JP2004156020A - Thermoplastic resin composition and its molding - Google Patents
Thermoplastic resin composition and its molding Download PDFInfo
- Publication number
- JP2004156020A JP2004156020A JP2003278705A JP2003278705A JP2004156020A JP 2004156020 A JP2004156020 A JP 2004156020A JP 2003278705 A JP2003278705 A JP 2003278705A JP 2003278705 A JP2003278705 A JP 2003278705A JP 2004156020 A JP2004156020 A JP 2004156020A
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- Prior art keywords
- component
- continuous phase
- weight
- resin
- resin composition
- 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.)
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- 239000011342 resin composition Substances 0.000 title claims abstract description 30
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 30
- 238000000465 moulding Methods 0.000 title abstract description 16
- 125000000524 functional group Chemical group 0.000 claims abstract description 39
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 229920006038 crystalline resin Polymers 0.000 claims abstract description 20
- 229920005672 polyolefin resin Polymers 0.000 claims description 12
- 230000004888 barrier function Effects 0.000 abstract description 51
- 229920005989 resin Polymers 0.000 abstract description 25
- 239000011347 resin Substances 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000007789 gas Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- 238000000635 electron micrograph Methods 0.000 description 22
- -1 polypropylene Polymers 0.000 description 22
- 239000000178 monomer Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229920006122 polyamide resin Polymers 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229920002647 polyamide Polymers 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920013716 polyethylene resin Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920005604 random copolymer Polymers 0.000 description 7
- 229920002302 Nylon 6,6 Polymers 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 239000003502 gasoline Substances 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 150000003440 styrenes Chemical class 0.000 description 6
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920005673 polypropylene based resin Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920005678 polyethylene based resin Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000005003 food packaging material Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 description 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- HEXDQNXIVJEYLG-UHFFFAOYSA-N (2-methylphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1C HEXDQNXIVJEYLG-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical class CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical class CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- CXJAFLQWMOMYOW-UHFFFAOYSA-N 3-chlorofuran-2,5-dione Chemical compound ClC1=CC(=O)OC1=O CXJAFLQWMOMYOW-UHFFFAOYSA-N 0.000 description 1
- AXGOOCLYBPQWNG-UHFFFAOYSA-N 3-ethylfuran-2,5-dione Chemical compound CCC1=CC(=O)OC1=O AXGOOCLYBPQWNG-UHFFFAOYSA-N 0.000 description 1
- FMEYPAIIOVKZRA-UHFFFAOYSA-N 3-ethylideneoxolane-2,5-dione Chemical compound CC=C1CC(=O)OC1=O FMEYPAIIOVKZRA-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
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- 239000004925 Acrylic resin Substances 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
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- 239000004677 Nylon Substances 0.000 description 1
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- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
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- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
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- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
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- 238000012690 ionic polymerization Methods 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
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- 239000012968 metallocene catalyst Substances 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は耐熱性、ガスバリア性、水蒸気バリア性、成形加工性に優れる熱可塑性樹脂組成物及びその成形体に関する。
本発明の熱可塑性樹脂組成物及びその成形体は、電子顕微鏡で観察するとモルフォロジーが、（Ｂ）成分がマトリックス（海）であり、（Ｃ）成分が主にドメイン（島）であってリボン状の特異な形状を示す熱可塑性樹脂組成物及びその成形体に関する。
The present invention relates to a thermoplastic resin composition having excellent heat resistance, gas barrier properties, water vapor barrier properties, and moldability, and a molded article thereof.
The morphology of the thermoplastic resin composition and the molded product of the present invention when observed with an electron microscope is such that the component (B) is a matrix (sea), the component (C) is mainly a domain (island), and a ribbon shape. And a molded article thereof.
２種類以上の樹脂を用いて樹脂材料の機能を高機能化、多様化する方法は、雑貨、包材、家電ＯＡ材料、自動車材料等の産業分野で幅広く用いられている。特に、ポリアミド系樹脂は耐熱性、耐油性、ガスバリア性に優れる樹脂であり、これを他樹脂とブレンドすることが盛んに行われている。例えば、ポリプロピレン／ポリアミドアロイ、ポリフェニレンエーテル／ポリアミドアロイ、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ）／ポリアミドアロイ等があり、自動車材料として実用化されていることが知られている（非特許文献１参照）。これらは、ポリアミド系樹脂と相手樹脂の特徴を生かし、また、例えばポリオレフィン系樹脂とアロイ化することにより、ポリアミド系樹脂の吸水性といった欠点を改良した材料となっている。 Methods for enhancing and diversifying the functions of resin materials using two or more types of resins are widely used in industrial fields such as miscellaneous goods, packaging materials, home appliance OA materials, and automobile materials. In particular, a polyamide resin is a resin excellent in heat resistance, oil resistance, and gas barrier properties, and blending it with other resins has been actively performed. For example, there are polypropylene / polyamide alloy, polyphenylene ether / polyamide alloy, acrylonitrile-butadiene-styrene copolymer (ABS) / polyamide alloy and the like, which are known to be put to practical use as automotive materials (Non-Patent Document 1). reference). These are materials that take advantage of the characteristics of the polyamide resin and the mating resin, and are improved in defects such as water absorption of the polyamide resin by alloying with, for example, a polyolefin resin.
また、ガスバリア性を要求される食品包装材には、機能性付与の方法としてアロイの手法ではなく、数種の樹脂を積層するという方法が用いられる。例えば、外層がポリエチレン、中間層が接着性ポリエチレン、内層がナイロンよりなる気体透過量が小さい三層容器が知られている（特許文献１参照）。また、外層に高密度ポリエチレンを用い、ポリアミド層を最内層または中間層に用いたガソリン透過防止性能に優れた多層型プラスチツク燃料タンクも知られている（特許文献２参照）。しかし、これらは多層成形体であり、単層の製造設備に比べ、設備コストが大きいといった経済性の面での欠点、あるいは成形品は多層体であるためにリサイクルできない（積層体は各層の混合物であるために、各層の工程に戻せない）といったリサイクル性の面での欠点、さらには高密度ポリエチレン相の耐熱性が低いために成形体の耐熱性が低くなるという欠点を持っている。
これらの欠点を解決するためには、多層成形体の特性を単層成形体で発現することが求められる。多層成形体のガスバリア性を単層成形体で発現するために、ガスバリア性を付与するポリアミド系樹脂をオレフィン系樹脂中に層状分散させることが知られている（特許文献３、非特許文献２参照）。しかしながら、オレフィン系樹脂が連続相であるために耐熱性が悪く、また層状分散のモルフォロジーを有する成形体では、まだガスバリア性に満足のいくものではなかった。
For food packaging materials that require gas barrier properties, a method of laminating several types of resins is used instead of the alloy method as a method of imparting functionality. For example, a three-layer container having a small gas permeation amount is known in which an outer layer is made of polyethylene, an intermediate layer is made of adhesive polyethylene, and an inner layer is made of nylon (see Patent Document 1). There is also known a multi-layer plastic fuel tank having excellent gasoline permeation prevention performance in which high-density polyethylene is used for the outer layer and a polyamide layer is used for the innermost layer or the middle layer (see Patent Document 2). However, these are multilayer molded products, and are economically disadvantageous in that the equipment cost is higher than single-layer production equipment, or molded products cannot be recycled because they are multilayer products (the laminate is a mixture of each layer). , It cannot be returned to the process of each layer), and the high-density polyethylene phase has low heat resistance, and the molded article has low heat resistance.
In order to solve these drawbacks, it is required that the properties of the multilayer molded article be expressed by a single-layer molded article. It is known that a polyamide resin imparting gas barrier properties is dispersed in a layered manner in an olefin resin in order to exhibit the gas barrier properties of a multilayer molded article in a single-layer molded article (see Patent Document 3 and Non-Patent Document 2). ). However, since the olefin resin is a continuous phase, heat resistance is poor, and a molded article having a layered dispersion morphology has not yet been satisfactory in gas barrier properties.
バリヤー性ポリマーがポリオレフィン相中に編目状の連続相として形成されていることを特徴とするポリマーブレンド成形体も知られている（特許文献４参照）。しかしながら、バリアー性ポリマーとポリオレフィンを相溶させる成分が含まれておらず、これより得られる成形体は耐衝撃性等の機械特性が十分に満足できるものではなかった。
また、ポリアミド樹脂と不飽和ジカルボン酸またはその無水物を含むポリオレフィンおよび／またはスチレン系共重合体とを含有する組成物も知られている。（特許文献５参照）。
しかしながら、上記組成物中には未変性のポリオレフィン、または未変性のスチレン系共重合体を含有していないため、成形時に金型に付着し、金型との離型が困難となり成形しにくいという欠点を有していた。
また、ポリアミド系樹脂の単層フィルムがあるが、これはガスバリア性が吸水によって変化するという欠点、水蒸気バリア性が悪いという欠点、一般的な成形加工温度である結晶融解温度以上では溶融張力が小さく、フィルム、シート、ブローといった成形が難しいという欠点を有している。
以上のように、いままで耐熱性、ガスバリア性、水蒸気バリア性、成形加工性に優れる成形体はなかった。
There is also known a polymer blend molded article characterized in that a barrier polymer is formed as a stitch-like continuous phase in a polyolefin phase (see Patent Document 4). However, a component that makes the barrier polymer and the polyolefin compatible with each other is not contained, and a molded article obtained therefrom was not sufficiently satisfactory in mechanical properties such as impact resistance.
Further, a composition containing a polyamide resin and a polyolefin and / or a styrene copolymer containing an unsaturated dicarboxylic acid or an anhydride thereof is also known. (See Patent Document 5).
However, since the composition does not contain an unmodified polyolefin or an unmodified styrene-based copolymer, it adheres to a mold at the time of molding, and is difficult to release from the mold and is difficult to mold. Had disadvantages.
In addition, there is a single-layer film of a polyamide resin, which has a disadvantage that the gas barrier property is changed by water absorption, a disadvantage that the water vapor barrier property is poor, and a low melt tension at a crystal melting temperature which is a general molding temperature. However, there is a disadvantage that molding such as film, sheet, and blow is difficult.
As described above, there has been no molded body having excellent heat resistance, gas barrier properties, water vapor barrier properties, and moldability.
本発明の目的は、耐熱性、ガスバリア性、水蒸気バリア性、成形加工性に優れる熱可塑性樹脂組成物及びその成形体を提供する事にある。 An object of the present invention is to provide a thermoplastic resin composition having excellent heat resistance, gas barrier properties, water vapor barrier properties, and moldability, and a molded article thereof.
本発明者等は、上記の目的を達成すべく鋭意検討を進めた結果、驚くべきことにある特定のモルフォロジーを熱可塑性樹脂組成物及びその成形体に持たせることに成功し、実現不可能であった、耐熱性、ガスバリア性、水蒸気バリア性に優れる熱可塑性樹脂組成物及びその成形体を完成した。
すなわち本発明は、（Ａ）官能基を有する熱可塑性重合体（以下、（Ａ）成分ということがある。）０．１重量部以上２０重量部以下、
（Ｂ）末端に該官能基と反応する成分を有する高分子鎖を含む結晶性樹脂（以下、（Ｂ）成分ということがある。）１重量部以上５０重量部以下、および、
（Ｃ）オレフィン系樹脂（以下、（Ｃ）成分ということがある。）３０重量部以上９８．９重量部以下、
の３成分よりなり、
（Ｂ）成分が連続相であり、連続相の平均厚みが２０００ｎｍ以下であることを特徴とする熱可塑性樹脂組成物及びその成形体である。
The present inventors have made intensive studies to achieve the above object, and as a result, surprisingly succeeded in having a certain morphology in a thermoplastic resin composition and a molded article thereof, which is not feasible. Thus, a thermoplastic resin composition having excellent heat resistance, gas barrier properties, and water vapor barrier properties and a molded article thereof were completed.
That is, the present invention relates to a thermoplastic polymer having a functional group (A) (hereinafter sometimes referred to as a component (A)) in an amount of 0.1 to 20 parts by weight,
(B) a crystalline resin containing a polymer chain having a component that reacts with the functional group at a terminal (hereinafter, may be referred to as a component (B)) in an amount of 1 to 50 parts by weight, and
(C) an olefin-based resin (hereinafter sometimes referred to as a component (C)) in an amount of 30 parts by weight or more and 98.9 parts by weight or less;
Consisting of three components,
(B) A thermoplastic resin composition and a molded article, wherein the component is a continuous phase, and the average thickness of the continuous phase is 2000 nm or less.
本発明の成形体は、今まで提供することの出来なかった耐熱性、ガスバリア性、水蒸気バリア性、成形加工性に高度に優れる熱可塑性樹脂組成物および成形体を提供することが出来る。 The molded article of the present invention can provide a thermoplastic resin composition and a molded article which are highly unsatisfactory in heat resistance, gas barrier properties, water vapor barrier properties, and moldability, which could not be provided so far.
以下、本発明に関して詳しく述べる。
本発明における（Ａ）官能基を有する熱可塑性重合体の官能基としては、アミノ基（−ＮＨ2 ）、カルボキシル基（−ＣＯＯＨ）、水酸基（−ＯＨ）、不飽和ジカルボン酸無水物基、エポキシ基、イソシアネート基、メルカプト基、オキサゾリン基等（以下官能基（ｆ）という。）があげられ、これら官能基（ｆ）は熱可塑性重合体の高分子鎖にグラフト結合、あるいはこれら官能基（ｆ）を含む重合性単量体を用い熱可塑性重合体の高分子鎖中に共重合、あるいは熱可塑性重合体の高分子鎖末端に結合させる方法で導入される。（Ａ）官能基（ｆ）を有する熱可塑性重合体の製造方法には何ら制限はない。官能基（ｆ）を有するラジカル反応性の不飽和単量体としては、メタクリル酸、アクリル酸、イタコン酸、マレイン酸、フマル酸、桂皮酸、２−ノルボネン−５，６−ジカルボン酸等の不飽和カルボン酸単量体、無水マレイン酸、無水イタコン酸、無水エチルマレイン酸、無水メチルイタコン酸、無水クロルマレイン酸、２−ノルボネン−５，６−ジカルボン酸無水物等の不飽和ジカルボン酸無水物単量体、グリシジルアクリレート、グリシジルメタクリレート、グリシジルアリルエーテル等のエポキシ基含有不飽和単量体をあげることができる。なかでも不飽和カルボン酸単量体、不飽和ジカルボン酸無水物単量体が好ましい。
Hereinafter, the present invention will be described in detail.
The functional group of the thermoplastic polymer having a functional group (A) in the present invention includes an amino group (—NH 2 ), a carboxyl group (—COOH), a hydroxyl group (—OH), an unsaturated dicarboxylic anhydride group, Group, isocyanate group, mercapto group, oxazoline group, etc. (hereinafter referred to as functional group (f)). These functional groups (f) are graft-bonded to the polymer chain of the thermoplastic polymer, or these functional groups (f) ) Is introduced into the thermoplastic polymer polymer chain by using a polymerizable monomer containing the same or by bonding to the polymer chain terminal of the thermoplastic polymer. (A) The method for producing the thermoplastic polymer having the functional group (f) is not particularly limited. Examples of the radical-reactive unsaturated monomer having the functional group (f) include unsaturated monomers such as methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and 2-norbonene-5,6-dicarboxylic acid. Saturated carboxylic acid monomers, unsaturated dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, ethyl maleic anhydride, methyl itaconic anhydride, chlormaleic anhydride, 2-norbonene-5,6-dicarboxylic anhydride Examples of the monomer include unsaturated monomers containing an epoxy group, such as a monomer, glycidyl acrylate, glycidyl methacrylate, and glycidyl allyl ether. Of these, unsaturated carboxylic acid monomers and unsaturated dicarboxylic anhydride monomers are preferred.
熱可塑性重合体への官能基（ｆ）の導入方法は、上記ラジカル反応性の不飽和単量体と熱可塑性重合体を構成する他の単量体とを、一般の重合法で共重合する方法、熱可塑性重合体と上記ラジカル反応性の不飽和単量体とを、ラジカル開始剤の存在下に溶融混練する方法、イオン重合リビング末端に結合させる方法等がある。
官能基（ｆ）を有する熱可塑性重合体における、熱可塑性重合体の種類に特に制約はないが、該熱可塑性重合体を構成する単量体としては、スチレンのほか、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、２，４−ジメチルスチレン、エチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレンなどの核アルキル置換スチレン、α−メチルスチレン、α−メチル−ｐ−メチルスチレンなどのα−アルキル置換スチレンなどのビニル芳香族化合物単量体、メチルメタクリレート（ＭＭＡ）、シクロヘキシルメタクリレート、メチルフェニルメタクリレート、イソプロピルメタクリレート、等のアルキルメタクリレート、メチルアクリレート、エチルアクリレート（ＥＡ）、ブチルアクリレート、２−エチルヘキシルアクリレート、シクロヘキシルメタクリレート等のアルキルアクリレートなどの不飽和カルボン酸アルキルエステル単量体、アクリロニトリル、メタクリロニトリル等の不飽和ニトリル系単量体、エチレン、炭素数３〜２０のオレフィン（炭素数３〜２０のオレフィンとしては、例えば、プロピレン、ブテン−１、ペンテン−１、ヘキセン−１、４−メチルペンテン−１、ヘプテン−１、オクテン−１、ノネン−１、デセン−１、ウンデセン−１、ドデセン−１等が挙げられる。）、ブタジエン、イソプレン、１，３−シクロヘキサジエン、１，３−ペンタジエン、２，３−ジメチル−１，３−ブタジエン等の共役ジエン化合物単量体、等が挙げられる。
The method of introducing the functional group (f) into the thermoplastic polymer is to copolymerize the above-mentioned radical-reactive unsaturated monomer and another monomer constituting the thermoplastic polymer by a general polymerization method. And a method in which the thermoplastic polymer and the above-mentioned radical-reactive unsaturated monomer are melt-kneaded in the presence of a radical initiator, and a method in which the terminal is bonded to a living terminal of ionic polymerization.
In the thermoplastic polymer having the functional group (f), the kind of the thermoplastic polymer is not particularly limited. Examples of monomers constituting the thermoplastic polymer include styrene, o-methylstyrene, and m-styrene. -Nucleated alkyl-substituted styrenes such as -methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene and p-tert-butylstyrene; α-alkyl such as α-methylstyrene and α-methyl-p-methylstyrene Vinyl aromatic compound monomers such as substituted styrene, methyl methacrylate (MMA), alkyl methacrylate such as cyclohexyl methacrylate, methylphenyl methacrylate, isopropyl methacrylate, etc., methyl acrylate, ethyl acrylate (EA), butyl acrylate, 2-ethylhexyl acrylate, Cyclo Unsaturated carboxylic acid alkyl ester monomers such as alkyl acrylates such as xyl methacrylate; unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile; ethylene; olefins having 3 to 20 carbon atoms (olefins having 3 to 20 carbon atoms) Examples thereof include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, and the like. And conjugated diene compound monomers such as butadiene, isoprene, 1,3-cyclohexadiene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene.
（Ａ）官能基（ｆ）を有する熱可塑性重合体としては、これら単量体を単独、あるいは２種類以上を溶液、塊状、縣濁、乳化、アニオン、配位アニオン、縮合重合等の通常の重合法で重合し、該重合時に又はその後に官能基（ｆ）を導入した熱可塑性重合体あるいは官能基（ｆ）を有するポリフェニレンエーテル系樹脂、ポリアセタール系樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂、ポリビニルアルコール、エチレンビニルアルコール等のポリビニルアルコール系樹脂、ポリカーボネート等のポリカーボネート系樹脂等が挙げられる。
分子構造は、リニアー型、分岐型、ブロック、ランダム等どのような構造でも構わない。具体例としては、スチレンブタジエンブロック共重合体、スチレンブタジエンランダム共重合体、スチレンイソプレンブロック共重合体、スチレンイソプレンランダム共重合体、水素添加スチレンブタジエンブロック共重合体、水素添加スチレンイソプレンブロック共重合体等の水素添加スチレン共役ジエンブロック共重合体、水素添加スチレンブタジエンランダム共重合体、水素添加スチレンイソプレンランダム共重合体、等の水素添加スチレン共役ジエンランダム共重合体、エチレンプロピレン共重合体、エチレンブチレン共重合体、エチレンスチレン共重合体等の無水マレイン酸変性物、スチレンメタクリル酸共重合体、スチレン無水マレイン酸共重合体、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性ポリエチレン、等を挙げることができる。
(A) As the thermoplastic polymer having a functional group (f), these monomers may be used alone or in combination of two or more kinds in a usual manner such as solution, bulk, suspension, emulsification, anion, coordination anion and condensation polymerization. A thermoplastic polymer having a functional group (f) introduced during or after polymerization by a polymerization method, or a polyester such as a polyphenylene ether-based resin having a functional group (f), a polyacetal-based resin, polyethylene terephthalate, or polyethylene naphthalate. Resin, polyvinyl alcohol such as polyvinyl alcohol and ethylene vinyl alcohol, and polycarbonate resin such as polycarbonate.
The molecular structure may be any structure such as linear, branched, block, and random. Specific examples include styrene-butadiene block copolymer, styrene-butadiene random copolymer, styrene-isoprene block copolymer, styrene-isoprene random copolymer, hydrogenated styrene-butadiene block copolymer, and hydrogenated styrene-isoprene block copolymer Hydrogenated styrene conjugated diene block copolymer, hydrogenated styrene butadiene random copolymer, hydrogenated styrene isoprene random copolymer, etc., hydrogenated styrene conjugated diene random copolymer, ethylene propylene copolymer, ethylene butylene Maleic anhydride modified products such as copolymers, ethylene styrene copolymers, styrene methacrylic acid copolymers, styrene maleic anhydride copolymers, maleic anhydride modified polypropylene, maleic anhydride modified polyethylene, etc. It can gel.
また（Ａ）官能基（ｆ）を有する熱可塑性重合体は２種以上を併用しても構わない。好ましいものとしては、無水マレイン酸変性ポリエチレン、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性水素添加スチレン共役ジエンブロック共重合体、エチレン−アクリル酸共重合体、エチレン−メタクリル酸共重合体が挙げられる。
（Ａ）官能基（ｆ）を有する熱可塑性重合体中の官能基を有する単量体の含有割合は、好ましくは０．００１重量％〜１０重量％、さらに好ましくは０．０１重量％〜５重量％であり、とりわけ好ましくは０．１５重量％〜３重量％である。０．００１重量％未満であると（Ｂ）成分との反応が行われず、界面の接着が不充分であり、成形品外観を悪化させたり、得られる成形体の強度が低下するために好ましくなく、また、（Ｂ）成分を連続相にし、連続相の厚みを本発明の範囲内にすることが困難になるために好ましくない。１０重量％を超えると、熱可塑性重合体のゲル化等の副反応制御が困難になり、熱可塑性重合体の熱可塑性が低下するため成形加工性が悪化し、また得られる組成物成形体の外観等が悪化し、好ましくなく、また、（Ｂ）成分を連続相にし、連続相の厚みを本発明の範囲内にすることが困難になるために好ましくない。官能基（ｆ）の量はＩＲ法、滴定法などにより定量することができる。（Ａ）成分は、（Ｂ）、（Ｃ）成分の相、及び（Ｂ）、（Ｃ）成分の界面相に存在することができる。
Further, two or more kinds of the thermoplastic polymer (A) having the functional group (f) may be used in combination. Preferred examples include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified hydrogenated styrene conjugated diene block copolymer, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer.
(A) The content ratio of the monomer having a functional group in the thermoplastic polymer having the functional group (f) is preferably 0.001% by weight to 10% by weight, more preferably 0.01% by weight to 5% by weight. %, Particularly preferably 0.15% to 3% by weight. When the amount is less than 0.001% by weight, the reaction with the component (B) does not take place, the adhesion at the interface is insufficient, the appearance of the molded product is deteriorated, and the strength of the obtained molded product is lowered. Further, it is not preferable because it is difficult to make the component (B) into a continuous phase and make the thickness of the continuous phase within the range of the present invention. If the content exceeds 10% by weight, it is difficult to control side reactions such as gelation of the thermoplastic polymer, and the thermoplasticity of the thermoplastic polymer is reduced, so that the moldability is deteriorated. It is not preferable because the appearance and the like are deteriorated, and it is difficult to make the component (B) into a continuous phase and make the thickness of the continuous phase within the range of the present invention. The amount of the functional group (f) can be determined by an IR method, a titration method, or the like. The component (A) can be present in the phases of the components (B) and (C) and in the interface phase of the components (B) and (C).
本発明における（Ｂ）末端に該官能基（ｆ）と反応する成分を有する高分子鎖を含む結晶性樹脂としては、アミノ基（−ＮＨ2 ）、カルボキシル基（−ＣＯＯＨ）、水酸基（−ＯＨ）、不飽和ジカルボン酸無水物基、エポキシ基、イソシアネート基、メルカプト基、オキサゾリン基等を有する高分子鎖を含む結晶性樹脂が挙げられる。（Ｂ）成分としては、具体的には、ポリアミド系樹脂、ポリエステル系樹脂、液晶高分子等がある。
また、本発明におけるガスバリア性とは、水蒸気以外のバリア性、例えば酸素のバリア性、ガソリンのバリア性をいう。酸素、ガソリンに対するバリア性に優れる代表的な（Ｂ）成分としては、ポリアミド系樹脂がある。
Examples of the crystalline resin containing a polymer chain having a component that reacts with the functional group (f) at the terminal (B) in the present invention include an amino group (—NH 2 ), a carboxyl group (—COOH), and a hydroxyl group (—OH). ), A crystalline resin containing a polymer chain having an unsaturated dicarboxylic anhydride group, an epoxy group, an isocyanate group, a mercapto group, an oxazoline group and the like. Specific examples of the component (B) include a polyamide resin, a polyester resin, and a liquid crystal polymer.
The gas barrier property in the present invention means a barrier property other than water vapor, for example, a barrier property against oxygen and a barrier property against gasoline. A typical example of the component (B) having excellent barrier properties against oxygen and gasoline is a polyamide resin.
ポリアミド系樹脂とは、アミノ酸、ラクタム、あるいはジアミンとジカルボン酸を主たる構成成分とするポリアミド系樹脂である。構成成分の具体例を挙げると、ε−カプロラクタム、エナントラクタム、ω−アミノカプロン酸、１１−アミノウンデカ酸、１２−アミノドデカン酸などのアミノ酸、テトラメチレンジアミン、ヘキサメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、２，２，４−トリメチルヘキサメチレンジアミン、２，４，４−トリメチルヘキサメチレンジアミン、５−メチルノナメチレンジアミン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン、１，３−ビスアミノメチルシクロヘキサン、１，４−ビスアミノメチルシクロヘキサン、ビス−ｐ−アミノシクロヘキシルメタン、ビス−ｐ−アミノシクロヘキシルプロパン、イソホロンジアミン、メタキシリレンジアミンなどのジアミン、アジピン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、１，４−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、ダイマー酸などのジカルボン酸がある。これらの構成成分は、単独あるいは二種以上の混合物の形で重合に供され、そうして得られるポリアミドホモポリマー、コポリマーいずれも本発明で用いることが出来る。例えば、ジアミンとジカルボン酸との重縮合で得られるポリアミド６６、ポリアミド６１０、ポリアミド６１２、ポリアミド４６、ポリアミド１２１２、ポリアミドＭＸＤ（メタキシリレンジアミン）６等があり、また、ラクタムの開環重合で得られるポリアミド６、ポリアミド１２等が挙げられる。またポリアミド共重合物として、ポリアミド６６／６、ポリアミド６６／６１０、ポリアミド６６／６１２、ポリアミド６６／６Ｔ（Ｔはテレフタル酸成分）、ポリアミド６６／６Ｉ（Ｉはイソフタル酸成分）、ポリアミド６Ｔ／６Ｉ等が挙げられる。またこれらのポリアミド樹脂のブレンド物も挙げられる。好ましいものはポリアミド６、ポリアミドＭＸＤ６である。これらのポリアミド樹脂の製造方法は、一般に公知に行われている方法で良い。ポリアミドの場合は、溶融重合方法が一般に実施されているが、バッチ式重合でもまた連続式重合でもよい。これらポリアミド系樹脂は末端にアミノ基およびまたはカルボキシル基を有し、これが官能基（ｆ）と反応する成分である。また（Ｂ）成分の結晶性樹脂は２種以上を併用しても構わない。
The polyamide resin is a polyamide resin containing amino acids, lactams, or diamines and dicarboxylic acids as main components. Specific examples of the constituent components include ε-caprolactam, enantholactam, amino acids such as ω-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylene. Diamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bisaminomethyl Diamines such as cyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, isophoronediamine, meta-xylylenediamine, adipic acid, suberic acid, azelaic acid Acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and dicarboxylic acids such as dimer acid. These constituents are subjected to polymerization in the form of a single compound or a mixture of two or more compounds, and any of the polyamide homopolymers and copolymers thus obtained can be used in the present invention. For example, there are polyamide 66, polyamide 610, polyamide 612, polyamide 46, polyamide 1212, polyamide MXD (meta-xylylenediamine) 6 obtained by polycondensation of diamine and dicarboxylic acid, and also obtained by ring-opening polymerization of lactam.
次に本発明における（Ｃ）オレフィン系樹脂について述べる。
（Ｃ）オレフィン系樹脂としては、大きく分けてポリエチレン系樹脂、ポリプロピレン系樹脂あるいはポリエチレン系樹脂とポリプロピレン系樹脂の混合物を使用することができる。
ポリエチレン系樹脂としては、高密度ポリエチレン（ＨＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、アクリル系ビニルモノマーとエチレンとの共重合体（ＥＥＡ、ＥＭＭＡ等）あるいは酢酸ビニルモノマーとエチレンとの共重合体（ＥＶＡ）等を挙げることができる。しかしながら、これらの中でも高密度ポリエチレン（ＨＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）及び直鎖状低密度ポリエチレン（ＬＬＤＰＥ）が、安価に入手できる為、特に好ましい。これらのポリエチレン系樹脂は、単独で用いても良いし、又、２種以上を組み合わせて用いても良い。
オレフィン系樹脂にポリエチレン系樹脂を用いる場合、密度０．８９ｇ／ｃｍ3 以上０．９５ｇ／ｃｍ3 以下であることが透明性の観点で望ましく、密度０．９０ｇ／ｃｍ3 以上０．９４ｇ／ｃｍ3 以下であることが更に望ましく、密度０．９１ｇ／ｃｍ3 以上０．９４ｇ／ｃｍ3 以下であることがとりわけ望ましい。単独でも２種以上を組み合わせた場合でも密度がこの範囲に入れば透明性が好ましくなる。
また、密度０．９４〜０．９７ｇ／ｃｍ3 のポリエチレンは、剛性、耐薬品性、バリヤー性の観点から、好ましく、その中でも密度が高いほど剛性、耐薬品性、バリヤー性の観点から更に好ましい。
Next, the olefin resin (C) in the present invention will be described.
(C) As the olefin-based resin, a polyethylene-based resin, a polypropylene-based resin, or a mixture of a polyethylene-based resin and a polypropylene-based resin can be broadly used.
Examples of the polyethylene resin include high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), copolymers of acrylic vinyl monomers and ethylene (EEA, EMMA, etc.) or vinyl acetate A copolymer of a monomer and ethylene (EVA) can be mentioned. However, among these, high-density polyethylene (HDPE), low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) are particularly preferable because they can be obtained at low cost. These polyethylene resins may be used alone or in combination of two or more.
When a polyethylene resin is used as the olefin resin, the density is preferably 0.89 g / cm 3 or more and 0.95 g / cm 3 or less from the viewpoint of transparency, and the density is 0.90 g / cm 3 or more and 0.94 g / cm 3. more desirably 3 or less, it is particularly desirable density 0.91 g / cm 3 or more 0.94 g / cm 3 or less. Transparency is preferred if the density falls within this range either alone or in combination of two or more.
In addition, polyethylene having a density of 0.94 to 0.97 g / cm 3 is preferable from the viewpoint of rigidity, chemical resistance, and barrier properties. Among them, the higher the density, the more preferable the rigidity, chemical resistance, and barrier properties. .
ポリプロピレン系樹脂を用いると、本願発明において得られる熱可塑性樹脂組成物及びその成形体は、流動性等の成形加工性、剛性等の機械的性質、ヒンジ特性、振動特性に優れ、剛性に優れる。
ポリプロピレン系樹脂としては、ホモのポリプロピレン、プロピレンとエチレン、ブテン−１、ペンテン−１、ヘキセン−１等の他のα−オレフィンとの共重合樹脂（ブロック、ランダムを含む）等を挙げることができる。
本発明で使用する（Ｃ）オレフィン系樹脂には、上述の如くポリエチレン系樹脂及び／又はポリプロピレン系樹脂があるが、ポリプロピレン系樹脂は、ポリエチレン系樹脂と比較して耐熱性が高く好ましい。中でもホモのポリプロピレン系樹脂、ブロック共重合ポリプロピレンは最も耐熱性が高くより好ましい。また、熱可塑性樹脂組成物及びその成形体表面に（Ｃ）オレフィン系樹脂よりなる相が存在すると、水蒸気バリア性がさらに改良され望ましい。
When a polypropylene-based resin is used, the thermoplastic resin composition and the molded product obtained in the present invention are excellent in moldability such as fluidity, mechanical properties such as rigidity, hinge characteristics, vibration characteristics, and rigidity.
Examples of the polypropylene resin include homopolypropylene, copolymer resins (including block and random) of propylene with other α-olefins such as ethylene, butene-1, pentene-1, and hexene-1. .
The olefin-based resin (C) used in the present invention includes a polyethylene-based resin and / or a polypropylene-based resin as described above, and the polypropylene-based resin is preferably higher in heat resistance than the polyethylene-based resin. Of these, homopolypropylene resins and block copolymerized polypropylene have the highest heat resistance and are more preferable. In addition, when a phase composed of the olefin-based resin (C) is present on the surface of the thermoplastic resin composition and the molded product thereof, the water vapor barrier property is further improved, which is desirable.
本発明においては（Ｂ）成分が連続相でなければならない。（Ｂ）成分が連続相でなければ、目標とする耐熱性、ガスバリア性が発現されない。
「（Ｂ）成分が連続相」の連続相とは、例えば２相の相分離を持つ場合、他の相に完全に覆われていない相のことを言う。本発明に関して言えば、（Ａ）、（Ｃ）成分（および他の重合体）よりなる相（熱可塑性樹脂組成物及びその成形体表面は除く）に完全に覆われていない相が、（Ｂ）成分よりなる連続相である。 （Ｂ）成分よりなる連続相の形成は、これらの電子顕微鏡写真（例えば、ＴＥＭ）等により判断することができる。
また、本発明においては、（Ｂ）成分が連続相であり、連続相の平均厚みが２０００ｎｍ以下でなければならない。好ましくは１０００ｎｍ以下であり、さらに好ましくは６００ｎｍ以下である。連続相の平均厚みが２０００ｎｍを超えると、水蒸気バリア性が悪化し、また、溶融張力が低下する等の理由で、ふくらまなっかたり、巻き取れなかったり、インフレーション成形が困難になる、延伸が困難になるなど成形加工性が悪化する。
In the present invention, the component (B) must be a continuous phase. If the component (B) is not a continuous phase, the desired heat resistance and gas barrier properties are not exhibited.
The continuous phase of “the component (B) is a continuous phase” means, for example, a phase that is not completely covered by another phase when it has two phases. In the context of the present invention, the phase that is not completely covered by the phase (excluding the thermoplastic resin composition and the surface of the molded product thereof) composed of the components (A) and (C) (and other polymers) is (B) ) Is a continuous phase composed of components. The formation of the continuous phase composed of the component (B) can be determined from these electron micrographs (for example, TEM).
In the present invention, the component (B) must be a continuous phase, and the average thickness of the continuous phase must be 2000 nm or less. Preferably it is 1000 nm or less, more preferably 600 nm or less. When the average thickness of the continuous phase exceeds 2000 nm, the water vapor barrier property is deteriorated, and the melt tension is reduced. Molding processability deteriorates, for example, becomes difficult.
また、本発明においては（Ｂ）成分が連続相であり、連続相の平均厚みが２０００ｎｍ以下であり、厚みが１０００ｎｍ以下である連続相部分が４０％以上であることが好ましい。厚みが１０００ｎｍ以下である連続相部分が４０％未満であると水蒸気バリア性、成形加工性が悪化する。好ましくは５０％以上であり、さらに好ましくは６０％以上であり、特に好ましくは７０％以上である。また、本発明においては、厚みが１０００ｎｍ以下である連続相部分の平均厚みが６００ｎｍ以下であることが好ましい。厚みが１０００ｎｍ以下である連続相部分の平均厚みが６００ｎｍを超えると、水蒸気バリア性、成形加工性が悪化する。さらに好ましくは５００ｎｍ以下であり、とりわけ好ましくは４００ｎｍ以下である。
また、本発明においては、（Ｂ）成分が連続相であり、連続相の平均厚みが２０００ｎｍ以下であり、厚みが３００ｎｍ以下である連続相部分が３０％以上であることが好ましい。厚みが３００ｎｍ以下である連続相部分が３０％未満であると、水蒸気バリア性、成形加工性が悪化する。さらに好ましくは４０％以上であり、とりわけ好ましくは５０％以上である。
In the present invention, it is preferable that the component (B) is a continuous phase, the average thickness of the continuous phase is 2000 nm or less, and the continuous phase portion having a thickness of 1000 nm or less is 40% or more. When the thickness of the continuous phase portion having a thickness of 1000 nm or less is less than 40%, the water vapor barrier property and the moldability deteriorate. It is preferably at least 50%, more preferably at least 60%, particularly preferably at least 70%. In the present invention, the average thickness of the continuous phase portion having a thickness of 1000 nm or less is preferably 600 nm or less. When the average thickness of the continuous phase portion having a thickness of 1000 nm or less exceeds 600 nm, the water vapor barrier property and the moldability deteriorate. It is more preferably at most 500 nm, particularly preferably at most 400 nm.
In the present invention, it is preferable that the component (B) is a continuous phase, the average thickness of the continuous phase is 2000 nm or less, and the continuous phase portion having a thickness of 300 nm or less is 30% or more. When the thickness of the continuous phase portion having a thickness of 300 nm or less is less than 30%, the water vapor barrier property and the moldability deteriorate. It is more preferably at least 40%, particularly preferably at least 50%.
本発明においては、ＪＩＳ Ｋ７２１０に準拠し、（Ｂ）成分の結晶性樹脂の融点＋３０℃以上１００℃以下、２．１６ｋｇ荷重で測定した、（Ｂ）成分のメルトフローレート値（ＭＦＲＢ）と（Ｃ）成分のメルトフローレート値（ＭＦＲＣ）の比（ＭＦＲＢ／ＭＦＲＣ）が４以上であることが好ましい。４未満であると、（Ｂ）成分を連続相にし、連続相の厚みを本発明の範囲内にすることが困難になるために好ましくない。さらに好ましくは１７以上であり、とりわけ好ましくは５０以上である。
また、（Ａ）官能基（ｆ）を有する熱可塑性重合体の量（Ｗａ重量部）と（Ｂ）末端に官能基（ｆ）と反応する成分を有する高分子鎖を含む結晶性樹脂の量（Ｗｂ重量部）が以下の式を満たす場合に、（Ｂ）成分を連続相にし、連続相の厚みを本発明の範囲内にすることができ、好ましい。
３＜Ｗｂ／Ｗａ＜１００、
さらに好ましい範囲は、３＜Ｗｂ／Ｗａ＜５０であり、とりわけ好ましい範囲は、３＜Ｗｂ／Ｗａ＜３０である。
In the present invention, the melt flow rate (MFRB) of the component (B) and the melt flow rate (MFRB) of the component (B) are measured at a load of 2.16 kg with a melting point of the crystalline resin of the component (B) + 30 ° C. to 100 ° C. in accordance with JIS K7210. It is preferable that the ratio (MFRB / MFRC) of the melt flow rate value (MFRC) of the component (C) is 4 or more. If it is less than 4, it is not preferable because it is difficult to make the component (B) into a continuous phase and make the thickness of the continuous phase within the range of the present invention. It is more preferably 17 or more, and particularly preferably 50 or more.
Also, (A) the amount (Wa parts by weight) of the thermoplastic polymer having the functional group (f) and (B) the amount of the crystalline resin containing a polymer chain having a component which reacts with the functional group (f) at the terminal. When (Wb parts by weight) satisfies the following formula, the component (B) can be a continuous phase, and the thickness of the continuous phase can be within the range of the present invention, which is preferable.
3 <Wb / Wa <100,
A more preferred range is 3 <Wb / Wa <50, and a particularly preferred range is 3 <Wb / Wa <30.
また、本発明の熱可塑性樹脂組成物及びその成形体においては、１５０℃を超える温度における（Ｂ）成分の結晶性樹脂成分の結晶化エンタルピー（ΔＨｃ１）と（Ｂ）成分の結晶性樹脂成分の融解エンタルピー（ΔＨｍ１）が、以下の式を満たすことが望ましい（ΔＨｃ１、ΔＨｍ１はＤＳＣ法で測定できる）。
Ｘ＝ΔＨｃ１／ΔＨｍ１
通常、０．３≦Ｘであるが、０．４≦Ｘが好ましく、０．５≦Ｘがより好ましい。耐熱性の観点からＸの値は０．５以上にすることが望ましく、０．６以上であることがさらに望ましく、０．７以上であることがとりわけ望ましい。
また、本発明の熱可塑性樹脂組成物及びその成形体においては、（Ｂ）成分の結晶性樹脂成分の融点が１５０℃を超えることが好ましい。１５０℃以下であると耐熱性が悪化する。好ましくは２００℃以上であり、さらに好ましくは２１０℃以上である。
In the thermoplastic resin composition of the present invention and the molded article thereof, the crystallization enthalpy (ΔHc1) of the crystalline resin component (B) and the crystalline resin component (B) at a temperature exceeding 150 ° C. It is desirable that the melting enthalpy (ΔHm1) satisfies the following expression (ΔHc1 and ΔHm1 can be measured by the DSC method).
X = ΔHc1 / ΔHm1
Usually, 0.3 ≦ X, preferably 0.4 ≦ X, more preferably 0.5 ≦ X. From the viewpoint of heat resistance, the value of X is desirably 0.5 or more, more desirably 0.6 or more, and particularly desirably 0.7 or more.
Further, in the thermoplastic resin composition of the present invention and the molded article thereof, it is preferable that the melting point of the crystalline resin component (B) exceeds 150 ° C. If the temperature is lower than 150 ° C., the heat resistance deteriorates. Preferably it is 200 degreeC or more, More preferably, it is 210 degreeC or more.
本発明の熱可塑性樹脂組成物及びその成形体は、（Ａ）官能基（ｆ）を有する熱可塑性重合体０．１重量部以上２０重量部以下、
（Ｂ）末端に該官能基（ｆ）と反応する成分を有する高分子鎖を含む結晶性樹脂１重量部以上５０重量部以下、および
（Ｃ）オレフィン系樹脂３０重量部以上９８．９重量部以下、
の３成分（（Ａ）成分＋（Ｂ）成分＋（Ｃ）成分＝１００重量部である。）よりなり、
（Ａ）官能基（ｆ）を有する熱可塑性重合体の量が０．１重量部未満であると、成形加工性が悪化し、２０重量部を超えると耐熱性、ガスバリア性を悪化させる。
（Ｂ）の結晶性樹脂の量が１重量部未満であると耐熱性、ガスバリア性が悪化し、５０重量部を超えると、水蒸気バリア性が悪化する。
（Ｃ）のオレフィン系樹脂の量が３０重量部未満であると水蒸気バリア性が悪化し、９８．９重量部を超えると、耐熱性、ガスバリア性が悪化する。
The thermoplastic resin composition of the present invention and the molded article thereof are (A) a thermoplastic polymer having a functional group (f) in an amount of 0.1 to 20 parts by weight,
(B) 1 to 50 parts by weight of a crystalline resin containing a polymer chain having a component which reacts with the functional group (f) at the terminal, and (C) 30 to 98.9 parts by weight of an olefin resin. Less than,
(Component (A) + component (B) + component (C) = 100 parts by weight)
When the amount of the thermoplastic polymer (A) having the functional group (f) is less than 0.1 part by weight, the moldability deteriorates, and when it exceeds 20 parts by weight, heat resistance and gas barrier properties deteriorate.
If the amount of the crystalline resin (B) is less than 1 part by weight, heat resistance and gas barrier properties will deteriorate, and if it exceeds 50 parts by weight, the water vapor barrier properties will deteriorate.
If the amount of the olefin-based resin (C) is less than 30 parts by weight, the water vapor barrier property deteriorates, and if it exceeds 98.9 parts by weight, heat resistance and gas barrier property deteriorate.
好ましい範囲は、（Ａ）官能基（ｆ）を有する熱可塑性重合体０．１重量部以上１０重量部以下、（Ｂ）末端に官能基（ｆ）と反応する成分を有する高分子鎖を含む結晶性樹脂５重量部以上５０重量部以下、および（Ｃ）オレフィン系樹脂４０重量部以上９４．９重量部以下、さらに好ましい範囲は、（Ａ）官能基（ｆ）を有する熱可塑性重合体０．１重量部以上８重量部以下、（Ｂ）末端に官能基（ｆ）と反応する成分を有する高分子鎖を含む結晶性樹脂６重量部以上４０重量部以下、および（Ｃ）オレフィン系樹脂５２重量部以上９３．９重量部以下、とりわけ好ましい範囲は、（Ａ）官能基（ｆ）を有する熱可塑性重合体０．１重量部以上６重量部以下、（Ｂ）末端に官能基（ｆ）と反応する成分を有する高分子鎖を含む結晶性樹脂６重量部以上３５重量部以下、および（Ｃ）オレフィン系樹脂５９重量部以上９３．９重量部以下である。
Preferred ranges include (A) a thermoplastic polymer having a functional group (f) in an amount of 0.1 to 10 parts by weight, and (B) a polymer chain having a component which reacts with the functional group (f) at the terminal. 5 parts by weight or more and 50 parts by weight or less of the crystalline resin, and (C) 40 parts by weight or more and 94.9 parts by weight or less of the olefin-based resin, more preferably (A) the thermoplastic polymer having a functional group (f) 0 1 to 8 parts by weight, (B) 6 to 40 parts by weight of a crystalline resin containing a polymer chain having a component which reacts with the functional group (f) at the terminal, and (C) an olefin resin. 52 parts by weight or more and 93.9 parts by weight or less, a particularly preferable range is (A) a thermoplastic polymer having a functional group (f) of 0.1 part by weight or more and 6 parts by weight or less, and (B) a functional group (f) at a terminal.
本発明の熱可塑性樹脂組成物及びその成形体は、（Ａ）成分＋（Ｂ）成分＋（Ｃ）成分＝１００重量部に対して他の熱可塑性重合体が１〜５００重量部まで添加されていても良い。添加することが出来る熱可塑性重合体としては、スチレン系樹脂（例えばスチレン単独重合体、ハイインパクトポリスチレン、スチレンメタクリル酸共重合体、耐候性樹脂であるＡＥＳ樹脂、ＡＳＡ樹脂（アクリロニトリル−スチレン−アクリルゴム共重合体）等）、ポリオレフィン系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリアセタール系樹脂、ポリフェニレンエーテル系樹脂、アクリル系樹脂等があげられ、各種相容化剤も使用できる。これらは本発明の目的を損なわない範囲でゴム補強されていてもよい。
また、本発明の熱可塑性樹脂組成物及びその成形体は、（Ａ）成分＋（Ｂ）成分＋（Ｃ）成分＝１００重量部に対してゴム成分を１〜５００重量部まで添加されていても良い。
The thermoplastic resin composition of the present invention and a molded article thereof are obtained by adding 1 to 500 parts by weight of another thermoplastic polymer to 100 parts by weight of the component (A) + the component (B) + the component (C). May be. Examples of the thermoplastic polymer that can be added include styrene resins (for example, styrene homopolymer, high impact polystyrene, styrene methacrylic acid copolymer, AES resin which is a weather resistant resin, ASA resin (acrylonitrile-styrene-acryl rubber). Copolymer)), polyolefin resin, polyamide resin, polyester resin, polyacetal resin, polyphenylene ether resin, acrylic resin, etc., and various compatibilizers can be used. These may be rubber-reinforced as long as the object of the present invention is not impaired.
In addition, the thermoplastic resin composition of the present invention and the molded article thereof have a rubber component added in an amount of 1 to 500 parts by weight based on 100 parts by weight of the component (A) + the component (B) + the component (C). Is also good.
添加することが出来るゴム成分としては、スチレン−ブタジエンランダム共重合体、スチレン−イソプレンランダム共重合体、スチレン−イソプレンブロック共重合体、スチレン−ブタジエンブロック共重合体、水素添加スチレン−イソプレンブロック共重合体（ＳＥＰＳ）、水素添加スチレン−ブタジエンブロック共重合体（ＳＥＢＳ）等の水素添加ブロック共重合体、エチレン−プロピレン共重合体、エチレン−ブチレン共重合体、エチレン−オクテン共重合体等のエチレン−α−オレフィン共重合体（メタロセン触媒によるものが好ましい）などがあげられ（ポリマー構造は問わない）、反応性官能基で変性されたものも含まれる。 また本発明における熱可塑性樹脂組成物及びその成形体には、それ自体公知の各種配合剤、例えば炭酸カルシウム、ケイ酸カルシウム、アパタイト、クレー、層状珪酸塩、カオリン、タルク、シリカ、ケイソウ土、雲母粉、アスベスト、アルミナ、硫酸バリウム、硫酸カルシウム、塩基性炭酸マグネシウム、二硫化モリブデン、グラファイト、ガラス繊維、ガラス球、シラスバルーン、カーボン繊維等の充填剤、カーボンブラック、酸化チタン、酸化亜鉛、酸化スズ、金属微粒子亜鉛華、ベンガラ、群青、紺青、アゾ顔料、ニトロソ顔料、レーキ顔料、フタロシアニン顔料、フェノール系、サルファイト系、フォスファイト系、アミン系等の耐熱安定剤、酸化防止剤、光安定剤、紫外線吸収剤、発泡剤、帯電防止剤、金属石ケン、ワックス等の滑剤、などが配合されていても良い。 Examples of the rubber component that can be added include styrene-butadiene random copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-butadiene block copolymer, and hydrogenated styrene-isoprene block copolymer. Copolymers (SEPS), hydrogenated block copolymers such as hydrogenated styrene-butadiene block copolymers (SEBS), ethylene-propylene copolymers, ethylene-butylene copolymers, ethylene-ethylene copolymers such as ethylene-octene copolymers, etc. α-olefin copolymer (preferably a metallocene catalyst) and the like (regardless of the polymer structure), and those modified with a reactive functional group are also included. The thermoplastic resin composition of the present invention and the molded article thereof include various known additives such as calcium carbonate, calcium silicate, apatite, clay, layered silicate, kaolin, talc, silica, diatomaceous earth, and mica. Powder, asbestos, alumina, barium sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, filler such as carbon fiber, carbon black, titanium oxide, zinc oxide, tin oxide , Metal fine particles zinc white, red iron blue, ultramarine blue, navy blue, azo pigment, nitroso pigment, lake pigment, phthalocyanine pigment, phenolic, sulfite, phosphite, amine-based heat stabilizers, antioxidants, light stabilizers , UV absorber, foaming agent, antistatic agent, metal soap, wax, etc. Lubricant, or the like may be blended.
特に、本発明の熱可塑性樹脂組成物及びその成形体の（Ｂ）成分の結晶性樹脂相に上記フィラー、特にクレー、層状粘度鉱物、層状珪酸塩、シリカ微粒子、アパタイト等をナノオーダーで分散させると、ガスバリア性を向上することができる。
本発明の熱可塑性樹脂組成物は、（Ａ）成分＋（Ｂ）成分＋（Ｃ）成分を、更に要すればこれらに上記他の熱可塑性重合体及び／又は上記各種配合剤を添加し、押出機等の常用の装置で溶融混合して得ることができる。
本発明の熱可塑性樹脂組成物からなる成形体は、射出成形、押出成形、ブロー成形、フィルム成形、シート成形、発泡シート成形、圧縮成形等の通常の成形法により得ることができ、他の樹脂と多層成形しても用いることができる。
本発明のシート、フィルム、発泡成形体は、圧空成形法、真空成形法、プラグアシスト成形法、熱板接触圧空成形法などの公知の方法により、二次成形することができる。
In particular, the filler, in particular, clay, lamellar clay mineral, lamellar silicate, silica fine particles, apatite, and the like are dispersed in the crystalline resin phase of the component (B) of the thermoplastic resin composition of the present invention and the molded product thereof in nano-order. And gas barrier property can be improved.
The thermoplastic resin composition of the present invention comprises (A) component + (B) component + (C) component, and further, if necessary, the above-mentioned other thermoplastic polymer and / or the above-mentioned various compounding agents. It can be obtained by melting and mixing with a conventional device such as an extruder.
The molded article made of the thermoplastic resin composition of the present invention can be obtained by ordinary molding methods such as injection molding, extrusion molding, blow molding, film molding, sheet molding, foamed sheet molding, compression molding, etc. It can be used even if it is multi-layer molded.
The sheet, film, and foam molded article of the present invention can be subjected to secondary molding by a known method such as a pressure forming method, a vacuum forming method, a plug assist forming method, and a hot plate contact pressure forming method.
また、本発明の熱可塑性樹脂組成物及びその成形体は、成形加工性、耐熱性、ガスバリア性に優れる食品包装材、食品容器及びその蓋、建材等に使用される。発泡シート等としても特に有用に用いることができる。窓枠、サッシ枠、敷居、外壁材、床材、内装材、外装材、装飾材、デッキ材、フェンス材、テラス材等の建材；パイプ、雨樋、各種構造材、家具、事務用機器、機械部品、各種装置のハウジング等、バンパー、ガソリンタンク等の自動車材料、道路標識等にも有用に用いられる。
さらに本発明の成形体は、その成形体、成形品を粉砕等して成形することにより容易にリサイクル使用できる。その場合本発明の成形体を再形成することが可能である。
なお、本発明の成形体に塗装、メッキ、シリカコーティング、シリカアルミナコーティング等の二次加工、表面処理をすることも可能である．
Further, the thermoplastic resin composition of the present invention and a molded article thereof are used for food packaging materials, food containers and lids thereof, building materials, and the like which are excellent in moldability, heat resistance, and gas barrier properties. It can be particularly usefully used as a foam sheet or the like. Building materials such as window frames, sash frames, sills, exterior wall materials, flooring materials, interior materials, exterior materials, decorative materials, deck materials, fence materials, terrace materials; pipes, rain gutters, various structural materials, furniture, office equipment, It is also useful for machine parts, housings for various devices, automobile materials such as bumpers and gas tanks, road signs, and the like.
Furthermore, the molded article of the present invention can be easily recycled by pulverizing the molded article or molded article and molding the molded article. In that case, the molded article of the present invention can be reformed.
The molded article of the present invention can be subjected to secondary processing and surface treatment such as painting, plating, silica coating, and silica-alumina coating.
以下実施例により本発明を更に詳しく説明するが、本発明は、これらにより限定されるものではない。
なお、これら実施例および比較例において、各種物性の評価に用いた試験法、原材料は以下の通りである。
１．試験法
（１）（Ｂ）成分の融点、（Ｃ）成分の融解終了温度（Ｔｍｃ）、（Ｂ）成分のΔＨｃ１およびΔＨｍ１の測定
示差走査熱量測定装置（ＤＳＣ：パーキンエルマー社製Ｐｙｒｉｓ１）を用いてＪＩＳ Ｋ７１２１に準じ、昇温速度、降温速度５０Ｋ／分で測定した。
成形体をアルミパンにいれる。その後、装置に設置し、結晶成分の融解終了温度（ＰＡ６を用いた系は２５０℃）以上に一旦昇温したあと、降温、昇温を行い測定を行った。
図３に示したように、（Ｂ）成分の融点、（Ｃ）成分の融解終了温度（Ｔｍｃ）、（Ｂ）成分のΔＨｃ１およびΔＨｍ１を求めた。
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
In these examples and comparative examples, test methods and raw materials used for evaluating various physical properties are as follows.
1. Test method (1) Measurement of melting point of component (B), melting end temperature (Tmc) of component (C), ΔHc1 and ΔHm1 of component (B) Using a differential scanning calorimeter (DSC: Pyris1 manufactured by PerkinElmer) In accordance with JIS K7121, measurement was performed at a heating rate and a cooling rate of 50 K / min.
Put the compact in an aluminum pan. After that, the temperature was set to be higher than the melting end temperature of the crystal component (250 ° C. for a system using PA6) and then lowered and raised to measure.
As shown in FIG. 3, the melting point of the component (B), the melting end temperature (Tmc) of the component (C), and ΔHc1 and ΔHm1 of the component (B) were determined.
（２）ガスバリア性、水蒸気バリア性
ＡＳＴＭ Ｄ１４３４に準拠して、気体透過度試験装置（東洋精機製作所製ＭＣ３：差圧法）を用いて成形体の２３℃の酸素透過係数を測定した。結果を表１に示した。この数値が低いほどガスバリア性が良いと判定できる。
また、ＡＳＴＭ Ｆ１２４９に準拠して、水蒸気透過度試験装置（ＭＯＣＯＮ社製ＰＥＲＭＡＴＲＡＮ−ＷＩＤ：モコン法）を用いて成形体の４０℃／９０％ＲＨの水蒸気透過係数を測定した。この数値が低いほど水蒸気バリア性が良いと判定できる。また、ＪＩＳ Ｚ０２０８に準拠して、市販ガソリンのガソリン透過性試験（カップ法：６０℃）を行い、１００時間後における透過度を測定したこの数値が低いほどガスバリア性が良いと判定できる。
（３）耐熱性
ＲＨＥＯＬＯＧＹ ＣＯ．，ＬＴＤ ＤＶＥ−Ｖ４ ＦＴレオスペクトラーを用いて、Ｅ’の温度依存性を測定した。３０℃におけるＥ’（３０）に対する（Ｃ）成分の融解終了温度（Ｔｍｃ）＋１０℃のＥ’（Ｔｍｃ＋１０）の比、Ｅ’（Ｔｍｃ＋１０）／Ｅ’（３０）を求めた。この数値が低いほど耐熱性が悪いと判定できる。
(2) Gas barrier property and water vapor barrier property According to ASTM D1434, the oxygen permeability coefficient at 23 ° C. of the molded body was measured using a gas permeability tester (MC3 manufactured by Toyo Seiki Seisaku-sho, Ltd .: differential pressure method). The results are shown in Table 1. It can be determined that the lower the value, the better the gas barrier property.
Further, in accordance with ASTM F1249, the water vapor permeability coefficient of the molded product at 40 ° C./90% RH was measured using a water vapor permeability tester (PERMATRAN-WID manufactured by MOCON). It can be determined that the lower the value, the better the water vapor barrier property. Further, a gasoline permeability test (cup method: 60 ° C.) of a commercial gasoline was performed in accordance with JIS Z0208, and the permeability after 100 hours was measured. The lower the value, the better the gas barrier property can be determined.
(3) Heat resistance RHEOLOGY CO. , LTD DVE-V4 FT Rheospectral was used to measure the temperature dependence of E ′. The ratio of the melting end temperature (Tmc) of the component (C) to E ′ (30) at 30 ° C. + E ′ (Tmc + 10) at 10 ° C., E ′ (Tmc + 10) / E ′ (30), was determined. It can be determined that the lower the value is, the lower the heat resistance is.
（４）連続相の観察
成形体（試験片）の断面を切り出し各成分を染色し、電子顕微鏡写真を測定した。得られた電子顕微鏡写真から連続相であるポリアミド系樹脂成分の厚みを測定し、連続相の平均の厚みを求めた。
ポリアミド系樹脂成分を染色する場合はリンタングステン酸染色法を用い、オレフィン系樹脂成分を染色する場合は、ルテニウム酸染色法を用いた。
連続相の厚みの測定：成形体の透過型電子顕微鏡写真（倍率５０００倍、測定視野範囲 横３６μｍ×縦４４μｍ）において、図１に例示するように、写真の短辺と平行に直線を引いた。直線と交差する連続相部分の厚みを測定した。さらに、その直線と平行に６μｍ間隔で複数の直線を引いて、同様に直線と交差する連続相部分の厚みを測定した。連続相部分の厚みとして、９０個以上の厚みを測定した。実施例１では厚みが３００ｎｍ以下のものは４８個あり、１μｍ下のものは８２個、１μｍを超えるものは１２個であった（計測した総数９４個）。全体（９４個）の平均厚みは４４９．８ｎｍであった。１μｍ以下（８２個）の平均厚みは３０８．４ｎｍであった。
他の実施例、比較例においても同様に測定した。
（５）成形加工性
成形条件については、後述する実施例１に記載した。
インフレーションフィルムの成形が行えたものを○、膨らまない、巻き取れないなどの理由でインフレーション成形が行えなかったものを×とした。
(4) Observation of continuous phase A cross section of the molded article (test piece) was cut out, each component was dyed, and an electron micrograph was measured. The thickness of the continuous phase polyamide-based resin component was measured from the obtained electron micrograph, and the average thickness of the continuous phase was determined.
When dyeing a polyamide resin component, a phosphotungstic acid dyeing method was used, and when dyeing an olefin resin component, a ruthenic acid dyeing method was used.
Measurement of the thickness of the continuous phase: As shown in FIG. 1, a straight line was drawn parallel to the short side of a transmission electron micrograph (magnification: 5,000 times, measurement field of view: 36 μm × 44 μm) in a transmission electron micrograph of the molded product. . The thickness of the continuous phase portion crossing the straight line was measured. Further, a plurality of straight lines were drawn at 6 μm intervals in parallel with the straight lines, and the thickness of the continuous phase portion intersecting the straight lines was measured in the same manner. As the thickness of the continuous phase portion, 90 or more thicknesses were measured. In Example 1, 48 had a thickness of 300 nm or less, 82 had a thickness of 1 μm or less, and 12 had a thickness of more than 1 μm (measured 94 in total). The average thickness of the whole (94 pieces) was 449.8 nm. The average thickness of 1 μm or less (82 pieces) was 308.4 nm.
The same measurement was performed in other examples and comparative examples.
(5) Moldability The molding conditions were described in Example 1 described later.
When the inflation film could be formed, it was evaluated as ○, and when the inflation film could not be formed, for example, because it did not swell or could not be rolled up, it was evaluated as x.
２．原材料
［（Ａ）官能基（ｆ）を有する熱可塑性重合体］
水素添加スチレンブタジエンブロック共重合体である旭化成株式会社製タフテックＨ１０５２を５０００ｇ、無水マレイン酸６０ｇ、パーヘキサ２５Ｂ（日本油脂製ラジカル開始剤）、エチルベンゼン１２ｇをヘンシェルミキサーで充分混合したあと、二軸押し出し機を用いて２００℃、２５０ｒｐｍのもと溶融混練した。得られた無水マレイン酸変性水素添加スチレンブタジエンブロック共重合体（表中Ｈ１と略記）の無水マレイン酸付加量は０．５重量％であった。
［（Ｂ）結晶性樹脂］
ポリアミド６（ＰＡ６）：三菱エンジニアリングプラスチック株式会社製ノバミッド１００７Ｊ（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ（０．２１２Ｎ）荷重で測定したメルトフローレート２００ｇ／１０分）（表中１００７Ｊと略記）、１０１３Ｃ（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定したメルトフローレート４３ｇ／１０分）（表中１０１３Ｃと略記）を用いた。
2. Raw material [(A) thermoplastic polymer having functional group (f)]
After 5,000 g of Asahi Kasei Corporation's Tuftec H1052 which is a hydrogenated styrene-butadiene block copolymer, 60 g of maleic anhydride, Perhexa 25B (a radical initiator made by NOF Corporation), and 12 g of ethylbenzene are sufficiently mixed with a Henschel mixer, and then a twin screw extruder is used. Was melt-kneaded at 200 ° C. and 250 rpm. The obtained maleic anhydride-modified hydrogenated styrene-butadiene block copolymer (abbreviated as H1 in the table) had a maleic anhydride addition amount of 0.5% by weight.
[(B) crystalline resin]
Polyamide 6 (PA6): Novamid 1007J manufactured by Mitsubishi Engineering-Plastics Corporation (Melt flow rate 200 g / 10 minutes measured at 250 ° C. and 2.16 Kg (0.212 N) according to JIS K7210) (abbreviated as 1007J in the table) ), 1013C (melt flow rate 43 g / 10 min measured at 250 ° C and a load of 2.16 kg according to JIS K7210) (abbreviated as 1013C in the table).
［（Ｃ）オレフィン系樹脂］
ポリエチレン系樹脂（ＰＥ）：旭化成株式会社製サンテックＦ２２０６（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定したメルトフローレート２．５ｇ／１０分、密度０．９２１ｇ／ｃｍ3 ）（表中Ｆ２２０６と略記）、Ｆ２２２５．４（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定したメルトフローレート１２．１ｇ／１０分、密度０．９２３ｇ／ｃｍ3 ）（表中Ｆ２２２５．４と略記）を用いた。
ポリエチレン系樹脂（ＰＥ）：旭化成株式会社製サンテックＦ１８４（ ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定したメルトフローレート０．１ｇ／１０分、密度０．９５４ｇ／ｃｍ3 ）（表中Ｆ１８４と略記）、同Ｓ３６３（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定したメルトフローレート１．７ｇ／１０分、密度０．９５４ｇ／ｃｍ3 ）（表中Ｓ３６３と略記）、同Ｊ７５１（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定したメルトフローレート３．０ｇ／１０分、密度０．９５２ｇ／ｃｍ3 ）（表中Ｊ７５１と略記）、を用いた。
尚、表中において、
Ｘ：ΔＨｃ１／ΔＨｍ１、
Ｗｂ／Ｗａ：（Ｂ）末端に官能基（ｆ）と反応する成分を有する高分子鎖を含む結晶性樹脂の量（重量部）／（Ａ）官能基（ｆ）を有する熱可塑性重合体の量（重量部）、
ＭＦＲＢ／ＭＦＲＣ：ＪＩＳ Ｋ７２１０に準拠（樹脂の融点＋３０℃以上、２．１６Ｋｇ荷重）して測定した、（Ｂ）成分のメルトフローレート値（ＭＦＲＢ）／（Ｃ）成分のメルトフローレート値（ＭＦＲＣ）、である。
[(C) olefin resin]
Polyethylene resin (PE): Suntech F2206 manufactured by Asahi Kasei Corporation (melt flow rate 2.5 g / 10 min, density 0.921 g / cm 3 measured at 250 ° C. under a load of 2.16 kg according to JIS K7210) (Table) Medium abbreviation F2206), F2225.4 (melt flow rate 12.1 g / 10 min, density 0.923 g / cm 3 measured at 250 ° C. under a load of 2.16 kg according to JIS K7210) (F2225.4 in the table) Abbreviation).
Polyethylene resin (PE): Suntech F184 manufactured by Asahi Kasei Corporation (melt flow rate 0.1 g / 10 min, density 0.954 g / cm 3 measured at 250 ° C. under a load of 2.16 kg according to JIS K7210) (Table) Medium F184) and S363 (melt flow rate 1.7 g / 10 min, density 0.954 g / cm 3 measured at 250 ° C. under a load of 2.16 kg according to JIS K7210) (abbreviated as S363 in the table) J751 (a melt flow rate of 3.0 g / 10 minutes and a density of 0.952 g / cm 3 measured at 250 ° C. and a load of 2.16 kg according to JIS K7210) (abbreviated as J751 in the table) was used.
In the table,
X: ΔHc1 / ΔHm1,
Wb / Wa: (B) Amount (parts by weight) of a crystalline resin containing a polymer chain having a component that reacts with a functional group (f) at the terminal (parts by weight) / (A) of a thermoplastic polymer having a functional group (f) Quantity (parts by weight),
MFRB / MFRC: Melt flow rate value of component (B) / melt flow rate value of component (C) (MFRC), measured in accordance with JIS K7210 (melting point of resin + 30 ° C. or more, load of 2.16 kg). ).
〈実施例１、２および比較例１、２〉
表１の組成の配合物を、２６０℃に設定された同方向回転二軸押出機（４０ｍｍφ、Ｌ／Ｄ＝４７）により溶融混練した後、ストランド状に押出し、ペレタイズした。次に組成物ペレットを２５０℃に設定された押出機に投入し、２５０℃に設定された円形ダイ（リップ厚１ｍｍ、直径１００ｍｍ）を用いてインフレーション成形を行った。得られる円筒形のフィルムの直径を３８２ｍｍ、厚みを７０μｍになるように調整し、フィルムを得た。また、７０μｍのフィルムを成形後引きつづいて、巻き取り速度を調整する以外は同じ条件で、３５μｍのフィルムの作成を行った。得られた７０μｍのフィルムを用いて、ガスバリア試験（酸素透過性）、水蒸気バリア試験、耐熱性試験を行った。結果を表１に示した。
［表中、Ｅ−ｎ（ｎは正の整数）は、１０-nを表わす。］
〈実施例３〜６および比較例３、４〉
表２の組成の配合物を、２６０℃に設定された同方向回転二軸押出機（４０ｍｍφ、Ｌ／Ｄ＝４７）により溶融混練した後、ストランド状に押出し、ペレタイズした。次に組成物ペレットを２６０℃に設定された射出成形機に投入し、射出成形を行った。長さ１０ｃｍ、幅１０ｃｍ、厚み２ｍｍの射出成形品を得た。得られた成形体を用いて、ガスバリア試験（ガソリン透過性）、水蒸気バリア試験、耐熱性試験を行った。結果を表２に示した。
<Examples 1 and 2 and Comparative Examples 1 and 2>
The composition having the composition shown in Table 1 was melt-kneaded by a co-rotating twin-screw extruder (40 mmφ, L / D = 47) set at 260 ° C., extruded into a strand, and pelletized. Next, the composition pellets were put into an extruder set at 250 ° C., and inflation molding was performed using a circular die (lip thickness 1 mm,
[In the table, En (n is a positive integer) represents 10- n . ]
<Examples 3 to 6 and Comparative Examples 3 and 4>
The composition having the composition shown in Table 2 was melt-kneaded by a co-rotating twin-screw extruder (40 mmφ, L / D = 47) set at 260 ° C., extruded into a strand, and pelletized. Next, the composition pellets were charged into an injection molding machine set at 260 ° C. to perform injection molding. An injection molded product having a length of 10 cm, a width of 10 cm, and a thickness of 2 mm was obtained. Using the obtained molded product, a gas barrier test (gasoline permeability), a water vapor barrier test, and a heat resistance test were performed. The results are shown in Table 2.
本発明の熱可塑性樹脂組成物及びその成形体は、成形加工性、耐熱性、ガスバリア性に優れる食品包装材、食品容器及びその蓋、建材、自動車材料等に使用される。 INDUSTRIAL APPLICABILITY The thermoplastic resin composition and the molded article of the present invention are used for food packaging materials, food containers and lids, building materials, automobile materials, and the like, which are excellent in moldability, heat resistance, and gas barrier properties.
Claims (6)
（Ｂ）成分が連続相であり、連続相の平均厚みが２０００ｎｍ以下であることを特徴とする熱可塑性樹脂組成物。 (A) 0.1 to 20 parts by weight of a thermoplastic polymer having a functional group, and (B) 1 to 50 parts by weight of a crystalline resin containing a polymer chain having a component which reacts with the functional group at the terminal. Parts by weight, and (C) 30 to 98.9 parts by weight of the olefin resin,
(B) The thermoplastic resin composition, wherein the component is a continuous phase, and the average thickness of the continuous phase is 2000 nm or less.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008029932A1 (en) * | 2006-09-01 | 2008-03-13 | Toyo Seikan Kaisha, Ltd. | Adsorbable ultrafine metal particle |
| JP2012164665A (en) * | 2004-08-06 | 2012-08-30 | Soc Bic | Fuel supply for fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012164665A (en) * | 2004-08-06 | 2012-08-30 | Soc Bic | Fuel supply for fuel cell |
| WO2008029932A1 (en) * | 2006-09-01 | 2008-03-13 | Toyo Seikan Kaisha, Ltd. | Adsorbable ultrafine metal particle |
| JPWO2008029932A1 (en) * | 2006-09-01 | 2010-01-21 | 東洋製罐株式会社 | Adsorbent metal ultrafine particle-containing resin composition |
| JP4820416B2 (en) * | 2006-09-01 | 2011-11-24 | 東洋製罐株式会社 | Adsorbent containing ultrafine metal particles |
| US8372904B2 (en) | 2006-09-01 | 2013-02-12 | Toyo Seikan Kaisha, Ltd. | Adsorptive ultra-fine metal particles |
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