JP2023088414A - Polyacetal resin composition used in application of radiation sterilization, and radiation resistance improvement method of polyacetal resin - Google Patents
Polyacetal resin composition used in application of radiation sterilization, and radiation resistance improvement method of polyacetal resin Download PDFInfo
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- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 57
- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 56
- 239000011342 resin composition Substances 0.000 title claims abstract description 33
- 230000005855 radiation Effects 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 title claims abstract description 20
- 239000011347 resin Substances 0.000 title claims abstract description 20
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 13
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 30
- -1 amine compound Chemical class 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 8
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical group CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 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 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- 229920004943 Delrin® Polymers 0.000 description 1
- 229920005177 Duracon® POM Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UKJARPDLRWBRAX-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 UKJARPDLRWBRAX-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、新たな放射線滅菌を行う用途に用いるポリアセタール樹脂組成物およびポリアセタール樹脂の放射線耐性向上方法に関する。 TECHNICAL FIELD The present invention relates to a polyacetal resin composition for use in radiation sterilization and a method for improving the radiation resistance of the polyacetal resin.
従来、医療機器の滅菌では、高圧蒸気滅菌やエチレンオキシドガスによる滅菌が行われてきたが、最近はγ線や電子線による放射線滅菌が多くなっている。医療機器ではプラスチックが多く使用されているが、放射線に対する耐性がプラスチック材料の選択に大きな影響を与えている。 Conventionally, high-pressure steam sterilization and ethylene oxide gas sterilization have been used for sterilization of medical devices, but recently radiation sterilization using γ-rays and electron beams has become popular. Plastics are often used in medical devices, and their resistance to radiation has a great influence on the selection of plastic materials.
例えば、特許文献１では多官能トリアジン化合物、具体的にはトリアリルイソシアヌレートを高分子に含有させる技術が報告されている。 For example, Patent Document 1 reports a technique of incorporating a polyfunctional triazine compound, specifically triallyl isocyanurate, into a polymer.
一方、ポリエチレン、ポリプロピレン、シリコーン樹脂等が医療機器への使用実績が重ねられてきたが、さらに強度や摺動特性の必要とされる用途へのプラスチック材料の拡大が求められている。しかしながら、上記化合物では、プラスチック材料との相溶性に問題が発生しやすく、例えばポリアセタール樹脂への適用は困難であった。近年、ポリアセタール樹脂の医療機器への用途拡大の要望が高まり、耐放射線性を向上したポリアセタール樹脂が求められてきた。 On the other hand, although polyethylene, polypropylene, silicone resins, etc. have been used in medical devices, there is a demand for expansion of the use of plastic materials for applications requiring greater strength and sliding properties. However, the above compounds tend to have compatibility problems with plastic materials, and are difficult to apply to polyacetal resins, for example. In recent years, there has been a growing demand for expanded use of polyacetal resins in medical devices, and polyacetal resins with improved radiation resistance have been sought.
本発明の目的は、放射線滅菌を行う用途に用いる新たなポリアセタール樹脂組成物およびポリアセタール樹脂の放射線耐性向上方法を提供することにある。 An object of the present invention is to provide a new polyacetal resin composition for use in radiation sterilization and a method for improving the radiation resistance of the polyacetal resin.
本発明は、下記によって達成された。 The present invention has been achieved by the following.
１． 放射線滅菌を行う用途に用いるポリアセタール樹脂組成物であって、
該ポリアセタール樹脂組成物が、ヒンダードアミン系化合物を含有するポリアセタール樹脂組成物であって、該ヒンダードアミン系化合物が、
（Ａ）分子量１０００以下のヒンダードアミン化合物、および
（Ｂ）分子量１０００を超える、ヒンダードアミン骨格をペンダントしたモノマーの重合体であって、末端にヒンダードアミン骨格を有するヒンダードアミンポリマー、
から選択される少なくとも１種である、ポリアセタール樹脂組成物。
２． 前記ヒンダードアミン系化合物が有するヒンダードアミン骨格が、２，２，６，６－テトラメチルピペリジン環構造である前記１記載のポリアセタール樹脂組成物。
３． 前記請求項１または２に記載のポリアセタール樹脂組成物を使用した、ポリアセタール樹脂の放射線耐性向上方法。
1. A polyacetal resin composition used for radiation sterilization,
The polyacetal resin composition is a polyacetal resin composition containing a hindered amine compound, wherein the hindered amine compound is
(A) a hindered amine compound having a molecular weight of 1000 or less; and (B) a hindered amine polymer having a hindered amine skeleton at its terminal end and a polymer of monomers having a molecular weight of more than 1000 and pendant hindered amine skeletons;
A polyacetal resin composition which is at least one selected from
2. 2. The polyacetal resin composition according to 1 above, wherein the hindered amine skeleton of the hindered amine compound has a 2,2,6,6-tetramethylpiperidine ring structure.
3. A method for improving the radiation resistance of a polyacetal resin using the polyacetal resin composition according to claim 1 or 2.
本発明によれば、放射線滅菌を行う用途に用いる新たなポリアセタール樹脂組成物およびポリアセタール樹脂の放射線耐性向上方法を提供することが可能となる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a new polyacetal resin composition for use in radiation sterilization and a method for improving the radiation resistance of the polyacetal resin.
以下、本発明の具体的な実施形態について、詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。 Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the purpose of the present invention. can do.
本発明のポリアセタール樹脂組成物は、放射線滅菌を行う用途に用いるポリアセタール樹脂組成物であって、該ポリアセタール樹脂組成物が、ヒンダードアミン系化合物を含有することを特徴とする。 The polyacetal resin composition of the present invention is a polyacetal resin composition for use in radiation sterilization, and is characterized by containing a hindered amine compound.
本発明のポリアセタール樹脂組成物は、少なくともポリアセタール樹脂とヒンダードアミン系化合物を含有する。 The polyacetal resin composition of the present invention contains at least a polyacetal resin and a hindered amine compound.
本発明のヒンダードアミン系化合物により、ポリアセタール樹脂組成物の耐放射線性が改善される理由は、ヒンダードアミン骨格が化合物の外側に配置されており、この形態がポリアセタール樹脂組成物においても維持されること、そしてポリアセタール樹脂とは適度な相溶性によりポリアセタール樹脂組成物から染み出すことはないが成形品の表面近傍により偏在し、放射線によって発生したラジカルを効率的にトラップしているからであると推測している。 The reason why the hindered amine compound of the present invention improves the radiation resistance of the polyacetal resin composition is that the hindered amine skeleton is arranged on the outside of the compound, and this form is maintained in the polyacetal resin composition, and Due to the moderate compatibility with polyacetal resin, it does not leak out from the polyacetal resin composition, but it is unevenly distributed near the surface of the molded product, and it is speculated that it efficiently traps radicals generated by radiation. .
＜ポリアセタール樹脂＞
本発明に使用されるポリアセタール樹脂は、オキシメチレン基（－ＯＣＨ２－）を構成単位とするホモポリマー（例えば米国ＤｕＰｏｎｔ社製、商品名「デルリン」等）でもよいし、オキシメチレン単位以外に他のコモノマー単位を有するコポリマー（例えば、ポリプラスチックス（株）製、商品名「ジュラコン」等）であってもよい。熱安定性などの点からコポリマーであることが好ましい。
<Polyacetal resin>
The polyacetal resin used in the present invention may be a homopolymer having an oxymethylene group (—OCH 2 —) as a constituent unit (for example, manufactured by DuPont in the United States, trade name “Delrin”, etc.), or other than the oxymethylene unit. (for example, Polyplastics Co., Ltd., trade name "Duracon", etc.) may be used. Copolymers are preferred from the viewpoint of thermal stability.
ポリアセタールコポリマーは、一般的にはホルムアルデヒド又はホルムアルデヒドの環状化合物を主モノマーとし、環状エーテルや環状ホルマールから選ばれた化合物をコモノマーとして共重合させることによって製造され、通常、熱分解、（アルカリ）加水分解等によって末端の不安定部分を除去して安定化される。 Polyacetal copolymers are generally produced by copolymerizing formaldehyde or a cyclic compound of formaldehyde as a main monomer and a compound selected from cyclic ethers and cyclic formals as a comonomer. It is stabilized by removing the terminal unstable portion by, for example.
特に、主モノマーとしてはホルムアルデヒドの環状三量体であるトリオキサンを用いるのが一般的である。トリオキサンは、一般的には酸性触媒の存在下でホルムアルデヒド水溶液を反応させることにより得られ、これを蒸留などの方法で精製して使用される。重合に用いるトリオキサンは、水、メタノール、蟻酸などの不純物の含有量が極力少ないものが好ましい。 In particular, trioxane, which is a cyclic trimer of formaldehyde, is generally used as the main monomer. Trioxane is generally obtained by reacting an aqueous formaldehyde solution in the presence of an acidic catalyst, and is used after being purified by a method such as distillation. The trioxane used for polymerization preferably contains as little impurities as possible such as water, methanol and formic acid.
コモノマーとしては、一般的な環状エーテル及び環状ホルマール、また分岐構造や架橋構造を形成可能なグリシジルエーテル化合物などを単独で又は二種以上組み合わせて使用できる。 As comonomers, general cyclic ethers and cyclic formals, glycidyl ether compounds capable of forming a branched structure or a crosslinked structure, and the like can be used alone or in combination of two or more.
上記の如きポリアセタールコポリマーは、一般には適量の分子量調整剤を添加し、カチオン重合触媒を用いてカチオン重合することにより得ることができる。使用される分子量調整剤、カチオン重合触媒、重合方法、重合装置、重合後の触媒の失活化処理、重合によって得られた粗ポリアセタールコポリマーの末端安定化処理法などは多くの文献によって公知であり、基本的にはそれらが何れも利用できる。 Polyacetal copolymers such as those described above can generally be obtained by adding an appropriate amount of a molecular weight modifier and carrying out cationic polymerization using a cationic polymerization catalyst. Molecular weight modifiers to be used, cationic polymerization catalysts, polymerization methods, polymerization equipment, catalyst deactivation treatment after polymerization, terminal stabilization treatment methods for crude polyacetal copolymers obtained by polymerization, etc. are known from many documents. , basically any of them can be used.
本発明で使用するポリアセタール樹脂の分子量は特に限定されないが、１，１，１，３，３，３－ヘキサフルオロイソプロパノールを溶離液とするＳＥＣ（サイズ排除クロマトグラフィー）法にて決定したポリメタクリル酸メチル相当の重量平均分子量が１０，０００～４００，０００のものが好ましい。また、樹脂の流動性の指標となるメルトインデックス（ＩＳＯ１１３３に準じ、１９０℃、荷重２.１６ｋｇで測定）が０．１～１００ｇ／１０分であるものが好ましく、さらに好ましくは０．５～８０ｇ／１０分である。 The molecular weight of the polyacetal resin used in the present invention is not particularly limited. Those having a weight average molecular weight equivalent to methyl of 10,000 to 400,000 are preferred. Further, the melt index (measured at 190° C. under a load of 2.16 kg according to ISO 1133), which is an index of resin fluidity, is preferably 0.1 to 100 g/10 minutes, more preferably 0.5 to 80 g. /10 minutes.
＜ヒンダードアミン系化合物＞
本発明のヒンダードアミン系化合物は、（Ａ）分子量１０００以下のヒンダードアミン化合物、および（Ｂ）分子量１０００を超える、ヒンダードアミン骨格をペンダントしたモノマーの重合体であって、末端にヒンダードアミン骨格を有するヒンダードアミンポリマー、から選択される少なくとも１種であることを特徴とする。
<Hindered amine compound>
The hindered amine compound of the present invention comprises (A) a hindered amine compound having a molecular weight of 1000 or less, and (B) a polymer of monomers having a molecular weight of more than 1000 and pendant hindered amine skeletons, the hindered amine polymer having a hindered amine skeleton at its end. It is characterized by being at least one selected.
ヒンダードアミン系化合物が有するヒンダードアミン骨格が、２，２，６，６－テトラメチルピペリジン環構造を有することが好ましく、ピペリジン環の窒素原子は、アルキル基で置換されていてもよい。末端に有するヒンダードアミン骨格は、ポリマー鎖の両末端に有しても良い。 The hindered amine skeleton of the hindered amine compound preferably has a 2,2,6,6-tetramethylpiperidine ring structure, and the nitrogen atom of the piperidine ring may be substituted with an alkyl group. The terminal hindered amine skeleton may be present at both ends of the polymer chain.
なお、ここで分子量は、構造式が明確なものはその構造式から計算される分子量を指し、構造が必ずしも明確でない重合度の異なる重合体の混合物等の場合は、推定される構造式の他、核磁気共鳴法、サイズ排除クロマトグラフィー法、光散乱法や蒸気圧降下法，沸点上昇法，凝固点(融点)降下法(ラスト法)，等温蒸留法(バージャー法)，質量分析法等、通常の方法を使用して測定することができる。 In addition, the molecular weight here refers to the molecular weight calculated from the structural formula when the structural formula is clear. In the case of a mixture of polymers with different degrees of polymerization whose structure is not necessarily clear, other , nuclear magnetic resonance method, size exclusion chromatography method, light scattering method, vapor pressure depression method, boiling point elevation method, freezing point (melting point) depression method (Last method), isothermal distillation method (Buger method), mass spectrometry, etc. can be measured using the method of
≪（Ａ）分子量１０００以下のヒンダードアミン化合物≫
本発明の（Ａ）分子量１０００以下のヒンダードアミン化合物としては、具体的には下記の化合物が挙げられる。
<<(A) Hindered amine compound having a molecular weight of 1000 or less>>
Specific examples of (A) the hindered amine compound having a molecular weight of 1,000 or less in the present invention include the following compounds.
≪（Ｂ）分子量１０００を超える、主鎖にヒンダードアミン構造をペンダントした重合体であって、末端にヒンダードアミン構造を有する重合体≫
本発明の（Ｂ）分子量１０００を超える、ヒンダードアミン骨格をペンダントしたモノマーの重合体であって、末端にヒンダードアミン骨格を有するヒンダードアミンポリマーは、ヒンダードアミン構造を有するモノマーの重合体であり、重合体の末端に、さらにヒンダードアミン構造を有するアミンを反応させた化合物であり、重合体主鎖にヒンダードアミン構造がペンダントし、末端にヒンダードアミン構造を有する重合体である。
<<(B) A polymer having a hindered amine structure pendant to its main chain and having a molecular weight of more than 1000, and having a hindered amine structure at its end>>
The (B) polymer of a monomer having a hindered amine skeleton pendant thereto having a molecular weight of more than 1,000 and having a hindered amine skeleton at the end of the present invention (B) is a polymer of a monomer having a hindered amine structure, and has a hindered amine structure at the end of the polymer. Furthermore, it is a compound obtained by reacting an amine having a hindered amine structure, and is a polymer having a hindered amine structure pendant to the main chain of the polymer and a hindered amine structure at the end.
具体的には下記に示す重合体が挙げられる。ｎは繰り返し単位であることを表す。また、ペンダントとは、重合体の主鎖からヒンダードアミン骨格がぶら下がっている構造をいう。 Specific examples include the polymers shown below. n represents a repeating unit. The term "pendant" refers to a structure in which a hindered amine skeleton hangs from the main chain of the polymer.
本発明においては、これらの化合物から選ばれた少なくとも一種又は二種以上を使用することができる。これらの化合物は、ＢＡＳＦジャパン株式会社、ＡＤＥＫＡ株式会社等から市販品を入手することができる。 In the present invention, at least one or two or more selected from these compounds can be used. These compounds are commercially available from BASF Japan Ltd., ADEKA Corporation and the like.
本発明におけるヒンダードアミン系化合物の含有量は、ポリアセタール樹脂１００質量部に対し、０．１～２．０質量部であり、０．２～１．５質量部であることがより好ましい。 The content of the hindered amine compound in the present invention is 0.1 to 2.0 parts by mass, more preferably 0.2 to 1.5 parts by mass, per 100 parts by mass of the polyacetal resin.
≪その他の成分≫
本発明のポリアセタール樹脂組成物には、本発明を阻害しない限り、必要に応じて、さらに、熱安定剤、耐衝撃性改良剤、摺動性改良剤、充填剤、着色剤、核剤、帯電防止剤、界面活性剤、相溶化剤などを一種又は二種以上配合することができる。
≪Other ingredients≫
If necessary, the polyacetal resin composition of the present invention may further contain a heat stabilizer, an impact resistance improver, a slidability improver, a filler, a coloring agent, a nucleating agent, and an electrifying agent, as long as it does not interfere with the present invention. One or two or more of inhibitors, surfactants, compatibilizers and the like can be blended.
＜用途＞
本発明のポリアセタール樹脂組成物は、本発明のヒンダードアミン系化合物を含ませることにより、耐放射線性を高めることができ、放射線滅菌を行う医療機器の用途に用いることができる。例えば薬剤吸入器具、注射器具、輸液用器具の部品等に使用することができる。
<Application>
By containing the hindered amine compound of the present invention, the polyacetal resin composition of the present invention can be improved in radiation resistance, and can be used for applications of medical devices that undergo radiation sterilization. For example, it can be used for drug inhalation devices, injection devices, parts for infusion devices, and the like.
＜耐放射線向上方法＞
本発明のポリアセタール樹脂組成物の耐放射線性向上方法は、ポリアセタール樹脂組成物に放射線耐性を発現する方法であって、ポリアセタール樹脂にヒンダードアミン系化合物を添加することを特徴としている。
<Method for Improving Radiation Resistance>
The method for improving radiation resistance of a polyacetal resin composition of the present invention is a method for developing radiation resistance in a polyacetal resin composition, and is characterized by adding a hindered amine compound to the polyacetal resin.
上述の通り、本発明のポリアセタール樹脂組成物を成形して得られる部材は放射線照射後も十分な機械特性を維持している。本発明のポリアセタール樹脂組成物の放射線耐性発現方法において、ポリアセタール樹脂に対するヒンダードアミン系化合物の好ましい添加量については、上述の本発明ポリアセタール樹脂組成物で説明した通りである。 As described above, the member obtained by molding the polyacetal resin composition of the present invention maintains sufficient mechanical properties even after irradiation. In the method for developing radiation resistance of the polyacetal resin composition of the present invention, the preferred amount of the hindered amine compound to be added to the polyacetal resin is as described above for the polyacetal resin composition of the present invention.
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these.
表１における各種成分は次のとおりである。表中の単位は質量部である。
・ポリアセタール樹脂（以下、ＰＯＭとも略す）
トリオキサン９６．７質量％と１，３－ジオキソラン３．３質量％とを共重合させてなるポリアセタールコポリマー（メルトインデックス（ＩＳＯ１１３３に準拠し、１９０℃，荷重２．１６ｋｇで測定）：９ｇ／１０ｍｉｎ）
Various components in Table 1 are as follows. Units in the table are parts by mass.
・Polyacetal resin (hereinafter also abbreviated as POM)
Polyacetal copolymer obtained by copolymerizing 96.7% by mass of trioxane and 3.3% by mass of 1,3-dioxolane (melt index (measured at 190° C. under a load of 2.16 kg according to ISO1133): 9 g/10 min)
・ヒンダードアミン系化合物
（Ａ－１）Ｎ，Ｎ’－１，６－ヘキサンジイル－ビス―Ｎ－（２，２，６，６－テトラメチル－４－ピペリジニル）フォルムアミド（Ｕｖｉｎｙｌ ４０５０ＦＦ、ＢＡＳＦジャパン株式会社製）分子量＝４５０
Hindered amine compound (A-1) N,N'-1,6-hexanediyl-bis-N-(2,2,6,6-tetramethyl-4-piperidinyl) formamide (Uvinyl 4050FF, BASF Japan Co., Ltd.) manufactured by the company) Molecular weight = 450
（Ａ－２）ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート（チヌビン ７７０ＤＦ、ＢＡＳＦジャパン社製）分子量＝４８１ (A-2) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (tinuvin 770DF, manufactured by BASF Japan) molecular weight = 481
（Ａ－３）テトラキス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－ブタン－１，２，３，４-テトラカルボキシレート（アデカスタブＬＡ－５２、ＡＤＥＫＡ株式会社製）分子量＝８４７ (A-3) Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-butane-1,2,3,4-tetracarboxylate (ADEKA STAB LA-52, manufactured by ADEKA Corporation) molecular weight = 847
（Ｂ－１） Ｃｈｉｍａｓｓｏｒｂ ２０２０ＦＤＬ（ＢＡＳＦジャパン株式会社製）分子量＝２６００～３４００ (B-1) Chimassorb 2020FDL (manufactured by BASF Japan Ltd.) molecular weight = 2600 to 3400
（Ａ’、Ｂ’）その他の化合物
（Ａ’－４）１，３，５－トリアリル－１，３，５－トリアジン-２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン （試薬 、関東化学株式会社製）分子量＝２４９
(A', B') Other compounds (A'-4) 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Reagent , Kanto Chemical Co., Ltd.) molecular weight = 249
（Ｂ’－２）ブタン酸ジメチルエステルポリマーと４－ヒドロキシ－２，２，６，６－テトラメチル－１－ピペリジンエタノールとの反応物（チヌビン６２２ＳＦ、ＢＡＳＦジャパン株式会社製）分子量＝３１００～４０００ (B'-2) Reaction product of butanoic acid dimethyl ester polymer and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol (tinuvin 622SF, manufactured by BASF Japan Ltd.) molecular weight = 3100 to 4000
（Ｂ’－３）Ｃｈｉｍａｓｓｏｒｂ ９４４ＦＤＬ（ＢＡＳＦジャパン株式会社製）分子量＝２０００～３１００ (B'-3) Chimassorb 944FDL (manufactured by BASF Japan Ltd.) molecular weight = 2000 to 3100
＜実施例及び比較例＞
表１に示す各種成分を表１に示す割合で添加混合し、二軸の押出機を用いてシリンダー温度２１０℃で溶融混練してペレット状のポリアセタール樹脂組成物を調製した。
<Examples and Comparative Examples>
Various components shown in Table 1 were added and mixed in the proportions shown in Table 1, melt-kneaded at a cylinder temperature of 210° C. using a twin-screw extruder, and pellet-shaped polyacetal resin compositions were prepared.
＜評価＞
上記ペレット状のポリアセタール樹脂組成物を使用し、下記条件で射出成形により厚さ４ｍｍのＩＳＯｔｙｐｅ１－Ａ多目的試験片を作製し、以下の評価を行った。
・成形機： αＳ１００ｉ－Ａ（ファナック（株））
・成形条件：シリンダー温度（℃） ノズル－Ｃ１－ Ｃ２－ Ｃ３
２００ ２００ １８０ １７０℃
保圧力 ６０（ＭＰａ）
射出速度 ８．０（ｍｍ／ｓ）
金型温度 ９０（℃）
<Evaluation>
Using the pellet-shaped polyacetal resin composition, an ISO type 1-A multi-purpose test piece having a thickness of 4 mm was prepared by injection molding under the following conditions, and the following evaluation was performed.
・Molding machine: αS100i-A (Fanuc Corporation)
・Molding conditions: Cylinder temperature (°C) Nozzle - C1 - C2 - C3
200 200 180 170°C
Holding pressure 60 (MPa)
Injection speed 8.0 (mm/s)
Mold temperature 90 (°C)
１）耐放射線の評価（機械的特性）
前記試験片およびその試験片に室温、常圧下で２５ｋＧｙの電子線を照射した後の試験片について、ＩＳＯ５２７－１、５２７－２に準拠し破断時の引張破断ひずみ（ＴＥ）測定を行った。測定室は、常圧、２３℃５０％ＲＨの雰囲気を保持した。照射後のＴＥの照射前ＴＥに対する比率であるＴＥ保持率（％）を求めた。結果を表１に示す。
1) Evaluation of radiation resistance (mechanical properties)
Tensile breaking strain (TE) at break was measured according to ISO527-1 and 527-2 for the test piece and the test piece after irradiating the test piece with 25 kGy electron beam at room temperature and normal pressure. The measurement chamber was kept under normal pressure, 23° C. and 50% RH. A TE retention rate (%), which is a ratio of TE after irradiation to TE before irradiation, was determined. Table 1 shows the results.
２）添加剤のＰＯＭ樹脂への溶解性（相溶性）：染み出し評価
前記試験片を１００℃の恒温槽に７日保持したあと、試験片の表面を目視で観察した。
表面の状況で以下の様に分別評価した。結果を表１に示す。Ｂ以上が、実用的に使用可能な範囲である。
Ａ：試験片表面に添加剤由来の曇りは見られない。
Ｂ：試験片表面の一部に添加剤由来の曇りが見られた。
Ｃ：試験片表面全体に添加剤由来の曇りが見られた。
2) Solubility (Compatibility) of Additives in POM Resin: Evaluation of Exudation After holding the test piece in a constant temperature bath at 100° C. for 7 days, the surface of the test piece was visually observed.
The surface conditions were classified and evaluated as follows. Table 1 shows the results. B or higher is the practically usable range.
A: Additive-derived haze is not observed on the surface of the test piece.
B: Additive-derived haze was observed on part of the surface of the test piece.
C: Additive-derived haze was observed on the entire surface of the test piece.
表１に示す通り、本発明ではＴＥ保持率が高く、耐放射線性に優れることがわかる。また相溶性に関しても実用的に問題のないことがわかる。
As shown in Table 1, the present invention has a high TE retention rate and excellent radiation resistance. It is also found that there are practically no problems with compatibility.
Claims (3)
該ポリアセタール樹脂組成物が、ヒンダードアミン系化合物を含有するポリアセタール樹脂組成物であって、該ヒンダードアミン系化合物が、
（Ａ）分子量１０００以下のヒンダードアミン化合物、および
（Ｂ）分子量１０００を超える、ヒンダードアミン骨格をペンダントしたモノマーの重合体であって、末端にヒンダードアミン骨格を有するヒンダードアミンポリマー、
から選択される少なくとも１種である、ポリアセタール樹脂組成物。 A polyacetal resin composition used for radiation sterilization,
The polyacetal resin composition is a polyacetal resin composition containing a hindered amine compound, wherein the hindered amine compound is
(A) a hindered amine compound having a molecular weight of 1000 or less; and (B) a hindered amine polymer having a hindered amine skeleton at its terminal end and a polymer of monomers having a molecular weight of more than 1000 and pendant hindered amine skeletons;
A polyacetal resin composition which is at least one selected from
A method for improving the radiation resistance of a polyacetal resin using the polyacetal resin composition according to claim 1 or 2.
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| PCT/JP2022/038030 WO2023112450A1 (en) | 2021-12-15 | 2022-10-12 | Polyacetal resin composition used in applications for performing radiation sterilization, and method for improving radiation resistance in polyacetal resin |
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| JP2021100990A (en) * | 2019-12-24 | 2021-07-08 | 公立大学法人 滋賀県立大学 | Resin composition, resin-molded article, and manufacturing method of resin-molded article |
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| EP1338622A3 (en) * | 2003-03-14 | 2003-09-10 | Ciba SC Holding AG | Stabilizer mixtures |
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| JPH01229052A (en) * | 1988-03-08 | 1989-09-12 | Nitto Kasei Co Ltd | Gamma-ray resistant thermoplastic resin composition |
| JPH10265585A (en) * | 1997-03-26 | 1998-10-06 | Polyplastics Co | Antimicrobial polyacetal resin composition |
| EP1339622A2 (en) * | 2000-12-04 | 2003-09-03 | Entegris, Inc. | Wafer carrier with stacking adaptor plate |
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