WO2023002726A1 - Polyacetal resin used in applications in which radiation sterilization is carried out, and method for improving radiation resistance of polyacetal resin - Google Patents
Polyacetal resin used in applications in which radiation sterilization is carried out, and method for improving radiation resistance of polyacetal resin Download PDFInfo
- Publication number
- WO2023002726A1 WO2023002726A1 PCT/JP2022/017680 JP2022017680W WO2023002726A1 WO 2023002726 A1 WO2023002726 A1 WO 2023002726A1 JP 2022017680 W JP2022017680 W JP 2022017680W WO 2023002726 A1 WO2023002726 A1 WO 2023002726A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyacetal resin
- resin composition
- radiation
- present
- applications
- Prior art date
Links
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 53
- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 52
- 230000005855 radiation Effects 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 title claims abstract description 24
- 239000011347 resin Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 13
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 13
- 239000011342 resin composition Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002989 phenols Chemical class 0.000 claims description 13
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 8
- -1 phenol compound Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 235000013824 polyphenols Nutrition 0.000 abstract description 8
- 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 5
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 4
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-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
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 description 2
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 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
- 239000000178 monomer Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 235000005875 quercetin Nutrition 0.000 description 2
- 229960001285 quercetin Drugs 0.000 description 2
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- TUYBEVLJKZQJPO-UHFFFAOYSA-N 19-(3,5-ditert-butyl-4-hydroxyphenyl)heptatriacontan-19-ylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCC(CCCCCCCCCCCCCCCCCC)(P(O)(O)=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 TUYBEVLJKZQJPO-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-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
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RDFLLVCQYHQOBU-GPGGJFNDSA-O Cyanin Natural products O([C@H]1[C@H](O)[C@H](O)[C@H](O)[C@H](CO)O1)c1c(-c2cc(O)c(O)cc2)[o+]c2c(c(O[C@H]3[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O3)cc(O)c2)c1 RDFLLVCQYHQOBU-GPGGJFNDSA-O 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
- CITFYDYEWQIEPX-UHFFFAOYSA-N Flavanol Natural products O1C2=CC(OCC=C(C)C)=CC(O)=C2C(=O)C(O)C1C1=CC=C(O)C=C1 CITFYDYEWQIEPX-UHFFFAOYSA-N 0.000 description 1
- FNUPUYFWZXZMIE-UHFFFAOYSA-N Fustin Natural products O1C2=CC(O)=CC=C2C(=O)C(O)C1C1=CC=C(O)C(O)=C1 FNUPUYFWZXZMIE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000005487 catechin Nutrition 0.000 description 1
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 229950001002 cianidanol Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- RDFLLVCQYHQOBU-ZOTFFYTFSA-O cyanin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C(=[O+]C1=CC(O)=C2)C=3C=C(O)C(O)=CC=3)=CC1=C2O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 RDFLLVCQYHQOBU-ZOTFFYTFSA-O 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 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
- 150000002206 flavan-3-ols Chemical class 0.000 description 1
- 235000011987 flavanols Nutrition 0.000 description 1
- 229930003949 flavanone Natural products 0.000 description 1
- 150000002208 flavanones Chemical class 0.000 description 1
- 235000011981 flavanones Nutrition 0.000 description 1
- 229930003944 flavone Natural products 0.000 description 1
- 150000002213 flavones Chemical class 0.000 description 1
- 235000011949 flavones Nutrition 0.000 description 1
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Natural products O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 description 1
- 150000002216 flavonol derivatives Chemical class 0.000 description 1
- 235000011957 flavonols Nutrition 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- FNUPUYFWZXZMIE-HUUCEWRRSA-N fustin Chemical compound C1([C@@H]2[C@@H](C(C3=CC=C(O)C=C3O2)=O)O)=CC=C(O)C(O)=C1 FNUPUYFWZXZMIE-HUUCEWRRSA-N 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
- CJWQYWQDLBZGPD-UHFFFAOYSA-N isoflavone Natural products C1=C(OC)C(OC)=CC(OC)=C1C1=COC2=C(C=CC(C)(C)O3)C3=C(OC)C=C2C1=O CJWQYWQDLBZGPD-UHFFFAOYSA-N 0.000 description 1
- 150000002515 isoflavone derivatives Chemical class 0.000 description 1
- 235000008696 isoflavones Nutrition 0.000 description 1
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 description 1
- 235000009498 luteolin Nutrition 0.000 description 1
- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
Definitions
- the present invention relates to a polyacetal resin used for new radiation sterilization applications and a method for improving the radiation resistance of the polyacetal resin.
- Patent Document 1 reports a technique for incorporating a polyfunctional triazine compound, specifically triallyl isocyanurate, into a polymer.
- the purpose of the present invention is to provide a polyacetal resin used for new radiation sterilization applications and a method for improving the radiation resistance of the polyacetal resin.
- the present invention has been achieved by the following.
- a polyacetal resin composition used for radiation sterilization A polyacetal resin composition comprising at least one compound selected from hindered phenolic compounds and polyphenolic compounds.
- the polyacetal resin composition according to 1 above wherein one of the carbon atoms adjacent to the carbon atom having the phenolic hydroxyl group of the hindered phenol compound has a methyl group or a methylene group as a substituent.
- 3. The polyacetal resin composition as described in 1 or 2 above, wherein the hindered phenolic compound is 2,2′-methylenebis(6-tert-butyl-4-methylphenol). 4.
- a method for improving the radiation resistance of a polyacetal resin using the polyacetal resin composition according to any one of 1 to 3 above.
- the present invention it is possible to provide a polyacetal resin used for new radiation sterilization applications and a method for improving the radiation resistance of the polyacetal resin.
- the polyacetal resin composition of the present invention is a polyacetal resin composition used for radiation sterilization, wherein the polyacetal resin composition contains at least one compound selected from hindered phenolic compounds and polyphenolic compounds. characterized by
- the polyacetal resin composition of the present invention contains at least a polyacetal resin and at least one compound selected from hindered phenolic compounds and polyphenolic compounds.
- the polyacetal resin used in the present invention may be a homopolymer having an oxymethylene group (—OCH 2 —) as a structural unit (for example, manufactured by DuPont in the United States, trade name “Delrin”, etc.). (for example, Polyplastics Co., Ltd., trade name "Duracon”, etc.) may be used. Copolymers are preferred from the viewpoint of thermal stability.
- 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.
- trioxane which is a cyclic trimer of formaldehyde
- 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.
- a polyacetal copolymer such as the one described above can generally be obtained by adding an appropriate amount of a molecular weight modifier and subjecting it to 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.
- 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.
- one of the carbons adjacent to the carbon having the phenolic hydroxyl group of the phenolic compound preferably has a methyl group or a methylene group as a substituent.
- Polyphenolic compounds used in the present invention include flavones, isoflavones, flavonols, flavanones, flavanols, anthocyans, and the like. Specific examples include luteolin, catechin, quercetin, cherry netin, fustin, cyanin, protoanthocyanidin, and the like. A polyphenol compound having 3 or more phenolic hydroxyl groups is preferred.
- At least one or two or more selected from these compounds can be used.
- the content of at least one compound selected from hindered phenol-based compounds and polyphenol-based compounds in the present invention is 0.1 to 2.0 parts by mass, and 0.2 to 1 0.5 parts by mass is more preferred.
- 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.
- 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.
- the polyacetal resin composition of the present invention contains at least one compound selected from the hindered phenolic compound and the polyphenolic compound of the present invention, so that radiation resistance can be improved, and radiation sterilization is performed for medical devices.
- the method for improving the radiation resistance of a polyacetal resin composition of the present invention is a method for expressing radiation resistance in a polyacetal resin composition, wherein at least one compound selected from hindered phenolic compounds and polyphenolic compounds is added to the polyacetal resin. is characterized by the addition of
- the member obtained by molding the polyacetal resin composition of the present invention maintains sufficient mechanical properties even after irradiation.
- the preferable addition amount of at least one compound selected from hindered phenolic compounds and polyphenolic compounds to the polyacetal resin is as described above in the polyacetal resin composition of the present invention.
- Table 1 Various components in Table 1 are as follows. Units in the table are parts by mass.
- POM Polyacetal resin
- Polyacetal copolymer obtained by copolymerizing 96.7% by mass of trioxane and 3.3% by mass of 1,3-dioxolane (melt index (according to ISO1133, measured at 190°C under a load of 2.16 kg): 9g/10min)
- B At least one compound selected from hindered phenolic compounds and polyphenolic compounds (B-1) 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (SUMILIZER MDP-S Sumitomo Chemical company) (B-2) Triethylene glycol-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Irganox245 manufactured by BASF) (B-3) Pentaerythritol-tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1010, manufactured by BASF) (B-4) Quercetin (reagent, manufactured by Kanto Kagaku Co., Ltd.) (B') Other compounds (B'-5) 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Reagent, Kanto Chemical Co., Ltd. ) made)
- TE Tensile breaking strain
- the present invention has a high TE retention rate and excellent radiation resistance. It is also found that at least one compound selected from the hindered phenol-based compound and the polyphenol-based compound of the present invention has high compatibility with the polyacetal resin.
Landscapes
- 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
The purpose of the present invention is to provide: a novel polyacetal resin used in applications in which radiation sterilization is carried out; and a method for improving the radiation resistance of the polyacetal resin. The purpose of the present invention can be achieved by providing a polyacetal resin composition used in applications in which radiation sterilization is carried out. The polyacetal resin composition contains at least one type of compound selected from among a hindered phenol-based compound and a polyphenol-based compound.
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。
The present invention relates to a polyacetal resin used for new radiation sterilization applications 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 to sterilize medical devices, but recently radiation sterilization using γ-rays and electron beams has become more common. 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 for 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用とへの用途拡大の要望が高まり、耐放射線のポリアセタール樹脂が求められてきた。
On the other hand, polyethylene, polypropylene, silicone resin, etc. have been used in medical devices, but there is a demand for expanding the use of plastic materials for applications that require even 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 expanding the use of polyacetal resins for use in medical devices, and radiation-resistant polyacetal resins have been desired.
本発明の目的は、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。
The purpose of the present invention is to provide a polyacetal resin used for new radiation sterilization applications 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、ヒンダードフェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の化合物を含有するポリアセタール樹脂組成物。
２． 前記ヒンダードフェノール系化合物のフェノール性水酸基を有する炭素原子に隣接する炭素原子の一つが、メチル基またはメチレン基を置換基として有する前記１記載のポリアセタール樹脂組成物。
３． 前記ヒンダードフェノール系化合物が、２,２’－メチレンビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール)である前記１または２に記載のポリアセタール樹脂組成物。
４． 前記１～３いずれか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,
A polyacetal resin composition comprising at least one compound selected from hindered phenolic compounds and polyphenolic compounds.
2. 2. The polyacetal resin composition according to 1 above, wherein one of the carbon atoms adjacent to the carbon atom having the phenolic hydroxyl group of the hindered phenol compound has a methyl group or a methylene group as a substituent.
3. 3. The polyacetal resin composition as described in 1 or 2 above, wherein the hindered phenolic compound is 2,2′-methylenebis(6-tert-butyl-4-methylphenol).
4. A method for improving the radiation resistance of a polyacetal resin, using the polyacetal resin composition according to any one of 1 to 3 above.
該ポリアセタール樹脂組成物が、ヒンダードフェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の化合物を含有するポリアセタール樹脂組成物。
２． 前記ヒンダードフェノール系化合物のフェノール性水酸基を有する炭素原子に隣接する炭素原子の一つが、メチル基またはメチレン基を置換基として有する前記１記載のポリアセタール樹脂組成物。
３． 前記ヒンダードフェノール系化合物が、２,２’－メチレンビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール)である前記１または２に記載のポリアセタール樹脂組成物。
４． 前記１～３いずれか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,
A polyacetal resin composition comprising at least one compound selected from hindered phenolic compounds and polyphenolic compounds.
2. 2. The polyacetal resin composition according to 1 above, wherein one of the carbon atoms adjacent to the carbon atom having the phenolic hydroxyl group of the hindered phenol compound has a methyl group or a methylene group as a substituent.
3. 3. The polyacetal resin composition as described in 1 or 2 above, wherein the hindered phenolic compound is 2,2′-methylenebis(6-tert-butyl-4-methylphenol).
4. A method for improving the radiation resistance of a polyacetal resin, using the polyacetal resin composition according to any one of 1 to 3 above.
本発明によれば、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。
According to the present invention, it is possible to provide a polyacetal resin used for new radiation sterilization applications 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、ヒンダードフェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の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 used for radiation sterilization, wherein the polyacetal resin composition contains at least one compound selected from hindered phenolic compounds and polyphenolic compounds. characterized by
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フェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の化合物を含有する。
The polyacetal resin composition of the present invention contains at least a polyacetal resin and at least one compound selected from hindered phenolic compounds and polyphenolic compounds.
＜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 structural unit (for example, manufactured by DuPont in the United States, trade name “Delrin”, etc.). (for example, Polyplastics Co., Ltd., trade name "Duracon", etc.) may be used. Copolymers are preferred from the viewpoint of thermal stability.
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 structural unit (for example, manufactured by DuPont in the United States, trade name “Delrin”, etc.). (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, it is common to use trioxane, which is a cyclic trimer of formaldehyde, 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, as well as glycidyl ether compounds capable of forming branched or crosslinked structures 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。
A polyacetal copolymer such as the one described above can generally be obtained by adding an appropriate amount of a molecular weight modifier and subjecting it to 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.
＜ヒンダードフェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の化合物＞
本発明において使用されるヒンダードフェノール系化合物は、フェノール系化合物のフェノール性水酸基を有する炭素に隣接する炭素の一つが、メチル基またはメチレン基を置換基として有することが好ましい。 <At least one compound selected from hindered phenol compounds and polyphenol compounds>
In the hindered phenolic compound used in the present invention, one of the carbons adjacent to the carbon having the phenolic hydroxyl group of the phenolic compound preferably has a methyl group or a methylene group as a substituent.
本発明において使用されるヒンダードフェノール系化合物は、フェノール系化合物のフェノール性水酸基を有する炭素に隣接する炭素の一つが、メチル基またはメチレン基を置換基として有することが好ましい。 <At least one compound selected from hindered phenol compounds and polyphenol compounds>
In the hindered phenolic compound used in the present invention, one of the carbons adjacent to the carbon having the phenolic hydroxyl group of the phenolic compound preferably has a methyl group or a methylene group as a substituent.
具体的には、２，２’－メチレンビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール）、２，２’－メチレンビス（６－ｔｅｒｔ－ブチル－４－エチルフェノール）、ヘキサメチレングリコール－ビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシヒドロシンナメート）、ペンタエリトリトール－テトラキス－３－（３、５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、トリエチレングリコール－ビス－３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ－ベンジル）ベンゼン、ｎ－オクタデシル－３－（４’－ヒドロキシ－３’，５’－ジ－ｔｅｒｔ－ブチルフェノール）プロピオネート、４，４’－メチレンビス（２，６－ジ－ｔｅｒｔ－ブチルフェノール）、４，４’－ブチリデン－ビス（６－ｔｅｒｔ－ブチル－３－メチル－フェノール）、ジ－ステアリル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホネート、２－ｔｅｒｔ－ブチル－６－（３－ｔｅｒｔ－ブチル－５－メチル－２－ヒドロキシベンジル）－４－メチルフェニルアクリレート、３，９－ビス｛２－〔３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ〕－１，１－ジメチルエチル｝－２，４，８，１０－テトラオキサスピロ〔５，５〕ウンデカン等が挙げられる。
Specifically, 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), hexamethylene glycol-bis(3 ,5-di-tert-butyl-4-hydroxyhydrocinnamate), pentaerythritol-tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl) Benzene, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol) propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4' -butylidene-bis(6-tert-butyl-3-methyl-phenol), di-stearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2-tert-butyl-6-(3-tert -butyl-5-methyl-2-hydroxybenzyl)-4-methylphenyl acrylate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- 1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane and the like.
本発明において使用されるポリフェノール系化合物としては、フラボン類、イソフラボン類、フラボノール類、フラバノン類、フラバノール類、アントシアン類等が挙げられる。具体的には、ルテオリン、カテキン、ケルセチン、サクラネチン、フスチン、シアニン、プロトアントシアニジン等が挙げられる。フェノール性水酸基の数が、３以上であるポリフェノール系化合物であることが好ましい。
Polyphenolic compounds used in the present invention include flavones, isoflavones, flavonols, flavanones, flavanols, anthocyans, and the like. Specific examples include luteolin, catechin, quercetin, cherry netin, fustin, cyanin, protoanthocyanidin, and the like. A polyphenol compound having 3 or more phenolic hydroxyl groups is preferred.
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。
In the present invention, at least one or two or more selected from these compounds can be used.
本発明におけるヒンダードフェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の化合物の含有量は、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 at least one compound selected from hindered phenol-based compounds and polyphenol-based compounds in the present invention is 0.1 to 2.0 parts by mass, and 0.2 to 1 0.5 parts by mass is more preferred.
≪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.
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フェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の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>
The polyacetal resin composition of the present invention contains at least one compound selected from the hindered phenolic compound and the polyphenolic compound of the present invention, so that radiation resistance can be improved, and radiation sterilization is performed for medical devices. can be used for For example, it can be used for drug inhalation devices, injection devices, parts for infusion devices, and the like.
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フェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の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>
The polyacetal resin composition of the present invention contains at least one compound selected from the hindered phenolic compound and the polyphenolic compound of the present invention, so that radiation resistance can be improved, and radiation sterilization is performed for medical devices. can be used for 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フェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の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 the radiation resistance of a polyacetal resin composition of the present invention is a method for expressing radiation resistance in a polyacetal resin composition, wherein at least one compound selected from hindered phenolic compounds and polyphenolic compounds is added to the polyacetal resin. is characterized by the addition of
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フェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の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 the radiation resistance of a polyacetal resin composition of the present invention is a method for expressing radiation resistance in a polyacetal resin composition, wherein at least one compound selected from hindered phenolic compounds and polyphenolic compounds is added to the polyacetal resin. is characterized by the addition of
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フェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の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 preferable addition amount of at least one compound selected from hindered phenolic compounds and polyphenolic compounds to the polyacetal resin is as described above in the polyacetal resin composition of the present invention. As explained.
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。
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。
（Ａ）ポリアセタール樹脂（ＰＯＭと略す）
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.
(A) Polyacetal resin (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 (according to ISO1133, measured at 190°C under a load of 2.16 kg): 9g/10min)
（Ａ）ポリアセタール樹脂（ＰＯＭと略す）
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.
(A) Polyacetal resin (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 (according to ISO1133, measured at 190°C under a load of 2.16 kg): 9g/10min)
（Ｂ）ヒンダードフェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の化合物
（Ｂ－１）２，２’－メチレンビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール)（ＳＵＭＩＬＩＺＥＲ ＭＤＰ－Ｓ 住友化学社製）
（Ｂ－２）トリエチレングリコール－ビス－３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート（Ｉｒｇａｎｏｘ２４５ ＢＡＳＦ社製）
（Ｂ－３）ペンタエリトリトール－テトラキス－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート（Ｉｒｇａｎｏｘ１０１０、ＢＡＳＦ社製）
（Ｂ－４）ケルセチン（試薬、関東化学(株)製）
（Ｂ’）その他の化合物
（Ｂ’－５）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）製）
（Ｂ’－６）Ｃｈｉｍａｓｓｏｒｂ９４４ （ＢＡＳＦ社製） (B) At least one compound selected from hindered phenolic compounds and polyphenolic compounds (B-1) 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (SUMILIZER MDP-S Sumitomo Chemical company)
(B-2) Triethylene glycol-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Irganox245 manufactured by BASF)
(B-3) Pentaerythritol-tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1010, manufactured by BASF)
(B-4) Quercetin (reagent, manufactured by Kanto Kagaku Co., Ltd.)
(B') Other compounds (B'-5) 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Reagent, Kanto Chemical Co., Ltd. ) made)
(B'-6) Chimassorb 944 (manufactured by BASF)
（Ｂ－１）２，２’－メチレンビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール)（ＳＵＭＩＬＩＺＥＲ ＭＤＰ－Ｓ 住友化学社製）
（Ｂ－２）トリエチレングリコール－ビス－３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート（Ｉｒｇａｎｏｘ２４５ ＢＡＳＦ社製）
（Ｂ－３）ペンタエリトリトール－テトラキス－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート（Ｉｒｇａｎｏｘ１０１０、ＢＡＳＦ社製）
（Ｂ－４）ケルセチン（試薬、関東化学(株)製）
（Ｂ’）その他の化合物
（Ｂ’－５）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）製）
（Ｂ’－６）Ｃｈｉｍａｓｓｏｒｂ９４４ （ＢＡＳＦ社製） (B) At least one compound selected from hindered phenolic compounds and polyphenolic compounds (B-1) 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (SUMILIZER MDP-S Sumitomo Chemical company)
(B-2) Triethylene glycol-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Irganox245 manufactured by BASF)
(B-3) Pentaerythritol-tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1010, manufactured by BASF)
(B-4) Quercetin (reagent, manufactured by Kanto Kagaku Co., Ltd.)
(B') Other compounds (B'-5) 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Reagent, Kanto Chemical Co., Ltd. ) made)
(B'-6) Chimassorb 944 (manufactured by BASF)
＜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.
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 produced by injection molding under the following conditions, and the following evaluations were 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)
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 produced by injection molding under the following conditions, and the following evaluations were 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 obtained. Table 1 shows the results.
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 obtained. 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.
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、本発明のヒンダードフェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の化合物が、ポリアセタール樹脂との相溶性の高いこともわかる。
As shown in Table 1, the present invention has a high TE retention rate and excellent radiation resistance. It is also found that at least one compound selected from the hindered phenol-based compound and the polyphenol-based compound of the present invention has high compatibility with the polyacetal resin.
As shown in Table 1, the present invention has a high TE retention rate and excellent radiation resistance. It is also found that at least one compound selected from the hindered phenol-based compound and the polyphenol-based compound of the present invention has high compatibility with the polyacetal resin.
Claims (4)
- 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、ヒンダードフェノール系化合物およびポリフェノール系化合物から選択される少なくとも一種の化合物を含有するポリアセタール樹脂組成物。 A polyacetal resin composition used for radiation sterilization,
A polyacetal resin composition comprising at least one compound selected from hindered phenolic compounds and polyphenolic compounds. - 前記ヒンダードフェノール系化合物のフェノール性水酸基を有する炭素原子に隣接する炭素原子の一つが、メチル基またはメチレン基を置換基として有する請求項１記載のポリアセタール樹脂組成物。 The polyacetal resin composition according to claim 1, wherein one of the carbon atoms adjacent to the carbon atom having the phenolic hydroxyl group of the hindered phenol compound has a methyl group or a methylene group as a substituent.
- 前記ヒンダードフェノール系化合物が、２，２’－メチレンビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール)である請求項１または２に記載のポリアセタール樹脂組成物。 The polyacetal resin composition according to claim 1 or 2, wherein the hindered phenolic compound is 2,2'-methylenebis(6-tert-butyl-4-methylphenol).
- 前記請求項１～３いずれか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。
A method for improving the radiation resistance of a polyacetal resin using the polyacetal resin composition according to any one of claims 1 to 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021120430A JP2023016241A (en) | 2021-07-21 | 2021-07-21 | Polyacetal resins for radiation sterilization applications and methods of improving radiation resistance of polyacetal resins |
| JP2021-120430 | 2021-07-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023002726A1 true WO2023002726A1 (en) | 2023-01-26 |
Family
ID=84979908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2022/017680 WO2023002726A1 (en) | 2021-07-21 | 2022-04-13 | Polyacetal resin used in applications in which radiation sterilization is carried out, and method for improving radiation resistance of polyacetal resin |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2023016241A (en) |
| WO (1) | WO2023002726A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63254158A (en) * | 1987-03-06 | 1988-10-20 | イー・アイ・デユポン・デ・ニモアス・アンド・カンパニー | Stabilized glass reinforced polyacetal composition |
| JPS6490239A (en) * | 1987-08-18 | 1989-04-06 | American Cyanamid Co | Improved radiation sterilizable composition |
| 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 |
-
2021
- 2021-07-21 JP JP2021120430A patent/JP2023016241A/en active Pending
-
2022
- 2022-04-13 WO PCT/JP2022/017680 patent/WO2023002726A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63254158A (en) * | 1987-03-06 | 1988-10-20 | イー・アイ・デユポン・デ・ニモアス・アンド・カンパニー | Stabilized glass reinforced polyacetal composition |
| JPS6490239A (en) * | 1987-08-18 | 1989-04-06 | American Cyanamid Co | Improved radiation sterilizable composition |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023016241A (en) | 2023-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5468295B2 (en) | Molding polyoxymethylene composition with improved processing stability and low release tendency | |
| EP2328974B1 (en) | Polyoxymethylene compositions and articles made from these | |
| JP2007051205A (en) | Polyacetal resin composition and resin-molded article | |
| JP5586996B2 (en) | Polyacetal resin composition | |
| JP2016516123A (en) | Polyoxymethylene copolymer and thermoplastic POM composition | |
| JP5612430B2 (en) | Polyacetal resin composition and method for producing the same | |
| DE4236465A1 (en) | Polyoxymethylene with improved stability against acids, process for its preparation and use | |
| KR101646977B1 (en) | Polyoxymethylene resin composition having good thermal-stability | |
| WO2023002726A1 (en) | Polyacetal resin used in applications in which radiation sterilization is carried out, and method for improving radiation resistance of polyacetal resin | |
| CN113677724B (en) | Polyacetal resin composition and method for producing same | |
| JP7374420B2 (en) | Resin composition, resin molded body, and method for producing resin molded body | |
| JPS63172760A (en) | Polyoxymethylene composition reduced in warpage | |
| JP5778518B2 (en) | Polyacetal resin composition and sliding part | |
| WO2014119393A1 (en) | Polyacetal resin composition, and sulfur fuel contact provided with molded article of polyacetal resin composition | |
| JP5612431B2 (en) | Polyacetal resin composition and method for producing the same | |
| WO2014119392A1 (en) | Polyacetal resin composition, and sulfur fuel contact provided with molded article of polyacetal resin composition | |
| US10961384B2 (en) | Process for improving the flexural toughness of moldings | |
| WO2023112450A1 (en) | Polyacetal resin composition used in applications for performing radiation sterilization, and method for improving radiation resistance in polyacetal resin | |
| JP2008156504A (en) | Polyacetal resin composition | |
| EP0391681A2 (en) | Acetal polymer blends | |
| JP7014347B1 (en) | Method for Producing Oxymethylene Copolymer Resin Composition and Oxymethylene Copolymer Resin Composition | |
| EP3545039A1 (en) | Polyoxymethylene compositions | |
| JP6865817B2 (en) | Polyoxymethylene resin composition | |
| JP2002201334A (en) | Polyacetal resin composition and its method product | |
| JP2882826B2 (en) | High sliding polyoxymethylene resin material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22845665 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 22845665 Country of ref document: EP Kind code of ref document: A1 |