order not to cause vitamin E to be thermally deteriorated, it is preferably 250 ° C. or lower.
  • the pressure at the time of molding is preferably 1 to 100 MPa.
  • the pressure is preferably 1 MPa or more, and more preferably 5 MPa or more. From the viewpoint of equipment cost, it is preferably 100 MPa or less, and more preferably 50 MPa or less. Further, from the viewpoint of preventing oxidative deterioration of vitamin E, it is preferable to mold after depressurizing the inside of the mold and discharging the air, or molding in an inert gas atmosphere.
  • vitamin E may be diffused in the molded article.
  • the molded product is immersed and diffused in liquid vitamin E.
  • ultra high molecular weight polyethylene and vitamin E in such a ratio that the ultra high molecular weight polyethylene is 97 to 99.99% by mass and vitamin E is 0.01 to 3% by mass.
  • the content of vitamin E is less than 0.01% by mass, the effect of adding vitamin E may be insufficient, and more preferably 0.1% by mass or more.
  • the content of the ultrahigh molecular weight polyethylene is 99.9% by mass or less.
  • the strength may decrease, and more preferably 1% by mass or less.
  • the content of the ultrahigh molecular weight polyethylene is 99% by mass or more.
  • the thus obtained molded product containing ultra high molecular weight polyethylene and vitamin E is irradiated with radiation.
  • the ultrahigh molecular weight polyethylene can be cross-linked, the wear resistance of the molded product can be improved, and a molded product with excellent long-term fatigue resistance can be obtained.
  • it can also sterilize by irradiating the said molded article with a radiation. At this time, it is important to irradiate the radiation at a temperature of 0 ° C. or less. By doing so, the amount of vitamin E radicals contained in the molded article immediately after irradiation can be reduced. Moreover, the formation of a double bond can also be suppressed by leaving an alkyl radical advantageous for the crosslinking reaction.
  • the process of sterilization by irradiation with radiation may be performed after adding ultra-high molecular weight polyethylene to vitamin E and then cross-linking, or may be performed after adding ultra-high molecular weight polyethylene after crosslinking to vitamin E. You may go after. Furthermore, you may perform a bridge
  • vitamin E By irradiating with radiation, a part of vitamin E ( ⁇ -tocopherol: the following formula (1)) becomes a vitamin E radical (formula (2)) in which hydrogen radicals are extracted from the phenolic hydroxyl group. .
  • This vitamin E radical is relatively stable in ultra-high molecular weight polyethylene, but in the long run, vitamin E radicals bind to each other to form a dimer (for example, the following formula (3)) or a trimer ( For example, the following formula (4)) is formed.
  • dimer for example, the following formula (3)
  • trimer For example, the following formula (4)
  • radicals may rearrange within the molecule, and vitamin E radicals may change to quinone ( ⁇ -tocopherylquinone: the following formula (5)).
  • radicals are generated in ultra high molecular weight polyethylene by irradiation.
  • a hydrogen atom is extracted from a polyethylene chain to form an alkyl radical (the following formula (6)).
  • an allyl radical (the following formula (7))
  • a polyenyl radical (the following formula (8)) are formed.
  • alkyl radicals are highly reactive and unstable, but allyl radicals are less reactive and polyenyl radicals are further less reactive. Therefore, it is preferable to leave the alkyl radical after irradiation from the viewpoint of efficiently proceeding the crosslinking reaction and suppressing the formation of double bonds.
  • the type of radiation to be irradiated is not particularly limited and can be irradiated with an electron beam, a gamma ray, or the like, but it is preferable to irradiate an electron beam from the viewpoint of production efficiency and cost.
  • the irradiation amount when irradiating with radiation is preferably 2 to 1000 kGy, more preferably 10 to 700 kGy, and still more preferably 50 to 500 kGy.
  • the temperature of the molded product when irradiated with radiation is 0 ° C. or less.
  • the temperature of the molded article is preferably ⁇ 20 ° C. or lower, more preferably ⁇ 50 ° C. or lower, and further preferably ⁇ 70 ° C. or lower.
  • the amount of vitamin E radicals contained in the molded article immediately after irradiation can be reduced by irradiating with radiation at a low temperature.
  • the amount of vitamin E radicals immediately after irradiation decreased because the vitamin E radicals once generated by irradiation reacted with highly reactive radicals such as alkyl radicals and quickly disappeared. It is thought that it was not extinguished by quinone formation.
  • the temperature of the molded product when irradiated with radiation is usually ⁇ 200 ° C. or higher.
  • the temperature of the molded product when irradiated with radiation refers to the temperature at the start of irradiation. Therefore, the temperature of the molded product may rise after starting irradiation and temporarily exceed the above range.
  • the method for adjusting the temperature when irradiating radiation to the above range is not particularly limited, and a known method can be adopted.
  • the atmosphere surrounding the molded product can be cooled, or the molded product can be cooled by direct heat transfer using a cooling plate or a cooling block. It is also possible to cool the molded product using a refrigerant, in which case ice, an ice-calcium chloride mixture, an ice-potassium chloride mixture, a cold brine coolant (for example, potassium formate).
  • Aqueous solution), dry ice (solid carbon dioxide), liquid nitrogen and other refrigerants can be appropriately selected.
  • the temperature can be easily controlled and the application to the radiation irradiation apparatus is easy.
  • radiation can be irradiated at the sublimation temperature of dry ice if it is sufficiently cooled.
  • the atmosphere during irradiation with radiation is an atmosphere that does not contain oxygen, such as under reduced pressure or an inert gas atmosphere.
  • the molded product can be housed and irradiated in a bag sealed by removing air by evacuation.
  • the molded product after irradiation with radiation may be used immediately, or may be used after being stored for a certain period of time. It is preferable to store at least one day at the following temperature. By doing so, it is possible to prevent vitamin E radicals generated by radiation irradiation from being changed into multimers or quinones during storage. Moreover, it can prevent that the alkyl radical useful for the crosslinking reaction of polyethylene deactivates.
  • vitamin E radicals generated by irradiation it is possible to prevent vitamin E radicals generated by irradiation from turning into multimers and quinones, and to prevent alkyl radicals generated by irradiation from being deactivated even when irradiated at room temperature. It is. Therefore, the rate of decrease of vitamin E radicals and alkyl radicals generated by radiation irradiation can also be reduced by irradiating the molded product without lowering the temperature and storing it for 1 day or longer at a temperature of 0 ° C. or lower. .
  • the storage temperature is preferably ⁇ 20 ° C. or lower, more preferably ⁇ 50 ° C. or lower, and further preferably ⁇ 70 ° C. or lower.
  • the storage temperature is usually ⁇ 200 ° C. or higher.
  • the number of storage days kept at a low temperature is not particularly limited, but it has been confirmed in a later example that a considerable amount of radicals remain even after one week, and a considerable amount of unstable alkyl radicals remain.
  • the storage days are preferably 50 days or less.
  • vitamin E radicals are known to be reduced to vitamin E by vitamin C or the like in vivo, it can be expected to return to vitamin E in vivo by storing at low temperature.
  • a highly reactive alkyl radical can remain for a long period of time, it is considered useful when this radical is subsequently used for a chemical reaction or a crosslinking reaction is advanced.
  • the method for adjusting the storage temperature to the above range is not particularly limited, and a known method can be adopted. For example, a method similar to that during radiation irradiation can be employed.
  • the atmosphere when storing the molded product after irradiation is preferably an atmosphere that does not contain oxygen, as in the case of irradiation with radiation.
  • the preferred use of the molded article of the present invention thus obtained is a medical implant, and is particularly preferably used as a sliding member for an artificial joint.
  • the sliding member is fixed to one bone via a metal member, and is used as an artificial joint by being slidably combined with the metal member fixed to the other bone. Since it is important that the artificial joint can be used while being slid for a long time after being implanted in the body, the cross-linking reaction can be promoted while suppressing the occurrence of double bonds, effectively generating wear powder.
  • the significance of adopting the production method of the present invention that can be suppressed to a large extent is great. Among them, it is particularly suitable as a sliding member for an artificial hip joint that requires strict wear resistance and fatigue resistance.
  • Example preparation To a medical grade ultra high molecular weight polyethylene powder “GUR1050” (manufactured by Ticona), 0.3 mass% vitamin E (Japanese Pharmacopoeia Tocopherol (dl- ⁇ -Tocopherol): Eisai Co., Ltd.) is stirred. After mixing, a bulk molded product “VE03” was produced by vacuum direct compression molding (pressure: 25 MPa, temperature: 220 ° C., time: 30 minutes). Further, a bulk molded product “Vir” was prepared in the same manner as described above except that only ultra-high molecular weight polyethylene was used without mixing vitamin E.
  • the bulk molded products “VE03” and “Vir” were shaved to prepare a cylindrical sample having a length of 40 mm and a diameter of 3.5 mm.
  • This sample was put in a plastic film bag, vacuum packaged, and the opening was heat sealed.
  • the package thus obtained was irradiated with an electron beam using an electron accelerator.
  • the operating conditions were an acceleration voltage of 10 MeV, an output of 200 kW, and an irradiation amount of 300 kGy.
  • electron beam irradiation was performed under two conditions of room temperature (25 ° C.) and a frozen environment.
  • ESR measurement method For each of the sample “VE03” and the sample “Vir”, ESR waveforms were obtained by the ESR method for both the sample irradiated with an electron beam at room temperature and the sample irradiated with an electron beam in a frozen environment. Moreover, the ESR waveform was similarly obtained about the sample which preserve
  • an electron spin resonance apparatus “TE-100” manufactured by JEOL Ltd. was used as an experimental apparatus. After wiping the sample with a cloth impregnated with ethanol, it was placed in a quartz sample tube and placed in the cavity of the apparatus.
  • An ESR signal of Mn 2+ / MnO was also measured as a standard sample.
  • FIG. 1 shows ESR waveforms of the sample “VE03” and the sample “Vir” immediately after electron beam irradiation at room temperature.
  • the vertical axis of the graph represents the signal strength of the waveform, and the horizontal axis represents the magnetic field strength. It can be seen that a peak peculiar to the sample “VE03” appears in the vicinity of the magnetic field strength of 336 mT.
  • the ESR waveform (VE radical) of the sample irradiated with ultraviolet rays instead of irradiating the electron beam with respect to the sample “VE03” is shown in FIG. 2 as a model showing the waveform of vitamin E radicals in UHMWPE.
  • a difference waveform (VE03-Vir correction) obtained by subtracting the ESR waveform immediately after electron beam irradiation of the sample “Vir” whose signal intensity ratio is corrected from the ESR waveform immediately after electron beam irradiation of the sample “VE03” is also shown. This is shown in 2.
  • the g value (indicated by the vertical line in FIG.
  • the amount of vitamin E radicals present in the sample was quantified. Specifically, the ESR waveform of the sample “Vir” and the ESR waveform of the vitamin E radical were added together by correcting the signal intensity. Then, the three points of the g value, the line width, and the signal intensity of the waveform observed by the addition were matched with the ESR waveform of the sample “VE03” to be measured. The signal intensity correction value of the vitamin E radical at this time indicates the amount of vitamin E radical in the sample “VE03”. As the ESR waveform of the vitamin E radical, the ESR waveform in the sample “VE03” irradiated with ultraviolet rays was used.
  • FIG. 3 also shows the ESR waveform of the sample “Vir” irradiated with an electron beam at room temperature (RT irradiation) and in a freezing environment (Cold irradiation).
  • RT irradiation room temperature
  • Cold irradiation cold irradiation
  • a waveform Gain-adjusted Cold irradiation
  • FIG. 4 shows a differential waveform (Ga-Cold-RT irradiation) obtained by subtracting the waveform (RT illumination) of the sample “Vir” irradiated below.
  • FIG. 8 shows the total amount of radicals in the sample “VE03” immediately after electron beam irradiation at room temperature and in a frozen environment.
  • FIG. 9 shows the total amount of radicals in the sample “Vir” immediately after electron beam irradiation at room temperature and in a frozen environment.
  • the vertical axis indicates the relative value of the total radical amount, and the relative value was compared with the average value of the total radical amount of the sample “VE03” when irradiated in a frozen environment as 100.
  • the total amount of radicals in the sample irradiated with the electron beam in a refrigerated environment was larger in both the sample “VE03” and the sample “Vir” than the sample irradiated with the electron beam at room temperature.
  • the total amount of radicals when irradiated with an electron beam at room temperature does not vary greatly depending on the presence or absence of vitamin E, but the total amount of radicals when irradiated with an electron beam in a frozen environment is greater when vitamin E is added. It was.
  • FIG. 10 shows the change over time in the vitamin E radical content when the sample “VE03” irradiated with an electron beam at room temperature and in a frozen environment is stored at room temperature and in a frozen environment.
  • irradiation at room temperature and storage in a frozen environment Normal, frozen
  • irradiation at room temperature and storage at room temperature Normal, RT
  • irradiation in a frozen environment and storage in a frozen environment Dryce, frozen
  • irradiation in a frozen environment -Four data stored at room temperature (Dryice, RT) were plotted simultaneously.
  • the vertical axis shows the relative value of the vitamin E radical content, and the value immediately after electron beam irradiation at room temperature is 1.
  • the vitamin E radical content immediately after electron beam irradiation was greater when irradiated at room temperature than when irradiated in a frozen environment. Regardless of the temperature at the time of electron beam irradiation, the decrease in the amount of radicals over time was suppressed by storing in a frozen environment.
  • FIG. 11 shows the time-dependent change in the content of the main chain radicals of polyethylene when the sample “Vir” irradiated with an electron beam at room temperature and in a frozen environment is stored at room temperature and in a frozen environment.
  • irradiation at room temperature and storage in a frozen environment irradiation at room temperature and storage in a frozen environment (RT irra, frozen)
  • RT irra, RT irradiation at room temperature and storage at room temperature
  • irradiation in a frozen environment and storage in a frozen environment Cold irra, frozen
  • frozen frozen
  • FIG. 12 shows the change over time in the content of the main chain radical of polyethylene when the sample “VE03” irradiated with an electron beam at room temperature and in a frozen environment is stored at room temperature and in a frozen environment.
  • a relative comparison was performed with the main chain radical amount in the sample “Vir” irradiated with the electron beam in a refrigerated environment as 100.
  • the amount of main chain radicals in each sample immediately after irradiation with an electron beam in a refrigerated environment was larger than that of a sample irradiated at room temperature.
  • a decrease in the amount of radicals over time was suppressed by storing in a frozen environment.
  • the degree of carbon-carbon double bond was measured by FT-IR measurement (Fourier transform infrared spectroscopy).
  • FT-IR “Microscope Spectrum Spotlight 200” manufactured by Perkin Elmer Co., Ltd. was used.
  • a disk-shaped thin piece sample having a diameter of 3.5 mm and a thickness of 50 ⁇ m was obtained from the cylindrical shaped article using a microtome.
  • the obtained flake sample was placed in an apparatus and irradiated with infrared rays, line analysis was performed at intervals of 200 ⁇ m, and transmitted light was measured in a wave number range of 750 to 4000 cm ⁇ 1 .
  • the ratio (b / a) was defined as the degree of carbon-carbon double bond (Double Bond Index).
  • FIG. 13 shows the carbon-carbon double bond degree in the sample “VE03” immediately after electron beam irradiation at room temperature and in a frozen environment. It was found that by irradiating an electron beam in a freezing environment, the degree of carbon-carbon double bond becomes smaller than that when irradiating an electron beam at room temperature.
  • the amount of main chain radicals immediately after irradiation showed a higher value by irradiating the electron beam at a low temperature than when irradiating the electron beam at room temperature.
  • the reason may be that the main chain radicals can be prevented from disappearing when irradiated at a lower temperature than when irradiated at room temperature.
  • the amount of main chain radicals in the sample “Vir” showed a high value by irradiating an electron beam at a lower temperature compared to normal temperature irradiation. It is thought that the reaction that the radical disappears only with the chain radical occurred.
  • the degree of carbon-carbon double bonds in the ultra-high molecular weight polyethylene showed a higher value when irradiated at room temperature than when irradiated at a low temperature. . In other words, it is considered that by irradiation at a low temperature, more reactive alkyl radicals remain than when irradiated at room temperature, making it difficult to form double bonds in the polyethylene chain.

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Transplantation (AREA)
  • Animal Behavior & Ethology (AREA)
  • Dermatology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Polymers & Plastics (AREA)
  • Epidemiology (AREA)
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  • Treatments Of Macromolecular Shaped Articles (AREA)
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  • Materials For Medical Uses (AREA)

Abstract

Selon la présente invention, lorsqu'un article moulé contenant du polyéthylène de poids moléculaire ultra-élevé et de la vitamine E est irradié par un rayonnement à une température inférieure ou égale à 0 °C afin de réticuler le polyéthylène de poids moléculaire ultra-élevé, les radicaux vitamine E compris dans l'article moulé immédiatement après irradiation peuvent être réduits, la génération de tocophéryl-quinone suite à la transposition des radicaux vitamine E pouvant ainsi être réduite et la sécurité biologique de l'article moulé pouvant être augmentée. En outre, en stockant l'article moulé pendant au moins un jour à une température inférieure ou égale à 0 °C après irradiation, la vitesse de réduction des radicaux vitamine E ou des radicaux alkyle générés par l'irradiation peut être réduite. L'article moulé ainsi obtenu présente d'excellentes propriétés de résistance à l'oxydation et de sécurité biologique, et est par conséquent approprié pour une utilisation comme implant médical.
PCT/JP2013/077554 2012-10-11 2013-10-10 Procédé de fabrication d'article moulé WO2014058003A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006515777A (ja) * 2003-01-16 2006-06-08 マサチューセッツ、ゼネラル、ホスピタル 耐酸化性ポリマー物質の製造方法
JP2006176924A (ja) * 2004-12-22 2006-07-06 Japan Atomic Energy Agency 炭化ケイ素マイクロチューブの冷却照射による壁厚制御法
JP2007536998A (ja) * 2004-05-11 2007-12-20 ザ　ジェネラル　ホスピタル　コーポレイション　ディー　ビー　エイ　マサチューセッツ　ジェネラル　ホスピタル 耐酸化性重合体状材料の製造方法
JP2009144067A (ja) * 2007-12-14 2009-07-02 Toyota Motor Corp 機能性膜の製造方法、及び燃料電池用電解質膜の製造方法
JP2010529213A (ja) * 2007-03-02 2010-08-26 ザ・ジェネラル・ホスピタル・コーポレイション 酸化防止剤含有ポリマーの架橋
WO2010129514A2 (fr) * 2009-05-04 2010-11-11 Smith & Nephew, Inc. Effets synergiques du mélange de plusieurs additifs dans le polyéthylène uhmwpe
JP2010538150A (ja) * 2007-09-04 2010-12-09 スミス・アンド・ネフュー・オルソペディクス・アーゲー 関節面用の超高分子量ポリエチレン

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2277561B1 (fr) * 2005-08-18 2012-09-19 Zimmer GmbH Articles de polyéthylène à poids moléculaire très élevé et procédés de formation d'articles de polyéthylène à poids moléculaire très élevé

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006515777A (ja) * 2003-01-16 2006-06-08 マサチューセッツ、ゼネラル、ホスピタル 耐酸化性ポリマー物質の製造方法
JP2007536998A (ja) * 2004-05-11 2007-12-20 ザ　ジェネラル　ホスピタル　コーポレイション　ディー　ビー　エイ　マサチューセッツ　ジェネラル　ホスピタル 耐酸化性重合体状材料の製造方法
JP2006176924A (ja) * 2004-12-22 2006-07-06 Japan Atomic Energy Agency 炭化ケイ素マイクロチューブの冷却照射による壁厚制御法
JP2010529213A (ja) * 2007-03-02 2010-08-26 ザ・ジェネラル・ホスピタル・コーポレイション 酸化防止剤含有ポリマーの架橋
JP2010538150A (ja) * 2007-09-04 2010-12-09 スミス・アンド・ネフュー・オルソペディクス・アーゲー 関節面用の超高分子量ポリエチレン
JP2009144067A (ja) * 2007-12-14 2009-07-02 Toyota Motor Corp 機能性膜の製造方法、及び燃料電池用電解質膜の製造方法
WO2010129514A2 (fr) * 2009-05-04 2010-11-11 Smith & Nephew, Inc. Effets synergiques du mélange de plusieurs additifs dans le polyéthylène uhmwpe

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TORU KAWASAKI ET AL.: "Annealing ni yoru Denshisen Shosha dl-alpha-Tocophenol Kongo Cho Kobunshi-ryo Polyethylene-nai ni Okeru Vitamin E Radical no Shometsu to Kakyo Sokushin", THE JAPAN SOCIETY OF MECHANICAL ENGINEERS DAI 22 KAI BIO FRONTIER KOENKAI KOEN RONBUNSHU, 6 October 2011 (2011-10-06), pages 5 - 6 *
TORU KAWASAKI ET AL.: "Annealing Treatment Stabilizes Vitamin E Radicals and Accelerates the Cross-linking Reaction in Electron-Beam-Irradiated dl-alpha-Tocophenol-Blended Ultra High Molecular Weight Polyethylene", BIOTRIBOLOGY SYMPOSIUM, 5 November 2011 (2011-11-05), pages 52 - 53 *

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