JP2007054621A - Rubber goods for medical purpose - Google Patents
Rubber goods for medical purpose Download PDFInfo
- Publication number
- JP2007054621A JP2007054621A JP2006206852A JP2006206852A JP2007054621A JP 2007054621 A JP2007054621 A JP 2007054621A JP 2006206852 A JP2006206852 A JP 2006206852A JP 2006206852 A JP2006206852 A JP 2006206852A JP 2007054621 A JP2007054621 A JP 2007054621A
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- Prior art keywords
- rubber
- fine powder
- parts
- weight
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 239000005060 rubber Substances 0.000 title claims abstract description 114
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- 239000000843 powder Substances 0.000 claims abstract description 38
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- 238000000034 method Methods 0.000 claims abstract description 30
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- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims abstract description 17
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- 230000005540 biological transmission Effects 0.000 claims abstract description 6
- 238000005266 casting Methods 0.000 claims abstract description 6
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- 238000002347 injection Methods 0.000 description 15
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- 238000010030 laminating Methods 0.000 description 4
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- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
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- 238000003475 lamination Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
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- 238000005245 sintering Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical class C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- DBOFPRDNHUMHGD-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-methylbuta-1,3-diene;2-methylprop-1-ene Chemical compound CC(C)=C.CC(=C)C=C.C=CC1=CC=CC=C1C=C DBOFPRDNHUMHGD-UHFFFAOYSA-N 0.000 description 1
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- JBAUPCNQUQGXJT-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene;2-methylprop-1-ene Chemical class CC(C)=C.CC1=CC=C(C=C)C=C1 JBAUPCNQUQGXJT-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- LWCFHRWBEUSHEE-UHFFFAOYSA-N 3-(difluoromethyl)-1,1,3,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-1-ene Chemical compound FC(C(C(F)(F)F)(C(C(C(F)F)(C=C(F)F)F)(F)F)F)(F)F LWCFHRWBEUSHEE-UHFFFAOYSA-N 0.000 description 1
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KRBGYJXDLGSDEX-UHFFFAOYSA-N 6-(diethylamino)-1h-1,3,5-triazine-2,4-dithione Chemical compound CCN(CC)C1=NC(=S)NC(=S)N1 KRBGYJXDLGSDEX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 229920005556 chlorobutyl Polymers 0.000 description 1
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- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
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- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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- 229940127557 pharmaceutical product Drugs 0.000 description 1
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- 229920002492 poly(sulfone) Polymers 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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- 150000003918 triazines Chemical class 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000008215 water for injection Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Medical Preparation Storing Or Oral Administration Devices (AREA)
- Infusion, Injection, And Reservoir Apparatuses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、高浸透性液体を密封することができ、かつ、初期摺動抵抗、経時摺動抵抗及び打栓抵抗が低く、ガスバリア性の高い医療用ゴム製品に関する。 The present invention relates to a medical rubber product that can seal a highly permeable liquid and has low initial sliding resistance, sliding resistance with time, and plugging resistance, and high gas barrier properties.
医薬品の剤形の一つである注射剤には、凍結乾燥され投与時に溶解される固形製剤と、溶液のまま製剤した液剤の剤形がある。また、注射剤を体内投与する手段には、注射器から直接薬液を体内に投与する方法と、投与直前に別の薬液容器に保持された他の薬液に混合(あるいは溶解)した後、注射器以外の医療用具、例えば点滴セットなどの投与システムを経由して、体内に導入する方法とがある。 Injections that are one of pharmaceutical dosage forms include solid preparations that are lyophilized and dissolved upon administration, and liquid dosage forms that are formulated as solutions. In addition, the means for administering the injection into the body includes a method of directly administering the drug solution into the body from a syringe, and mixing (or dissolving) with another drug solution held in another drug solution container immediately before administration, There is a method of introducing into the body via a medical device, for example, an administration system such as an infusion set.
ところで、注射器兼容器内に予め注射剤を製剤(充填)しておき、端部を密封栓で封止した状態で輸送、保管し、投与の際には注射筒先端側に注射針又は投与用器具を取り付け、注射器のピストンを先端側に押し込み注射筒内を摺動させることにより、注射剤を注射針側から流出させ、投与できる、いわゆるプレフィルド型注射器があり、これは、操作が簡単であること、緊急時でも薬剤を誤用することなく正確な投与量で投与できること、薬剤を移し替える操作がなく微生物や異物による汚染を回避しやすく衛生性が高いこと等、種々の利点があるため、医療現場での治療の効率化、細菌汚染防止の観点から近年多用されるようになってきている。また、固形剤と溶解用注射用水や薬液を一つのシステム内に組み合わせた、所謂キット製品等の使用も同様の理由から奨励されている。 By the way, the injection preparation is pre-prepared (filled) in the syringe / container and transported and stored in a state where the end is sealed with a sealing plug. There is a so-called prefilled syringe that can be injected and discharged from the injection needle side by attaching the instrument, pushing the piston of the syringe toward the tip side, and sliding in the syringe barrel, which is easy to operate In addition, there are various advantages such as being able to administer in the correct dosage without misuse of the drug even in an emergency, and being easy to avoid contamination by microorganisms and foreign substances without the operation of transferring the drug, so that there are various advantages. In recent years, it has been frequently used from the viewpoint of improving the efficiency of on-site treatment and preventing bacterial contamination. For the same reason, the use of so-called kit products in which a solid agent and water for injection for injection or a chemical solution are combined in one system is also encouraged.
プレフィルド型注射器は、前記のように便利ではあるが、薬剤充填後の保管時には高い密封性が要求されると同時に、薬剤投与時には密封していた栓を摺動させる必要があり、密封性と摺動性という相反する特性が要求される。
この問題を解決するため、従来の注射器では、ピストンにシリコーンオイルを塗布して、密封性と摺動性を両立させていたが、近年、シリコーンオイルへの薬剤有効成分の吸着による力価低下や、シリコーンオイル自体の剥離物である微粒子による薬剤汚染とこれによる人体への悪影響(シリコーンオイルの毒性)が問題となっており、シリコーンオイル使用回避の方向にある。
Although the prefilled syringe is convenient as described above, it is required to have high sealing performance during storage after filling the drug, and at the same time, it is necessary to slide the sealed stopper during drug administration. The contradictory characteristics of mobility are required.
In order to solve this problem, in conventional syringes, silicone oil was applied to the piston to achieve both sealing and sliding properties. However, in recent years, the titer has decreased due to the adsorption of active pharmaceutical ingredients to silicone oil. In addition, chemical contamination by fine particles, which are exfoliated products of silicone oil itself, and adverse effects on the human body (toxicity of silicone oil) have become problems, and the use of silicone oil is avoided.
本願出願人は上記の事情に基づき、シリコーンオイルの使用なしに、ピストンの密封性と摺動性を両立させ、しかも衛生性、安全性の高い注射器、注射器兼容器を実現してきた。例えば、表面をテトラフルオロエチレン−エチレン共重合樹脂(以下「ETFE」と略記する場合もある)で被覆したピストン用ゴムや、テトラフルオロエチレン樹脂(以下「PTFE」と略記する場合もある)フィルムで被覆したピストン用ゴム、PTFE又はETFEと超高分子ポリエチレン樹脂とからなるフィルムをラミネートしたピストン用ゴム(特許文献1、2参照)を提案している。また、環状オレフィン系プラスチックからなり、前記ピストン用ゴムと組み合わせて密封性、摺動性を両立できる注射筒(シリンジ)も提案している(特許文献3参照)。 Based on the above circumstances, the applicant of the present application has realized a syringe and a syringe / container that are compatible with the sealing performance and sliding performance of the piston without using silicone oil, and that have high hygiene and safety. For example, a rubber for a piston whose surface is coated with a tetrafluoroethylene-ethylene copolymer resin (hereinafter sometimes abbreviated as “ETFE”) or a tetrafluoroethylene resin (hereinafter abbreviated as “PTFE”) film. Proposed rubber for piston, laminated rubber made of PTFE or ETFE and ultra high molecular weight polyethylene resin (see Patent Documents 1 and 2). Further, a syringe (syringe) made of a cyclic olefin plastic and capable of achieving both sealing performance and sliding performance in combination with the piston rubber has been proposed (see Patent Document 3).
また、ジエン系ゴムに熱可塑性フッ素樹脂を添加することによりシール性を低下させず、摩擦係数を低くした摺動材料が提案されている(特許文献4照)。しかし、この摺動材料は、ゴム自体の水蒸気透過率が高いこと、成形時に可塑剤が必要であること、またラミネートをしていないため、医療用ゴム製品には使用できない。
さらに、エチレン−α−オレフィン共重合体ゴムと、含フッ素単量体とオレフィンとを共重合させて予め加硫したフッ素ゴムと、を配合した耐熱性ゴムが提案されている(特許文献5照)。しかし、フッ素ゴムは高価であり、フッ素ゴムの加硫工程を経た後に、フッ素ゴムを粉砕し、エチレン−α−オレフィン共重合体に添加しなければならず、工程が複雑化し、作業効率が悪いという問題があった。
In addition, a sliding material having a low coefficient of friction has been proposed without adding a thermoplastic fluororesin to diene rubber to reduce the sealing performance (see Patent Document 4). However, this sliding material cannot be used for medical rubber products because the rubber itself has a high water vapor transmission rate, requires a plasticizer during molding, and is not laminated.
Furthermore, a heat-resistant rubber is proposed in which an ethylene-α-olefin copolymer rubber and a fluorine rubber obtained by copolymerizing a fluorine-containing monomer and an olefin and vulcanized in advance are blended (see Patent Document 5). ). However, fluoro rubber is expensive, and after passing through the vulcanization process of fluoro rubber, the fluoro rubber must be pulverized and added to the ethylene-α-olefin copolymer, which complicates the process and lowers the work efficiency. There was a problem.
ところで、第14改正日本薬局方の製剤総則において、注射剤の容器は密封容器(Hermetic container)でなければならないと規定されており、通則においては「密封容器とは、日常の取扱をし、又は通常の保存状態において、気体又は微生物の侵入のおそれのない容器をいう」と定義されている。この公定基準に照らして先行技術を検討するとき、樹脂フィルム積層密封栓は栓本体ゴム成分の溶出抑制の効果は大であるものの、シリコーンオイルを使用しないために密封性が低下する傾向がある。
本発明者らが開発してきた前記の密封栓においては、十分な密封度を保つためには密封栓の外径とシリンジ内径の差をある程度大きく設計する必要があり、そのために薬剤投与時に摺動抵抗が若干大きくなるという問題があった。
By the way, the 14th revision Japanese Pharmacopoeia General Rules for Preparations stipulates that the container of an injection must be a hermetic container, and the general rule is that “a sealed container is a daily handling, or It is defined as “a container that does not allow gas or microorganisms to enter during normal storage conditions”. When the prior art is examined in light of this official standard, the resin film laminated sealing plug has a great effect of suppressing the elution of the rubber component of the plug body, but there is a tendency that the sealing performance is lowered because silicone oil is not used.
In the above-described sealing plugs developed by the present inventors, it is necessary to design the difference between the outer diameter of the sealing plug and the inner diameter of the syringe to a certain extent in order to maintain a sufficient sealing degree. There was a problem that the resistance slightly increased.
また、ブチル系ゴムの加硫物を医療用ゴム製品に用いた場合には、注射針を刺す際の抵抗が大きく、しかも注射針を抜いた後の薬液漏れが問題となっていた。そこで本発明者らは、ハロゲン化ブチルゴムに超高分子量ポリエチレン微粉末を添加し、トリアジンチオール誘導体を加硫剤とし、亜鉛化合物の不存在下に加硫したゴム成形体を提案した(特許文献6参照)。
しかし、上記提案において、亜鉛の溶出、注射針を刺す際の抵抗及び注射針を抜いた後の薬液漏れは改善されたが、注射器ピストン用ゴムとして用いた場合の初期摺動性及び打栓性の改善については、必ずしも充分とは言えない場合があった。
Further, when a butyl rubber vulcanizate is used for a medical rubber product, there is a large resistance when the needle is inserted, and there is a problem of chemical leakage after the needle is pulled out. Therefore, the present inventors have proposed a rubber molded body obtained by adding ultra-high molecular weight polyethylene fine powder to halogenated butyl rubber, using a triazine thiol derivative as a vulcanizing agent, and vulcanizing it in the absence of a zinc compound (Patent Document 6). reference).
However, in the above proposal, the elution of zinc, the resistance when piercing the injection needle, and the chemical leakage after removing the injection needle were improved, but the initial slidability and plugging ability when used as a rubber for a syringe piston were improved. In some cases, the improvement was not always sufficient.
一方において、近年、高浸透性薬剤と呼ばれる、有機系材料からなる容器やゴム栓、ピストン等と馴染みやすく、よってこれらの隙間に入り込み液漏れを引き起こしやすい薬剤が知られているが、そのような高浸透性の薬剤についても、液剤化およびプレフィルド化の要望が高まってきている。このような要望に応えるために、形状に工夫をしたピストンを提案した(特許文献7)。
しかし、材料同士の親和性に起因する液漏れを形状で防ぐのには限度があり、更なる改善が望まれている。
On the other hand, in recent years, there has been known a drug called a highly penetrating drug, which is easy to be familiar with a container made of an organic material, a rubber stopper, a piston, etc., and thus easily enters these gaps and causes liquid leakage. The demand for liquid formulation and prefilling is also increasing for highly permeable drugs. In order to meet such a demand, a piston with a devised shape has been proposed (Patent Document 7).
However, there is a limit to prevent liquid leakage due to the affinity between materials in the form, and further improvements are desired.
本発明は、以上のような問題を解消するためになされたものであって、吸水性が低く、初期および経時の摺動抵抗が低く、打栓性がよく、焼却時の灰分が少ない医療用ゴム製品を提供することを目的とする。
また、本発明は、高浸透性を有する薬剤等の液体を密封することに特に優れた医療用ゴム製品であって、しかもゴム製品の表面にラミネートをし、樹脂製の容器と組み合わせて使用する等、より液漏れを発生しやすい条件で使用する場合にも、液漏れを良好に防ぐことができる医療用ゴム製品を提供することを目的とする。
The present invention has been made to solve the above-described problems, and has a low water absorption, low initial and time sliding resistance, good plugging property, and low ash content during incineration. The purpose is to provide rubber products.
In addition, the present invention is a medical rubber product that is particularly excellent in sealing a liquid such as a drug having high permeability, and is laminated on the surface of the rubber product and used in combination with a resin container. It is an object of the present invention to provide a medical rubber product that can satisfactorily prevent liquid leakage even when used under conditions where liquid leakage is more likely to occur.
本発明は、上記目的を達成し、薬剤適合性とともに特に密封性、摺動性に優れた高浸透性液体密封用ゴム製品を提供するために、以下の構成を有する。
(1)ブチル系ゴムまたはウレタン系ゴム(以下、これらを「ゴム成分」と記すこともある)100重量部に対し、平均粒径が1〜5μmのフッ素樹脂微粉末を10〜80重量部含有したゴム組成物を構成部品とする、高浸透性液体密封用ゴム製品であり、このブチル系ゴムは、ハロゲン化ブチルゴムであることが好ましく、またこれらのゴム成分およびフッ素樹脂微粉末と共に平均粒径10〜30μmの超高分子量ポリエチレン微粉末をゴム成分100重量部に対し5〜70重量部含有することが好ましい。また、本発明において、上記の高浸透性液体とは、表面張力45mN/m以下の液体であることが適している。
(2)さらに、本発明における高浸透性液体密封用ゴム製品の25℃でのショアA硬度は45〜75、水蒸気透過率は1g/m2・day・atm以下、初期摺動抵抗が7.0未満である。
(3)加えて、本発明における高浸透性液体密封用ゴム製品は、キャスティング法により成形したフッ素樹脂フィルムを表面にラミネートしたものであってもよい。
The present invention has the following configuration in order to achieve the above object and to provide a highly permeable liquid sealing rubber product which is excellent in drug compatibility and particularly in sealing and sliding properties.
(1) 10 to 80 parts by weight of fluororesin fine powder having an average particle size of 1 to 5 μm per 100 parts by weight of butyl rubber or urethane rubber (hereinafter sometimes referred to as “rubber component”) A rubber product for high-permeability liquid sealing, comprising the rubber composition as a component. The butyl rubber is preferably a halogenated butyl rubber, and the average particle size together with these rubber components and fluororesin fine powder. It is preferable to contain 5 to 70 parts by weight of ultrahigh molecular weight polyethylene fine powder of 10 to 30 μm with respect to 100 parts by weight of the rubber component. In the present invention, the high permeability liquid is preferably a liquid having a surface tension of 45 mN / m or less.
(2) Further, the Shore A hardness at 25 ° C. of the highly permeable liquid sealing rubber product in the present invention is 45 to 75, the water vapor transmission rate is 1 g / m 2 · day · atm or less, and the initial sliding resistance is 7. Is less than zero.
(3) In addition, the highly permeable liquid sealing rubber product in the present invention may be a laminate of a fluororesin film formed by a casting method on the surface.
本発明は、吸水性が低く、初期摺動抵抗、経時摺動抵抗及び打栓抵抗が低く、ガスバリア性が高く、焼却時の灰分が少ないばかりでなく、ゴム弾性を注射針の刺しやすい程度とし得る医療用ゴム製品を提供することができる。
また、表面張力が45mN/m以下、通常45〜35mN/m程度の高浸透性の液体を密封することに優れ、さらには35mN/m以下の超高浸透性液体を密封することに特に優れた医療用ゴム製品を提供し、しかも樹脂製の容器と組み合わせて使用することにより、より液漏れを発生しやすい条件で使用する場合においても、液漏れを良好に防ぐことができる医療用ゴム製品を提供することができる。
The present invention has low water absorption, low initial sliding resistance, low sliding resistance and plugging resistance, high gas barrier properties, low ash content during incineration, and rubber elasticity that is easy to pierce an injection needle. Obtained medical rubber products can be provided.
Moreover, it is excellent in sealing a highly permeable liquid having a surface tension of 45 mN / m or less, usually about 45 to 35 mN / m, and particularly excellent in sealing a super permeable liquid having a surface tension of 35 mN / m or less. Providing medical rubber products and using them in combination with resin containers, medical rubber products that can prevent liquid leakage even when used under conditions that are more likely to cause liquid leakage Can be provided.
本発明の高浸透性液体密封用ゴム製品は、ブチル系ゴムやウレタン系ゴムを主成分とし、平均粒径が1〜5μmのフッ素樹脂微粉末と必要により超高分子量ポリエチレン微粉末を含有し、ゴム製品の25℃でのショアA硬度が45〜75、水蒸気透過率が1g/m2・day・atm以下、初期摺動抵抗が7.0未満の特性を有する医療用ゴム組成物を成形してなるものであり、フッ素樹脂フィルム等で一部または全体がラミネートされていてもよく、上記の高浸透性液体は表面張力が45mN/m以下、通常45〜35mN/mの高浸透性液体であることが適しており、特に表面張力35mN/m以下の超高浸透性液体であることが適している。 The highly permeable liquid sealing rubber product of the present invention contains butyl rubber or urethane rubber as a main component, and contains fluororesin fine powder having an average particle size of 1 to 5 μm and, if necessary, ultrahigh molecular weight polyethylene fine powder, Molding a rubber composition for medical use having a Shore A hardness of 45 to 75 at 25 ° C., a water vapor transmission rate of 1 g / m 2 · day · atm or less, and an initial sliding resistance of less than 7.0 It may be partly or wholly laminated with a fluororesin film or the like, and the above-mentioned highly permeable liquid is a highly permeable liquid having a surface tension of 45 mN / m or less, usually 45 to 35 mN / m. It is particularly suitable to be an ultra-highly permeable liquid having a surface tension of 35 mN / m or less.
本発明におけるブチル系ゴムは、イソブチレンに少量のイソプレンを共重合させたゴムであり、優れた気体不透過性、耐熱性、耐オゾン性をもつが、一般には不飽和度が低いため加硫速度が遅い。
本発明で使用できるブチル系ゴムとしては、ブチルゴム、臭素化ブチルゴム、塩素化ブチルゴム、臭素化イソブチレン−パラメチルスチレン、架橋イソブチレン−イソプレン−ジビニルベンゼン三元共重合体などの医療用ゴム製品に一般的に使用されるブチル系ゴムが挙げられるが、中でも、上記したブチル系ゴムの優れた特性を維持しつつ、加硫速度を速くした、ハロゲン化ブチルゴムが、生産性、ガスバリア性及び溶出特性の点から好ましい。
The butyl rubber in the present invention is a rubber obtained by copolymerizing a small amount of isoprene with isobutylene, and has excellent gas impermeability, heat resistance, and ozone resistance. Is slow.
The butyl rubber that can be used in the present invention is generally used for medical rubber products such as butyl rubber, brominated butyl rubber, chlorinated butyl rubber, brominated isobutylene-paramethylstyrene, and crosslinked isobutylene-isoprene-divinylbenzene terpolymer. But, among them, the halogenated butyl rubber that has increased the vulcanization speed while maintaining the excellent characteristics of the above-mentioned butyl rubber is the point of productivity, gas barrier properties and elution characteristics To preferred.
一方、本発明で使用できるウレタン系ゴムとしては、ポリエステル型ウレタンエラストマー、ポリエーテル型ウレタンエラストマー、ポリエステル−ポリエーテル型ウレタンエラストマーが挙げられる。
前記ポリエステル型ウレタンエラストマーは、ポリエステルポリオールとイソシアネート化合物とを主成分とする組成物を反応させて得られるエラストマーであり、前記ポリエーテル型ウレタンエラストマーは、ポリエーテルポリオールとイソシアネート化合物とを主成分とする組成物を反応させて得られるエラストマーであり、前記ポリエステル−ポリエーテル型ウレタンエラストマーは、ポリエステルポリオールとポリエーテルポリオールとイソシアネート化合物とを主成分とする組成物を反応させて得られるエラストマーである。
これらのウレタン系ゴムを使用する場合には、ブチル系ゴムを使用する場合に比べ、ガスバリヤ性はやや劣るものの、初期摺動抵抗はより低くすることができる。
On the other hand, examples of the urethane rubber that can be used in the present invention include a polyester type urethane elastomer, a polyether type urethane elastomer, and a polyester-polyether type urethane elastomer.
The polyester-type urethane elastomer is an elastomer obtained by reacting a composition having a polyester polyol and an isocyanate compound as main components, and the polyether-type urethane elastomer has a polyether polyol and an isocyanate compound as main components. It is an elastomer obtained by reacting a composition, and the polyester-polyether type urethane elastomer is an elastomer obtained by reacting a composition mainly comprising a polyester polyol, a polyether polyol and an isocyanate compound.
When these urethane rubbers are used, the initial sliding resistance can be further reduced, although the gas barrier properties are slightly inferior to those when butyl rubbers are used.
本発明において、上記のブチル系ゴムやウレタン系ゴムに配合するフッ素樹脂微粉末は、例えば、テトラフルオロエチレン、ヘキサフルオロプロピレン、ペンタフルオロプロピレン、フッ化ビニリデン、フッ化ビニルなどのモノマーをそれぞれ、1種類のみで重合したホモポリマー、複数種のモノマーで重合したコポリマーからなるフッ素樹脂の粉末が挙げられる。
前記ホモポリマーとしては、例えば、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン、ポリペンタフルオロプロピレン、ポリフッ化ビニリデン、ポリフッ化ビニル、ポリフルオロクロロエチレンなどが挙げられ、これらは、1種単独で使用してもよいし、複数種を混合して使用してもよい。
前記コポリマーとしては、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン−ペルフルオロエチレン共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−エチレン共重合体、トリフルオロクロロエチレン−エチレン共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン−パーフルオロアルキルビニルエーテル共重合体などが挙げられ、これらは、1種単独で使用してもよいし、複数種を混合して使用してもよい。
これらのフッ素樹脂の中でも、ポリテトラフルオロエチレン(PTFE)が、表面滑性及び低反応性、低表面自由エネルギー化の点で特に好適である。
なお、表面自由エネルギーとは表面張力と類似する概念であり、組成物分子間の相互作用により決定するエネルギーである。固体の表面自由エネルギーが高いほど、その表面に付着した液滴を広げる力が大きくなり、結果として、接触角θが小さく、つまりは固体と液滴との濡れ性が高くなる。固体と液体のぬれ性が高いほど、液体はわずかな隙間から漏れやすくなり、密封には不利になる。
In the present invention, the fluororesin fine powder blended in the butyl rubber or urethane rubber includes, for example, monomers such as tetrafluoroethylene, hexafluoropropylene, pentafluoropropylene, vinylidene fluoride, and vinyl fluoride. Examples thereof include a fluoropolymer powder composed of a homopolymer polymerized by only one kind and a copolymer polymerized by plural kinds of monomers.
Examples of the homopolymer include polytetrafluoroethylene, polyhexafluoropropylene, polypentafluoropropylene, polyvinylidene fluoride, polyvinyl fluoride, polyfluorochloroethylene, and the like. Alternatively, a plurality of types may be mixed and used.
Examples of the copolymer include tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-perfluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, trifluorochloro. Examples include ethylene-ethylene copolymers, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymers, and these may be used alone or in combination of two or more. Also good.
Among these fluororesins, polytetrafluoroethylene (PTFE) is particularly suitable in terms of surface lubricity, low reactivity, and low surface free energy.
The surface free energy is a concept similar to surface tension and is energy determined by the interaction between composition molecules. The higher the surface free energy of the solid, the greater the force that spreads the droplets attached to the surface, resulting in a smaller contact angle θ, that is, higher wettability between the solid and the droplets. The higher the wettability between the solid and the liquid, the more likely the liquid will leak through a small gap, which is disadvantageous for sealing.
本発明では、上記のようなフッ素樹脂であって、粉砕しやすく分散性をよくするために低分子量(分子量:数千〜数十万)タイプで、平均粒径が1〜5μmの微粉末を使用する。平均粒径が5μmを超えると、ゴム組成物中におけるフッ素樹脂微粉末の分散性が悪くなり、1μm未満では、配合時にフッ素樹脂微粉末の飛散が起こる。好ましい平均粒径は、加工や飛散等の問題から1〜2μm程度である。
なお、配合時におけるフッ素樹脂微粉末の飛散を極力抑制するために、フッ素樹脂微粉末を数回に分けて添加する等が好ましい。
In the present invention, a fine powder having a low molecular weight (molecular weight: thousands to hundreds of thousands) type and an average particle diameter of 1 to 5 μm is used for the above fluororesin so as to be easily pulverized and improve dispersibility. use. When the average particle diameter exceeds 5 μm, the dispersibility of the fluororesin fine powder in the rubber composition is deteriorated. When the average particle diameter is less than 1 μm, the fluororesin fine powder is scattered during blending. A preferable average particle diameter is about 1 to 2 μm because of problems such as processing and scattering.
In addition, in order to suppress the scattering of the fluororesin fine powder as much as possible, it is preferable to add the fluororesin fine powder in several portions.
本発明では、上記のフッ素樹脂微粉末を、医療用ゴム製品の表面自由エネルギー低下剤として、またゴム製品の耐摩耗性、摺動性を改善する目的で、配合する。
本発明で使用するフッ素樹脂微粉末は、上記のうち、PTFEパウダーや、PTFE/パーフルオロ(アルコキシトリフルオロエチレン)共重合体等のファインパウダーであって、低分子量(分子量:数千〜数十万)タイプの、平均粒径が1〜5μmの微粉末が特に好ましい。
In the present invention, the above-mentioned fluororesin fine powder is blended as a surface free energy reducing agent for medical rubber products and for the purpose of improving the wear resistance and slidability of rubber products.
Among the above, the fluororesin fine powder used in the present invention is a fine powder such as PTFE powder or PTFE / perfluoro (alkoxytrifluoroethylene) copolymer, and has a low molecular weight (molecular weight: several thousand to several tens). A fine powder having an average particle size of 1 to 5 μm is particularly preferred.
本発明におけるフッ素樹脂微粉末の配合割合は、少なすぎると、高浸透性液体の濡れ性が高くなるばかりか、水蒸気透過率が1g/m2・day・atm以下、初期摺動抵抗が7.0未満で、かつゴム弾性が注射針の刺しやすい程度を維持したゴム製品を得ることができず、多すぎると、高浸透性液体の濡れ性は低くなるが、上記所望のゴム弾性が得られ難くなる上、コスト高となってしまうため、ゴム成分100重量部に対して10〜80重量部、好ましくは30〜60重量部の範囲とする。 When the blending ratio of the fluororesin fine powder in the present invention is too small, not only the wettability of the highly permeable liquid is increased, but also the water vapor permeability is 1 g / m 2 · day · atm or less and the initial sliding resistance is 7. A rubber product having a rubber elasticity of less than 0 and maintaining a rubber elasticity that is easy to pierce an injection needle cannot be obtained. If the rubber product is too much, the wettability of the highly permeable liquid is lowered, but the desired rubber elasticity is obtained. In addition to being difficult and costly, the amount is set to 10 to 80 parts by weight, preferably 30 to 60 parts by weight with respect to 100 parts by weight of the rubber component.
また、本発明においては、ゴム組成物の補強剤として、超高分子量ポリエチレン微粉末を配合することが好ましい。この超高分子量ポリエチレン微粉末は、分子量が100万〜300万の超高分子量で、平均粒径が10〜30μmの微粉末が好ましく、例えば商品名ハイゼックスミリオンメター240、三井化学社製商品名MIPELON等が使用できる。
超高分子量ポリエチレン微粉末の平均粒径が10μm未満であると、取り扱いが困難になる場合があり、30μmを超えると、ゴム組成物中での分散性が悪くなる場合がある。
Moreover, in this invention, it is preferable to mix | blend ultra high molecular weight polyethylene fine powder as a reinforcing agent of a rubber composition. The ultra high molecular weight polyethylene fine powder is preferably a ultra high molecular weight molecular weight of 1,000,000 to 3,000,000 and a fine powder having an average particle size of 10 to 30 μm. For example, trade name “HIEX Million Metal 240”, trade name “MIPELON” manufactured by Mitsui Chemicals, Inc. Etc. can be used.
When the average particle size of the ultrahigh molecular weight polyethylene fine powder is less than 10 μm, handling may be difficult, and when it exceeds 30 μm, dispersibility in the rubber composition may be deteriorated.
上記の超高分子量ポリエチレン微粉末の配合によって、ハロゲン化ブチルゴムの加硫の遅れによる表面のタック性が減少し、耐摩耗性、耐薬品性、ゴム材の持つ粘着性等を改善し、硬度を増加させる。
配合割合は、ゴム成分100重量部に対し5〜70重量部とすることが適しており、配合割合が多いほど上記特性を向上させるが、医療用ゴムの用途により要求特性は異なるため、目的に応じて配合割合を変えることが望ましい。例えば、容器用ゴム栓の場合には、注射針を刺し込むときの抵抗を少なくするために、タック性の除去に重点をおいた、ゴム成分100重量部に対して5〜25重量部の割合が、注射器用ゴム栓の場合には、硬度を高め、適切な密封性を出すために、ゴム成分100重量部に対し20〜70重量部の割合が好適である。上記の各下限量未満では、各ゴム栓に必要な硬さを付与することができないばかりか、ゴム材の持つ粘着性を抑えることができず、また硬度不足に起因する液漏れの発生等の問題があり、上記の各上限量を超えると、それぞれのゴム栓が硬くなりすぎ、各ゴム栓の弾性や伸び等が低下したり、コアリングの問題が発生する。
By blending the above ultra-high molecular weight polyethylene fine powder, surface tackiness due to delay in vulcanization of halogenated butyl rubber is reduced, improving wear resistance, chemical resistance, adhesiveness of rubber material, etc. increase.
The blending ratio is suitably 5 to 70 parts by weight with respect to 100 parts by weight of the rubber component. The larger the blending ratio is, the more the above characteristics are improved, but the required characteristics differ depending on the use of the medical rubber. It is desirable to change the blending ratio accordingly. For example, in the case of a rubber stopper for a container, a ratio of 5 to 25 parts by weight with respect to 100 parts by weight of the rubber component, with an emphasis on removal of tackiness, in order to reduce resistance when the injection needle is inserted. However, in the case of a rubber stopper for a syringe, a ratio of 20 to 70 parts by weight is preferable with respect to 100 parts by weight of the rubber component in order to increase the hardness and to obtain an appropriate sealing property. If the amount is less than the above lower limit amounts, not only the required hardness cannot be imparted to each rubber stopper, but also the adhesiveness of the rubber material cannot be suppressed, and the occurrence of liquid leakage due to insufficient hardness, etc. There is a problem, and when the above upper limit amounts are exceeded, the respective rubber plugs become too hard, and the elasticity and elongation of the respective rubber plugs are reduced, or a coring problem occurs.
本発明のゴム製品において、フッ素樹脂微粉末と超高分子量ポリエチレンとを含有させることによって、加硫あるいは硬化後の医療用ゴム製品の硬度等の物性の調整が容易となる。
具体的には、フッ素樹脂微粉末と超高分子量ポリエチレン微粉末とを配合して、加硫あるいは硬化後の医療用ゴム製品の25℃でのショアA硬度が50〜70、水蒸気透過率が1g/m2・day・atom以下、初期摺動抵抗が7.0未満であって、表面張力45mN/m以下、好ましくは35mN/m以下の液体を長期にわたって密封することができる医療用ゴム製品を製造するために、フッ素樹脂と超高分子量ポリエチレンの配合比を調整しつつ、これらを配合することが好ましい。
なお、表面張力35mN/m以下の超高浸透性液体の場合、表面にフッ素樹脂をラミネートしたピストンでは一般には密封が困難であるとされているが、本発明のゴム製品においては、表面にフッ素樹脂をラミネートしたものであっても、長期にわたって効果的な密封を実現できる。
By including the fluororesin fine powder and the ultra high molecular weight polyethylene in the rubber product of the present invention, it becomes easy to adjust physical properties such as hardness of the medical rubber product after vulcanization or curing.
Specifically, a fluororesin fine powder and an ultrahigh molecular weight polyethylene fine powder are blended, and a vulcanized or cured medical rubber product has a Shore A hardness of 50 to 70 at 25 ° C. and a water vapor permeability of 1 g. / M 2 · day · atom or less, an initial sliding resistance of less than 7.0, and a medical rubber product capable of sealing a liquid having a surface tension of 45 mN / m or less, preferably 35 mN / m or less over a long period of time In order to produce, it is preferable to mix | blend these, adjusting the compounding ratio of a fluororesin and ultra high molecular weight polyethylene.
In the case of an ultra-highly permeable liquid having a surface tension of 35 mN / m or less, it is generally difficult to seal with a piston laminated with a fluororesin on the surface. Even if the resin is laminated, effective sealing can be realized over a long period of time.
また、本発明では、上記の超高分子量ポリエチレン微粉末と共に、あるいは該微粉末に代えて、他の有機系補強剤及び/又は有機系充填剤を配合することができる。
他の有機系補強剤(及び/又は有機系充填剤)としては、ポリエチレン(PE)、ポリプロピレン(PP)、ポリカーボネート(PC)、ポリブタジエン(BR)、1,2−結合スチレンブタジエンゴム(SBR)、ポリスルホン系樹脂(例えば、商品名VDEL)などが挙げられる。
In the present invention, other organic reinforcing agents and / or organic fillers can be blended together with or in place of the ultra-high molecular weight polyethylene fine powder.
Other organic reinforcing agents (and / or organic fillers) include polyethylene (PE), polypropylene (PP), polycarbonate (PC), polybutadiene (BR), 1,2-bonded styrene butadiene rubber (SBR), Polysulfone resin (for example, trade name VDEL) etc. are mentioned.
さらに、本発明においては、その他の添加剤として、架橋剤、カップリング剤、老化防止剤、安定剤、加工助剤などを添加することもできる。
上記の超高分子量ポリエチレンを使用した場合の架橋剤としては、医療用ゴム製品として、注射針刺し性に優れると共に、注射針抜き取り後の薬液漏れ防止性確保のために、有機過酸化物、トリアジン誘導体等の加硫剤を使用するのが好ましい。
この有機過酸化物としては、医療用ゴム製品として一般的に使用されるものが使用でき、具体的には、1,3−(t−ブチルパーオキシイソプロピル)ベンゼン、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン−3、1,1−ジ(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、ジイソブチルパーオキシド、n−ブチル−4,4−ビス(t−ブチルパーオキシ)バレレート等が挙げられる。
トリアジン誘導体としては、2−置換−4,6−ジチオール−s−トリアジン誘導体が、2,4,6−トリチオール−s−トリアジン(トリチオシアヌル酸)、2−ブチルアミノ−4,6−ジチオール−s−トリアジン、2−エチルアミノ−4,6−ジチオール−s−トリアジン・ジオクチルアミン及び2−ブチル−4,6−ジチオール−s−トリアジン・ジトリエチルアンモニウム塩等が挙げられる。
これらの架橋剤は、ブチルゴム100重量部当り、0.1〜5重量部配合するのが好ましい。
Further, in the present invention, as other additives, a crosslinking agent, a coupling agent, an anti-aging agent, a stabilizer, a processing aid, and the like can be added.
As a crosslinking agent in the case of using the above ultra-high molecular weight polyethylene, as a medical rubber product, it is excellent in injection needle sticking property, and in order to ensure prevention of chemical leakage after removal of the injection needle, an organic peroxide, a triazine derivative It is preferable to use a vulcanizing agent such as
As this organic peroxide, those generally used as medical rubber products can be used. Specifically, 1,3- (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2 , 5-Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, 1,1-di (t-butylperoxy) -3, Examples include 3,5-trimethylcyclohexane, diisobutyl peroxide, n-butyl-4,4-bis (t-butylperoxy) valerate.
As triazine derivatives, 2-substituted-4,6-dithiol-s-triazine derivatives are 2,4,6-trithiol-s-triazine (trithiocyanuric acid), 2-butylamino-4,6-dithiol-s-. Examples include triazine, 2-ethylamino-4,6-dithiol-s-triazine / dioctylamine, and 2-butyl-4,6-dithiol-s-triazine / ditriethylammonium salt.
These crosslinking agents are preferably blended in an amount of 0.1 to 5 parts by weight per 100 parts by weight of butyl rubber.
上記のカップリング剤としては、医療用ゴム製品として一般的に使用されるものが使用できるが、具体的には、シランカップリング剤(例えば、ビニルトリメキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、テトラキス(2−エチルヘキシル)チタネート、ジプロポキシビス(アセチルアセトナト)チタン〔チタンアセチルアセトナート〕、硫黄、ステアリン酸、トリアリルシアヌレート、トリアリルイソシアヌレート、トリメチロールプロパントリメタクリレート、1,2−ポリブタジエン、m−フェニレンビスマレイミド、酸化マグネシウム、酸化チタン、酸化亜鉛、ビス(2−ジエチルアミノ)−4,6−ジメルカプト−s−トリアジン)などが挙げられる。
これらカップリング剤の添加量は、ゴム組成物全体を100重量部として、0〜5重量部添加することができる。
As the above-mentioned coupling agent, those generally used as medical rubber products can be used. Specifically, silane coupling agents (for example, vinyltrimexylsilane, γ-methacryloxypropyltrimethoxysilane) can be used. , Γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, tetrakis (2-ethylhexyl) titanate, dipropoxybis (acetylacetonato) Titanium [titanium acetylacetonate], sulfur, stearic acid, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, 1,2-polybutadiene, m-phenylene bismaleimide, magnesium oxide, titanium oxide, Zinc, bis (2-diethylamino) -4,6-dimercapto -s- triazine) and the like.
These coupling agents can be added in an amount of 0 to 5 parts by weight based on 100 parts by weight of the entire rubber composition.
上記の老化防止剤としては、医療用ゴム製品として一般的に使用されるものが使用でき、例えば、2,6−ジ−t−ブチル−p−クレゾール、n−オクタデシル−β−(4'−ヒドロキシ−3',5'−ジ−t−ブチルフェニル)プロピオネート、テトラキス〔メチレン−3(3',5'−ジ−t−ブチル−4'−ヒドロキシフェニル)プロピオネート〕メタンなどが挙げられる。
老化防止剤の添加量は、ゴム組成物全体を100重量部として、0.05〜1重量部添加することができる。
As the anti-aging agent, those generally used as medical rubber products can be used. For example, 2,6-di-t-butyl-p-cresol, n-octadecyl-β- (4′- Hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, tetrakis [methylene-3 (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and the like.
The addition amount of the anti-aging agent can be 0.05 to 1 part by weight based on 100 parts by weight of the entire rubber composition.
上記の安定剤としては、医療用ゴム製品として一般的に使用されるものが使用でき、例えば、亜鉛華(酸化亜鉛)、酸化マグネシウムなどが挙げられる。
上記の加工助剤としては、医療用ゴム製品として一般的に使用されるものが使用でき、例えば、アクリル系加工助剤などが挙げられる。
As said stabilizer, what is generally used as a medical rubber product can be used, For example, zinc white (zinc oxide), magnesium oxide, etc. are mentioned.
As said processing aid, what is generally used as a medical rubber product can be used, for example, acrylic processing aid etc. are mentioned.
なお、本発明の医療用ゴム製品は、重金属化合物、例えば鉛、カドミウム、白金など比重6.0以上の重金属類は配合しないことが好ましい。
過酸化鉛、酸化鉛等の鉛系化合物、塩化白金酸、コロイド白金、塩化スズなどは、ゴム組成物の架橋時間を短縮したり架橋密度を向上する架橋助剤として作用する例が知られているが、本発明においては、最終ゴム製品としての使用分野において重金属の存在は避けるべきものであることから、架橋効果があっても使用しないことが好ましい。
The medical rubber product of the present invention preferably does not contain heavy metal compounds such as heavy metals having a specific gravity of 6.0 or more such as lead, cadmium and platinum.
Lead compounds such as lead peroxide and lead oxide, chloroplatinic acid, colloidal platinum, tin chloride, etc. are known to act as crosslinking aids that shorten the crosslinking time or improve the crosslinking density of rubber compositions. However, in the present invention, since heavy metals should be avoided in the field of use as the final rubber product, it is preferable not to use them even if they have a crosslinking effect.
本発明のゴム製品の成形方法としては、金型を用いて架橋を行うと同時に成形する静的架橋方法による成形方法、あるいは、押出機、インターナルミキサー、カールなどによる動的架橋方法によりゴム組成物を架橋した後に、打ち抜き加工や切削加工により成形する方法などが挙げられる。
前記静的架橋方法及び動的架橋方法における架橋手段としては、加熱、光照射、放射線照射などを用いることができる。
The rubber product molding method of the present invention includes a rubber composition by a static crosslinking method in which molding is performed simultaneously with a mold, or a dynamic crosslinking method by an extruder, an internal mixer, a curl or the like. Examples of the method include a method of forming a product by punching or cutting after cross-linking the object.
As the crosslinking means in the static crosslinking method and the dynamic crosslinking method, heating, light irradiation, radiation irradiation and the like can be used.
加熱による架橋方法としては、例えば、金型中で温度140〜200℃に加熱して架橋成形する方法、インターナルミキサーや押出機中で140〜300℃で加熱して動的架橋する方法がある。
放射線を用いた架橋方法としては、例えば、吸収線量で50kGy〜200kGyの照射、特に電子線照射による架橋方法が挙げられる。
また、少量の架橋剤を用いて静的架橋又は動的架橋を行ったゴム製品に、50kGy〜200kGy程度の電子線を照射して再架橋を行ってもよい。
この方法では、架橋剤の添加量を少なくすることができ、かつ医療用品、医薬品用製品に必要な滅菌処理を同時に行うことができる。
As a crosslinking method by heating, for example, there is a method of crosslinking at a temperature of 140 to 200 ° C. in a mold, and a method of dynamic crosslinking by heating at 140 to 300 ° C. in an internal mixer or an extruder. .
As a crosslinking method using radiation, for example, a crosslinking method by irradiation of 50 kGy to 200 kGy in an absorbed dose, particularly electron beam irradiation can be mentioned.
Further, re-crosslinking may be performed by irradiating an electron beam of about 50 kGy to 200 kGy to a rubber product subjected to static crosslinking or dynamic crosslinking using a small amount of a crosslinking agent.
In this method, the amount of the crosslinking agent added can be reduced, and sterilization necessary for medical supplies and pharmaceutical products can be simultaneously performed.
本発明のゴム製品は、表面にフッ素樹脂フィルムを積層することが好ましい。表面にフッ素樹脂フィルムを積層することによって、ゴム製品の摺動性が向上するだけでなく、保管時や使用時の耐熱性や耐薬品性もさらに向上する。
なお、本発明においては、ブチル系あるいはウレタン系のゴムにフッ素樹脂微粉末を混合することにより、ゴム組成物自体の成形時の流れ性を改善することができ、フィルムを積層したゴム製品を成形するときのフィルムへの負荷を軽減できるため、フィルムが延伸されるときに生ずる目に見えない微細な亀裂が抑制でき、また微細な亀裂が生じたとしても、亀裂から露出するゴム組成物は表面自由エネルギーの低いゴムであることから、高浸透性液体の漏れも生じず、かつ経時による摺動抵抗の上昇も抑制された考えられる。
前記フッ素樹脂フィルムの製造方法としては、スカイビング法やキャスティング法がある。
The rubber product of the present invention preferably has a fluororesin film laminated on the surface. By laminating a fluororesin film on the surface, not only the slidability of the rubber product is improved, but also the heat resistance and chemical resistance during storage and use are further improved.
In the present invention, by mixing fluororesin fine powder with butyl rubber or urethane rubber, the flowability of the rubber composition itself during molding can be improved, and a rubber product in which films are laminated is molded. Since the load on the film can be reduced, invisible fine cracks that occur when the film is stretched can be suppressed, and even if fine cracks occur, the rubber composition exposed from the cracks is Since the rubber has a low free energy, it is considered that the leakage of the highly permeable liquid does not occur and the increase in sliding resistance with time is suppressed.
As a method for producing the fluororesin film, there are a skiving method and a casting method.
前記スカイビング法では、以下のようにしてフッ素樹脂フィルムが製造される。
まず、平均粒子径が10μm以下のフッ素樹脂の成形加工用微粉末状樹脂原料を焼結成形用金型に充填し、室温、100〜1000kg/cm2の圧力で圧縮プレスして予備成形した後、360〜380℃で数時間焼結し、一次成型品を得る。この一次成型品を旋盤機に取り付け、回転させながら、金属製の刃物で削ることによって、フッ素樹脂フィルムが得られる。
一方、前記キャスティング法では、以下のようにしてフッ素樹脂フィルムが製造される。
フッ素樹脂の微粒子の懸濁液に、ラテックス乳化液を加え、これを金属面上に薄く流延した後、焼成することによって、フッ素樹脂フィルムが得られる。
前記スカイビング法により製造されたフッ素樹脂フィルムは、フィルムにピンホールや切削傷が発生し易いため、前記キャスティング法により製造されたフッ素樹脂フィルムを用いるのが好ましい。
In the skiving method, a fluororesin film is produced as follows.
First, a fine powdery resin raw material for molding processing of fluororesin having an average particle size of 10 μm or less is filled in a sintering mold, and is pre-molded by compression pressing at room temperature and a pressure of 100 to 1000 kg / cm 2. And sintering at 360 to 380 ° C. for several hours to obtain a primary molded product. A fluororesin film is obtained by attaching the primary molded product to a lathe machine and cutting it with a metal blade while rotating.
On the other hand, in the casting method, a fluororesin film is produced as follows.
A latex emulsion is added to a suspension of fine particles of a fluororesin, and this is thinly cast on a metal surface, followed by firing to obtain a fluororesin film.
Since the fluororesin film produced by the skiving method is likely to cause pinholes and cutting flaws in the film, it is preferable to use the fluororesin film produced by the casting method.
ゴム製品へのフッ素樹脂フィルムの積層は、以下のようにして行われる。
加硫前のゴムシートとフッ素樹脂フィルムとを、該ゴムシートの粘着力により積層させて積層シートとし、該積層シートを金型に投入して成形・加硫することによって、金型によるゴム製品の成形・加硫とフッ素樹脂フィルムの積層とを同時に行うことができる。
これにより、接着剤を一切使用せずにゴム製品の表面にフッ素樹脂フィルムを積層することができる。
Lamination of the fluororesin film to the rubber product is performed as follows.
A rubber sheet made of a mold is obtained by laminating a rubber sheet and a fluororesin film before vulcanization with the adhesive force of the rubber sheet to form a laminated sheet, and then molding and vulcanizing the laminated sheet by putting it in a mold. The molding and vulcanization and the lamination of the fluororesin film can be performed simultaneously.
Thereby, a fluororesin film can be laminated | stacked on the surface of a rubber product, without using an adhesive agent at all.
本発明のゴム製品には、滅菌処理を施すのが好ましい。前記滅菌処理の方法としては、高圧高温の水蒸気等による滅菌処理や放射線による滅菌処理が挙げられる。特に、放射線処理による滅菌は、滅菌操作が容易で好ましい。
前記放射線による滅菌処理に用いる放射線としては、α線(ヘリウムの原子核)、β線(電子線)及びγ線があるが、滅菌には加速器で作られたβ線(電子線)や、60Coや137Csから発生するγ線が好ましい。
放射線として電子線を用いる場合には、電子線の線量率が極めて高いので(γ線の数万倍)、滅菌処理時間は短いが、粒子線である為に透過力が小さい。
一方、放射線としてγ線(X線も同じ)を用いる場合には、γ線は電磁波の一種であって、透過力は大きいが、線量率が電子線に較べて小さいので、処理時間は長時間必要である。透過力の大きいγ線でゴム製品を滅菌する場合、ダンボール箱で外包した見掛けの容量の大きな物品も容易に照射滅菌が可能であるが、γ線は線量率が低いので、所定の線量を照射するに要する処理時間も数時間に及ぶ場合がある。
The rubber product of the present invention is preferably sterilized. Examples of the sterilization method include sterilization with high-pressure and high-temperature steam and sterilization with radiation. In particular, sterilization by radiation treatment is preferable because sterilization is easy.
The radiation used for the sterilization treatment by the radiation includes α rays (helium nuclei), β rays (electron rays) and γ rays. For sterilization, β rays (electron rays) produced by an accelerator, 60 Co And γ rays generated from 137 Cs are preferred.
When an electron beam is used as radiation, the dose rate of the electron beam is extremely high (tens of thousands times that of γ-rays), so the sterilization treatment time is short, but since it is a particle beam, its permeability is small.
On the other hand, when γ-rays (same as X-rays) are used as radiation, γ-rays are a kind of electromagnetic waves and have a high transmission power, but the dose rate is small compared to electron beams, so the processing time is long. is necessary. When sterilizing rubber products with γ-rays with high penetrating power, it is possible to easily sterilize articles with a large apparent volume enclosed in a cardboard box, but γ-rays have a low dose rate, so they are irradiated with a prescribed dose. The processing time required for this may be several hours.
(実施例1)
表1に示すように、ブチル系ゴム100重量部に対し、フッ素樹脂微粉末(平均粒子径2μm)50重量部、超高分子量ポリエチレン微粉末(分子量200万、平均粒子径20μm)50重量部、亜鉛華1.5重量部、ジペンタメチレンチウラムテトラサルファイド(架橋助剤)2.5重量部、酸化チタン1重量部、シランカップリング剤0.5重量部を、バンバリーミキサーに投入し混練し、混練された配合物をカレンダーロールで更に十分に練り込み、配合物を厚さ10mmのシート状の未加硫ゴム組成物として取り出した。
前記厚さ10mmシート状ゴム組成物と厚さ30μmのフッ素樹脂フィルムとを積層し、金型に入れ、プレフィルド注射器に用いるピストン用ゴムを成形・加硫した。
Example 1
As shown in Table 1, with respect to 100 parts by weight of butyl rubber, 50 parts by weight of fluororesin fine powder (average particle diameter 2 μm), 50 parts by weight of ultrahigh molecular weight polyethylene fine powder (molecular weight 2 million, average particle diameter 20 μm), 1.5 parts by weight of zinc white, 2.5 parts by weight of dipentamethylene thiuram tetrasulfide (crosslinking aid), 1 part by weight of titanium oxide, 0.5 parts by weight of silane coupling agent are charged into a Banbury mixer and kneaded. The kneaded compound was further sufficiently kneaded with a calender roll, and the compound was taken out as a sheet-like unvulcanized rubber composition having a thickness of 10 mm.
The 10 mm-thick sheet rubber composition and a 30 μm-thick fluororesin film were laminated, put into a mold, and molded and vulcanized for a rubber for a piston used in a prefilled syringe.
(実施例2〜4)
実施例1の組成物を表1に示す組成物(フッ素樹脂微粉末と超高分子量ポリエチレン微粉末の粒径と分子量は実施例1と同じで、トリアジンは2−ブチルアミノー4,6−ジオール−s−トリアジン、過酸化物はベンゾイルパーオキサイドを使用)に変更した以外は、実施例1と同様に行った。
(Examples 2 to 4)
The composition of Example 1 is the composition shown in Table 1 (the particle size and molecular weight of the fluororesin fine powder and the ultrahigh molecular weight polyethylene fine powder are the same as in Example 1, and the triazine is 2-butylamino-4,6-diol-s. -Performed in the same manner as in Example 1 except that benzoyl peroxide was used as the triazine and peroxide.
(実施例5)
フッ素樹脂フィルムを積層する代わりに、熱架橋して得られたゴム製品の表面にシリコーンコート(0.5μg/mm2)を施した以外は、実施例1と同様に行った。
(Example 5)
Instead of laminating the fluororesin film, the same procedure as in Example 1 was performed, except that a silicone coat (0.5 μg / mm 2 ) was applied to the surface of the rubber product obtained by thermal crosslinking.
(比較例1〜2、4)
実施例1の組成物を表1に示す組成物に変更した以外は、実施例1と同様に行った。
(Comparative Examples 1-2, 4)
The same procedure as in Example 1 was performed except that the composition of Example 1 was changed to the composition shown in Table 1.
(比較例3)
フッ素樹脂フィルムを積層する代わりに、ゴム製品の表面にシリコーンコートを施した以外は、比較例1と同様に行った。
(Comparative Example 3)
It carried out similarly to the comparative example 1 except having provided the silicone coat on the surface of the rubber product instead of laminating | stacking a fluororesin film.
(評価)
<摺動抵抗>
容量1mLのプラスチック(環状オレフィンポリマー)製注射器を用意し、上記実施例1〜5及び比較例1〜3で得られたピストン用ゴムを該注射器に対応するサイズのピストンに成形してプランジャーロッドに装着し、注射筒に挿入する。その後、蒸留水を1mL注射筒内へ吸入し、注射筒のノズル部にノズルキャップを嵌めて密封し、1日、1週間、2週間、3週間、1ヶ月静置し、試料注射器とする。
各期間経過後、注射器のノズル部からノズルキャップを外し、該ノズル部に規定サイズ(27G)の市販のディスポーザブル注射針をしっかり挿入する。
注射筒のノズル部を下に向けて治具で固定し、圧力センサー付き「(株)島津製作所製、オートグラフAG−1KND(商品名)」の球座式圧縮試験用圧盤により、100mm/secの速度でプランジャーロッドをノズル側に押し込み、この時の摺動抵抗値を測定する。得られた摺動測定チャートから最大値を読み取り、摺動抵抗値とする。
製造直後の摺動抵抗値を初期摺動抵抗値として表1に示し、製造後所定期間経過後の摺動抵抗値を表2に示す。なお、各試験についてサンプル数(n)は20とし、表の数値はそれらの平均値である。
(Evaluation)
<Sliding resistance>
A syringe made of plastic (cyclic olefin polymer) having a capacity of 1 mL is prepared, and the piston rubber obtained in Examples 1 to 5 and Comparative Examples 1 to 3 is molded into a piston of a size corresponding to the syringe, and a plunger rod And insert it into the syringe barrel. Then, distilled water is inhaled into a 1 mL syringe, and a nozzle cap is fitted into the syringe barrel and sealed, and left for 1 day, 1 week, 2 weeks, 3 weeks, and 1 month to form a sample syringe.
After each period, the nozzle cap is removed from the nozzle part of the syringe, and a commercially available disposable injection needle of a prescribed size (27G) is firmly inserted into the nozzle part.
Fix the syringe with the jig facing the nozzle part downward, and use a pressure plate with a pressure sensor of “Autograph AG-1KND (trade name) manufactured by Shimadzu Corporation” for 100 mm / sec. Push the plunger rod toward the nozzle at the speed of, and measure the sliding resistance at this time. The maximum value is read from the obtained sliding measurement chart and used as the sliding resistance value.
The sliding resistance value immediately after production is shown in Table 1 as the initial sliding resistance value, and the sliding resistance value after the lapse of a predetermined period after production is shown in Table 2. In addition, the number of samples (n) is 20 for each test, and the numerical values in the table are average values thereof.
<ガス(水蒸気)透過性>
ガス(水蒸気)透過性の評価は、JIS Z 0208に準拠する方法(カップ法)により行い、結果を表1に合わせて示す。
<Gas (water vapor) permeability>
The gas (water vapor) permeability is evaluated by a method (cup method) based on JIS Z 0208, and the results are shown in Table 1.
<ショア硬度A>
ショア硬度Aの評価は、JIS K 6253に準拠する方法(タイプAデュロメーターを使用)により行い、結果を表1に合わせて示す。
<Shore hardness A>
The Shore hardness A is evaluated by a method according to JIS K 6253 (using a type A durometer), and the results are shown in Table 1.
<高浸透性液体密封性>
上記の摺動抵抗の評価試験要領と同様のプラスチック製注射器を用意し、上記実施例1〜5及び比較例1〜3で得られたピストン用ゴムを該注射器に対応するサイズのピストンに成形してプランジャーロッドに装着し、注射筒に挿入する。その後、蒸留水を表面張力が35mN/mの液体を所定量注射筒内へ吸入し、注射筒のノズル部にノズルキャップを嵌めて密封し、1日、1週間、2週間、3週間、1ヶ月静置し、試料注射器とする。
この試料注射筒を保管倉庫に保管し、1日、1週間、2週間、3週間、1ヶ月静置後に目視にて観察し、液漏れの有無を確認した。結果を表3に示す。
<High permeability liquid sealing>
A plastic syringe similar to the above-mentioned sliding resistance evaluation test procedure is prepared, and the piston rubber obtained in Examples 1 to 5 and Comparative Examples 1 to 3 is molded into a piston of a size corresponding to the syringe. Attach to plunger rod and insert into syringe. Thereafter, distilled water is sucked into the syringe barrel with a predetermined amount of liquid having a surface tension of 35 mN / m, and the nozzle portion of the syringe barrel is fitted with a nozzle cap and sealed, 1 day, 1 week, 2 weeks, 3 weeks, Let stand for months and use as a sample syringe.
This sample syringe was stored in a storage warehouse, and was observed visually after standing for 1 day, 1 week, 2 weeks, 3 weeks, and 1 month to confirm the presence or absence of liquid leakage. The results are shown in Table 3.
本発明の医療用ゴム製品は、医療用具一般に用いることができるが、注射器のピストン用ゴム、点滴用パック等における注射針を貫通させるためのゴム栓等、特に、最近注目されているプレフィルド型注射器に好適に使用することができる。
また、高浸透性液体を密封させる必要のあるピストン用ゴムや容器用ゴム栓等のゴム製品に用いて極めて有益である。
The medical rubber product of the present invention can be used for medical devices in general, but a rubber plug for penetrating an injection needle in a syringe piston, a drip pack, etc. Can be suitably used.
Further, it is extremely useful when used for rubber products such as rubber for pistons and rubber stoppers for containers that need to seal a highly permeable liquid.
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WO2016056149A1 (en) * | 2014-10-07 | 2016-04-14 | 有限会社コーキ・エンジニアリング | Gasket using slidable medical silicone rubber, and syringe using said gasket |
KR102261795B1 (en) * | 2019-12-23 | 2021-06-04 | 셰플러코리아 유한책임회사 | An ACM Compound For Seal Having Improved Wear Resistance |
WO2022202881A1 (en) | 2021-03-25 | 2022-09-29 | テルモ株式会社 | Continuous administration device |
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