JP6115286B2 - PROPYLENE RESIN COMPOSITION FOR MEDICAL MEMBER AND MEDICAL MEMBER - Google Patents
PROPYLENE RESIN COMPOSITION FOR MEDICAL MEMBER AND MEDICAL MEMBER Download PDFInfo
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- JP6115286B2 JP6115286B2 JP2013092089A JP2013092089A JP6115286B2 JP 6115286 B2 JP6115286 B2 JP 6115286B2 JP 2013092089 A JP2013092089 A JP 2013092089A JP 2013092089 A JP2013092089 A JP 2013092089A JP 6115286 B2 JP6115286 B2 JP 6115286B2
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- Prior art keywords
- propylene
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- medical
- random copolymer
- resin composition
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- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 72
- 239000011342 resin composition Substances 0.000 title claims description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 71
- -1 propylene-ethylene Chemical group 0.000 claims description 51
- 229920005604 random copolymer Polymers 0.000 claims description 37
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 34
- 239000005977 Ethylene Substances 0.000 claims description 34
- 229920001400 block copolymer Polymers 0.000 claims description 26
- 230000005855 radiation Effects 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 19
- 239000002667 nucleating agent Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 description 22
- 239000008280 blood Substances 0.000 description 21
- 210000004369 blood Anatomy 0.000 description 21
- 230000001954 sterilising effect Effects 0.000 description 18
- 238000004659 sterilization and disinfection Methods 0.000 description 18
- 210000003734 kidney Anatomy 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
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- 238000005259 measurement Methods 0.000 description 8
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- 239000002699 waste material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
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- 229920005668 polycarbonate resin Polymers 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000017531 blood circulation Effects 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
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- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
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- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- GIJXXHSNDRJBLI-UHFFFAOYSA-N 2-methoxyethoxycarbonyloxy 2-methoxyethyl carbonate Chemical compound COCCOC(=O)OOC(=O)OCCOC GIJXXHSNDRJBLI-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
- MEOTZVDTOBWNPZ-UHFFFAOYSA-N 2-methylhexoxycarbonyloxy 2-methylhexyl carbonate Chemical compound CCCCC(C)COC(=O)OOC(=O)OCC(C)CCCC MEOTZVDTOBWNPZ-UHFFFAOYSA-N 0.000 description 1
- JKYXHNHXUIKLIV-UHFFFAOYSA-N 2-tert-butylperoxy-3,3,5-trimethylcyclohexan-1-one Chemical compound CC1CC(=O)C(OOC(C)(C)C)C(C)(C)C1 JKYXHNHXUIKLIV-UHFFFAOYSA-N 0.000 description 1
- UADCSAMCEHXQPQ-UHFFFAOYSA-N 2-tert-butylperoxycyclohexan-1-one Chemical compound CC(C)(C)OOC1CCCCC1=O UADCSAMCEHXQPQ-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-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
- 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
- UIXOHXMSPVARMA-UHFFFAOYSA-N C(C(=O)O)(=[O+][O-])O Chemical compound C(C(=O)O)(=[O+][O-])O UIXOHXMSPVARMA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- 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
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FBGXOLGXOBEPSB-UHFFFAOYSA-N benzylperoxyperoxymethylbenzene Chemical compound C(OOOOCc1ccccc1)c1ccccc1 FBGXOLGXOBEPSB-UHFFFAOYSA-N 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- QZYRMODBFHTNHF-UHFFFAOYSA-N ditert-butyl benzene-1,2-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OOC(C)(C)C QZYRMODBFHTNHF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- MNLMLEWXCMFNFO-UHFFFAOYSA-K ethanol;trichlorotitanium Chemical compound CCO.Cl[Ti](Cl)Cl MNLMLEWXCMFNFO-UHFFFAOYSA-K 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- NZYMWGXNIUZYRC-UHFFFAOYSA-N hexadecyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NZYMWGXNIUZYRC-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N n-decyl alcohol Natural products CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- OXUCOTSGWGNWGC-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2-] OXUCOTSGWGNWGC-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229920006285 olefinic elastomer Polymers 0.000 description 1
- 150000002891 organic anions Chemical group 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Description
本発明は、医療向け部材用プロピレン系樹脂組成物および医療用部材に関し、詳しくは、透析型人工腎臓装置承認基準のうち、透析液供給部及び透析液回路の品質及び試験法 １（２）を満足することが可能で、透明性に優れた医療向け部材用プロピレン系樹脂組成物およびそれを用いた医療用部材に関する。 The present invention relates to a propylene-based resin composition for medical members and medical members, and in particular, among dialysis-type artificial kidney device approval criteria, the quality and test method 1 (2) of the dialysate supply unit and dialysate circuit The present invention relates to a propylene-based resin composition for medical members that can be satisfied and has excellent transparency, and a medical member using the same.
プロピレン系重合体は、その優れた安全衛生性や成形加工性、力学特性、ガスバリヤー性の特徴を生かし、各種の医療器具の部材に使用されている。そして、その滅菌方法もＥＯＧ（エチレンオキサイド）滅菌や高圧蒸気滅菌、放射線滅菌などが行われているが、特に近年は、効率面等から放射線滅菌の要望が高まっている。
一方、放射線滅菌にて、プロピレン系重合体は、分子切断等により、製品の衝撃強度が著しく低下することが知られている。医療用部材において、使用時等に破損することは避けるべきことであり、特に、透明性が求められるシリンジやダイアライザーでは、透明性と耐衝撃性の両立を追求した検討が行われ、さまざまな工夫がなされてきている。
Propylene-based polymers are used in various medical device members by taking advantage of their excellent safety and hygiene, molding processability, mechanical properties, and gas barrier properties. As the sterilization method, EOG (ethylene oxide) sterilization, high-pressure steam sterilization, radiation sterilization, and the like are performed. In recent years, in particular, the demand for radiation sterilization is increasing from the viewpoint of efficiency.
On the other hand, it is known that, due to radiation sterilization, the impact strength of a propylene-based polymer is significantly reduced by molecular cutting or the like. In medical parts, it should be avoided that they are damaged during use, and in particular, syringes and dialyzers that require transparency have been studied in pursuit of both transparency and impact resistance. Has been made.
医療器具の例として、以下にダイアライザーの例を説明する。
腎臓の機能が低下すると、人工腎臓と呼ばれる装置で、血液から水分や老廃物を取り出すとともに、血液が酸性にならないような調節が行なわれる。一般に、これを人工透析と言う。その概念を図１に、血液をきれいにするダイアライザーの例を図２に示す。
An example of a dialyzer will be described below as an example of a medical instrument.
When kidney function declines, a device called an artificial kidney removes water and waste products from the blood and makes adjustments to keep the blood from becoming acidic. In general, this is called artificial dialysis. FIG. 1 shows the concept, and FIG. 2 shows an example of a dialyzer that cleans blood.
図１において、透析を受ける人の腕１の血管に針を刺し、血液ポンプ３で連続的に血液を取り出す。血液ポンプ３は、ローラーを柔らかいチューブ２に押しつけながら回転することによって血液を一方向へ送ることができる。そして、血液をきれいにする部分が、ダイアライザー５と呼ばれる用具である。ダイアライザー５に空気が入ると効率が悪くなり、また透析を受ける人の安全を守るために、空気が入らないようにエアートラップ４と呼ばれる筒がダイアライザーの前後に取り付けられている。ダイアライザー５では、半透膜を介して、血液から過剰な水や老廃物を排出し、血液をきれいにすることができる。その際、コンソール６という調節装置によって、透析液が正確にダイアライザー５へ送られ、内部の水や老廃物が混じった透析液が外部へ運び出される。コンソール６には各種の警報も付いており、安全に人工透析ができるようになっている。
In FIG. 1, a needle is inserted into the blood vessel of the arm 1 of a person undergoing dialysis, and blood is continuously taken out by the blood pump 3. The blood pump 3 can send blood in one direction by rotating while pressing the roller against the soft tube 2. The part that cleans the blood is a tool called the dialyzer 5. When air enters the dialyzer 5, the efficiency deteriorates, and in order to protect the safety of the person undergoing dialysis, a cylinder called an air trap 4 is attached to the front and rear of the dialyzer so that the air does not enter. In the dialyzer 5, excess water and waste products can be discharged from the blood through the semipermeable membrane to clean the blood. At that time, the dialysate is accurately sent to the dialyzer 5 by the adjusting device called the
ダイアライザー５は、長さが３０ｃｍほどの円筒状のプラスチック製容器で構成されており、その中には、図２に示すように、半透膜であるホローファイバー１１という極めて細い糸が１万本程度、該容器に対し平行に束ねて収められている。ホローファイバー１１はマカロニのように中心部に穴があいており、その穴の中を血液が流れ、ホローファイバー１１の外側を透析液が流れている。ホローファイバー１１は水や老廃物を、透析液へと通すように作られているので、連続的に血液を送ることによって血液をきれいにすることができる。
また、ダイアライザー５は、円筒状の外筒１２と外筒１２に蓋をするためのヘッダー１３とから構成されている。両側のヘッダー１３同士は、ホローファイバー１１と結合しており、一方のヘッダー１３の血液流入口７から血液が流れ込み、ホローファイバー１１の中を血液が流れる際、血液中の水や老廃物がホローファイバー１１の外側である透析液へ排出され、その後、もう一方のヘッダー１３の血液流出口８から血液が流れ出る構造となっている。また、外筒１２には、透析液の流入口９と透析液の流出口１０が設けられており、ダイアライザー５内に透析液を循環させることにより水や老廃物を取り出す構造となっている。
The dialyzer 5 is composed of a cylindrical plastic container having a length of about 30 cm, and as shown in FIG. 2, 10,000 very thin yarns such as
The dialyzer 5 includes a cylindrical
現在、このようなダイアライザーの外筒やヘッダー部分は、ポリカーボネート樹脂を素材とするものが主流である（例えば、特許文献１、２参照）。ポリカーボネート樹脂は、透明性や耐衝撃性に優れているため、ダイアライザーが稼動中、内部の状態が見えやすく安心して使用できる点、運搬や使用時において壊れ難いという点で優位な素材である。しかし、その反面、ポリカーボネート樹脂は、成形する前に乾燥工程を必要とするため作業効率が悪く、融点が高いため成形温度が高くエネルギー効率が悪いといった問題や、原料に起因する化学物質の溶出による悪影響の懸念や、高価格であるという問題も含んでいた。 At present, the outer cylinder and header part of such a dialyzer are mainly made of polycarbonate resin (for example, see Patent Documents 1 and 2). Polycarbonate resin is superior in terms of transparency and impact resistance, and is advantageous in that it can be used safely and easily when the dialyzer is in operation, and it is difficult to break during transportation and use. However, on the other hand, the polycarbonate resin requires a drying process before molding, so the working efficiency is poor, the melting point is high, the molding temperature is high and the energy efficiency is poor, and the elution of chemical substances caused by the raw materials It included concerns about adverse effects and high prices.
そのため、ポリカーボネート樹脂に代わる、優れた耐衝撃性、透明性および成形性を有し、透析型人工腎臓装置承認基準のうち、透析液供給部及び透析液回路の品質及び試験法
１（２）を満足し得る素材が望まれているのが現状である。さらに、人工透析用部材は、使い捨ての注射筒などと異なり、血液と長い時間接触する為、滑剤などの溶出する成分が含まれていると好ましくなく、透析型人工腎臓装置承認基準を満足する必要がある。
Therefore, it has excellent impact resistance, transparency and moldability instead of polycarbonate resin. Among the dialysis artificial kidney device approval criteria, the quality and test method 1 (2) of the dialysate supply section and dialysate circuit At present, satisfactory materials are desired. Furthermore, unlike disposable syringes, the members for artificial dialysis are in contact with blood for a long period of time, so it is not preferable to include components that elute such as lubricants, and it is necessary to satisfy the dialysis artificial kidney device approval criteria There is.
本発明の目的（課題）は、上記問題点を解決し、特に、放射線滅菌される医療用部材として好適なプロピレン系樹脂組成物および医療用部材、特に、透析型人工腎臓装置承認基準のうち、透析液供給部及び透析液回路の品質及び試験法 １（２）を満足し、かつ透明性に優れた人工透析用部材、およびその他、ディスポーザブルシリンジ等の放射線滅菌される医療用部材に好適なプロピレン系樹脂組成物および医療用部材を提供することにある。 The object (problem) of the present invention is to solve the above-mentioned problems, in particular, a propylene-based resin composition suitable as a medical member to be sterilized by radiation and a medical member, in particular, a dialysis artificial kidney device approval standard, Propylene suitable for dialysis fluid supply part and dialysate circuit quality and test method 1 (2) and excellent in transparency, and other dialysis medical devices such as disposable syringes It is in providing a resin composition and a medical member.
本発明者らは、上記課題を解決するために鋭意研究の結果、特定のプロピレン系重合体を基材とし、特定の造核剤を用いたプロピレン系樹脂組成物が、放射線滅菌される医療用部材として好適であることを見出し、本発明を完成するに至った。
本発明は、以下のプロピレン系樹脂組成物および医療用部材を提供する。
As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a propylene-based resin composition using a specific propylene-based polymer as a base material and a specific nucleating agent is radiation-sterilized. It has been found that it is suitable as a member, and the present invention has been completed.
The present invention provides the following propylene-based resin composition and medical member.
［１］エチレン含有量が０〜５重量％であるプロピレン系（共）重合体成分（Ａ）を４０〜９５重量％と、エチレン含有量が１０〜３０重量％であるプロピレン−エチレンランダム共重合体成分（Ｂ）を５〜６０重量％の割合で含み、プロピレン−エチレンランダム共重合体成分（Ｂ）とプロピレン系（共）重合体成分（Ａ）の極限粘度の比（［η］Ｂ／［η］Ａ）が０．５〜１．３の範囲にあるプロピレン系ブロック共重合体１００質量部に対し、下記一般式（１）で示される造核剤を０．０１〜０．６重量部含有することを特徴とする医療向け部材用プロピレン系樹脂組成物。
［２］メルトフローレート（ＪＩＳ Ｋ７２１０準拠、２３０℃、２．１６ｋｇ荷重）が０．５〜１００ｇ／１０分であり、プロピレン系（共）重合体成分（Ａ）とプロピレン−エチレンランダム共重合体成分（Ｂ）がチーグラー触媒により製造される上記［１］に記載の医療向け部材用プロピレン系樹脂組成物。
［３］上記［１］または［２］に記載の医療向け部材用プロピレン系樹脂組成物からなり、放射線滅菌されてなることを特徴とする医療用部材。
［４］ダイアライザーの外筒および／またはヘッダーである上記［３］に記載の医療用部材。
［５］ディスポーザブルシリンジの外筒である上記［３］に記載の医療用部材。
[2] Melt flow rate (according to JIS K7210, 230 ° C., 2.16 kg load) is 0.5 to 100 g / 10 min, propylene-based (co) polymer component (A) and propylene-ethylene random copolymer The propylene-based resin composition for medical members according to the above [1], wherein the component (B) is produced by a Ziegler catalyst.
[3] A medical member comprising the propylene-based resin composition for medical members according to the above [1] or [2] and sterilized by radiation.
[4] The medical member according to [3], which is an outer cylinder and / or header of a dialyzer.
[5] The medical member according to [3], which is an outer cylinder of a disposable syringe.
本発明の医療向け部材用プロピレン系樹脂組成物およびそれからなる医療用部材は、透析型人工腎臓装置承認基準のうち、透析液供給部及び透析液回路の品質及び試験法 １（２）を満足することが可能であり、かつ透明性に優れ、さらに成形性や滅菌後の耐衝撃性に優れるので、人工透析用部材、および、その他ディスポーザブルシリンジ等の放射線滅菌される医療用部材として、好適に使用することができる。 The propylene-based resin composition for medical members of the present invention and the medical member comprising the same satisfy the quality and test method 1 (2) of the dialysate supply unit and dialysate circuit among the dialysis artificial kidney device approval criteria. It is possible to be used as a member for artificial dialysis and other medical devices that are sterilized by radiation, such as disposable syringes, because it has excellent transparency and excellent moldability and impact resistance after sterilization. can do.
本発明の医療向け部材用プロピレン系樹脂組成物は、エチレン含有量が０〜５重量％であるプロピレン系（共）重合体成分（Ａ）を４０〜９５重量％と、エチレン含有量が１０〜３０重量％であるプロピレン−エチレンランダム共重合体成分（Ｂ）を５〜６０重量％の割合で含み、プロピレン−エチレンランダム共重合体成分（Ｂ）とプロピレン系（共）重合体成分（Ａ）の極限粘度の比（［η］Ｂ／［η］Ａ）が０．５〜１．３の範囲にあるプロピレン系ブロック共重合体１００質量部に対し、前記一般式（１）で示される造核剤を０．０１〜０．６重量部含有することを特徴とする。 The propylene-based resin composition for medical members of the present invention has a propylene-based (co) polymer component (A) having an ethylene content of 0 to 5% by weight, 40 to 95% by weight, and an ethylene content of 10 to 10%. 30% by weight of propylene-ethylene random copolymer component (B) is contained in a proportion of 5 to 60% by weight, and propylene-ethylene random copolymer component (B) and propylene-based (co) polymer component (A) For 100 parts by mass of the propylene-based block copolymer in which the ratio of intrinsic viscosity ([η] B / [η] A) is in the range of 0.5 to 1.3. It contains 0.01 to 0.6 parts by weight of a nucleating agent.
以下、本発明の医療向け部材用プロピレン系樹脂組成物の構成成分および医療用部材について、詳細に説明する。
なお、本明細書において、「〜」とは、特に断りのない限り、その前後に記載される数値を下限値および上限値として含む意味で使用される。
Hereinafter, the constituent components and medical members of the propylene-based resin composition for medical members of the present invention will be described in detail.
In the present specification, unless otherwise specified, “to” is used in a sense that includes numerical values described before and after it as a lower limit value and an upper limit value.
（１）プロピレン系ブロック共重合体
本発明の医療向け部材用プロピレン系樹脂組成物に用いるプロピレン系ブロック共重合体は、エチレン含有量が０〜５重量％であるプロピレン系（共）重合体成分（Ａ）を４０〜９５重量％と、エチレン含有量が１０〜３０重量％であるプロピレン−エチレンランダム共重合体成分（Ｂ）を５〜６０重量％の割合で含むプロピレン系ブロック共重合体であって、プロピレン−エチレンランダム共重合体成分（Ｂ）とプロピレン系（共）重合体成分（Ａ）との極限粘度比［η］Ｂ／［η］Ａが０．５〜１．３の範囲にあるプロピレン系ブロック共重合体である。
(1) Propylene-based block copolymer The propylene-based block copolymer used in the propylene-based resin composition for medical members of the present invention is a propylene-based (co) polymer component having an ethylene content of 0 to 5% by weight. A propylene-based block copolymer comprising (A) 40 to 95% by weight and a propylene-ethylene random copolymer component (B) having an ethylene content of 10 to 30% by weight in a proportion of 5 to 60% by weight. The intrinsic viscosity ratio [η] B / [η] A of the propylene-ethylene random copolymer component (B) and the propylene-based (co) polymer component (A) is in the range of 0.5 to 1.3. A propylene-based block copolymer.
このようなプロピレン系ブロック共重合体は、いわゆるブロック共重合体と通称されているものであり、プロピレン系（共）重合体成分（Ａ）とプロピレン−エチレンランダム共重合体成分（Ｂ）のブレンド状態にあり、双方が重合で結合しているものではない。 Such a propylene-based block copolymer is commonly called a so-called block copolymer, and is a blend of a propylene-based (co) polymer component (A) and a propylene-ethylene random copolymer component (B). It is in a state where both are not bonded by polymerization.
本発明で用いられる上記プロピレン系ブロック共重合体は、結晶性であるプロピレン系（共）重合体成分（Ａ）と低結晶性であるプロピレン−エチレンランダム共重合体成分（Ｂ）とからなる。
プロピレン系（共）重合体成分（Ａ）は、上記のとおり、エチレン含有量が０〜５重量％であり、プロピレン単独重合体であっても、プロピレンを主体とし、エチレンとの共重合体であっても、それらを２種以上含む混合物であってもよい。但し、プロピレン系（共）重合体成分（Ａ）のエチレン量が５重量％を超えると、剛性不足や成形性悪化の懸念が生じるため、５重量％までが好ましい。プロピレンと共重合されるものとして、エチレン以外にもブテン−１やヘキセン−１が挙げられるが、エチレンが物性バランスにおいて好適である。
The propylene-based block copolymer used in the present invention comprises a propylene-based (co) polymer component (A) that is crystalline and a propylene-ethylene random copolymer component (B) that is low-crystalline.
As described above, the propylene-based (co) polymer component (A) has an ethylene content of 0 to 5% by weight, and even if it is a propylene homopolymer, it is mainly composed of propylene and is a copolymer with ethylene. Even if it exists, the mixture containing 2 or more types of them may be sufficient. However, when the amount of ethylene of the propylene-based (co) polymer component (A) exceeds 5% by weight, there is a concern of insufficient rigidity and deterioration of moldability, so that it is preferably up to 5% by weight. Examples of the copolymerized with propylene include butene-1 and hexene-1 in addition to ethylene, and ethylene is preferable in terms of the balance of physical properties.
プロピレン−エチレンランダム共重合体成分（Ｂ）は、エチレン含有量が１０〜３０重量％である。プロピレン単位の含有量が９０重量％を超える場合、成形品である医療用部材の低温耐衝撃性が不十分となり、一方、３０重量％未満の場合には、医療用部材の透視性および透明性が低下する。プロピレン−エチレンランダム共重合体成分（Ｂ）中のエチレン含有量は、好ましくは１５〜２８重量％であり、より好ましくは２０〜２５重量％である。 The propylene-ethylene random copolymer component (B) has an ethylene content of 10 to 30% by weight. When the content of the propylene unit exceeds 90% by weight, the low-temperature impact resistance of the medical member that is a molded product becomes insufficient. On the other hand, when the content is less than 30% by weight, the medical member has transparency and transparency. Decreases. The ethylene content in the propylene-ethylene random copolymer component (B) is preferably 15 to 28% by weight, more preferably 20 to 25% by weight.
プロピレン−エチレンランダム共重合体成分（Ｂ）は、１３５℃のテトラリン中で測定した極限粘度［η］Ｂが０．５〜２．０ｄｌ／ｇであることが好ましく、より好ましくは１．３〜２．０ｄｌ／ｇの範囲にあることが好ましい。 The propylene-ethylene random copolymer component (B) preferably has an intrinsic viscosity [η] B measured in tetralin at 135 ° C. of 0.5 to 2.0 dl / g, more preferably 1.3 to It is preferably in the range of 2.0 dl / g.
プロピレン−エチレンランダム共重合体成分（Ｂ）の極限粘度［η］Ｂとプロピレン系（共）重合体成分（Ａ）の極限粘度［η］Ｂの比［η］Ｂ／［η］Ａは、０．３〜１．３の範囲にあることが必要である。［η］Ｂ／［η］Ａがこのような範囲にあることで、透明性が良好となる。［η］Ｂ／［η］Ａは、好ましくは０．４〜１．２である。なお、［η］Ｂ及び［η］Ａは、１３５℃のテトラリン中で同一の条件にて測定される。 Ratio [η] B / [η] A of intrinsic viscosity [η] B of propylene-ethylene random copolymer component (B) and intrinsic viscosity [η] B of propylene-based (co) polymer component (A) is It is necessary to be in the range of 0.3 to 1.3. When [η] B / [η] A is in such a range, the transparency is improved. [Η] B / [η] A is preferably 0.4 to 1.2. [Η] B and [η] A are measured under the same conditions in 135 ° C. tetralin.
本発明で用いられるプロピレン系ブロック共重合体は、ＪＩＳ Ｋ７２１０（２３０℃、２．１６ｋｇ荷重）に準拠したメルトフローレートが０．５〜１００ｇ／１０分であることが好ましく、５〜５０ｇ／１０分がより好ましく、さらには１０〜３０ｇ／１０分好ましい。メルトフローレートが０．５ｇ／１０分未満では、成形不良が発生する懸念があり、メルトフローレートが１００ｇ／１０分を超えると、耐衝撃性など物性低下の懸念が生じる。
なお、過酸化物によってメルトフローレートを調整してペレット化する際、跳ね上げ倍率が１０倍を超えると、ペレット形状が歪になる等の不具合が発生する恐れがあり、跳ね上げ倍率は好ましくは６倍以内であり、更に好ましくは４倍以内である。過酸化物によってメルトフローレートを調整する場合は、調整前のプロピレン系ブロック共重合体のメルトフローレートは、０．５〜１２ｇ／１０分がよく、好ましくは３〜１０ｇ／１０分である。この範囲では製造を行いやすく、物性バランスも良好となる。
The propylene block copolymer used in the present invention preferably has a melt flow rate of 0.5 to 100 g / 10 min in accordance with JIS K7210 (230 ° C., 2.16 kg load), and 5 to 50 g / 10. Minute is more preferable, and further 10 to 30 g / 10 minutes is preferable. When the melt flow rate is less than 0.5 g / 10 minutes, there is a concern that molding defects may occur, and when the melt flow rate exceeds 100 g / 10 minutes, there is a concern about deterioration of physical properties such as impact resistance.
In addition, when pelletizing by adjusting the melt flow rate with peroxide, if the flip-up magnification exceeds 10 times, there is a risk of problems such as the pellet shape becoming distorted, the flip-up magnification is preferably It is within 6 times, more preferably within 4 times. When the melt flow rate is adjusted with a peroxide, the melt flow rate of the propylene-based block copolymer before adjustment is preferably 0.5 to 12 g / 10 minutes, and preferably 3 to 10 g / 10 minutes. In this range, the production is easy and the physical property balance is good.
本発明で用いるプロピレン系ブロック共重合体の製造方法としては、上記の諸特性を満足すればいかなる方法で製造してもよい。プロピレン系（共）重合体成分（Ａ）とプロピレン−エチレンランダム共重合体成分（Ｂ）を別々に重合したものを混合装置で混合してもよいが、プロピレン系（共）重合体成分（Ａ）を重合する工程とプロピレン−エチレンランダム共重合体成分（Ｂ）を重合する工程からなる多段重合により製造することがこのましい。
プロピレン系重合体の極限粘度を調整する方法は、水素もしくは他の公知の分子量調整剤で行うことができ、重合時に供給する水素ガスの量を調整することにより行われる。
As a method for producing the propylene-based block copolymer used in the present invention, any method may be used as long as the above properties are satisfied. The propylene-based (co) polymer component (A) and the propylene-ethylene random copolymer component (B) separately polymerized may be mixed with a mixing device, but the propylene-based (co) polymer component (A ) And a step of polymerizing the propylene-ethylene random copolymer component (B).
The method for adjusting the intrinsic viscosity of the propylene-based polymer can be carried out with hydrogen or other known molecular weight regulators, and is carried out by adjusting the amount of hydrogen gas supplied during the polymerization.
使用する触媒は、立体規則性触媒が好ましい。立体規則性触媒としてはメタロセン触媒などもあるが、物性バランスにおいて、チーグラー触媒を使用することが好ましい。 The catalyst used is preferably a stereoregular catalyst. The stereoregular catalyst includes a metallocene catalyst, but it is preferable to use a Ziegler catalyst in terms of the balance of physical properties.
チーグラー触媒としては、三塩化チタン、四塩化チタン、トリクロロエトキシチタン等のハロゲン化チタン化合物、これらハロゲン化チタン化合物とハロゲン化マグネシウムに代表されるマグネシウム化合物との接触物等の、遷移金属成分とアルキルアルミニウム化合物又はそれらのハロゲン化物、水素化物、アルコキシド等の有機金属成分との２成分系触媒、更にそれらの成分に窒素、炭素、リン、硫黄、酸素、ケイ素等を含む電子供与性化合物を加えた３成分系触媒等が挙げられる。三塩化チタン系触媒の１例としては、Ｓｏｌｖｅｙ触媒が挙げられる。 Ziegler catalysts include transition metal components and alkyl compounds such as titanium trichloride, titanium tetrachloride, and halogenated titanium compounds such as trichloroethoxytitanium, and contacts between these titanium halide compounds and magnesium compounds typified by magnesium halide. Aluminum compounds or their two-component catalysts with organic metal components such as halides, hydrides and alkoxides, and further electron-donating compounds containing nitrogen, carbon, phosphorus, sulfur, oxygen, silicon, etc., were added to these components. A three-component catalyst can be used. As an example of the titanium trichloride catalyst, there is a Solvey catalyst.
プロピレン系ブロック共重合体の製造方法としては、上記触媒の存在下に、不活性溶媒を用いたスラリー法、溶液法、実質的に溶媒を用いない気相法や、あるいは重合モノマーを溶媒とするバルク重合法等が挙げられる。 Propylene-based block copolymers can be produced by a slurry method using an inert solvent, a solution method, a gas phase method substantially using no solvent, or using a polymerization monomer as a solvent in the presence of the above catalyst. Examples include a bulk polymerization method.
例えば、スラリー重合法の場合には、ｎ−ブタン、イソブタン、ｎ−ペンタン、イソペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、ベンゼン、トルエン、キシレン等の不活性炭化水素又は液状モノマー中で行うことができる。重合温度は、通常−８０〜＋１５０℃であり、好ましくは４０〜１２０℃である。重合圧力は、１〜６０気圧が好ましい。 For example, in the case of the slurry polymerization method, it can be carried out in an inert hydrocarbon or liquid monomer such as n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and the like. . The polymerization temperature is usually −80 to + 150 ° C., preferably 40 to 120 ° C. The polymerization pressure is preferably 1 to 60 atmospheres.
（２）造核剤
本発明で用いるプロピレン系樹脂組成物に用いられる造核剤は、下記一般式（１）で表されるものである。
(2) Nucleating agent The nucleating agent used in the propylene-based resin composition used in the present invention is represented by the following general formula (1).
上記式中、ｎは、０〜２の整数であり、Ｒ１〜Ｒ５は、同一または異なって、それぞれ水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ６は炭素数が１〜２０のアルキル基である。 In the above formula, n is an integer of 0 to 2, and R 1 to R 5 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group, A halogen group and a phenyl group, and R 6 is an alkyl group having 1 to 20 carbon atoms.
本発明においては、透明性に優れている点、及び成形収縮率の異方性が少ない点で、上記一般式（１）で表される造核剤が好ましい。成形収縮率の異方性とは、射出成形により得た成形品の流れ方向とそれに対して垂直方向の収縮率の差のことである。この異方性が著しいと、医療用部材、例えば、ダイアライザーの外筒は円筒形状である場合が多いが、射出成形によって得られた成形品は正確な円形状が得られにくくなり、円柱形状が曲がってしまう恐れがある。 In the present invention, the nucleating agent represented by the above general formula (1) is preferable from the viewpoint of excellent transparency and low anisotropy of molding shrinkage. The anisotropy of the molding shrinkage is the difference between the shrinkage rate in the direction perpendicular to the flow direction of the molded product obtained by injection molding. When this anisotropy is significant, the outer member of a medical member, for example, a dialyzer is often cylindrical, but a molded product obtained by injection molding is difficult to obtain an accurate circular shape, and the cylindrical shape is There is a risk of bending.
上記一般式（１）中、ｎが０〜２の整数であり、Ｒ１、Ｒ２、Ｒ４及びＲ５が水素原子であり、Ｒ３は、水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ６が炭素数１〜２０のアルキル基であるものが好ましい。 In the general formula (1), n is an integer of 0 to 2, R 1 , R 2 , R 4 and R 5 are hydrogen atoms, and R 3 is a hydrogen atom or an alkyl having 1 to 20 carbon atoms. Group, alkenyl group, alkoxy group, carbonyl group, halogen group and phenyl group, and R 6 is preferably an alkyl group having 1 to 20 carbon atoms.
一般式（１）で表される造核剤としては、下記の化学式（２）で示されるミリケン・アンド・カンパニー社製の透明造核剤で商品名「ミラッドＮＸ８０００」として市販されているものが挙げられる。この透明造核剤は、透明性が優れるばかりでなく、低溶出性にも優れているので特に好ましい。 As the nucleating agent represented by the general formula (1), a transparent nucleating agent manufactured by Milliken & Company, represented by the following chemical formula (2), which is commercially available under the trade name “Mirad NX8000” is available. Can be mentioned. This transparent nucleating agent is particularly preferable because it is excellent not only in transparency but also in low elution.
上記造核剤の配合量は、上記プロピレン系ブロック共重合体１００質量部に対し、０．０１〜０．６重量部であり、好ましくは０．１〜０．５重量部であり、より好ましくは、０．２〜０．３重量部である。造核剤の配合量が、０．０１重量部未満では十分な効果が得られ難く、０．６重量部を超えて用いると、さらなる性能の向上が期待できないばかりか溶出し易くなり好ましくない。 The blending amount of the nucleating agent is 0.01 to 0.6 parts by weight, preferably 0.1 to 0.5 parts by weight, more preferably 100 parts by weight of the propylene-based block copolymer. Is 0.2 to 0.3 parts by weight. When the blending amount of the nucleating agent is less than 0.01 parts by weight, it is difficult to obtain a sufficient effect, and when it exceeds 0.6 parts by weight, further improvement in performance cannot be expected and it is easy to elute.
（３）その他の成分
本発明に用いられるプロピレン系樹脂組成物には、前記プロピレン系ブロック共重合体および前記造核剤の他に、本発明の効果を阻害しない範囲で、公知の樹脂用配合剤、例えば、中和剤、酸化防止剤、熱安定剤、光安定剤、有機染料、帯電防止剤、スリップ剤、脂肪酸金属塩等の分散剤、着色剤、充填剤、オレフィン系エラストマー等をそれ自体公知の処方で配合させることができる。
(3) Other components In addition to the propylene-based block copolymer and the nucleating agent, the propylene-based resin composition used in the present invention is a known compounding for resin as long as the effects of the present invention are not impaired. For example, neutralizing agents, antioxidants, heat stabilizers, light stabilizers, organic dyes, antistatic agents, slip agents, dispersants such as fatty acid metal salts, colorants, fillers, olefinic elastomers, etc. It can be blended in a formulation known per se.
但し、放射線滅菌を行うにあたり、放射線滅菌後の着色の観点から、一般にフェノール系酸化防止剤は添加しない方が好ましく、通常はリン系酸化防止剤を０．０１〜０．２重量％（例えばＡＤＥＫＡ社製商品名「アデガスタブ２１１２」等）と、ヒンダードアミン系紫外線安定剤（略称：ＨＡＬＳ、例えばＢＡＳＦジャパン社製商品名「ＴＩＮＵＶＩＮ６２２ＬＤ」）０．０１〜０．２重量％を組み合わせた処方で放射線照射に対応させることが好ましい。 However, when performing radiation sterilization, from the viewpoint of coloring after radiation sterilization, it is generally preferable not to add a phenolic antioxidant, and usually 0.01% to 0.2% by weight of a phosphorus antioxidant (for example, ADEKA). A combination of 0.01 to 0.2% by weight of a product name “Adegas Tab 2112”) and a hindered amine UV stabilizer (abbreviation: HALS, for example, product name “TINUVIN622LD” manufactured by BASF Japan) It is preferable to make it correspond.
中和剤の具体例としては、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウムなどの金属脂肪酸塩、ＤＨＴ−４Ａ（商品名：協和化学工業（株）製、下記一般式（３）で表されるマグネシウムアルミニウム複合水酸化物塩）、ミズカラック（商品名：水澤化学工業（株）製、下記一般式（４）で表されるリチウムアルミニウム複合水酸化物塩）などが挙げられる。特に、ダイアライザーなど長期接液する部材として用いる場合には、接触する液体に溶出しないＤＨＴ−４Ａやミズカラックが有利である。
Ｍｇ１−ｘＡｌｘ（ＯＨ）２（ＣＯ３）ｘ／２・ｍＨ２Ｏ ・・・（３）
（式（３）中、ｘは０≦ｘ≦０．５であり、ｍは３以下の数である。）
［Ａｌ２Ｌｉ（ＯＨ）６］ｎＸ・ｍＨ２Ｏ ・・・（４）
（式（４）中、Ｘは無機または有機のアニオンであり、ｎはアニオン（Ｘ）の価数であり、ｍは３以下である。）
Specific examples of the neutralizing agent include metal fatty acid salts such as calcium stearate, zinc stearate, and magnesium stearate, DHT-4A (trade name: manufactured by Kyowa Chemical Industry Co., Ltd., represented by the following general formula (3). Magnesium aluminum composite hydroxide salt), Mizukarak (trade name: lithium aluminum composite hydroxide salt represented by the following general formula (4), manufactured by Mizusawa Chemical Co., Ltd.), and the like. In particular, when used as a member that is in contact with the liquid for a long time, such as a dialyzer, DHT-4A or Mizukarak that does not elute into the liquid that comes into contact is advantageous.
Mg 1-x Al x (OH) 2 (CO 3 ) x / 2 · mH 2 O (3)
(In the formula (3), x is 0 ≦ x ≦ 0.5, and m is a number of 3 or less.)
[Al 2 Li (OH) 6 ] n X · mH 2 O (4)
(In the formula (4), X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less.)
但し、ダイアライザーの本体は円柱状に形状をしている場合が多く、この場合、良好な離型性が必要となり、その際は中和剤として離型性効果もあるステアリン酸カルシウムなどを使用するとよい。一般に用いられる滑剤であるオレイン酸アミドやエルカ酸アミドなどは溶出しやすいので好ましくない。ステアリン酸カルシウムなどの添加量としては、０．０３〜０．２５重量％がよく、より好ましくは０．０８〜０．１２重量部が良好である。０．０３重量部未満では離型性効果が充分でなく、０．２５重量部を超えると射出成形時に金型汚染が発生する場合があり好ましくない。 However, the dialyzer body often has a cylindrical shape, and in this case, good releasability is required. In this case, calcium stearate having a releasability effect may be used as a neutralizing agent. . Generally used lubricants such as oleic acid amide and erucic acid amide are not preferable because they are easily eluted. The addition amount of calcium stearate and the like is preferably 0.03 to 0.25% by weight, more preferably 0.08 to 0.12 parts by weight. If it is less than 0.03 parts by weight, the mold release effect is not sufficient, and if it exceeds 0.25 parts by weight, mold contamination may occur during injection molding, which is not preferable.
安定剤（酸化防止剤、光安定剤、紫外線吸収剤）としては、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジ−フォスファイト、ジ−ステアリル−ペンタエリスリトール−ジ−フォスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトール−ジ−フォスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレン−ジ−フォスフォナイト、テトラキス（２，４−ジ−ｔ−ブチル−５−メチルフェニル）−４，４’−ビフェニレン−ジ−フォスフォナイト、６−［３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロポキシ］−２，４，８，１０−テトラ−ｔ−ブチルジベンズ［ｄ，ｆ］［１．３．２］ジオキサホスフェピン等のリン系酸化防止剤、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、テトラキス［メチレン（３，５−ジ−ｔ−ブチル−４−ヒドロキシヒドロシンナメート）］メタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ハイドロキシベンジル）ベンゼン、トリス（３，５−ジ−ｔ−ブチル−４−ハイドロキシベンジル）イソシアヌレート等のフェノール系酸化防止剤、ジ−ステアリル−ββ’−チオ−ジ−プロピオネート、ジ−ミリスチル−ββ’−チオ−ジ−プロピオネート、ジ−ラウリル−ββ’−チオ−ジ−プロピオネート等のチオ系酸化防止剤、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール等の紫外線吸収剤、ｎ−ヘキサデシル−３，５−ジ−ｔ−ブチル−４−ヒドロキシベンゾエート、２，４−ジ−ｔ−ブチルフェニル−３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシベンゾエート、ビス（２，２，６，６−テトラメチル−４−ピぺリジル）セバケート、コハク酸ジメチル−２−（４−ヒドロキシ−２，２，６，６−テトラメチル−１−ピペリジル）エタノール縮合物、ポリ｛［６−〔（１，１，３，３−テトラメチルブチル）アミノ〕−１，３，５−トリアジン−２，４ジイル］〔（２，２，６，６−テトラメチル−４−ピペリジル）イミノ〕ヘキサメチレン〔（２，２，６，６−テトラメチル−４−ピペリジル）イミノ〕｝、Ｎ，Ｎ’−ビス（３−アミノプロピル）エチレンジアミン−２，４−ビス〔Ｎ−ブチル−Ｎ−（１，２，２，６，６−ペンタメチル−４−ピペリジル）アミノ〕−６−クロロ−１，３，５−トリアジン縮合物等の光安定剤、放射線処理で変色がなく耐ＮＯｘガス変色性が良好な化学式（５）や一般式（６）で表されるアミン系酸化防止剤、化学式（７）等のビタミンＥ系酸化防止剤を挙げることができる。 As stabilizers (antioxidants, light stabilizers, UV absorbers), bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, di-stearyl-pentaerythritol- Di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-) t-butylphenyl) -4,4′-biphenylene-diphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylene-diphosphonite, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f [1.3.2] Phosphorous antioxidants such as dioxaphosphin, 2,6-di-t-butyl-p-cresol, tetrakis [methylene (3,5-di-t-butyl-4- Hydroxyhydrocinnamate)] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t -Butyl-4-hydroxybenzyl) isocyanurate and other phenolic antioxidants, di-stearyl-ββ'-thio-di-propionate, di-myristyl-ββ'-thio-di-propionate, di-lauryl-ββ ' -Thio antioxidants such as thio-di-propionate, 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) UV absorbers such as -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, n-hexadecyl-3,5-di- t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, dimethyl-2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol condensate, poly {[6-[(1,1, 3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2 , 6,6-Te Tramethyl-4-piperidyl) imino]}, N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4) -Piperidyl) amino] -6-chloro-1,3,5-triazine condensate and other light stabilizers, chemical formula (5) and general formula (6) which have no discoloration and no discoloration resistance due to radiation treatment Examples thereof include amine-based antioxidants and vitamin E-based antioxidants such as chemical formula (7).
過酸化物としては、例えば、アセチルシクロヘキシルスルホニルパーオキサイド、イソブチルパーオキサイド、ジイソプロピルパーオキシジカルボネート、ジ−ｎ−プロピルパーオキシジカルボネート、ジ（２−メトキシエチル）パーオキシジカルボネート、ジ（メトキシイソプロピル）パーオキシジカルボネート、ジ（２−メチルヘキシル）パーオキシジカルボネート、ｔ−ブチルパーオキシネオデカノエート、２，４−ジクロロベンゾイルパーオキサイド、ｔ−ブチルパーオキシパイバレート、３，５，５−トリメチルヘキサノールパーオキサイド、オクタノールパーオキサイド、デカノールパーオキサイド、ラウロールパーオキサイド、ステアロールパーオキサイド、プロピオニルパーオキサイド、アセチルパーオキサイド、ｔ−ブチルパーオキシ（２−エチルヘキサノエート）、ベンゾキシパーオキサイド、ｔ−ブチルパーオキシイソブチレート、１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサノン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサノン、ｔ−ブチルパーオキシマレイン酸、琥珀酸オキサイド、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシ３，５，５−トリメチルヘキサノエート、シクロヘキサノンパーオキサイド、ｔ−ブチルパーオキシイソプロピルカルボネート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシアセテート、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルジパーオキシフタレート、ｎ−ブチル−４，４−ビス（ｔ−ブチルパーオキシ）バラレート、メチルエチルケトンパーオキサイド、ジクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、ｔ−ブチルクミルパーオキシド、ｔ−ブチルハイドロパーオキサイド、ジ−イソプロピルベンゼンハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｐ−メンタンハイドロパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、１，１，３，３−テトラメチルブチルハイドロパーオキサイド、２，５−ジメチルヘキサン−２，５−ジハイドロキシパーオキサイド、１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、クメンハイドロパーオキサイド等が挙げられる。 Examples of the peroxide include acetylcyclohexylsulfonyl peroxide, isobutyl peroxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-methoxyethyl) peroxydicarbonate, di (methoxyisopropyl). ) Peroxydicarbonate, di (2-methylhexyl) peroxydicarbonate, t-butylperoxyneodecanoate, 2,4-dichlorobenzoyl peroxide, t-butylperoxypivalate, 3,5,5 -Trimethylhexanol peroxide, octanol peroxide, decanol peroxide, laurol peroxide, stearol peroxide, propionyl peroxide, acetyl peroxide, t-butyl Peroxy (2-ethylhexanoate), benzoxyperoxide, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexanone, 1,1-bis (T-butylperoxy) cyclohexanone, t-butylperoxymaleic acid, oxalic acid oxide, t-butylperoxylaurate, t-butylperoxy3,5,5-trimethylhexanoate, cyclohexanone peroxide, t -Butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2,2-bis (t-butylperoxy) butane, t-butyl Peroxybenzoate, di-t-butyldiperoxyphthalate, n- Til-4,4-bis (t-butylperoxy) valerate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumylper Oxide, t-butyl hydroperoxide, di-isopropylbenzene hydroperoxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) Hexyne-3, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide, 1,3-bis (t-butylperoxyisopropyl) benzene, Examples include cumene hydroperoxide.
（４）プロピレン系樹脂組成物の製造方法
本発明の医療向け部材用プロピレン系樹脂組成物は、前記プロピレン系ブロック共重合体と前記造核剤、及び、必要に応じて配合する他の樹脂用配合剤の各成分をヘンシェルミキサー、スーパーミキサー、リボンブレンダー等を用いて配合し、通常の単軸押出機、二軸押出機、バンバリーミキサー、プラベンダー、ロール等で１９０〜２６０℃の温度範囲で溶融混練することにより得ることができる。
(4) Propylene-based resin composition production method The propylene-based resin composition for medical members of the present invention is for the propylene-based block copolymer, the nucleating agent, and other resins blended as necessary. Each component of the compounding agent is compounded using a Henschel mixer, super mixer, ribbon blender, etc., and in a temperature range of 190 to 260 ° C. with a normal single screw extruder, twin screw extruder, Banbury mixer, plastic bender, roll, etc. It can be obtained by melt-kneading.
（５）医療用部材
本発明の医療用部材は、上記プロピレン系樹脂組成物を、例えば射出成形法、押出成形法、ブロー成形法など各種の成形法によって成形することにより得られる。
医療用部材としては、人工透析用の部材、ディスポーザブルシリンジ、プレフィルドシリンジ等の各種シリンジ類、薬液容器、真空採血管、輸血用フィルター等が好ましく例示される。
(5) Medical member The medical member of this invention is obtained by shape | molding the said propylene-type resin composition by various shaping | molding methods, such as an injection molding method, an extrusion molding method, a blow molding method, for example.
Preferred examples of the medical member include artificial dialysis members, various syringes such as disposable syringes and prefilled syringes, chemical liquid containers, vacuum blood collection tubes, and blood transfusion filters.
前述したように、医療用部材は近年、放射線滅菌が施されることが多くなっているが、本発明の樹脂組成物からなる医療用部材は、放射線滅菌後も製品の衝撃強度と透明性の低下が極めて少ないので、放射線滅菌する医療部材として好適に利用でき、特に透明性と耐衝撃性の両方が重視される人工透析用部材やシリンジとして好適である。 As described above, medical members are often subjected to radiation sterilization in recent years. However, medical members made of the resin composition of the present invention have a high impact strength and transparency even after radiation sterilization. Since the reduction is extremely small, it can be suitably used as a medical member for radiation sterilization, and is particularly suitable as a member for artificial dialysis or a syringe in which both transparency and impact resistance are important.
人工透析用部材としては、ダイアライザーの外筒やヘッダー及びその関連部材を挙げることができる。人工透析用部材は、放射線滅菌（電子線やγ線など）が施され、放射線としては、γ線や電子線を挙げることができ、本発明による人工透析用部材には、１〜５０ＫＧｙの照射が行われていることが好ましく、５〜３０ＫＧｙの照射がされていることがより好ましい。照射量が、１ＫＧｙ未満では十分な効果が得られ難く、５０ＫＧｙを超えて用いると、放射線照射後の物性低下が著しくなり、良好な製品が得られなくなる恐れがある。 Examples of the member for artificial dialysis include an outer cylinder and header of a dialyzer and related members. The member for artificial dialysis is subjected to radiation sterilization (electron beam, γ ray, etc.), and examples of the radiation include γ ray and electron beam. The member for artificial dialysis according to the present invention is irradiated with 1 to 50 KGy. Is preferably performed, and more preferably 5 to 30 KGy is irradiated. If the irradiation dose is less than 1 KGy, it is difficult to obtain a sufficient effect, and if it is used in excess of 50 KGy, the physical properties after irradiation are markedly deteriorated, and a good product may not be obtained.
以下、実施例により、本発明をさらに詳細に説明するが、本発明はこれらの記載により何ら限定されるものではない。
各実施例及び比較例において用いた各成分、物性測定法は、以下の通りである。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these description.
Each component and the physical property measuring method used in each Example and Comparative Example are as follows.
［物性測定法］
（１）エチレン含有量：
１３Ｃ−ＮＭＲにより組成を検定したエチレン−プロピレンランダムコポリマーを基準物質として７３３ｃｍ−１の特性吸収体を用いる赤外分光法により、ランダムコポリマー中のエチレン含量を測定した。ペレットをプレス成形により約５００ミクロンの厚さのフィルムとしたものを用いた。
（２）極限粘度（単位：ｄｌ／ｇ）：
溶媒としてテトラリン（テトラヒドロナフタリン）を用い、１３５℃の温度条件下、自動粘度測定装置を使用し測定した。
（３）ＭＦＲ：
ＪＩＳ Ｋ７２１０に準拠して、２３０℃、２．１６Ｋｇ荷重に準拠して測定した。
[Physical property measurement method]
(1) Ethylene content:
The ethylene content in the random copolymer was measured by infrared spectroscopy using an ethylene-propylene random copolymer whose composition was verified by 13 C-NMR as a reference material and a characteristic absorber of 733 cm −1 . The pellets were formed into a film having a thickness of about 500 microns by press molding.
(2) Intrinsic viscosity (unit: dl / g):
Tetralin (tetrahydronaphthalene) was used as a solvent, and measurement was performed using an automatic viscosity measuring device under a temperature condition of 135 ° C.
(3) MFR:
In accordance with JIS K7210, the measurement was performed in accordance with 230 ° C. and a 2.16 kg load.
（４）ヘイズ値：
厚さ１ｍｍのシート片を用いて、通常の滅菌せずにＪＩＳ Ｋ７１３６に準拠して測定し、更に別途、２５ＫＧｙのγ線を照射し、１週間後ＪＩＳ Ｋ７１３６に準拠して測定した。
（５）曲げ弾性率：
通常の滅菌せずにＪＩＳ Ｋ７１７１に準拠して測定し、更に別途、試験片に２５ＫＧｙのγ線を照射し、１週間後ＪＩＳ Ｋ７１７１に準拠して２３℃で測定した。
（６）シャルピー衝撃値：
通常の滅菌せずにＪＩＳ Ｋ７１１１に準拠して測定し、更に別途、試験片に２５ＫＧｙの電子線を照射し、１週間後ＪＩＳ Ｋ７１１１に準拠して２３℃と０℃で測定した。
(4) Haze value:
Using a sheet piece having a thickness of 1 mm, measurement was performed in accordance with JIS K7136 without normal sterilization. Separately, 25 KGy γ-rays were irradiated, and one week later, measurement was performed in accordance with JIS K7136.
(5) Flexural modulus:
Measurement was performed in accordance with JIS K7171 without normal sterilization, and separately, the test piece was irradiated with 25 KGy of γ-ray, and one week later, measurement was performed at 23 ° C. in accordance with JIS K7171.
(6) Charpy impact value:
Measurement was performed in accordance with JIS K7111, without normal sterilization, and a test piece was separately irradiated with a 25 KGy electron beam, and after 1 week, measured at 23 ° C. and 0 ° C. in accordance with JIS K7111.
（７）透析型人工腎臓装置承認基準のうち、透析液供給部及び透析液回路の品質及び試験法
透析型人工腎臓装置承認基準のうち、透析液供給部及び透析液回路の品質及び試験法 １（２）に従って、ペレットにγ線２５ＫＧｙを照射したのちに測定を実施した。なお、溶出試験結果の基準は、以下の（ｉ）〜（ｖｉｉ）であり、これらを全て満たしたものが「適合」となる。
（ｉ）外観：無色燈明、異物なし
（ｉｉ）あわだち：３分以内に消失
（ｉｉｉ）ｐＨ：ブランクとの差が１．５以下
（ｉｖ）亜鉛：標準溶液以下
（ｖ）過マンガン酸カリウム還元性物質：標準溶液との過マンガン酸カリウム消費量の差１．０ｍｌ以下
（ｖｉ）蒸発残留物：１．０ｍｇ以下
（ｖｉｉ）紫外吸収スペクトル：０．１以下
(7) Dialysis fluid supply unit and dialysate circuit quality and test method among dialysis type artificial kidney device approval criteria. Dialysis fluid supply unit and dialysate circuit quality and test method among dialysis type artificial kidney device approval criteria 1 According to (2), the measurement was carried out after irradiating the pellet with γ-ray 25KGy. In addition, the reference | standard of a dissolution test result is the following (i)-(vii), and the thing which satisfy | filled all these becomes "conformity".
(I) Appearance: Colorless, no foreign matter (ii) Abalone: Disappears within 3 minutes (iii) pH: Difference from blank is 1.5 or less (iv) Zinc: Standard solution or less (v) Potassium permanganate reduction Substance: Difference in consumption of potassium permanganate from the standard solution 1.0 ml or less (vi) Evaporation residue: 1.0 mg or less (vii) Ultraviolet absorption spectrum: 0.1 or less
［使用材料］
＜プロピレン系ブロック共重合体＞
本発明での規定を満たすプロピレン系ブロック共重合体として、以下のＰＰ１〜ＰＰ６を使用した。
・プロピレン系ブロック共重合体（ＰＰ１）：
エチレン含有量が２．４重量％とするプロピレン−エチレンランダム共重合体成分（Ａ）を８６重量％、エチレン含有量が２５重量％とするプロピレン−エチレンランダム共重合体成分（Ｂ）を１４重量％で、極限粘度比［η］Ｂ／［η］Ａが１．０でＭＦＲ＝２５ｇ／１０分。チーグラー触媒で重合。
・プロピレン系ブロック共重合体（ＰＰ２）：
エチレン含有量が２．４重量％とするプロピレン−エチレンランダム共重合体成分（Ａ）を９０重量％、エチレン含有量が２５重量％とするプロピレン−エチレンランダム共重合体成分（Ｂ）を１０重量％で、極限粘度比［η］Ｂ／［η］Ａが１．０でＭＦＲ＝２５ｇ／１０分。チーグラー触媒で重合。
・プロピレン系ブロック共重合体（ＰＰ３）：
エチレン含有量が２．５重量％とするプロピレン−エチレンランダム共重合体成分（Ａ）を９４重量％、エチレン含有量が２５重量％とするプロピレン−エチレンランダム共重合体成分（Ｂ）を６重量％で、極限粘度比［η］Ｂ／［η］Ａが１．０でＭＦＲ＝２５ｇ／１０分。チーグラー触媒で重合。
・プロピレン系ブロック共重合体（ＰＰ４）：
エチレン含有量が２．４重量％とするプロピレン−エチレンランダム共重合体成分（Ａ）を８０重量％、エチレン含有量が２５重量％とするプロピレン−エチレンランダム共重合体成分（Ｂ）を２０重量％で、極限粘度比［η］Ｂ／［η］Ａが１．０でＭＦＲ＝３７ｇ／１０分。チーグラー触媒で重合。
・プロピレン系ブロック共重合体（ＰＰ５）：
エチレン含有量が２．４重量％とするプロピレン−エチレンランダム共重合体成分（Ａ）を９０重量％、エチレン含有量が２５重量％とするプロピレン−エチレンランダム共重合体成分（Ｂ）を１０重量％で、極限粘度比［η］Ｂ／［η］Ａが０．７５でＭＦＲ＝２５ｇ／１０分。チーグラー触媒で重合。
・プロピレン系ブロック共重合体（ＰＰ６）：
エチレン含有量が２．４重量％とするプロピレン−エチレンランダム共重合体成分（Ａ）を９０重量％、エチレン含有量が２５重量％とするプロピレン−エチレンランダム共重合体成分（Ｂ）を１０重量％で、極限粘度比［η］Ｂ／［η］Ａが１．１でＭＦＲ＝２５ｇ／１０分。チーグラー触媒で重合。
[Materials used]
<Propylene block copolymer>
The following PP1 to PP6 were used as propylene-based block copolymers that satisfy the provisions of the present invention.
Propylene block copolymer (PP1):
86% by weight of propylene-ethylene random copolymer component (A) having an ethylene content of 2.4% by weight and 14% by weight of propylene-ethylene random copolymer component (B) having an ethylene content of 25% by weight %, Intrinsic viscosity ratio [η] B / [η] A is 1.0 and MFR = 25 g / 10 min. Polymerized with Ziegler catalyst.
Propylene block copolymer (PP2):
90% by weight of propylene-ethylene random copolymer component (A) having an ethylene content of 2.4% by weight and 10% by weight of propylene-ethylene random copolymer component (B) having an ethylene content of 25% by weight %, Intrinsic viscosity ratio [η] B / [η] A is 1.0 and MFR = 25 g / 10 min. Polymerized with Ziegler catalyst.
Propylene block copolymer (PP3):
94% by weight of propylene-ethylene random copolymer component (A) having an ethylene content of 2.5% by weight and 6% of propylene-ethylene random copolymer component (B) having an ethylene content of 25% by weight %, Intrinsic viscosity ratio [η] B / [η] A is 1.0 and MFR = 25 g / 10 min. Polymerized with Ziegler catalyst.
Propylene block copolymer (PP4):
80% by weight of propylene-ethylene random copolymer component (A) having an ethylene content of 2.4% by weight and 20% by weight of propylene-ethylene random copolymer component (B) having an ethylene content of 25% by weight %, Intrinsic viscosity ratio [η] B / [η] A is 1.0 and MFR = 37 g / 10 min. Polymerized with Ziegler catalyst.
Propylene block copolymer (PP5):
90% by weight of propylene-ethylene random copolymer component (A) having an ethylene content of 2.4% by weight and 10% by weight of propylene-ethylene random copolymer component (B) having an ethylene content of 25% by weight %, The intrinsic viscosity ratio [η] B / [η] A is 0.75, and MFR = 25 g / 10 min. Polymerized with Ziegler catalyst.
Propylene block copolymer (PP6):
90% by weight of propylene-ethylene random copolymer component (A) having an ethylene content of 2.4% by weight and 10% by weight of propylene-ethylene random copolymer component (B) having an ethylene content of 25% by weight %, Intrinsic viscosity ratio [η] B / [η] A is 1.1 and MFR = 25 g / 10 min. Polymerized with Ziegler catalyst.
本発明での規定を満たさないプロピレン系共重合体として、以下のＰＰ７〜ＰＰ９を使用した。
・プロピレン系ブロック共重合体（ＰＰ７）：
エチレン含有量が２．５重量％とするプロピレン−エチレンランダム共重合体成分（Ａ）を９９重量％、エチレン含有量が２５重量％とするプロピレン−エチレンランダム共重合体成分（Ｂ）を１重量％で、極限粘度比［η］Ｂ／［η］Ａが１．０でＭＦＲ＝２５ｇ／１０分。チーグラー触媒で重合。
・プロピレン−エチレンランダム共重合体（ＰＰ８）：
エチレン含有量２．５重量％、ＭＦＲ＝２５ｇ／１０分のプロピレン−エチレンランダム共重合体、チーグラー触媒で重合。
・プロピレン−エチレンランダム共重合体（ＰＰ９）：
エチレン含有量３．９重量％、ＭＦＲ＝２５ｇ／１０分のプロピレン−エチレンランダム共重合体、チーグラー触媒で重合。
The following PP7 to PP9 were used as propylene-based copolymers that do not satisfy the provisions of the present invention.
Propylene block copolymer (PP7):
99% by weight of propylene-ethylene random copolymer component (A) having an ethylene content of 2.5% by weight, 1% of propylene-ethylene random copolymer component (B) having an ethylene content of 25% by weight %, Intrinsic viscosity ratio [η] B / [η] A is 1.0 and MFR = 25 g / 10 min. Polymerized with Ziegler catalyst.
Propylene-ethylene random copolymer (PP8):
Polymerized with a propylene-ethylene random copolymer having an ethylene content of 2.5% by weight and MFR = 25 g / 10 min, Ziegler catalyst.
Propylene-ethylene random copolymer (PP9):
Polymerized with propylene-ethylene random copolymer having an ethylene content of 3.9% by weight and MFR = 25 g / 10 min, Ziegler catalyst.
＜造核剤＞
前記式（２）で示す造核剤であるミリケン社製、商品名「ＮＸ８０００」を使用した。
＜樹脂用配合剤＞
・中和剤：
ステアリン酸カルシウム
・フォスファイト系酸化防止剤
「アデガスタブ２１１２」、（ＡＤＥＫＡ社製、商品名）
・ヒンダードアミン系紫外線安定剤
「ＴＩＮＵＶＩＮ６２２ＬＤ」、（ＢＡＳＦ製、商品名）
<Nucleating agent>
The product name “NX8000” manufactured by Milliken, which is a nucleating agent represented by the formula (2), was used.
<Resin compounding agent>
·Neutralizer:
Calcium stearate phosphite antioxidant “Adegas Tab 2112” (trade name, manufactured by ADEKA)
・ Hindered amine UV stabilizer “TINUVIN622LD” (trade name, manufactured by BASF)
（実施例１〜６、比較例１〜３）
以下の表１に記載のプロピレン系重合体１００重量部に対して、造核剤「ＮＸ８０００」を０．３重量部、ステアリン酸カルシウムを０．０５重量部、「アデガスタブ２１１２」を０．１０重量部および「ＴＩＮＵＶＩＮ６２２ＬＤ」を０．０５重量部、スーパーミキサーでドライブレンドした後、３５ミリ径の２軸押出機を用いて溶融混練した。ダイ出口部温度２５０℃でダイから押し出しペレット化した。
得られたペレットを射出成形機により、樹脂温度２４０℃、射出圧力９００ｋｇ／ｃｍ２及び金型温度４０℃で射出成形し、試験片をつくり、物性を測定した。その結果を表１に示す。
(Examples 1-6, Comparative Examples 1-3)
The nucleating agent “NX8000” is 0.3 parts by weight, the calcium stearate is 0.05 parts by weight, and “Adegas tub 2112” is 0.10 parts by weight with respect to 100 parts by weight of the propylene-based polymer described in Table 1 below. Then, 0.05 part by weight of “TINUVIN622LD” was dry blended with a super mixer, and then melt-kneaded using a 35 mm diameter twin screw extruder. Extruded pellets from the die at a die outlet temperature of 250 ° C.
The obtained pellets were injection-molded with an injection molding machine at a resin temperature of 240 ° C., an injection pressure of 900 kg / cm 2 and a mold temperature of 40 ° C., test specimens were prepared, and physical properties were measured. The results are shown in Table 1.
表１から明らかなように、実施例１〜６は、透明性があり、放射線滅菌後も耐衝撃性に優れていることが判る。一方、本発明の規定を満たさない比較例１〜３は、透明性はよいものの、放射線滅菌後の耐衝撃性は、実施例に比べて劣る。
また、本発明の規定を満たす配合であれば、透析型人工腎臓装置承認基準のうち、透析液供給部及び透析液回路の品質及び試験法 １（２）に適合し、耐衝撃性に優れていることがわかる。
As can be seen from Table 1, Examples 1 to 6 are transparent and have excellent impact resistance even after radiation sterilization. On the other hand, Comparative Examples 1 to 3 that do not satisfy the provisions of the present invention have good transparency, but the impact resistance after radiation sterilization is inferior to that of the Examples.
In addition, if the composition satisfies the provisions of the present invention, it conforms to the quality and test method 1 (2) of the dialysate supply section and dialysate circuit among the dialysis artificial kidney device approval criteria, and has excellent impact resistance. I understand that.
本発明の医療用部材は、特に透析型人工腎臓装置承認基準のうち、透析液供給部及び透析液回路の品質及び試験法 １（２）を満足し、かつ、耐衝撃性、透明性、成形性に優れたものであることから、人工透析用部材、特にディスポーザブルシリンジの外筒などに適している。また、医療用部材は、放射線滅菌が行われているが、本発明の医療用部材は、放射線照射による物性低下が極めて少ない。さらに、本発明によるディスポーザブルシリンジの外筒や、ダイアライザーの外筒やヘッダーは、その優れた透明性から、使用時の内部状態を外部からはっきりと観察することができ、溶出特性にも優れていることから、安心して実用に供することができる。 The medical member of the present invention satisfies the quality and test method 1 (2) of the dialysate supply part and dialysate circuit among the dialysis-type artificial kidney device approval standards, and has impact resistance, transparency, and molding. Since it has excellent properties, it is suitable for a member for artificial dialysis, particularly an outer cylinder of a disposable syringe. Moreover, although the medical member is sterilized by radiation, the medical member of the present invention has very little deterioration in physical properties due to radiation irradiation. Furthermore, the outer cylinder of the disposable syringe according to the present invention and the outer cylinder and header of the dialyzer can clearly observe the internal state from the outside due to their excellent transparency, and have excellent elution characteristics. Therefore, it can be put to practical use with peace of mind.
１ 透析を受ける人の腕
２ チューブ
３ 血液ポンプ
４ エアートラップ
５ ダイアライザー
６ コンソール
７ 血液流入口
８ 血液流出口
９ 透析液流入口
１０ 透析液流出口
１１ ホローファイバー
１２ ダイアライザーの外筒
１３ ダイアライザーのヘッダー
1 Arm of person undergoing dialysis 2 Tube 3 Blood pump 4 Air trap 5
8 Blood Outlet 9
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