JP4596124B2 - Medical container - Google Patents
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- Publication number
- JP4596124B2 JP4596124B2 JP2004066024A JP2004066024A JP4596124B2 JP 4596124 B2 JP4596124 B2 JP 4596124B2 JP 2004066024 A JP2004066024 A JP 2004066024A JP 2004066024 A JP2004066024 A JP 2004066024A JP 4596124 B2 JP4596124 B2 JP 4596124B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- cyclic polyolefin
- component
- medical container
- propylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 polyethylene Polymers 0.000 claims description 63
- 229920005672 polyolefin resin Polymers 0.000 claims description 61
- 125000004122 cyclic group Chemical group 0.000 claims description 60
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 54
- 238000010828 elution Methods 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 48
- 239000000565 sealant Substances 0.000 claims description 47
- 239000000178 monomer Substances 0.000 claims description 39
- 229920001577 copolymer Polymers 0.000 claims description 38
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 36
- 230000009477 glass transition Effects 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- 239000004711 α-olefin Substances 0.000 claims description 23
- 239000005977 Ethylene Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005194 fractionation Methods 0.000 claims description 12
- 230000000630 rising effect Effects 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 229920013716 polyethylene resin Polymers 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 9
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 9
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000636 poly(norbornene) polymer Polymers 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 86
- 238000004806 packaging method and process Methods 0.000 description 53
- 230000001954 sterilising effect Effects 0.000 description 31
- 238000004659 sterilization and disinfection Methods 0.000 description 31
- 238000006116 polymerization reaction Methods 0.000 description 22
- 229920000098 polyolefin Polymers 0.000 description 20
- 238000007789 sealing Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 14
- 239000003814 drug Substances 0.000 description 13
- 229940079593 drug Drugs 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000004840 adhesive resin Substances 0.000 description 3
- 229920006223 adhesive resin Polymers 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000002872 contrast media Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 150000001925 cycloalkenes Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000002526 effect on cardiovascular system Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 229940124599 anti-inflammatory drug Drugs 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003978 infusion fluid Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002503 metabolic effect Effects 0.000 description 2
- 150000002848 norbornenes Chemical class 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000012217 radiopharmaceutical Substances 0.000 description 2
- 229940121896 radiopharmaceutical Drugs 0.000 description 2
- 230000002799 radiopharmaceutical effect Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 229940124549 vasodilator Drugs 0.000 description 2
- 239000003071 vasodilator agent Substances 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- LSIXBBPOJBJQHN-UHFFFAOYSA-N 2,3-Dimethylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C(C)=C(C)C1C2 LSIXBBPOJBJQHN-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 1
- YPVPQMCSLFDIKA-UHFFFAOYSA-N 3-ethylpent-1-ene Chemical compound CCC(CC)C=C YPVPQMCSLFDIKA-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- SUJVAMIXNUAJEY-UHFFFAOYSA-N 4,4-dimethylhex-1-ene Chemical compound CCC(C)(C)CC=C SUJVAMIXNUAJEY-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- JFMXMDVWTVJDGK-UHFFFAOYSA-N 4-(chloromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(CCl)C2 JFMXMDVWTVJDGK-UHFFFAOYSA-N 0.000 description 1
- APIHKEKYBYXFPG-UHFFFAOYSA-N 4-bicyclo[2.2.1]hept-2-enyl(trimethyl)silane Chemical compound C1CC2C=CC1([Si](C)(C)C)C2 APIHKEKYBYXFPG-UHFFFAOYSA-N 0.000 description 1
- OPMUAJRVOWSBTP-UHFFFAOYSA-N 4-ethyl-1-hexene Chemical compound CCC(CC)CC=C OPMUAJRVOWSBTP-UHFFFAOYSA-N 0.000 description 1
- WXOFQPMQHAHBKI-UHFFFAOYSA-N 4-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(CC)C2 WXOFQPMQHAHBKI-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000006677 Appel reaction Methods 0.000 description 1
- UTBCLIMIBBSDLG-UHFFFAOYSA-N C12=CC=CCC2C2CC2C2C1C2 Chemical compound C12=CC=CCC2C2CC2C2C1C2 UTBCLIMIBBSDLG-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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- 108090000790 Enzymes Proteins 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920003354 Modic® Polymers 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- UGGIERTXTWFEES-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-2,3-dicarbonitrile Chemical compound C1CC2C(C#N)=C(C#N)C1C2 UGGIERTXTWFEES-UHFFFAOYSA-N 0.000 description 1
- KOKLYLSZOGGBHE-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-4-carbonitrile Chemical compound C1CC2C=CC1(C#N)C2 KOKLYLSZOGGBHE-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003177 cardiotonic effect Effects 0.000 description 1
- 239000002327 cardiovascular agent Substances 0.000 description 1
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- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- LORADGICSMRHTR-UHFFFAOYSA-N cyclohexyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(OCC)C1CCCCC1 LORADGICSMRHTR-UHFFFAOYSA-N 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- RNWDNEVYZAPIBG-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-4-carboxylate Chemical compound C1CC2C=CC1(C(=O)OC)C2 RNWDNEVYZAPIBG-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XBFJAVXCNXDMBH-GEDKWGBFSA-N molport-035-785-283 Chemical compound C1[C@@H](C23)C=C[C@H]1C3[C@@H]1C[C@H]2CC1 XBFJAVXCNXDMBH-GEDKWGBFSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JHVNMGWNEQGGDU-UHFFFAOYSA-N tert-butyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C(C)(C)C)OCC JHVNMGWNEQGGDU-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Landscapes
- Packages (AREA)
- Wrappers (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
- Laminated Bodies (AREA)
Description
本発明は、内容物の成分が容器内壁に吸着したり、容器から内容物へ低分子量成分が溶出したりすることによる、内容物の組成変化や内容物汚染のおそれが可及的に低減され、しかも、１１０℃以上の高圧蒸気滅菌処理によっても容器の変形や液漏れが発生しない包装袋、及び当該包装袋を形成可能な積層フィルムに関する。 The present invention reduces the risk of content change and content contamination as much as possible by adsorbing the components of the content on the inner wall of the container or eluting low molecular weight components from the container into the content. In addition, the present invention relates to a packaging bag in which deformation or liquid leakage of a container does not occur even by high-pressure steam sterilization at 110 ° C. or higher, and a laminated film capable of forming the packaging bag.
医療分野においてはプラスチック容器を用いて医薬品を保存・流通させることが一般的であり、また、該プラスチック容器の材質としては、ポリエチレン、ポリプロピレン等が一般的である。内容液を容器に収容するに際しては、容器に内容液を充填・密封した後、１１０℃以上の温度にて高圧蒸気滅菌処理が通常行なわれる。 In the medical field, it is common to store and distribute pharmaceuticals using a plastic container, and polyethylene, polypropylene, etc. are common as the material of the plastic container. When the content liquid is accommodated in the container, the high-pressure steam sterilization process is usually performed at a temperature of 110 ° C. or higher after the container is filled and sealed with the content liquid.
ここで、ポリエチレンやポリプロピレン等が容器内壁として用いられた容器に特定の内容物が収容されて上記高圧蒸気滅菌処理が施される場合には、内容物の成分組成が変化する場合がある。例えば微量の元素（例えばマンガンなど）、ビタミン類、硝酸イソソルビト等を有効成分として含有する投与薬剤が内容物となる場合、容器内壁にこれらの成分が吸着され使用の際に有効成分が完全には投与されないといった場合がある。
一方、プラスチック容器の材質には未反応モノマーや各種添加剤といった低分子量成分が含まれていることが多く、ポリエチレンやポリプロピレン等が容器内壁として用いられている場合には、容器の構成部材に含まれる上記低分子量成分が内容液中に溶出し、それらが内容液中の各種成分と反応して副生物が生成してしまう場合もある。
Here, when specific contents are stored in a container in which polyethylene, polypropylene, or the like is used as the inner wall of the container and the above-mentioned high-pressure steam sterilization is performed, the component composition of the contents may change. For example, when an administered drug containing a trace amount of elements (such as manganese), vitamins, isosorbate nitrate, etc. as an active ingredient is the content, these ingredients are adsorbed on the inner wall of the container and the active ingredient is completely There are cases where it is not administered.
On the other hand, plastic container materials often contain low molecular weight components such as unreacted monomers and various additives. When polyethylene or polypropylene is used as the inner wall of the container, it is included in the components of the container. In some cases, the low molecular weight components eluted in the content liquid react with various components in the content liquid to produce by-products.
このような問題を解決するため、例えば特許文献１：再表９９／０３９６７９号公報には、環状オレフィンコポリマーを使用した容器が提案されている。しかし、この容器は内側よりポリオレフィン、環状オレフィンコポリマー、ポリオレフィンの順の層構成となっており、内容液に直接接触するポリオレフィン自体の厚みを薄く設定することにより内容液成分の吸着や収着を少量に抑えることができるものの、内容液成分の吸着や収着が生じることに変わりはない。
また、特許文献２：特開２００１−１５７７０４号公報、特許文献３：特開２００１−１５７７０５号公報には、ポリエチレンやα−オレフィンポリマー、エチレン・α−オレフィン共重合体、エチレン・α−オレフィン・他オレフィン系モノマー三元共重合体と、環状オレフィンの開環重合体若しくはその水素添加体との混合物、又は、環状オレフィンの開環重合体若しくはその水素添加体を用いて中間層を構成する輸液用包装材料が提案されている。しかし、これらの包装材料においても容器を形成する際に内容物と接触する最内層としてはＬＤＰＥやＬＬＤＰＥなどのオレフィン系樹脂を使用するものであり、内容液成分の吸着や収着が生じることに変わりはない。
In order to solve such a problem, for example, Patent Document 1: No. 99/039679 proposes a container using a cyclic olefin copolymer. However, this container has a layer structure of polyolefin, cyclic olefin copolymer, and polyolefin in that order from the inside. By setting the thickness of the polyolefin itself in direct contact with the content liquid to be thin, adsorption and sorption of the content liquid component is small. Although the content of the liquid components can be reduced to the above, the adsorption and sorption of the components of the contents will remain.
Patent Document 2: JP 2001-157704 A and Patent Document 3: JP 2001-157705 A include polyethylene, α-olefin polymers, ethylene / α-olefin copolymers, ethylene / α-olefins, and the like. A mixture of another olefinic monomer terpolymer and a cyclic olefin ring-opening polymer or a hydrogenated product thereof, or an infusion solution constituting an intermediate layer using a cyclic olefin ring-opening polymer or a hydrogenated product thereof. Packaging materials have been proposed. However, in these packaging materials, an olefin resin such as LDPE or LLDPE is used as the innermost layer that comes into contact with the contents when forming the container, and the adsorption and sorption of the contents liquid components occur. There is no change.
更に、容器からの微量成分の内容物への溶出を解決することを目的として、特許文献４：特許第３２２７７０９号公報には最内層に熱可塑性飽和ノルボルネン系ポリマーを使用する医療用または食品包装用容器が、また、特許文献５：特開平５−２７７１５４号公報には、α−オレフィンに由来する繰り返し単位と環状オレフィンに由来する繰り返し単位とを有し、且つガラス転移温度（Ｔｇ）が７０℃以下である環状オレフィン系共重合体を用いて容器最内層を構成した医療用輸液バッグが提案されている。しかしながら、これらのいずれの容器においても、１１０℃以上の高圧蒸気滅菌への適性という点からはなお改善の余地があった。 Furthermore, for the purpose of solving the elution of trace components from the container into the contents, Patent Document 4: Japanese Patent No. 3227709 discloses a medical or food packaging that uses a thermoplastic saturated norbornene polymer as the innermost layer. The container also has a repeating unit derived from an α-olefin and a repeating unit derived from a cyclic olefin in JP-A-5-277154, and a glass transition temperature (Tg) is 70 ° C. The medical infusion bag which comprised the container innermost layer using the following cyclic olefin type copolymers is proposed. However, any of these containers still had room for improvement in terms of suitability for high-pressure steam sterilization at 110 ° C. or higher.
本発明は、上記事情に鑑みなされたもので、容器内壁が内容品の有効成分を取込んだり、容器の構成材料自体に用いられている低分子量成分（残留モノマーやその多量体など）が内容品中に溶出して２〜５μｍ程度の微粒子を発生させたり、内容品の劣化や変性などを引き起こしたりすることがなく、更に、容器内壁のヒートシール性に優れ、しかも１１０℃以上の高圧蒸気滅菌処理によっても容器の変形や液漏れが発生しない包装袋、及び当該包装袋を形成可能な積層フィルムを提供することを目的とする。 The present invention has been made in view of the above circumstances, and the inner wall of the container takes in the active ingredients of the contents, or the low molecular weight components (residual monomers and multimers thereof, etc.) used in the constituent material of the container itself. Elution into the product does not generate fine particles of about 2 to 5 μm, does not cause deterioration or modification of the contents, and is excellent in heat sealability of the inner wall of the container, and high-pressure steam at 110 ° C. or higher It is an object of the present invention to provide a packaging bag that does not cause deformation or leakage of a container even by sterilization, and a laminated film that can form the packaging bag.
本発明者は、上記目的を達成するため鋭意検討の結果、シーラント層により内壁面が形成される包装袋を構成するに際し、前記シーラント層としてガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂を主成分として含むシーラント層を採用し、かつ前記シーラント層に積層されて前記包装袋の外壁面を形成する基材層として融点１１０〜２２０℃のポリオレフィン系樹脂を主成分として含む基材層を採用することにより、内容物の成分が容器内壁に吸着したり、容器から内容物へ低分子量成分が溶出したりする虞が可及的に低減され、しかも良好なヒートシール性と耐熱性とを具備した包装袋が実現可能であることを知見し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventor has mainly used a cyclic polyolefin resin having a glass transition temperature of 100 to 170 ° C. as the sealant layer when forming a packaging bag in which the inner wall surface is formed by the sealant layer. A sealant layer containing as a component is adopted, and a base material layer containing a polyolefin resin having a melting point of 110 to 220 ° C. as a main component is adopted as a base material layer laminated on the sealant layer to form the outer wall surface of the packaging bag. As a result, the risk of the components of the contents adsorbing on the inner wall of the container or the elution of low molecular weight components from the container to the contents is reduced as much as possible, and it has good heat sealability and heat resistance. The present inventors have found that a packaging bag is feasible and have made the present invention.
即ち、本発明は、以下の医療用容器を提供する。
請求項１：
基材層と、基材層の一面側に積層されたシーラント層とを含む積層フィルムを用いて形成され、１１０℃以上の温度での滅菌が可能な医療用容器において、
前記基材層が融点１１０〜２２０℃のポリオレフィン系樹脂を主成分として含み、かつ、前記シーラント層がガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂を主成分として含むとともに、
ガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂を主成分として含む材料が少なくとも内壁に使用されて外側がポリエチレン樹脂にて被覆されたポート部材が前記シーラント層に液漏れしないようにシールされたことを特徴とする医療用容器。
請求項２：
前記ポリオレフィン系樹脂が、直鎖状低密度ポリエチレン、または下記（Ａ）成分を含むプロピレン系共重合体組成物である請求項１記載の医療用容器。
（Ａ）成分：プロピレンと、エチレン及び／又は炭素数４〜８のα−オレフィンとからなるプロピレン系共重合体成分であって、温度上昇溶離分別法（温度：０〜１４０℃、溶媒：ｏ−ジクロロベンゼン）を用いた場合に、０℃での溶出分の割合が全溶出量に対して１５質量％以上５０質量％以下、６０℃以上９０℃以下での溶出分の割合が全溶出量に対して５質量％以上１５質量％未満であるプロピレン系共重合体。
請求項３：
前記プロピレン系共重合体組成物が、さらに下記（Ｂ）成分を含む請求項２記載の医療用容器。
（Ｂ）成分：プロピレンと、エチレン及び／又は炭素数４〜８のα−オレフィンとからなるプロピレン系共重合体成分であって、温度上昇溶離分別法（温度：０〜１４０℃、溶媒：ｏ−ジクロロベンゼン）を用いた場合に、０℃での溶出分の割合が全溶出量に対して０質量％以上２５質量％以下、６０℃以上９０℃以下での溶出分の割合が全溶出量に対して１５質量％以上７０質量％以下であるプロピレン系共重合体。
請求項４：
前記積層フィルムの前記環状ポリオレフィン系樹脂が、ノルボルネン系モノマーを重合して得られるポリノルボルネン系樹脂の１種または２種以上の組合せである請求項１，２又は３記載の医療用容器。
請求項５：
前記積層フィルムの前記環状ポリオレフィン系樹脂が、ガラス転移温度１００℃未満の環状ポリオレフィン系樹脂を３０質量％以下含有する請求項１乃至４のいずれか１項記載の医療用容器。
請求項６：
前記ポート部材の前記環状ポリオレフィン系樹脂が、前記積層フィルムの前記環状ポリオレフィン系樹脂と同一である請求項１乃至５のいずれか１項記載の医療用容器。
請求項７：
前記ポート部材の前記環状ポリオレフィン系樹脂のガラス転移温度が、前記積層フィルムの前記環状ポリオレフィン系樹脂のガラス転移温度より低い請求項１乃至５のいずれか１項記載の医療用容器。
請求項８：
前記ポート部材の前記環状ポリオレフィン系樹脂は、熱可塑性エラストマーが２０％以下の混合比率で混合された請求項１乃至７のいずれか１項記載の医療用容器。
請求項９：
前記ポート部材の前記環状ポリオレフィン系樹脂に配合される熱可塑性エラストマーがスチレン系エラストマーである請求項１乃至８のいずれか１項記載の医療用容器。
請求項１０：
前記ポート部材は、外側の一部がポリエチレン樹脂にて被覆された請求項１乃至９のいずれか１項記載の医療用容器。
請求項１１：
前記ポート部材は、外側の一部がポリエチレン樹脂にて被覆され、ポリエチレン樹脂が被覆されずに露出した前記ポート部材の内壁の前記環状ポリオレフィン系樹脂にて前記シーラント層にシールされた請求項１乃至１０のいずれか１項記載の医療用容器。
請求項１２：
前記ポート部材は、外側が直鎖状ポリエチレンにて被覆され、前記ポート部材の直鎖状ポリエチレンが前記シーラント層にシールされた請求項１乃至１１のいずれか１項記載の医療用容器。
That is, the present invention provides the following medical containers.
Claim 1:
In a medical container formed using a laminated film including a base material layer and a sealant layer laminated on one surface side of the base material layer and capable of being sterilized at a temperature of 110 ° C. or higher,
The base material layer includes a polyolefin resin having a melting point of 110 to 220 ° C. as a main component, and the sealant layer includes a cyclic polyolefin resin having a glass transition temperature of 100 to 170 ° C. as a main component.
As a port including materials with glass transition temperature 100 to 170 ° C. of cyclic polyolefin resin as a main component and less used in the inner wall also has an outer coated with a polyethylene resin member dripless the sealant layer A medical container characterized in that it is sealed.
Claim 2:
The medical container according to claim 1, wherein the polyolefin-based resin is a linear low-density polyethylene or a propylene-based copolymer composition containing the following component (A).
Component (A): a propylene copolymer component composed of propylene and ethylene and / or an α-olefin having 4 to 8 carbon atoms, and a temperature rising elution fractionation method (temperature: 0 to 140 ° C., solvent: o -Dichlorobenzene), the proportion of elution at 0 ° C. is 15 mass% to 50 mass% and the proportion of elution at 60 ° C. to 90 ° C. is the total amount of elution. A propylene-based copolymer that is 5% by mass or more and less than 15% by mass with respect to.
Claim 3:
The medical container according to claim 2, wherein the propylene copolymer composition further comprises the following component (B).
Component (B): a propylene copolymer component composed of propylene and ethylene and / or an α-olefin having 4 to 8 carbon atoms, and a temperature rising elution fractionation method (temperature: 0 to 140 ° C., solvent: o -Dichlorobenzene), the proportion of elution at 0 ° C. is 0% to 25% by mass, and the proportion of elution at 60 ° C. to 90 ° C. is the total amount eluted. A propylene-based copolymer that is 15% by mass or more and 70% by mass or less based on the weight.
Claim 4:
The medical container according to claim 1, 2 or 3, wherein the cyclic polyolefin resin of the laminated film is one or a combination of two or more polynorbornene resins obtained by polymerizing norbornene monomers.
Claim 5:
The medical container according to any one of claims 1 to 4, wherein the cyclic polyolefin resin of the laminated film contains 30% by mass or less of a cyclic polyolefin resin having a glass transition temperature of less than 100 ° C.
Claim 6:
The medical container according to any one of claims 1 to 5, wherein the cyclic polyolefin resin of the port member is the same as the cyclic polyolefin resin of the laminated film.
Claim 7:
The medical container according to any one of claims 1 to 5, wherein a glass transition temperature of the cyclic polyolefin resin of the port member is lower than a glass transition temperature of the cyclic polyolefin resin of the laminated film.
Claim 8:
The medical container according to any one of claims 1 to 7, wherein the cyclic polyolefin-based resin of the port member is mixed with a thermoplastic elastomer at a mixing ratio of 20% or less.
Claim 9 :
The medical container according to any one of claims 1 to 8 , wherein the thermoplastic elastomer blended in the cyclic polyolefin resin of the port member is a styrene elastomer.
Claim 10:
The medical container according to claim 1, wherein a part of the outer side of the port member is covered with a polyethylene resin.
Claim 11:
The port member is sealed to the sealant layer with the cyclic polyolefin-based resin on the inner wall of the port member that is partly covered with polyethylene resin and exposed without being covered with polyethylene resin. The medical container according to any one of 10.
Claim 12:
The medical container according to any one of claims 1 to 11, wherein the port member is coated with linear polyethylene on the outside, and the linear polyethylene of the port member is sealed by the sealant layer.
本発明の包装袋は、内容物の成分が容器内壁に吸着する虞が可及的に低減され、また、容器から内容物へ低分子量成分等が溶出したりすることによる内容物の組成変化又は内容物汚染の虞が可及的に低減された包装袋である。しかも、本発明の包装袋は１１０℃以上の高圧蒸気滅菌処理によっても袋の変形や液漏れが発生しないため、特に輸液、薬液、Ｘ線造影剤、ホルモン剤、放射性医薬品、循環器官用剤、消化器系製剤、蛋白アミノ製剤、循環器系製剤、酵素製剤、代謝性医薬品、抗生物質、抗炎症薬、腫瘍薬、生物学的製剤等の医薬品又はビタミン剤、微量元素等を収容する医療用容器として好適である。さらに本発明の包装袋は、内容物の成分が容器内壁に吸着する虞が可及的に低減され、また、容器から内容物へ低分子量成分等が溶出したりすることによる内容物の組成変化又は内容物汚染の虞が可及的に低減された包装袋であるため、１１０℃以上の高圧蒸気滅菌処理を行わない内容液、あるいは粉末状、固形状、半固形状の内容物を包装する包装袋としても利用することが可能である。また、本発明の積層フィルムは、前記包装袋を形成するに際し好適に適用可能な積層フィルムである。 In the packaging bag of the present invention, the possibility that the components of the contents are adsorbed on the inner wall of the container is reduced as much as possible, and the composition change of the contents due to elution of low molecular weight components or the like from the container to the contents, or It is a packaging bag in which the risk of content contamination is reduced as much as possible. In addition, since the packaging bag of the present invention does not cause deformation or leakage of the bag even by high-pressure steam sterilization at 110 ° C. or higher, in particular, infusion solution, drug solution, X-ray contrast agent, hormone agent, radiopharmaceutical, circulatory organ agent, Gastrointestinal preparations, protein amino preparations, circulatory system preparations, enzyme preparations, metabolic drugs, antibiotics, anti-inflammatory drugs, tumor drugs, biological drugs, etc. Suitable as a container. Furthermore, the packaging bag of the present invention reduces the possibility of the components of the contents adsorbing to the inner wall of the container as much as possible, and changes in the composition of the contents due to elution of low molecular weight components and the like from the container to the contents Or, because it is a packaging bag in which the risk of contamination of content is reduced as much as possible, it is used to wrap content liquids that are not subjected to high-pressure steam sterilization at 110 ° C or higher, or powdered, solid, and semisolid contents It can also be used as a packaging bag. Moreover, the laminated film of the present invention is a laminated film that can be suitably applied when forming the packaging bag.
以下、本発明につき更に詳しく説明する。
本発明の積層フィルムは、基材層と、基材層の一面側に積層されたシーラント層とを含む積層フィルムにおいて、前記基材層が融点１１０〜２２０℃のポリオレフィン系樹脂を主成分として含み、かつ、前記シーラント層がガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂を主成分として含むことを特徴とする積層フィルムであり、また、本発明の包装袋は、前記積層フィルムを用いて形成した包装袋である。
ここで、本発明の包装袋としては、前記積層フィルムのシーラント層により内壁面が形成される包装袋であって、かつ前記シーラント層に積層された基材層により外壁面が形成された包装袋であることが好適である。
Hereinafter, the present invention will be described in more detail.
The laminated film of the present invention is a laminated film comprising a base material layer and a sealant layer laminated on one side of the base material layer, wherein the base material layer contains a polyolefin resin having a melting point of 110 to 220 ° C. as a main component. And the said sealant layer is a laminated film characterized by including cyclic polyolefin-type resin with a glass transition temperature of 100-170 degreeC as a main component, Moreover, the packaging bag of this invention is formed using the said laminated film It is a packaging bag.
Here, as the packaging bag of the present invention, a packaging bag in which an inner wall surface is formed by the sealant layer of the laminated film and an outer wall surface is formed by a base material layer laminated on the sealant layer. It is preferable that
本発明の積層フィルムは、シーラント層としてガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂を主成分として採用しているため、包装袋滅菌（レトルト滅菌）時にも十分な耐熱性を有し、かつ内容物中の有効成分をシーラント層が吸着するといった不都合のおそれを可及的に低減することが可能である。
ここで、従来、ガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂を主成分とするシーラント層を採用する場合、容器を形成するための積層フィルム同士あるいは積層フィルムとポート部材とのシール性に著しく劣る場合や、シール時にシール部が変形したり、シールエッジ部が破断したりするといった不都合が生じる場合があった。しかしながら、本発明においては基材層として融点１１０〜２２０℃のポリオレフィン系樹脂を主成分として採用し、かつ当該基材を前記シーラント層と併用することにより、包装袋を形成するためのシール時にシール部が変形したり、シールエッジ部が破断したりするといった不都合を解消しているのみならず、詳細は明らかでないが、シーラント層のヒートシール性をも向上させている。このようなシーラント層と基材層とを組み合わせた積層フィルムにて形成される本発明の包装袋は、包装袋滅菌（レトルト滅菌）時にも十分な耐熱性を有し、しかも柔軟性及び落下強度にも優れる包装袋である。
Since the laminated film of the present invention employs a cyclic polyolefin resin having a glass transition temperature of 100 to 170 ° C. as a main component as a sealant layer, it has sufficient heat resistance during packaging bag sterilization (retort sterilization), and It is possible to reduce as much as possible the inconvenience that the sealant layer adsorbs the active ingredients in the contents.
Here, conventionally, when a sealant layer mainly composed of a cyclic polyolefin resin having a glass transition temperature of 100 to 170 ° C. is adopted, the sealing properties between the laminated films or the laminated film and the port member for forming the container are remarkably increased. In some cases, the inferior case may be inferior, or the seal part may be deformed at the time of sealing or the seal edge part may be broken. However, in the present invention, a polyolefin resin having a melting point of 110 to 220 ° C. is used as a main component as a base material layer, and the base material is used in combination with the sealant layer, thereby sealing at the time of sealing for forming a packaging bag. Not only are the inconveniences that the part is deformed and the seal edge part is broken, but the heat sealability of the sealant layer is also improved, although details are not clear. The packaging bag of the present invention formed of a laminated film combining such a sealant layer and a base material layer has sufficient heat resistance during packaging bag sterilization (retort sterilization), and also has flexibility and drop strength. It is an excellent packaging bag.
本発明の積層フィルムにおいて、前記基材層を構成する材料としては、融点１１０〜２２０℃のポリオレフィン系樹脂を主成分として含むものが用いられる。本発明において「主成分」とは、着目する成分が、当該成分が含まれるマトリックス全体に占める割合が５０質量％以上であることを意味するものであり、上記の場合には、融点１１０〜２２０℃のポリオレフィン系樹脂が、前記基材層を構成する材料全体中に占める割合が５０質量％以上であることを意味する。 In the laminated film of the present invention, as the material constituting the base material layer, a material containing a polyolefin resin having a melting point of 110 to 220 ° C. as a main component is used. In the present invention, the “main component” means that the component of interest accounts for 50% by mass or more of the entire matrix including the component, and in the above case, the melting point is 110 to 220. It means that the proportion of the polyolefin-based resin at 0 ° C. in the entire material constituting the base material layer is 50% by mass or more.
本発明において、融点１１０〜２２０℃のポリオレフィン系樹脂が、前記基材層を構成する材料全体中に占める割合としては５０質量％以上、好ましくは７０質量％以上、より好ましくは９０質量％以上であり、１００質量％であっても良い。また、本発明において基材層に主成分として含まれるポリオレフィン系樹脂の融点としては、１１０℃以上、好ましくは１３０℃以上、より好ましくは１５０℃以上、上限として２２０℃以下、好ましくは２１０℃以下である。融点１１０〜２２０℃のポリオレフィン系樹脂が、基材層中に占める割合が５０質量％未満であったり、基材層に主成分として含まれる前記ポリオレフィン系樹脂の融点が１１０℃未満であったりすると、包装袋を形成するためのシール時にシール部が変形したり、シールエッジ部が破断する場合があり、また１１０℃以上の高圧蒸気滅菌を行った場合に包装袋が変形・破袋したり、あるいは液漏れして本願発明の目的を達成し得ない。
なお、本発明において「融点」とは、ＪＩＳ Ｋ７１２１（ＤＳＣ）にて測定した融解ピーク温度の値を意味する。
In the present invention, the proportion of the polyolefin resin having a melting point of 110 to 220 ° C. in the entire material constituting the base material layer is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more. Yes, it may be 100% by mass. In the present invention, the melting point of the polyolefin resin contained as a main component in the base material layer is 110 ° C. or higher, preferably 130 ° C. or higher, more preferably 150 ° C. or higher, and the upper limit is 220 ° C. or lower, preferably 210 ° C. or lower. It is. When the proportion of the polyolefin resin having a melting point of 110 to 220 ° C. in the base material layer is less than 50% by mass, or the melting point of the polyolefin resin contained as a main component in the base material layer is less than 110 ° C. The seal part may be deformed at the time of sealing to form the packaging bag, the seal edge part may be broken, or the packaging bag may be deformed or broken when subjected to high-pressure steam sterilization at 110 ° C. or higher. Or the liquid leaks and the object of the present invention cannot be achieved.
In the present invention, the “melting point” means a melting peak temperature value measured by JIS K7121 (DSC).
前記融点１１０〜２２０℃のポリオレフィン系樹脂としては、直鎖状低密度ポリエチレン、又は下記（Ａ）成分を含むプロピレン系共重合体組成物であることが、耐熱性と柔軟性と透明性の観点から特に好適である。また、下記（Ｂ）成分を（Ａ）成分と共に併用したプロピレン系共重合体組成物であることが、表面のべたつき感を低減させ、適度なコシを付与することができるため特に好適である。 The polyolefin resin having a melting point of 110 to 220 ° C. is a linear low density polyethylene or a propylene copolymer composition containing the following component (A), from the viewpoint of heat resistance, flexibility and transparency. Are particularly preferred. Further, a propylene-based copolymer composition in which the following component (B) is used in combination with the component (A) is particularly suitable because it can reduce the stickiness of the surface and impart an appropriate stiffness.
（Ａ）成分：プロピレンと、エチレン及び／又は炭素数４〜８のα−オレフィンとからなるプロピレン系共重合体成分であって、温度上昇溶離分別法（温度：０〜１４０℃、溶媒：ｏ−ジクロロベンゼン）を用いた場合に、０℃での溶出分の割合が全溶出量に対して１５質量％以上５０質量％以下、６０℃以上９０℃以下での溶出分の割合が全溶出量に対して５質量％以上１５質量％未満であるプロピレン系共重合体。
（Ｂ）成分：プロピレンと、エチレン及び／又は炭素数４〜８のα−オレフィンとからなるプロピレン系共重合体成分であって、温度上昇溶離分別法（温度：０〜１４０℃、溶媒：ｏ−ジクロロベンゼン）を用いた場合に、０℃での溶出分の割合が全溶出量に対して０質量％以上２５質量％以下、６０℃以上９０℃以下での溶出分の割合が全溶出量に対して１５質量％以上７０質量％以下であるプロピレン系共重合体。
Component (A): a propylene copolymer component composed of propylene and ethylene and / or an α-olefin having 4 to 8 carbon atoms, and a temperature rising elution fractionation method (temperature: 0 to 140 ° C., solvent: o -Dichlorobenzene), the proportion of elution at 0 ° C. is 15 mass% to 50 mass% and the proportion of elution at 60 ° C. to 90 ° C. is the total amount of elution. A propylene-based copolymer that is 5% by mass or more and less than 15% by mass with respect to.
Component (B): a propylene copolymer component composed of propylene and ethylene and / or an α-olefin having 4 to 8 carbon atoms, and a temperature rising elution fractionation method (temperature: 0 to 140 ° C., solvent: o -Dichlorobenzene), the proportion of elution at 0 ° C. is 0% to 25% by mass, and the proportion of elution at 60 ° C. to 90 ° C. is the total amount eluted. A propylene-based copolymer that is 15% by mass or more and 70% by mass or less based on the weight.
ここで、温度上昇溶離分別法（Ｔｅｍｐｅｒａｔｕｒｅ Ｒｉｓｉｎｇ Ｅｌｕｔｉｏｎ Ｆｒａｃｔｉｏｎａｔｉｏｎ；ＴＲＥＦ）とは、ポリマーの組成分布を分析する公知の方法であって、原理的には個々のポリマー成分が異なる結晶構造を有するため溶媒中での析出速度あるいは溶解速度が個々のポリマー毎に異なることを利用して、ポリマーの組成分布を分析する方法である。即ち、高温でポリマーを溶媒に完全に溶解させた後に不活性坦体の存在下で徐々に冷却すると、まず結晶化し易い高結晶性のポリマー成分が前記不活性担体の表面に先に析出してポリマー層が形成され、その後、結晶化しにくい低結晶性あるいは非晶性のポリマー成分が析出してポリマー層が形成されることとなる。次に、このようにポリマー層を形成後、連続的又は段階的に昇温すると、今度は低結晶性あるいは非晶性のポリマー成分から溶出し、最後に高結晶性ポリマー成分が溶出することとなる。つまり、この各温度での溶出量と溶出温度とによって描かれる溶出曲線から、ポリマーの組成分布を分析することが可能となる。本発明においては、温度上昇溶離分別法に用いる溶媒としてｏ−ジクロロベンゼンを使用し、温度範囲として０〜１４０℃を採用している。 Here, temperature rising elution fractionation (TREF) is a known method for analyzing the composition distribution of a polymer, and in principle, since each polymer component has a different crystal structure, In this method, the composition distribution of the polymer is analyzed by utilizing the fact that the deposition rate or dissolution rate of the polymer is different for each polymer. That is, when a polymer is completely dissolved in a solvent at a high temperature and then gradually cooled in the presence of an inert carrier, first, a highly crystalline polymer component that is easily crystallized first precipitates on the surface of the inert carrier. A polymer layer is formed, and then a low crystalline or amorphous polymer component that is difficult to crystallize is deposited to form a polymer layer. Next, after the polymer layer is formed in this way, when the temperature is raised continuously or stepwise, the low crystalline or amorphous polymer component is eluted, and the high crystalline polymer component is finally eluted. Become. That is, it is possible to analyze the polymer composition distribution from the elution curve drawn by the elution amount and elution temperature at each temperature. In the present invention, o-dichlorobenzene is used as a solvent used in the temperature rising elution fractionation method, and a temperature range of 0 to 140 ° C. is employed.
本発明において、上記（Ａ）成分の０℃での溶出量が全溶出量に対して占める割合としては１５質量％以上、好ましくは１８質量％以上、上限として５０質量％以下、好ましくは４０質量％以下である。当該割合が小さすぎると、プロピレン系共重合体組成物の柔軟性が低下し、内容液の排出を容易に行なうことができず、本願発明の効果が達成されない場合があり、しかも、作成された包装袋の感触が強ばり、落下強度が劣る傾向となる。一方、当該割合が大きすぎると、１１０℃以上の滅菌処理を施した場合に、包装袋の外面にべたつき感が発生する場合があり、滅菌処理時に他の包装袋とスティッキングを発生させる場合がある。この傾向は、１２１℃の滅菌処理を行なうとより顕著にあらわれる。 In the present invention, the proportion of the component (A) eluted at 0 ° C. is 15% by mass or more, preferably 18% by mass or more, and the upper limit is 50% by mass or less, preferably 40% by mass. % Or less. If the proportion is too small, the flexibility of the propylene-based copolymer composition is reduced, the content liquid cannot be easily discharged, and the effect of the present invention may not be achieved, and it was created. The feel of the packaging bag is strong and the drop strength tends to be inferior. On the other hand, if the ratio is too large, sticking may occur on the outer surface of the packaging bag when sterilization is performed at 110 ° C. or higher, and sticking may occur with other packaging bags during sterilization. . This tendency becomes more prominent when sterilization at 121 ° C. is performed.
また、上記（Ａ）成分の６０℃以上９０℃以下での溶出量が全溶出量に対して占める割合としては５質量％以上、好ましくは６質量％以上、上限として１５質量％未満、好ましくは１０質量％以下である。当該割合が小さすぎると、プロピレン系共重合体組成物の透明性に劣る場合があり、一方、当該割合が大きすぎると、プロピレン系共重合体組成物の耐熱性に劣り、得られた包装袋が１１０℃での滅菌処理時に変形してしまう場合がある。この傾向は、１２１℃の滅菌処理を行なうとより顕著にあらわれる。また包装袋を形成するためのシール時にシール部が変形したり、シールエッジ部が破断する場合がある。 The proportion of the component (A) eluted at 60 ° C. or more and 90 ° C. or less is 5% by mass or more, preferably 6% by mass or more, and the upper limit is less than 15% by mass, preferably less than 15% by mass. It is 10 mass% or less. If the proportion is too small, the transparency of the propylene-based copolymer composition may be inferior. On the other hand, if the proportion is too large, the heat resistance of the propylene-based copolymer composition is inferior, and the resulting packaging bag. May be deformed during sterilization at 110 ° C. This tendency becomes more prominent when sterilization at 121 ° C. is performed. Further, the seal part may be deformed or the seal edge part may be broken at the time of sealing for forming the packaging bag.
本発明において、上記（Ｂ）成分の０℃での溶出量が全溶出量に対して占める割合としては０質量％以上、好ましくは２質量％以上、上限として２５質量％以下、好ましくは１５質量％以下である。当該割合が大きすぎると、１１０℃以上での滅菌処理を施した場合に包装袋が変形したり、包装袋表面にべたつき感が生じる場合がある。 In the present invention, the proportion of the component (B) eluted at 0 ° C. accounts for 0% by mass or more, preferably 2% by mass or more, and the upper limit is 25% by mass or less, preferably 15% by mass. % Or less. If the ratio is too large, the packaging bag may be deformed or sticky on the surface of the packaging bag when sterilization is performed at 110 ° C. or higher.
また、上記（Ｂ）成分の６０℃以上９０℃以下での溶出量が全溶出量に対して占める割合としては１５質量％以上、好ましくは２０質量％以上、上限として７０質量％以下、好ましくは６０質量％以下である。当該割合が小さすぎると、包装袋に適度なコシを持たせることができない場合があり、一方、当該割合が大きすぎると、プロピレン系共重合体組成物の耐熱性が劣り、作成された容器が１１０℃以上の滅菌時に包装袋が変形する場合がある。この傾向は、１２１℃の滅菌処理を行なうとより顕著にあらわれる。 The proportion of the component (B) eluted at 60 ° C. or higher and 90 ° C. or lower is 15% by mass or more, preferably 20% by mass or more, and the upper limit is 70% by mass or less, preferably 70% by mass or less. 60% by mass or less. If the ratio is too small, the packaging bag may not have a proper stiffness. On the other hand, if the ratio is too large, the heat resistance of the propylene-based copolymer composition is inferior, and the prepared container is The packaging bag may be deformed during sterilization at 110 ° C. or higher. This tendency becomes more prominent when sterilization at 121 ° C. is performed.
本発明における前記プロピレン系共重合体組成物としては、前記（Ａ）成分を主成分（５０質量％以上、好ましくは５５質量％以上）として含むものであることが好適であり、前記（Ａ）成分単独であっても良いが、前記（Ｂ）成分を前記（Ａ）成分と併用することも好適である。（Ａ）成分は、耐熱性と柔軟性に優れる成分であり、（Ｂ）成分は、耐熱性に優れ、かつ前記最外層に適度なコシを与えることが可能な成分であって包装袋の後工程での取り扱い性を向上させることができる。（Ｂ）成分を（Ａ）成分に配合することにより、得られた包装袋を１１０℃以上で滅菌処理した後であってもべたつき感がなく、透明性と柔軟性、コシを合わせ持った状態を維持することが可能である。
なお、（Ｂ）成分が、前記プロピレン系共重合体組成物中に占める割合としては通常５０質量％以下、好ましくは４５質量％以下である。（Ｂ）成分の配合比率が５０質量％を超えると、包装袋が硬くなり、内容液の排出性に劣り、医療用として適さない包装袋となる場合がある。
The propylene-based copolymer composition in the present invention preferably contains the component (A) as a main component (50% by mass or more, preferably 55% by mass or more), and the component (A) alone However, it is also suitable to use the component (B) together with the component (A). The component (A) is a component excellent in heat resistance and flexibility, and the component (B) is a component excellent in heat resistance and capable of giving an appropriate stiffness to the outermost layer after the packaging bag. The handleability in the process can be improved. By blending component (B) with component (A), there is no stickiness even after sterilization of the resulting packaging bag at 110 ° C. or higher, and it has transparency, flexibility and stiffness. Can be maintained.
In addition, as a ratio for which the (B) component accounts in the said propylene-type copolymer composition, it is 50 mass% or less normally, Preferably it is 45 mass% or less. When the blending ratio of the component (B) exceeds 50% by mass, the packaging bag becomes hard, the discharge of the content liquid is inferior, and the packaging bag may not be suitable for medical use.
前記（Ａ）成分と（Ｂ）成分との配合比としては、通常（Ａ）成分：（Ｂ）成分＝１００：０〜５０：５０（質量比）、好ましくは９８：２〜５５：４５、より好ましくは９０：１０〜６０：４０（質量比）の割合である。（Ａ）成分の配合比が小さすぎると、得られた包装袋の柔軟性が低下し、搬送、外層包装などの後工程などで破袋の危険が高まったり、排出性に問題が発生する場合がある。 The compounding ratio of the component (A) to the component (B) is usually (A) component: (B) component = 100: 0-50: 50 (mass ratio), preferably 98: 2-55: 45, More preferably, the ratio is 90:10 to 60:40 (mass ratio). When the blending ratio of the component (A) is too small, the flexibility of the obtained packaging bag is lowered, and there is a risk of bag breakage in the subsequent process such as transportation and outer layer packaging, or there is a problem with the discharge property. There is.
上記（Ａ）成分および（Ｂ）成分のプロピレン系共重合体は、プロピレンと、エチレン及び／又は炭素数４〜８のα−オレフィンとからなるプロピレン系共重合体である。
ここで、上記炭素数４〜８のα−オレフィンとしては、例えば、ブテン−１、３−メチルブテン−１、ペンテン−１、４−メチルペンテン−１、へキセン−１、オクテン−１等が挙げられ、これらは１種を単独で、又は２種以上を併用することも可能である。
本発明における上記プロピレン系共重合体成分としてより具体的には、プロピレンとエチレンとからなる共重合体成分、又はプロピレンとエチレンと炭素数４〜８のα−オレフィンとからなるプロピレン系共重合体成分であることが好ましく、炭素数４〜８のα−オレフィンとしてはブテン−１を採用することが好適である。
The propylene copolymer of the component (A) and the component (B) is a propylene copolymer composed of propylene and ethylene and / or an α-olefin having 4 to 8 carbon atoms.
Here, examples of the α-olefin having 4 to 8 carbon atoms include butene-1, 3-methylbutene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and the like. These can be used alone or in combination of two or more.
More specifically, as the propylene-based copolymer component in the present invention, a copolymer component composed of propylene and ethylene, or a propylene-based copolymer composed of propylene, ethylene, and an α-olefin having 4 to 8 carbon atoms. It is preferable that it is a component, and it is preferable to employ butene-1 as the α-olefin having 4 to 8 carbon atoms.
このような上記（Ａ）成分および（Ｂ）成分のプロピレン系共重合体の製造方法としては、例えば下記（ｉ）〜（ｉｉｉ）の方法、
（ｉ）少なくとも二段以上の逐次重合を行なうに際し、一段目重合時においてプロピレン単独重合体、またはプロピレンと少量のエチレン及び／又は炭素数４〜８のα−オレフィンを導入してランダム共重合体を製造した後、二段目以降の重合時において、前段で得られた重合体の存在下、プロピレンとエチレン及び／又は炭素数４〜８のα−オレフィンのランダム共重合体を製造する方法、
（ｉｉ）プロピレン単独重合体、またはプロピレンと少量のエチレン及び／又は炭素数４〜８のα−オレフインとのランダム共重合体と、エチレンと炭素数４〜８のα−オレフィンとのランダム共重合体と、をブレンドする方法、
（ｉｉｉ）プロピレン単独重合体、またはプロピレンと少量のエチレン及び／又は炭素数４〜８のα−オレフインとのランダム共重合体と、エチレン及び／又は炭素数４〜８とプロピレンとのランダム共重合体と、をブレンドする方法、
を採用することができる。中でも、経済性の観点から上記（ｉ）の方法を用いることが好適である。
Examples of the method for producing the propylene copolymer of the component (A) and the component (B) include the following methods (i) to (iii):
(I) When performing sequential polymerization of at least two stages, a random copolymer by introducing propylene homopolymer or propylene and a small amount of ethylene and / or an α-olefin having 4 to 8 carbon atoms at the first stage polymerization A process for producing a random copolymer of propylene and ethylene and / or an α-olefin having 4 to 8 carbon atoms in the presence of the polymer obtained in the previous stage after the second stage polymerization.
(Ii) Propylene homopolymer, or random copolymer of propylene with a small amount of ethylene and / or α-olefin having 4 to 8 carbon atoms, and ethylene and α-olefin having 4 to 8 carbon atoms A blending method,
(Iii) Propylene homopolymer, or a random copolymer of propylene and a small amount of ethylene and / or α-olefin having 4 to 8 carbon atoms, and random copolymer of ethylene and / or 4 to 8 carbon atoms and propylene A blending method,
Can be adopted. Among these, it is preferable to use the method (i) from the viewpoint of economy.
上記（ｉ）の逐次重合に用いる触媒としては、特に限定されるものではないが、有機アルミニウム化合物と、チタン原子、マグネシウム原子、ハロゲン原子、及び電子供与性化合物を必須とする固体成分とからなるものが好ましい。 Although it does not specifically limit as a catalyst used for the sequential polymerization of said (i), It consists of an organic aluminum compound and the solid component which essentially needs a titanium atom, a magnesium atom, a halogen atom, and an electron-donating compound. Those are preferred.
上記有機アルミニウム化合物としては、例えば一般式Ｒ1 mＡlＸ(3-m)（式中、Ｒ1は炭素原子数１〜１２の炭化水素残基、Ｘはハロゲン原子を示し、ｍは１〜３の数である）で表される化合物が使用される。かかる有機アルミニウム化合物の具体例としては、例えばトリメチルアルミニウムクロリド、トリエチルアルミニウムクロリド等のトリアルキルアルミニウムハライド、ジメチルアルミニウムクロリド、ジエチルアルミニウムクロリド等のジアルキルアルミニウムハライド、メチルアルミニウムセスキクロリド、エチルアルミニウムセスキクロリド等のアルキルアルミニウムセスキハライド、メチルアルミニウムジクロリド、エチルアルミニウムジクロリド等のアルキルアルミニウムジハライド、ジエチルアルミニウムハイドライド等のアルキルアルミニウムハイドライド、等が挙げられる。 Examples of the organoaluminum compound include a general formula R 1 m AlX (3-m) (wherein R 1 represents a hydrocarbon residue having 1 to 12 carbon atoms, X represents a halogen atom, and m represents 1 to 3). Is used). Specific examples of such organoaluminum compounds include trialkylaluminum halides such as trimethylaluminum chloride and triethylaluminum chloride, dialkylaluminum halides such as dimethylaluminum chloride and diethylaluminum chloride, alkyls such as methylaluminum sesquichloride and ethylaluminum sesquichloride. Examples include aluminum sesquihalides, alkylaluminum dihalides such as methylaluminum dichloride and ethylaluminum dichloride, and alkylaluminum hydrides such as diethylaluminum hydride.
また、上記チタン原子、マグネシウム原子、ハロゲン原子、及び電子供与性化合物を必須とする固体成分としては、この種の重合において公知のものが使用でき、チタン原子の供給源となるチタン化合物としては、例えば一般式Ｔｉ（ＯＲ2）(4-n)Ｘn（式中、Ｒ2は炭素原子数１〜１０の炭化水素残基、Ｘはハロゲン原子を示し、ｎは０〜４の数である）で表される化合物が使用される。中でも、四塩化チタン、テトラエトキシチタン、テトラブトキシチタン等が好ましく用いられる。 In addition, as a solid component essentially including the above titanium atom, magnesium atom, halogen atom, and electron donating compound, those known in this kind of polymerization can be used, and as a titanium compound serving as a titanium atom supply source, For example, the general formula Ti (OR 2 ) (4-n) X n (wherein R 2 represents a hydrocarbon residue having 1 to 10 carbon atoms, X represents a halogen atom, and n is a number from 0 to 4). ) Is used. Of these, titanium tetrachloride, tetraethoxy titanium, tetrabutoxy titanium and the like are preferably used.
上記マグネシウム原子の供給源となるマグネシウム化合物としては、例えば、ジアルキルマグネシウム、マグネシウムジハライド、ジアルコキシマグネシウム、アルコキシマグネシウムハライド等が挙げられ、中でもマグネシウムジハライド等が好ましい。ハロゲン原子としては、例えば弗素、塩素、臭素、沃素が挙げられ、中でも塩素が好ましい。ハロゲン原子は、通常、前記のチタン化合物やマグネシウム化合物から供給されるが、アルミニウムのハロゲン化物、珪素のハロゲン化物、タングステンのハロゲン化物などの他のハロゲン供給源から供給されてもよい。 Examples of the magnesium compound that serves as a supply source of the magnesium atom include dialkyl magnesium, magnesium dihalide, dialkoxy magnesium, and alkoxy magnesium halide. Among these, magnesium dihalide is preferable. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Among them, chlorine is preferable. The halogen atom is usually supplied from the above-described titanium compound or magnesium compound, but may be supplied from another halogen source such as an aluminum halide, a silicon halide, or a tungsten halide.
上記電子供与性化合物としては、例えばアルコール類、フェノール類、ケトン類、アルデヒド類、カルボン酸類、有機酸または無機酸およびその誘導体などの含酸素化合物、アンモニア、アミン類、ニトリル類、イソシアネート類などの含窒素化合物などが挙げられ、中でも無機酸エステル、有機酸エステル、有機酸ハライドが好適であり、特に珪酸エステル、フタル酸エステル、酢酸セロソルブエステル、フタル酸ハライドが好適である。 Examples of the electron donating compound include alcohols, phenols, ketones, aldehydes, carboxylic acids, oxygen-containing compounds such as organic acids or inorganic acids and derivatives thereof, ammonia, amines, nitriles, isocyanates, and the like. Nitrogen-containing compounds and the like can be mentioned, among which inorganic acid esters, organic acid esters, and organic acid halides are preferable, and silicic acid esters, phthalic acid esters, acetic acid cellosolve esters, and phthalic acid halides are particularly preferable.
ここで、上記の珪酸エステルとしては、例えば一般式Ｒ3Ｒ4 (3-p)Ｓｉ（ＯＲ5）p（式中、Ｒ3は炭素原子数３〜２０（好ましくは４〜１０）の分岐脂肪族炭化水素残基または炭素原子数５〜２０（好ましくは６〜１０）の環状脂肪族炭化水素残基を示し、Ｒ4は炭素原子数１〜２０（好ましくは１〜１０）の分岐または直鎖脂肪族炭化水素残基を示し、Ｒ5は炭素原子数１〜１０（好ましくは１〜４）の脂肪族炭化水素残基を示し、ｐは１〜３の数である）で表される有機珪素化合物が挙げられる。かかる有機珪素化合物の具体例としては、例えばｔ−ブチル−メチル−ジメトキシシラン、ｔ−ブチル−メチル−ジエトキシシラン、シクロヘキシル−メチル−ジメトキシシラン、シクロヘキシル−メチル−ジエトキシシラン等が挙げられる。 Here, as said silicic acid ester, for example, R 3 R 4 (3-p) Si (OR 5 ) p (wherein R 3 is a branch having 3 to 20 carbon atoms (preferably 4 to 10). An aliphatic hydrocarbon residue or a cyclic aliphatic hydrocarbon residue having 5 to 20 carbon atoms (preferably 6 to 10 carbon atoms), wherein R 4 is a branched or branched group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms); A straight-chain aliphatic hydrocarbon residue, R 5 represents an aliphatic hydrocarbon residue having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms, and p is a number of 1 to 3). Organic silicon compounds. Specific examples of such organosilicon compounds include t-butyl-methyl-dimethoxysilane, t-butyl-methyl-diethoxysilane, cyclohexyl-methyl-dimethoxysilane, and cyclohexyl-methyl-diethoxysilane.
本発明における上記（Ａ）成分および（Ｂ）成分のプロピレン系共重合体を製造するに際して上記（ｉ）の製造方法を採用する場合には、一段目重合時においてプロピレン又はプロピレンと少量のエチレン及び／又は炭素数４〜８のα−オレフィンを供給し、上記のような触媒の存在下、重合温度５０〜１５０℃、好ましくは５０〜１００℃、プロピレンの分圧０．５〜４．５ＭＰａ、好ましくは１．０〜３．５ＭＰａの条件で重合を実施し、引き続いて二段目重合時において、一段目重合で得られた重合体の存在下、プロピレンとエチレン及び／又は炭素数４〜８のα−オレフィンを供給し、前記触媒の存在下に温度５０〜１５０℃、好ましくは５０〜１００℃で、プロピレンとエチレン及び／又は炭素数４〜８のα−オレフィンの分圧各０．３〜４．５ＭＰａ、好ましくは０．５〜３．５ＭＰａの条件として、共重合を行なうことができる。 When the production method (i) is employed in producing the propylene copolymer of the component (A) and the component (B) in the present invention, propylene or propylene and a small amount of ethylene and / Or an α-olefin having 4 to 8 carbon atoms is supplied, and in the presence of the catalyst as described above, a polymerization temperature of 50 to 150 ° C., preferably 50 to 100 ° C., a partial pressure of propylene of 0.5 to 4.5 MPa, The polymerization is preferably carried out under the conditions of 1.0 to 3.5 MPa, and subsequently, in the second stage polymerization, propylene and ethylene and / or carbon atoms of 4 to 8 in the presence of the polymer obtained by the first stage polymerization. In the presence of the catalyst at a temperature of 50 to 150 ° C., preferably 50 to 100 ° C., and a partial pressure of propylene and ethylene and / or an α-olefin having 4 to 8 carbon atoms, respectively. 3～4.5MPa, preferably be as a condition of 0.5～3.5MPa, performing copolymerization.
なお、その際の重合方式としては回分式、連続式、半回分式のいずれであってもよいが、一段目及び二段目の重合は気相又は液相中で実施するのが好ましく、各段階の滞留時間は通常各々０．５〜１０時間、好ましくは１〜５時間とすることができる。又、このような方法により製造される組成物の粉体粒子にベタツキ等の間題が生じる場合は、粉体粒子に流動性を付与する目的で、一段目重合後であって二段目重合の開始前又は二段目重合の重合途中に、触媒の固体成分中のチタン原子に対して１００〜１０００倍モルで、かつ触媒の有機アルミニウム化合物に対して２〜５倍モルの範囲で活性水素含有化合物を添加することが好ましい。このような活性水素含有化合物としては、例えば、水、アルコール類、フェノール類、アルデヒド類、カルボン酸類、酸アミド類、アンモニア、アミン類等が挙げられる。 In this case, the polymerization method may be any of batch, continuous, and semi-batch methods, but the first and second polymerizations are preferably carried out in the gas phase or liquid phase. The residence time of the stages can usually be 0.5 to 10 hours, preferably 1 to 5 hours, respectively. In addition, when there is a problem such as stickiness in the powder particles of the composition produced by such a method, the second-stage polymerization is performed after the first-stage polymerization for the purpose of imparting fluidity to the powder particles. Active hydrogen in the range of 100 to 1000 times mol of titanium atoms in the solid component of the catalyst and 2 to 5 times mol of the organoaluminum compound of the catalyst before the start of the polymerization or during the second stage polymerization It is preferable to add a containing compound. Examples of such active hydrogen-containing compounds include water, alcohols, phenols, aldehydes, carboxylic acids, acid amides, ammonia, amines and the like.
本発明における上記（Ａ）成分および（Ｂ）成分としてのプロピレン系共重合体は、ｏ−ジクロロベンゼンを溶媒として用いた温度０〜１４０℃の間の温度上昇溶離分別における０℃での溶出分および６０℃以上９０℃以下での溶出分の割合がそれぞれ特定範囲となるように調整されたものであるが、このような条件を満たすようにポリマーの溶出割合を調整する方法としては、プロピレン以外のエチレン及び／又は炭素数４〜８のα−オレフインを多段共重合することによりプロピレン系重合体の結晶性をコントロールする方法や、触媒を選択することによりプロピレン系重合体の立体規則性をコントロールする方法が挙げられる。 The propylene-based copolymer as the component (A) and the component (B) in the present invention is an elution fraction at 0 ° C. in temperature rising elution fractionation between 0 ° C. and 140 ° C. using o-dichlorobenzene as a solvent. In addition, the ratio of the amount of elution at 60 ° C. or more and 90 ° C. or less is adjusted to be in a specific range. Control of crystallinity of propylene polymer by multi-stage copolymerization of ethylene and / or α-olefin having 4 to 8 carbon atoms and control of stereoregularity of propylene polymer by selecting catalyst The method of doing is mentioned.
なお、本発明における上記基材層には上記ポリオレフィン系樹脂に加え、従来公知の酸化防止剤、光安定剤、中和剤、α晶核剤、β晶核剤、アンチブロッキング剤、滑剤等の各種添加剤を、本発明の目的を損なわない範囲で適宜配合することができる。 In addition to the polyolefin resin, the base layer in the present invention includes conventionally known antioxidants, light stabilizers, neutralizing agents, α crystal nucleating agents, β crystal nucleating agents, antiblocking agents, lubricants, and the like. Various additives can be appropriately blended within a range not impairing the object of the present invention.
本発明の積層フィルムにおけるシーラント層としては、内容物の有効成分を吸着することがなく、容器から内容物へ低分子量成分等が溶出したりすることによる内容物の組成変化又は内容物汚染が可及的に低減され、かつ適切なヒートシール性を発現し、しかも適度な耐熱性を有するシーラント層として、以下の（Ｃ）成分、
（Ｃ）ガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂、
を主成分として含むシーラント層が採用される。
本発明において、上記（Ｃ）成分が上記シーラント層中に占める割合としては５０質量％以上、好ましくは７０質量％以上、より好ましくは８０質量％以上であり、１００質量％であっても良い。また、本発明においてシーラント層を構成する材料中に主成分として含まれる環状ポリオレフィン系樹脂のガラス転移温度としては、１００℃以上、好ましくは１０５℃以上、より好ましくは１２０℃以上、上限として１７０℃以下、好ましくは１６５℃以下である。ガラス転移温度１００℃以上の環状ポリオレフィン系樹脂が、包装袋のシーラント層を構成する材料全体中に占める割合が５０質量％未満であったり、シーラント層の主成分として含まれる上記環状ポリオレフィン系樹脂のガラス転移温度が１００℃未満であったりすると、１１０℃以上の高圧蒸気滅菌を行った場合に包装袋が変形・破袋して本願発明の目的を達成し得ない。
なお、本発明において「ガラス転移温度」とは、ＪＩＳ Ｋ７１２１（ＤＳＣ）にて測定した値を意味する。
The sealant layer in the laminated film of the present invention does not adsorb the active ingredients of the contents, and can change the composition of the contents or contaminate the contents due to the elution of low molecular weight components from the container to the contents. The following (C) component as a sealant layer that is reduced as much as possible and expresses an appropriate heat-sealing property and has appropriate heat resistance:
(C) a cyclic polyolefin resin having a glass transition temperature of 100 to 170 ° C.,
A sealant layer containing as a main component is employed.
In the present invention, the proportion of the component (C) in the sealant layer is 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass. The glass transition temperature of the cyclic polyolefin resin contained as a main component in the material constituting the sealant layer in the present invention is 100 ° C. or higher, preferably 105 ° C. or higher, more preferably 120 ° C. or higher, and the upper limit is 170 ° C. Hereinafter, it is preferably 165 ° C. or lower. The cyclic polyolefin resin having a glass transition temperature of 100 ° C. or higher accounts for less than 50% by mass of the total material constituting the sealant layer of the packaging bag, or the cyclic polyolefin resin contained as a main component of the sealant layer. If the glass transition temperature is less than 100 ° C., the packaging bag is deformed and broken when high-pressure steam sterilization at 110 ° C. or higher is performed, and the object of the present invention cannot be achieved.
In the present invention, “glass transition temperature” means a value measured according to JIS K7121 (DSC).
また、本発明における上記シーラント層には、ヒートシール性の向上の観点から、上記（Ｃ）成分に加え、以下の（Ｄ）成分、
（Ｄ）ガラス転移温度１００℃未満の環状ポリオレフィン系樹脂、
を併用することが好適である。本発明において、上記（Ｄ）成分が、シーラント層を構成する材料全体中に占める割合としては通常５０質量％以下、好ましくは３０質量％以下、より好ましくは２５質量％以下、更に好ましくは２０質量％以下である。（Ｄ）成分の配合量が多すぎると、シール性は向上するものの滅菌時に十分な耐熱性が保持できず、容器が変形して本発明の目的が達成し得ない。
In addition, the sealant layer in the present invention has the following component (D) in addition to the component (C), from the viewpoint of improving heat sealability:
(D) a cyclic polyolefin resin having a glass transition temperature of less than 100 ° C.,
It is suitable to use together. In the present invention, the proportion of the component (D) in the entire material constituting the sealant layer is usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass. % Or less. If the amount of component (D) is too large, the sealing property is improved, but sufficient heat resistance cannot be maintained during sterilization, and the container cannot be deformed to achieve the object of the present invention.
前記（Ｃ）成分のガラス転移温度と前記（Ｄ）成分のガラス転移温度との、ガラス転移温度の温度差としては、特に限定されるものではないが、通常２０℃以上、好ましくは２５℃以上、更に好ましくは３０℃以上である。前記（Ａ）成分のガラス転移温度と（Ｂ）成分のガラス転移温度とのガラス転移温度の温度差が２０℃未満であると、用時混合する複室容器とする場合に、十分な弱シール温度範囲が得られず、またシール温度も２２０℃以上の高温となり安定な弱シールが得られない場合がある。 The temperature difference between the glass transition temperature of the component (C) and the glass transition temperature of the component (D) is not particularly limited, but is usually 20 ° C. or higher, preferably 25 ° C. or higher. More preferably, it is 30 ° C. or higher. When the temperature difference between the glass transition temperature of the component (A) and the glass transition temperature of the component (B) is less than 20 ° C., a sufficiently weak seal is obtained in the case of a multi-chamber container that is mixed at the time of use. There is a case where a temperature range cannot be obtained, and the seal temperature is a high temperature of 220 ° C. or higher, and a stable weak seal cannot be obtained.
前記（Ｃ）成分及び（Ｄ）成分は、環状オレフィンモノマーを含むモノマー組成物を重合して得られた環状ポリオレフィン系樹脂である。
環状オレフィンモノマーとしては、例えばノルボルネン、ノルボルナジエン、メチルノルボルネン、ジメチルノルボルネン、エチルノルボルネン、塩素化ノルボルネン、クロロメチルノルボルネン、トリメチルシリルノルボルネン、フェニルノルボルネン、シアノノルボルネン、ジシアノノルボルネン、メトキシカルボニルノルボルネン、ピリジルノルボルネン、ナヂック酸無水物、ナヂック酸イミドなどの二環シクロオレフィン；ジシクロペンタジエン、ジヒドロジシクロペンタジエンやそのアルキル、アルケニル、アルキリデン、アリール置換体などの三環シクロオレフィン；ジメタノヘキサヒドロナフタレン、ジメタノオクタヒドロナフタレンやそのアルキル、アルケニル、アルキリデン、アリール置換体などの四環シクロオレフィン；トリシクロペンタジエンなどの五環シクロオレフィン；ヘキサシクロヘプタデセンなどの六環シクロオレフィンなどが挙げられる。また、ジノルボルネン、二個のノルボルネン環を炭化水素鎖またはエステル基などで結合した化合物、これらのアルキル、アリール置換体などのノルボルネン環を含む化合物が挙げられる。これらは１種を単独で、又は２種以上を併用しても良い。２種以上使用する場合には、熱可塑性樹脂となる１つの二重結合を有するモノマーと、熱硬化性樹脂となる複数の二重結合を有するモノマーを適宜組み合わせると種々の物性を有する樹脂を入手することができ、また、単一モノマーを使用する場合と比較して、凝固点降下により、モノマーを液状として取扱える範囲が拡がる場合があるため好適である。
The component (C) and the component (D) are cyclic polyolefin resins obtained by polymerizing a monomer composition containing a cyclic olefin monomer.
Examples of the cyclic olefin monomer include norbornene, norbornadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene, chlorinated norbornene, chloromethylnorbornene, trimethylsilylnorbornene, phenylnorbornene, cyanonorbornene, dicyanonorbornene, methoxycarbonylnorbornene, pyridylnorbornene, nadic anhydride Products, bicyclic cycloolefins such as nadic imides; tricyclocycloolefins such as dicyclopentadiene, dihydrodicyclopentadiene and their alkyl, alkenyl, alkylidene, and aryl substituents; dimethanohexahydronaphthalene, dimethanooctahydronaphthalene, Tetracyclic cycloolefins such as alkyl, alkenyl, alkylidene and aryl substituents Pentacyclic cycloolefins such as tricyclopentadiene; and hexacyclic cycloolefins such as hexamethylene cycloheptanone decene and the like. Further, dinorbornene, a compound in which two norbornene rings are bonded by a hydrocarbon chain or an ester group, and a compound containing a norbornene ring such as an alkyl or aryl substituent thereof can be used. These may be used alone or in combination of two or more. When two or more types are used, a resin having various physical properties can be obtained by appropriately combining a monomer having one double bond to be a thermoplastic resin and a monomer having a plurality of double bonds to be a thermosetting resin. In addition, compared with the case where a single monomer is used, the range in which the monomer can be handled as a liquid may be expanded due to the freezing point depression, which is preferable.
中でも、本発明において好適に用いられる環状オレフィンモノマーとしては、ジシクロペンタジエン、ノルボルネン、テトラシクロドデセンといったノルボルネン系モノマー（ここで、「ノルボルネン系」とは、分子骨格中にノルボルネン骨格が含まれることを意味する。）が挙げられる。 Among them, examples of the cyclic olefin monomer suitably used in the present invention include norbornene monomers such as dicyclopentadiene, norbornene, and tetracyclododecene (here, “norbornene-based” means that the molecular skeleton includes a norbornene skeleton. Means).
なお、内容物中の微量成分等との相互作用をなるべく低減し、不透水性をより高める観点から、上記環状オレフィンモノマーとしては極性基をなるべく含まないもののみを用いることが好適であるが、内容物に応じ、本発明の目的を損なわない範囲で一部極性基を有するモノマーを併用することも可能である。このようなモノマーとしては、例えば、上述したノルボルネン系モノマーに塩素や臭素などのハロゲン基やエステル基を導入した置換体を挙げることができる。但し、このような極性基を有するモノマーの、環状オレフィンモノマー総量中に占める割合としては通常３０％以下である。３０％を超えると、得られるポリマーの吸水性が大きくなり、本願発明の目的を達成し得ない場合がある。 In addition, from the viewpoint of reducing the interaction with trace components in the contents as much as possible and further improving the water impermeability, it is preferable to use only those that do not contain polar groups as much as possible, Depending on the contents, a monomer having a partial polar group may be used in combination as long as the object of the present invention is not impaired. As such a monomer, for example, a substituent obtained by introducing a halogen group such as chlorine or bromine or an ester group into the above-described norbornene-based monomer can be given. However, the proportion of the monomer having such a polar group in the total amount of the cyclic olefin monomer is usually 30% or less. If it exceeds 30%, the water absorption of the resulting polymer increases, and the object of the present invention may not be achieved.
また、上記モノマー組成物中には、本発明の目的を損なわない範囲で、上記環状オレフィンモノマーと共に他のモノマーを併用することも可能である。
このような他のモノマーとしては、炭素数２以上のα−オレフィン等が挙げられ、より具体的には、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−ヘキセン、４,４−ジメチル−１−ヘキセン、４,４−ジメチル−１−ペンテン、４−エチル−１−ヘキセン、３−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセンおよび１−エイコセン等が挙げられる。これらは単独であるいは組み合わせて使用することができる。これらのうち、エチレンまたはプロピレンが好ましく、さらにエチレンが特に好ましい。
Moreover, in the said monomer composition, it is also possible to use another monomer together with the said cyclic olefin monomer in the range which does not impair the objective of this invention.
Examples of such other monomers include α-olefins having 2 or more carbon atoms, and more specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1- Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl- 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc. It is done. These can be used alone or in combination. Of these, ethylene or propylene is preferable, and ethylene is particularly preferable.
環状オレフィンモノマーと他のモノマーとを併用する場合の配合比としては、特に限定されるものではないが、（環状オレフィンモノマー）／（他のモノマー）（質量比）として通常９８／２〜３０／７０、好ましくは９５／５〜４０／６０である。環状オレフィンモノマーの配合量が多すぎると、十分なシール性が得られない場合があり、一方、少なすぎると、内容成分の非吸着性が損なわれる場合がある。
なお、複数種のモノマーを併用する場合の重合方法や重合機構としては、公知の方法を用いることができ、モノマー時に配合して共重合を行っても良いし、ある程度重合した後に配合してブロック共重合しても良い。また、開環重合であっても、付加重合であっても良い。
The compounding ratio when the cyclic olefin monomer and other monomer are used in combination is not particularly limited, but is usually 98/2 to 30 / as (cyclic olefin monomer) / (other monomer) (mass ratio). 70, preferably 95/5 to 40/60. If the amount of the cyclic olefin monomer is too large, sufficient sealing properties may not be obtained. On the other hand, if the amount is too small, the non-adsorbability of the content components may be impaired.
In addition, as a polymerization method and a polymerization mechanism in the case of using a plurality of types of monomers in combination, a known method can be used, and the copolymerization may be performed by blending at the time of the monomer, or the block may be blended after polymerization to some extent. It may be copolymerized. Further, it may be ring-opening polymerization or addition polymerization.
本発明において「環状ポリオレフィン系樹脂」とは、上述した環状オレフィンモノマーを含むモノマー組成物を重合して得られる樹脂、或いはその誘導体を意味する。ここで「誘導体」とは、環状オレフィンモノマーを含むモノマー組成物を重合して得られる樹脂の水素添加体などを意味する。
本発明における環状ポリオレフィン系樹脂としては、上記ノルボルネン系モノマーの１種又は２種以上を重合して得られるポリノルボルネン系樹脂の、１種又は２種以上の組合せであること、又は、上記ノルボルネン系モノマーの１種又は２種以上を重合して得られるポリノルボルネン系樹脂の水素添加体の、１種又は２種以上の組合せであることが、良好なヒートシール性を有し、しかも、輸液、薬液、Ｘ線造影剤、ホルモン剤、放射性医薬品、循環器官用剤、消化器系製剤、蛋白アミノ製剤、循環器系製剤、酵素製剤、代謝性医薬品、抗生物質、抗炎症薬、腫瘍薬、生物学的製剤等の医薬品又はビタミン剤、微量元素等を収容する医療用容器などの医療用途に使用可能な包装袋を実現する観点から好適である。
In the present invention, the “cyclic polyolefin resin” means a resin obtained by polymerizing a monomer composition containing the above-mentioned cyclic olefin monomer, or a derivative thereof. Here, the “derivative” means a hydrogenated product of a resin obtained by polymerizing a monomer composition containing a cyclic olefin monomer.
The cyclic polyolefin resin in the present invention is one or a combination of two or more polynorbornene resins obtained by polymerizing one or more of the norbornene monomers, or the norbornene-based resin. It is a combination of one or more of the hydrogenated polynorbornene resins obtained by polymerizing one or more of the monomers, and has good heat sealability, Drug solution, X-ray contrast agent, hormone agent, radiopharmaceutical, cardiovascular agent, digestive system preparation, protein amino preparation, circulatory system preparation, enzyme preparation, metabolic drug, antibiotic, anti-inflammatory drug, tumor drug, biological It is preferable from the viewpoint of realizing a packaging bag that can be used for medical use such as a medical container containing a pharmaceutical or vitamin preparation such as a pharmaceutical preparation, a trace element and the like.
上記環状ポリオレフィン系樹脂の具体的な構造としては、例えば、下記一般式（１）又は（２）で表される構造式を示すことができる。 As a specific structure of the cyclic polyolefin-based resin, for example, a structural formula represented by the following general formula (1) or (2) can be shown.
上記炭素数１〜２０の有機基として、より具体的には、例えばメチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、ｔ−ブチル、ｉ−ペンチル、ｔ−ペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、ｔ−オクチル（１,１−ジメチル−３,３−ジメチルブチル）、２−エチルヘキシル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、イコシル等のアルキル基；シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル等のシクロアルキル基；１−メチルシクロペンチル、１−メチルシクロヘキシル、１−メチル−４−ｉ−プロピルシクロヘキシル等のアルキルシクロアルキル基；アリル、プロペニル、ブテニル、２−ブテニル、ヘキセニル、シクロヘキセニル等のアルケニル基；フェニル基、ナフチル基、メチルフェニル基、メトキシフェニル基、ビフェニル基、フェノキシフェニル基、クロロフェニル基、スルホフェニル基等のアリール基；ベンジル基、２−フェニルエチル基（フェネチル基）、α−メチルベンジル基、α，α−ジメチルベンジル基等のアラルキル基等を挙げることができるが、これらに限定されるものではない。また、これらは１種を単独で、あるいは２種以上を併用しても良い。 More specifically, examples of the organic group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, i-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, t-octyl (1,1-dimethyl-3,3-dimethylbutyl), 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Alkyl groups such as pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl; 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methyl-4-i-propyl Alkylcycloalkyl groups such as cyclohexyl; , Alkenyl groups such as propenyl, butenyl, 2-butenyl, hexenyl, cyclohexenyl; aryl groups such as phenyl, naphthyl, methylphenyl, methoxyphenyl, biphenyl, phenoxyphenyl, chlorophenyl, and sulfophenyl; Examples of the aryl group include, but are not limited to, a benzyl group, a 2-phenylethyl group (phenethyl group), an α-methylbenzyl group, and an α, α-dimethylbenzyl group. These may be used alone or in combination of two or more.
このような環状ポリオレフィンのガラス転移温度は、上記一般式（１），（２）中のｌ、ｍ、ｎ、ｐの値、あるいは置換基を適宜選択することにより適宜調整することが可能である。上記一般式（１），（２）以外の環状ポリオレフィンのガラス転移温度についても、用いるモノマー種、モノマー種の配合割合、モノマー配列、置換基の種類などを適宜設定することにより、任意に調整することができる。 The glass transition temperature of such a cyclic polyolefin can be appropriately adjusted by appropriately selecting the values of l, m, n, and p in the above general formulas (1) and (2), or substituents. . The glass transition temperatures of the cyclic polyolefins other than the above general formulas (1) and (2) are also arbitrarily adjusted by appropriately setting the monomer species to be used, the blending ratio of the monomer species, the monomer arrangement, the type of substituents, and the like. be able to.
上記一般式（１）で示される環状ポリオレフィンとしては市販品を用いることができ、例えば日本ゼオン株式会社製のゼオネックス、ゼオノアを好適に用いることができる。 Commercially available products can be used as the cyclic polyolefin represented by the general formula (1), and for example, ZEONEX and ZEONOR manufactured by ZEON CORPORATION can be suitably used.
上記一般式（２）で示される環状ポリオレフィンとしては市販品を用いることができ、例えば三井化学株式会社製のアペル、ＴＩＣＯＮＡ社製のＴＯＰＡＳを好適に用いることができる。 As the cyclic polyolefin represented by the general formula (2), a commercially available product can be used. For example, Appel manufactured by Mitsui Chemicals, Inc. and TOPAS manufactured by TICONA can be preferably used.
なお、本発明における上記シーラント層には、更に必要に応じ種々の添加剤、例えば顔料、分散剤、酸化防止剤、紫外線吸収剤、光安定剤、無機充填剤等を添加することもできる。 In addition, various additives such as pigments, dispersants, antioxidants, ultraviolet absorbers, light stabilizers, inorganic fillers and the like can be further added to the sealant layer in the present invention as necessary.
内容物の有効成分を吸着することがなく、容器から内容物へ低分子量成分等が溶出したりすることによる内容物の組成変化又は内容物汚染が可及的に低減され、かつ適切なヒートシール性を発現し、しかも適度な耐熱性を有するシーラント層としては、上記環状ポリオレフィン系樹脂が最も好ましいが、ポリエステル系樹脂として、シーラブルポリエステルやポリエステル系エラストマーあるいは、ＰＡＮ、ＰＢＴ、ＥＶＯＨ系樹脂を用いても同様の効果が期待できるが、環状ポリオレフィン系樹脂に比べてその効果は劣る。 It does not adsorb the active ingredients of the contents, and changes in the composition of the contents or contamination of the contents due to the elution of low molecular weight components etc. from the container to the contents are reduced as much as possible, and appropriate heat sealing As the sealant layer exhibiting the properties and having appropriate heat resistance, the above-mentioned cyclic polyolefin resin is most preferable, but as the polyester resin, sealable polyester, polyester elastomer, or PAN, PBT, EVOH resin is used. However, the same effect can be expected, but the effect is inferior to that of the cyclic polyolefin resin.
本発明の包装袋には、１１０℃以上の高圧蒸気滅菌処理を行なうことができ、かつ内容物の適切な排出を行なう観点から、ガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂を主成分として含むポート部材を具備することが好適である。ここで、ポート部材の形成材料としては、ポート部材とシーラント層との良好な熱溶着性を発現させる観点から、上述したシーラント層と同一の構成材料であるか、または該シーラント層の構成材料よりもガラス転移温度の低い材料であることが好適である。
ここで、ポート部材の形成材料に主成分として含まれる上記環状ポリオレフィン系樹脂のガラス転移温度としては、通常１００〜１７０℃であり、好ましくは１００〜１４０℃、より好ましくは１０５〜１２０℃である。ガラス転移温度が１００℃未満であると、シールすること自体は容易となるが１１０℃以上の高圧蒸気滅菌処理を行うことでポートが変形したり液漏れが発生したりする場合がある。一方、１７０℃を超えると、ポート自体が硬くなり軟化させにくく溶着することが困難となり、ポートの溶着を確実に行なうためには包装袋の外部から過度の熱を加える必要が生じ、フィルムが変形したり、フィルム自体がシールにより破断したり、ポート部の際が硬くなったり、ポートのシール部より液漏れが発生したりする場合がある。
なお、上記ガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂が、ポート部材を形成する組成物中に占める割合としては、通常５０質量％以上、好ましくは７０質量％以上、より好ましくは８０質量％以上であり、１００質量％であっても良い。
The packaging bag of the present invention is mainly composed of a cyclic polyolefin resin having a glass transition temperature of 100 to 170 ° C. from the viewpoint of being able to be subjected to high-pressure steam sterilization at 110 ° C. or higher and appropriately discharging the contents. It is preferable to provide a port member that includes. Here, the material for forming the port member is the same material as that of the above-described sealant layer, or from the material of the sealant layer, from the viewpoint of expressing good heat-weldability between the port member and the sealant layer. Is preferably a material having a low glass transition temperature.
Here, the glass transition temperature of the cyclic polyolefin resin contained as a main component in the material for forming the port member is usually 100 to 170 ° C, preferably 100 to 140 ° C, more preferably 105 to 120 ° C. . If the glass transition temperature is less than 100 ° C., sealing itself is easy, but performing high-pressure steam sterilization at 110 ° C. or higher may cause the port to deform or cause liquid leakage. On the other hand, when the temperature exceeds 170 ° C., the port itself becomes hard and difficult to be softened and difficult to weld, and it is necessary to apply excessive heat from the outside of the packaging bag in order to reliably weld the port, and the film is deformed. In some cases, the film itself may be broken by the seal, the port portion may become hard, or liquid leakage may occur from the seal portion of the port.
The proportion of the cyclic polyolefin resin having a glass transition temperature of 100 to 170 ° C. in the composition forming the port member is usually 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass. It is above and may be 100 mass%.
上記ポート部材の形成材料には、ポートに柔軟性を付与し、シートとのシール性を向上させる観点から、熱可塑性エラストマーが２０％以下の混合比率で混合されていても良い。該熱可塑性エラストマーが上記ポート部材の形成材料中に占める割合としては通常２０質量％以下、好ましくは１５質量％以下、より好ましくは１０質量％以下である。該割合が２０質量％を超えると、内容成分がポートに吸着されてしまうおそれが大きくなったり、包装袋の高圧蒸気滅菌適性が劣ったりする場合がある。
なお、ポート部材としては、上記形成材料をポート部材内壁に使用し、外側をポリエチレン樹脂にて被覆した二色成形品を使用してもよい。この場合、包装袋内面のシーラント層とシールされるのは、二色成形ポートから一部出ているポート内壁に使用した環状ポリオレフィンであってもよいし、外側に被覆したポリエチレン樹脂であってもよい。前記ポリエチレン樹脂として直鎖状低密度ポリエチレンを用いた場合、包装袋内面のシーラント層と好適にシールすることが可能となり、ポート部からの液漏れ発生などを防止することが可能となるため好適である。
In the material for forming the port member, a thermoplastic elastomer may be mixed in a mixing ratio of 20% or less from the viewpoint of imparting flexibility to the port and improving the sealing property with the sheet. The proportion of the thermoplastic elastomer in the material for forming the port member is usually 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less. If the ratio exceeds 20% by mass, the content component may be more likely to be adsorbed to the port, or the packaging bag may be less suitable for high-pressure steam sterilization.
In addition, as a port member, you may use the two-color molded product which uses the said forming material for a port member inner wall, and coat | covered the outer side with the polyethylene resin. In this case, what is sealed with the sealant layer on the inner surface of the packaging bag may be a cyclic polyolefin used for a port inner wall partially protruding from the two-color molded port, or a polyethylene resin coated on the outer side. Good. When linear low density polyethylene is used as the polyethylene resin, it can be suitably sealed with the sealant layer on the inner surface of the packaging bag, and it is possible to prevent the occurrence of liquid leakage from the port portion. is there.
本発明の積層フィルム構成としては、上述の基材層に、上述のシーラント層を直接積層した２層構成のシートであっても良いし、１１０℃以上の温度での滅菌適性、ポート部のシール性、液漏れ防止、ハンドリング性、基材層とシーラント層の接着性の観点に鑑み、シーラント層と基材層との間に１層又は２層以上の中間層を介在させた多層構成としても良い。なお、このような中間層としては特に制限はなく、ドライラミネーション用の接着剤にて接着層を形成しても良いが、溶剤を用いずに確実な積層構成を実現する観点から、上記シーラント層と上記基材層とを良好に接着させることが可能な接着性樹脂により中間層を構成することが好適である。
本発明の積層フィルムは、シーラント層としてガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂を主成分として採用し、基材層として融点１１０〜２２０℃のポリオレフィン系樹脂を主成分として採用していることから、包装袋を形成するためのシール時にシール部が変形したり、シールエッジ部が破断したりすることなく、シールすることが可能となる。この理由は明らかでないが、シール温度において、シーラント層である環状ポリオレフィン系樹脂の溶融粘度が大きく低下するのに対して、基材層であるポリオレフィン系樹脂は溶融粘度の低下が少なく、剛性を維持するためと考えられる。
The laminated film structure of the present invention may be a sheet having a two-layer structure in which the above-mentioned base material layer is directly laminated with the above-mentioned sealant layer, and is suitable for sterilization at a temperature of 110 ° C. or more, and sealing of the port part. In view of properties, liquid leakage prevention, handling properties, and adhesion between the base material layer and the sealant layer, a multilayer structure in which one or more intermediate layers are interposed between the sealant layer and the base material layer good. In addition, there is no restriction | limiting in particular as such an intermediate | middle layer, Although you may form an adhesive layer with the adhesive for dry lamination, from a viewpoint of implement | achieving a reliable laminated structure without using a solvent, the said sealant layer It is preferable that the intermediate layer is made of an adhesive resin capable of satisfactorily bonding the substrate layer and the base material layer.
The laminated film of the present invention employs a cyclic polyolefin resin having a glass transition temperature of 100 to 170 ° C. as a main component as a sealant layer, and a polyolefin resin having a melting point of 110 to 220 ° C. as a main component as a base material layer. For this reason, it is possible to perform sealing without deforming the seal part or breaking the seal edge part at the time of sealing for forming the packaging bag. The reason for this is not clear, but at the sealing temperature, the melt viscosity of the cyclic polyolefin resin, which is the sealant layer, is greatly reduced, whereas the polyolefin resin, which is the base layer, has little decrease in melt viscosity and maintains rigidity. It is thought to do.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
〔実施例１〜９、比較例１〜３〕
表１，２に示す構成材料にて表面層、必要に応じて中間層、及びシーラント層を有する積層フィルムを多層共押出し法により作成した。また、表１，２に示す構成材料にてポート部を射出成形により作成すると共に、これらの多層シート及びポート部を用いて包装袋を作成した。包装袋外周シール部及びポートシール部のシール条件としては、表１，２に示すシール条件を採用した。なお、表１における構成材料欄中の「第一」、「第二」、「第三」、「第四」という表記については、表面層側から順に「第一中間層」、「第二中間層」、「第三中間層」、「第四中間層」が積層されていることを意味する。
得られた包装袋につき、外周シール部及びポートシール部のシール後の外観、外周シール部のヒートシール強度を測定すると共に、表１，２に示す所定の内容物を所定の内容量をもって充填密封後、同じく表１，２に示す所定の滅菌条件にて滅菌処理を行い、滅菌処理後に所定の圧力を印加した場合に液漏れが生ずるか否かについての評価した。更に、滅菌処理後の内容物につき、第１４改正日本薬局方プラスチック製医薬品容器試験法（プラスチック製水性注射剤容器 １．ポリエチレン製又はポリプロピレン製水性注射剤容器）に準拠した方法で試験を行なった。結果を表１，２に併せて示す。
[Examples 1-9, Comparative Examples 1-3]
A laminated film having a surface layer, an intermediate layer and, if necessary, a sealant layer made of the constituent materials shown in Tables 1 and 2 was prepared by a multilayer coextrusion method. Moreover, while creating the port part by the injection molding with the constituent material shown in Tables 1 and 2, a packaging bag was created using these multilayer sheets and the port part. The sealing conditions shown in Tables 1 and 2 were adopted as the sealing conditions for the packaging bag outer periphery seal part and the port seal part. In addition, regarding the notation of “first”, “second”, “third”, “fourth” in the constituent material column in Table 1, “first intermediate layer”, “second intermediate” in order from the surface layer side. It means that “layer”, “third intermediate layer”, and “fourth intermediate layer” are laminated.
For the obtained packaging bag, the outer appearance after sealing of the outer peripheral seal portion and the port seal portion and the heat seal strength of the outer peripheral seal portion are measured, and the predetermined contents shown in Tables 1 and 2 are filled and sealed with predetermined internal volumes. Thereafter, sterilization treatment was performed under the same sterilization conditions as shown in Tables 1 and 2, and it was evaluated whether or not liquid leakage occurred when a predetermined pressure was applied after the sterilization treatment. Furthermore, the contents after sterilization were tested by a method in accordance with the 14th revised Japanese Pharmacopoeia plastic drug container test method (plastic water injection container 1. polyethylene or polypropylene water injection container). . The results are shown in Tables 1 and 2.
ａ：融点１６０℃のプロピレン系共重合体［（Ａ）成分：ｏ−ジクロロベンゼンを溶媒として用いた温度０℃から１４０℃の間の温度上昇溶離分別における０℃での溶出分が全溶出量に対して占める割合が２３質量％であり、６０℃以上９０℃以下での溶出分が全溶出量に対して占める割合が８質量％である三菱化学（株）製重合型ポリプロピレン系ＴＰＯ。］。
ｂ：融点１１５℃のＬＬＤＰＥ(東ソー製：ペトロセン)。
ｃ：融点１６０℃のプロピレン系共重合体［（Ａ）成分：ｏ−ジクロロベンゼンを溶媒として用いた温度０℃から１４０℃の間の温度上昇溶離分別における０℃での溶出分が全溶出量に対して占める割合が２３質量％であり、６０℃以上９０℃以下での溶出分が全溶出量に対して占める割合が８質量％である三菱化学（株）製重合型ポリプロピレン系ＴＰＯ。］８５質量％、融点１４３℃のポリプロピレン系共重合体［（Ｂ）成分：プロピレン系共重合体成分の、ｏ−ジクロロベンゼンを溶媒として用いた温度０℃から１４０℃の間の温度上昇溶離分別における０℃での溶出分が全溶出量に対して占める割合が７質量％であり、６０℃以上９０℃以下での溶出分が全溶出量に対して占める割合が５０質量％である三菱化学（株）製重合型ポリプロピレン系ＴＰＯ。］を１５質量％の割合で混合した混合物。
ｄ：融点１６０℃のプロピレン系共重合体［（Ａ）成分：ｏ−ジクロロベンゼンを溶媒として用いた温度０℃から１４０℃の間の温度上昇溶離分別における０℃での溶出分が全溶出量に対して占める割合が２３質量％であり、６０℃以上９０℃以下での溶出分が全溶出量に対して占める割合が８質量％である三菱化学（株）製重合型ポリプロピレン系ＴＰＯ。］を７０質量％、融点１３６℃のポリプロピレン系共重合体［（Ｂ）成分：プロピレン系共重合体成分の、ｏ−ジクロロベンゼンを溶媒として用いた温度０℃から１４０℃の間の温度上昇溶離分別における０℃での溶出分が全溶出量に対して占める割合が６質量％であり、６０℃以上９０℃以下での溶出分が全溶出量に対して占める割合が４０質量％であるチッソ製のランダムポリプロピレン。］３０質量％の割合で混合した混合物。
ｅ：融点１０５℃のＬＬＤＰＥ(日本ポリエチレン製：ハーモレックス)。
ｆ：融点１１０℃のＬＬＤＰＥ(出光石油化学製：モアテック)
ｇ：融点２００℃のポリエステル系エラストマー（イーストマン製：ＥＣＤＥＬ）
ｈ：接着性樹脂（三菱化学製モディック）
ｉ：接着性樹脂（三井化学製アドマー）
ｊ：ポリエステル系ウレタン接着剤（三井武田製）
ｋ：２軸延伸ナイロン（ユニチカ製）
ｌ：ＬＬＤＰＥ(出光石油化学製：モアテック) を８５質量％、スチレン系エラストマー(ＪＳＲ製:ダイナロン)を１５質量％の比率で混合した混合物
a: Propylene copolymer having a melting point of 160 ° C. [Component (A): Elution fraction at 0 ° C. in the temperature rising elution fractionation between 0 ° C. and 140 ° C. using o-dichlorobenzene as a solvent is the total elution amount A polymerization type polypropylene TPO manufactured by Mitsubishi Chemical Co., Ltd., in which the proportion of leaching at 60 ° C. or more and 90 ° C. or less is 8% by mass. ].
b: LLDPE having a melting point of 115 ° C. (manufactured by Tosoh: Petrocene).
c: Propylene copolymer having a melting point of 160 ° C. [Component (A): Elution fraction at 0 ° C. in the temperature rising elution fraction between 0 ° C. and 140 ° C. using o-dichlorobenzene as a solvent is the total elution amount A polymerization type polypropylene TPO manufactured by Mitsubishi Chemical Co., Ltd., in which the proportion of leaching at 60 ° C. or more and 90 ° C. or less is 8% by mass. ] 85% by mass, polypropylene copolymer having a melting point of 143 [deg.] C. [Component (B): Elution fractionation of temperature rise between 0 [deg.] C. and 140 [deg.] C. using propylene copolymer component as a solvent using o-dichlorobenzene The proportion of elution at 0 ° C. in the total elution amount is 7% by mass, and the proportion of elution at 60 ° C. or more and 90 ° C. or less in the total elution amount is 50% by mass. Polymerization type polypropylene TPO manufactured by Co., Ltd. ] In a proportion of 15% by mass.
d: Propylene copolymer having a melting point of 160 ° C. [Component (A): Elution fraction at 0 ° C. in the temperature rising elution fractionation between 0 ° C. and 140 ° C. using o-dichlorobenzene as a solvent is the total elution amount A polymerization type polypropylene TPO manufactured by Mitsubishi Chemical Co., Ltd., in which the proportion of leaching at 60 ° C. or more and 90 ° C. or less is 8% by mass. ] 70 mass%, polypropylene copolymer having a melting point of 136 ° C. [component (B): elution of a propylene copolymer component at a temperature rise of 0 to 140 ° C. using o-dichlorobenzene as a solvent] The proportion of the fraction eluted at 0 ° C. relative to the total amount eluted is 6% by mass, and the proportion of the fraction eluted from 60 ° C. to 90 ° C. relative to the total amount eluted is 40% by mass. Made of random polypropylene. ] Mixture mixed at a ratio of 30% by mass.
e: LLDPE having a melting point of 105 ° C. (made by Nippon Polyethylene: Harmolex).
f: LLDPE having a melting point of 110 ° C. (manufactured by Idemitsu Petrochemicals: Moretec)
g: Polyester elastomer having a melting point of 200 ° C. (Ecman: ECDEL)
h: Adhesive resin (Mitchi Chemical Modic)
i: Adhesive resin (Mitsui Chemicals Admer)
j: Polyester urethane adhesive (Mitsui Takeda)
k: Biaxially stretched nylon (Made by Unitika)
l: A mixture of 85% by mass of LLDPE (manufactured by Idemitsu Petrochemicals: Moretec) and 15% by mass of styrene elastomer (manufactured by JSR: Dynalon)
Ｉ：ガラス転移温度(以下Ｔｇとする)が１３６℃の環状ポリオレフィン(日本ゼオン:ゼオノア１４２０Ｒ)
ＩＩ：Ｔｇが１０５℃の環状ポリオレフィン(日本ゼオン:ゼオノア１０２０Ｒ)を２０質量％、Ｔｇが１３６℃の環状ポリオレフィン(日本ゼオン:ゼオノア１４１０Ｒ)を８０質量％の比率で混合した環状ポリオレフィン混合物
ＩＩＩ：Ｔｇが７５℃の環状ポリオレフィン(日本ゼオン:ゼオノア７５０Ｒ)を２０％、Ｔｇが１３６℃の環状ポリオレフィン(日本ゼオン:ゼオノア１４２０Ｒ)を８０％の比率で混合した混合物
ＩＶ：ガラス転移温度(以下Ｔｇとする)が７５℃の環状ポリオレフィン(日本ゼオン:ゼオノア７５０Ｒ)
Ｖ：Ｔｇが１０５℃の環状ポリオレフィン(日本ゼオン:ゼオノア１０２０Ｒ)
ＶＩ：Ｔｇが１０５℃の環状ポリオレフィン(日本ゼオン:ゼオノア１０２０Ｒ)を９０質量％、ポリスチレン系エラストマー（ＪＳＲ製ダイナロン）を１０質量％混合した混合物
ＶＩＩ：Ｔｇが１０５℃の環状ポリオレフィン(日本ゼオン:ゼオノア１０２０Ｒ)を８５質量％、Ｔｇが７５℃の環状ポリオレフィン(日本ゼオン:ゼオノア７５０Ｒ)を１５質量％の比率で混合した混合物
I: Cyclic polyolefin having a glass transition temperature (hereinafter referred to as Tg) of 136 ° C. (Nippon ZEON: ZEONOR 1420R)
II: Cyclic polyolefin mixture obtained by mixing 20% by mass of cyclic polyolefin (Nippon ZEON: Zeonore 1020R) having a Tg of 105 ° C. and 80% by mass of cyclic polyolefin having a Tg of 136 ° C. (Nippon ZEON: Zeonore 1410R) III: Tg Is a mixture of cyclic polyolefin (Nippon ZEON: ZEONOR 750R) with 75% at 20% and cyclic polyolefin (Nippon ZEON: ZEONOR 1420R) with Tg at 136 ° C at a ratio of 80% IV: Glass transition temperature (hereinafter referred to as Tg) ) Is a cyclic polyolefin (Nippon ZEON: ZEONOR 750R) at 75 ° C
V: Cyclic polyolefin having a Tg of 105 ° C. (Nippon ZEON: ZEONOR 1020R)
VI: A mixture of 90% by mass of a cyclic polyolefin (Nippon ZEON: ZEONOR 1020R) having a Tg of 105 ° C and 10% by mass of a polystyrene elastomer (JSR Dynalon) VII: a cyclic polyolefin having a Tg of 105 ° C (Nippon ZEON: ZEONOR) 1020R) and a mixture of cyclic polyolefin (Nippon ZEON: ZEONOR 750R) having a Tg of 75 ° C. at a ratio of 15% by mass.
シール後外観
○：良好
×：変形が著しい、及び／又はシール部エッジより破断
外周シール部強度
ＪＩＳ Ｚ ０２３８に準拠したＭＤ方向サンプルのヒートシール強度（１８０°剥離強度）。
内容物
水：注射用蒸留水
薬剤１：循環器系製剤（血管拡張剤：ニトログリセリン注射溶液）
薬剤２：Ｘ線造影剤（ヨウ素化合物製剤）
薬剤３：循環器系製剤（強心剤）
薬剤４：循環器系製剤（血管拡張剤：硝酸イソソルビト注射液）
日本薬局方試験
第１４改正日本薬局方プラスチック製医薬品容器試験法（プラスチック製水性注射剤容器 １．ポリエチレン製又はポリプロピレン製水性注射剤容器）に準拠した方法で試験を行なった。
Appearance after sealing ○: Good ×: Significant deformation and / or fracture from the edge of the seal
Peripheral seal part strength Heat seal strength (180 ° peel strength) of MD direction sample based on JIS Z 0238.
Contents : Water: Distilled water for injection 1: Cardiovascular preparation (vasodilator: nitroglycerin injection solution)
Agent 2: X-ray contrast agent (iodine compound preparation)
Drug 3: Cardiovascular preparation (cardiotonic)
Drug 4: Cardiovascular product (vasodilator: isosorbate nitrate injection)
The Japanese Pharmacopoeia Test 14th revision Japanese Pharmacopoeia plastic drug container test method (plastic water-based injection container 1. polyethylene or polypropylene water-based injection container).
Claims (12)
前記基材層が融点１１０〜２２０℃のポリオレフィン系樹脂を主成分として含み、かつ、前記シーラント層がガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂を主成分として含むとともに、
ガラス転移温度１００〜１７０℃の環状ポリオレフィン系樹脂を主成分として含む材料が少なくとも内壁に使用されて外側がポリエチレン樹脂にて被覆されたポート部材が前記シーラント層に液漏れしないようにシールされたことを特徴とする医療用容器。 In a medical container formed using a laminated film including a base material layer and a sealant layer laminated on one surface side of the base material layer and capable of being sterilized at a temperature of 110 ° C. or higher,
The base material layer includes a polyolefin resin having a melting point of 110 to 220 ° C. as a main component, and the sealant layer includes a cyclic polyolefin resin having a glass transition temperature of 100 to 170 ° C. as a main component.
As a port including materials with glass transition temperature 100 to 170 ° C. of cyclic polyolefin resin as a main component and less used in the inner wall also has an outer coated with a polyethylene resin member dripless the sealant layer A medical container characterized in that it is sealed.
（Ａ）成分：プロピレンと、エチレン及び／又は炭素数４〜８のα−オレフィンとからなるプロピレン系共重合体成分であって、温度上昇溶離分別法（温度：０〜１４０℃、溶媒：ｏ−ジクロロベンゼン）を用いた場合に、０℃での溶出分の割合が全溶出量に対して１５質量％以上５０質量％以下、６０℃以上９０℃以下での溶出分の割合が全溶出量に対して５質量％以上１５質量％未満であるプロピレン系共重合体。 The medical container according to claim 1, wherein the polyolefin-based resin is a linear low-density polyethylene or a propylene-based copolymer composition containing the following component (A).
Component (A): a propylene copolymer component composed of propylene and ethylene and / or an α-olefin having 4 to 8 carbon atoms, and a temperature rising elution fractionation method (temperature: 0 to 140 ° C., solvent: o -Dichlorobenzene), the proportion of elution at 0 ° C. is 15 mass% to 50 mass% and the proportion of elution at 60 ° C. to 90 ° C. is the total amount of elution. A propylene-based copolymer that is 5% by mass or more and less than 15% by mass with respect to.
（Ｂ）成分：プロピレンと、エチレン及び／又は炭素数４〜８のα−オレフィンとからなるプロピレン系共重合体成分であって、温度上昇溶離分別法（温度：０〜１４０℃、溶媒：ｏ−ジクロロベンゼン）を用いた場合に、０℃での溶出分の割合が全溶出量に対して０質量％以上２５質量％以下、６０℃以上９０℃以下での溶出分の割合が全溶出量に対して１５質量％以上７０質量％以下であるプロピレン系共重合体。 The medical container according to claim 2, wherein the propylene copolymer composition further comprises the following component (B).
Component (B): a propylene copolymer component composed of propylene and ethylene and / or an α-olefin having 4 to 8 carbon atoms, and a temperature rising elution fractionation method (temperature: 0 to 140 ° C., solvent: o -Dichlorobenzene), the proportion of elution at 0 ° C. is 0% to 25% by mass, and the proportion of elution at 60 ° C. to 90 ° C. is the total amount eluted. A propylene-based copolymer that is 15% by mass or more and 70% by mass or less based on the weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004066024A JP4596124B2 (en) | 2004-03-09 | 2004-03-09 | Medical container |
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|---|---|---|---|
| JP2004066024A JP4596124B2 (en) | 2004-03-09 | 2004-03-09 | Medical container |
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| JP2005254508A JP2005254508A (en) | 2005-09-22 |
| JP4596124B2 true JP4596124B2 (en) | 2010-12-08 |
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| JP2004066024A Expired - Fee Related JP4596124B2 (en) | 2004-03-09 | 2004-03-09 | Medical container |
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