JP2005112990A - Thermoplastic resin composition and molded form thereof - Google Patents
Thermoplastic resin composition and molded form thereof Download PDFInfo
- Publication number
- JP2005112990A JP2005112990A JP2003348648A JP2003348648A JP2005112990A JP 2005112990 A JP2005112990 A JP 2005112990A JP 2003348648 A JP2003348648 A JP 2003348648A JP 2003348648 A JP2003348648 A JP 2003348648A JP 2005112990 A JP2005112990 A JP 2005112990A
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- JP
- Japan
- Prior art keywords
- weight
- resin composition
- acid
- thermoplastic resin
- polyamide
- 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.)
- Pending
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- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 31
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 21
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 21
- -1 vinyl aromatic compound Chemical class 0.000 claims description 47
- 229920001400 block copolymer Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 12
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000000088 plastic resin Substances 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 description 24
- 239000007789 gas Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000003502 gasoline Substances 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 229920013716 polyethylene resin Polymers 0.000 description 7
- 229920002302 Nylon 6,6 Polymers 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 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
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000005003 food packaging material Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 229920006249 styrenic copolymer Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 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
- 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
- 230000008901 benefit Effects 0.000 description 2
- 238000000071 blow moulding Methods 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
- 238000006243 chemical reaction Methods 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
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000000524 functional group Chemical group 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
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- 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
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 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
- 239000000344 soap Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- FSQQTNAZHBEJLS-OWOJBTEDSA-M (e)-4-amino-4-oxobut-2-enoate Chemical compound NC(=O)\C=C\C([O-])=O FSQQTNAZHBEJLS-OWOJBTEDSA-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
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QTTAWIGVQMSWMV-UHFFFAOYSA-N 3,4-dimethylhexa-1,3-diene Chemical compound CCC(C)=C(C)C=C QTTAWIGVQMSWMV-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
- BLRZZXLJCJKJII-UHFFFAOYSA-N 3-carbamoylbut-3-enoic acid Chemical compound NC(=O)C(=C)CC(O)=O BLRZZXLJCJKJII-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
- OCTVDLUSQOJZEK-UHFFFAOYSA-N 4,5-diethylocta-1,3-diene Chemical compound CCCC(CC)C(CC)=CC=C OCTVDLUSQOJZEK-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-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
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229920008466 Novamid® 1007J Polymers 0.000 description 1
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
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Images
Abstract
Description
本発明は気体／液体バリア性、成形加工性、耐熱性、耐衝撃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。特に、ポリアミド樹脂、オレフィン系樹脂、及び特定の相容化材を所定の比率で配合することにより得られる特定の相構造を有する熱可塑性樹脂組成物及びその成形体に関する。
本発明における気体／液体バリア性とは、水蒸気以外のバリア性をいう。具体的には酸素のバリア性、ガソリンやオイル等無極性溶剤やその蒸気に対するバリア性、エチルアルコールやメチルエチルケトン等の有機溶剤やその蒸気に対するバリア性をいう。
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、少量成分の（Ｂ）が連続相（海）であり、（Ｃ）が分散相（島）である特異な相構造を有する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 gas / liquid barrier properties, molding processability, heat resistance and impact resistance, and a molded product thereof. In particular, the present invention relates to a thermoplastic resin composition having a specific phase structure obtained by blending a polyamide resin, an olefin resin, and a specific compatibilizer in a predetermined ratio, and a molded product thereof.
The gas / liquid barrier property in the present invention refers to a barrier property other than water vapor. Specifically, it refers to barrier properties against oxygen, nonpolar solvents such as gasoline and oil and their vapor, barrier properties against organic solvents such as ethyl alcohol and methyl ethyl ketone, and their vapor.
The thermoplastic resin composition and molded product thereof according to the present invention have a unique morphology in which the morphology is small when (B) is a continuous phase (sea) and (C) is a dispersed phase (island) when observed with an electron microscope. The present invention relates to a thermoplastic resin composition having a phase structure and a molded body thereof.
ポリアミド樹脂は、耐薬品性に優れ且つ酸素バリア性に優れるため食品包装材、食品容器等の分野に使用されている。また、ガソリンやオイル等の耐薬品性、バリア性に優れる為、自動車部品等の分野にも広く使用されている。
しかし、ポリアミド樹脂は、成形温度での溶融張力が小さく、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。
このためポリアミド樹脂の特徴を維持し、成形性を改良する目的でポリオレフィン系樹脂とのアロイ化が検討されている。
ポリアミド樹脂とポリオレフィン系樹脂とのアロイの場合、ポリアミド樹脂の特徴、例えば気体／液体バリア性の機能を最大限発揮するためには、ポリアミド樹脂を連続相（海）、ポリオレフィン系樹脂を分散相（島）とすることが最も好ましい。
このような相構造を持つポリアミド樹脂とポリオレフィン系樹脂とのアロイについては、既に知られている（特許文献１、２、３、４参照）。
Polyamide resins are used in the fields of food packaging materials, food containers and the like because of their excellent chemical resistance and oxygen barrier properties. In addition, since it has excellent chemical resistance and barrier properties such as gasoline and oil, it is widely used in the field of automobile parts.
However, the polyamide resin has a drawback that it has a low melt tension at the molding temperature and is difficult to mold such as a film, a sheet, and a blow.
For this reason, alloying with a polyolefin resin has been studied for the purpose of maintaining the characteristics of the polyamide resin and improving moldability.
In the case of an alloy of a polyamide resin and a polyolefin resin, in order to maximize the characteristics of the polyamide resin, for example, the gas / liquid barrier function, the polyamide resin is a continuous phase (sea) and the polyolefin resin is a dispersed phase ( Island) is most preferable.
An alloy of a polyamide resin having such a phase structure and a polyolefin resin is already known (see Patent Documents 1, 2, 3, and 4).
しかしながら、特許文献１は、単にポリアミド樹脂とポリオレフィン樹脂を特定の溶融粘度条件下で混練したものであるため、機械物性面で充分ではなかった。また、特許文献２では、特定溶融粘度のポリアミド樹脂とジカルボン酸変性ポリオレフィンからなる組成物であるため、熱安定性に劣るという問題点および組成物構成成分の全てが吸湿性の物であり吸湿により気体／液体バリア性が悪くなるという問題点があった。
また、特許文献３、４では多量のポリアミド系樹脂が連続相であるためフィルム、シート、ブロー等の成形が難しく、且つポリアミド組成比が高いためコスト高になるといった問題点があった。
Further, Patent Documents 3 and 4 have a problem in that since a large amount of polyamide-based resin is a continuous phase, it is difficult to form films, sheets, blows, and the like, and the polyamide composition ratio is high, resulting in high costs.
本発明の目的は、本発明は気体／液体バリア性、成形加工性、耐熱性に優れ、特に耐衝撃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である。 An object of the present invention is to provide a thermoplastic resin composition excellent in gas / liquid barrier property, molding processability and heat resistance, and particularly excellent in impact resistance, and a molded product thereof.
本発明者は、この目的を達成すべく鋭意検討した結果、ポリアミド樹脂、オレフィン系樹脂、及び特定の相溶化剤を所定の比率で配合することにより得られる熱可塑性樹脂組成物が、気体／液体バリア性、成形加工性、耐熱性に優れ、且つ高い衝撃強度を有することを見出し、本発明を完成するに至った。
すなわち本発明は、（１）（Ａ）酸変性水添ブロック共重合体０．１〜２５重量％と、（Ｂ）ポリアミド樹脂１〜５０重量％と、（Ｃ）オレフィン系樹脂３０〜９８重量％との３成分よりなり、（Ｂ）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、
As a result of intensive studies to achieve this object, the present inventors have found that a thermoplastic resin composition obtained by blending a polyamide resin, an olefin resin, and a specific compatibilizing agent in a predetermined ratio is a gas / liquid. It has been found that it has excellent barrier properties, molding processability, heat resistance and high impact strength, and has completed the present invention.
That is, the present invention comprises (1) (A) 0.1 to 25% by weight of an acid-modified hydrogenated block copolymer, (B) 1 to 50% by weight of a polyamide resin, and (C) 30 to 98% by weight of an olefin resin. %, The thermoplastic resin composition, wherein (B) is a continuous phase, and the average thickness of the continuous phase is 2000 nm or less,
（２）（Ａ）が、少なくとも１個のビニル芳香族化合物重合体ブロックＳと共役ジエン化合物部分の不飽和度が２０％をこえない程度にまで水添された少なくとも１個のオレフィン化合物を主体とする重合体ブロックＥとからなり、ビニル芳香族化合物の含有量が１０〜６０重量％であるブロック共重合体に、カルボン酸基またはその誘導体を含有する分子単位が該ブロック共重合体１００重量部あたり０．０５〜１０重量部結合した変性ブロック共重合体である熱可塑性樹脂組成物、
（３）（Ａ）、（Ｂ）、（Ｃ）の比率が、各々０．１〜１５重量％、１０〜４０重量％、４５〜８５重量％であることを特徴とする前記（１）〜（２）の熱可塑性樹脂組成物、
（４）前記（１）〜（３）のいずれかに記載の熱可塑性樹脂組成物からなることを特徴とする成形体である。
(2) (A) mainly comprises at least one olefin compound hydrogenated to such an extent that the degree of unsaturation of at least one vinyl aromatic compound polymer block S and the conjugated diene compound portion does not exceed 20%. A block copolymer having a vinyl aromatic compound content of 10 to 60% by weight and a molecular unit containing a carboxylic acid group or a derivative thereof is 100% by weight of the block copolymer. A thermoplastic resin composition which is a modified block copolymer bonded to 0.05 to 10 parts by weight per part,
(3) The ratio of (A), (B), (C) is 0.1 to 15% by weight, 10 to 40% by weight, 45 to 85% by weight, respectively (1) to (2) the thermoplastic resin composition,
(4) A molded article comprising the thermoplastic resin composition according to any one of (1) to (3).
本発明の熱可塑性組成物及びその成形体は、ポリアミド樹脂、オレフィン系樹脂、及び特定の相溶化剤を所定の比率で配合することにより、気体／液体バリア性、成形性、耐熱性、耐衝撃性に優れたものとなる。 The thermoplastic composition of the present invention and the molded product thereof include a polyamide resin, an olefinic resin, and a specific compatibilizing agent in a predetermined ratio, whereby a gas / liquid barrier property, moldability, heat resistance, and impact resistance. Excellent in properties.
本発明の組成物における（Ａ）酸変性水添ブロック共重合体とは、スチレン系共重合体水素添加物を不飽和カルボン酸またはその誘導体により変性したものである。
スチレン系共重合体水素添加物とは、ビニル芳香族−共役ジエンブロック共重合体、ビニル芳香族−共役ジエンランダム共重合体等の水素添加物等が挙げられる。特にビニル芳香族−共役ジエンブロック共重合体を水素添加したものが好ましい。
本発明に使用される、スチレン系共重合体水素添加物はビニル芳香族化合物を主体と
するブロックＳと、共役ジエン化合物部分の不飽和度が２０％を越えない程度にまで水素添加されたオレフィン化合物を主体とする重合体Ｅとからなる。
The (A) acid-modified hydrogenated block copolymer in the composition of the present invention is obtained by modifying a styrene copolymer hydrogenated product with an unsaturated carboxylic acid or a derivative thereof.
Examples of the styrene copolymer hydrogenated product include hydrogenated products such as vinyl aromatic-conjugated diene block copolymers and vinyl aromatic-conjugated diene random copolymers. In particular, a hydrogenated vinyl aromatic-conjugated diene block copolymer is preferred.
The hydrogenated styrenic copolymer used in the present invention is composed of a block S mainly composed of a vinyl aromatic compound and an olefin hydrogenated to such an extent that the unsaturation of the conjugated diene compound portion does not exceed 20%. And a polymer E mainly composed of a compound.
ビニル芳香族化合物を主体とする重合体ブロックＳは、ビニル芳香族化合物と共役ジエン化合物との重量比が１００／０〜５１／４９、好ましくは１００／０〜７０／３０の組成範囲からなる重合体ブロックであり、ビニル芳香族化合物と共役ジエン化合物が共重合した場合、このブロックにおける共役ジエン化合物の分布は、ランダム、テーパー（分子鎖に沿ってモノマー成分が増加または減少するもの）、一部ブロック状またはこれら任意の組合せのいずれでもあってよい。 The polymer block S mainly composed of a vinyl aromatic compound has a weight ratio in which the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 100/0 to 51/49, preferably 100/0 to 70/30. When a vinyl aromatic compound and a conjugated diene compound are copolymerized, the distribution of the conjugated diene compound in this block is random, tapered (in which the monomer component increases or decreases along the molecular chain), and part It can be either in block form or any combination thereof.
また、共役ジエン化合物を主体とする重合体ブロックＥは、ビニル芳香族化合物と共役ジエン化合物との重量比が０／１００〜４９／５１、好ましくは０／１００〜３０／７０の組成範囲からなる重合体ブロックであり、共役ジエン化合物とビニル芳香族化合物が共重合した場合、このブロックにおけるビニル芳香族化合物の分布は、ランダム、テーパー（分子鎖に沿ってモノマー成分が増加または減少するもの）、一部ブロック状またはこれら任意の組合せのいずれであってもよい。ここで供するビニル芳香族化合物としては、スチレン、α−メチルスチレン、ｐ−メチルスチレンやｐ−ターシャリブチルスチレン等のアルキルスチレン、パラメトキシスチレン、ビニルナフタレン等のうちから１種または２種以上が選ばれ、中でもスチレン、ｐ−メチルスチレンが特に好ましい。 The polymer block E mainly composed of a conjugated diene compound has a composition ratio in which the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 0/100 to 49/51, preferably 0/100 to 30/70. When the polymer block is a copolymer of a conjugated diene compound and a vinyl aromatic compound, the distribution of the vinyl aromatic compound in this block is random, tapered (in which the monomer component increases or decreases along the molecular chain), It may be partly in block form or any combination thereof. As the vinyl aromatic compound provided here, one or more of styrene, α-methylstyrene, alkylstyrene such as p-methylstyrene and p-tertiarybutylstyrene, paramethoxystyrene, vinylnaphthalene, and the like may be used. Among them, styrene and p-methylstyrene are particularly preferable.
また共役ジエン化合物としては、ブタジエン、イソプレン、ピペリレン、メチルペンタジエン、フェニルブタジエン、３，４−ジメチル− １，３−ヘキサジエン、４，５−ジエチル−１，３−オ クタジエン等のうちから１種または２種以上が選ばれ、中でもブタジエンおよび／またはイソプレンが特に好ましい。
ビニル芳香族化合物の含有量は、１０〜６０重量％が好ましく、６０重量％を越えると、それ自身樹脂状となり、組成物の耐衝撃性が低いものになってしまう。また、上記ブロック共重合体の分子構造は、直鎖状、分岐状、放射状またはこれらの組合せなどいずれでもよい。そして、ビニル芳香族化合物を主体とする重合体ブロックＳあるいは共役ジエンを主体とするブロックＥのそれぞれは、同一の構造であってもよいし、モノマー成分含有量、それらの分子鎖における分布、ブロックの分子量、ミクロ構造などの各構造が異なるものであってもよい。
As the conjugated diene compound, one or more of butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, etc. Two or more types are selected, and butadiene and / or isoprene are particularly preferable.
The content of the vinyl aromatic compound is preferably 10 to 60% by weight, and if it exceeds 60% by weight, the vinyl aromatic compound itself becomes resinous and the impact resistance of the composition is low. The molecular structure of the block copolymer may be any of linear, branched, radial, or a combination thereof. Each of the polymer block S mainly composed of a vinyl aromatic compound or the block E mainly composed of a conjugated diene may have the same structure, the monomer component content, the distribution in the molecular chain, the block Each structure such as molecular weight and microstructure may be different.
ブロック共重合体の製造法としては、例えば特公昭３６−１９２８６号公報、特公昭４３−１４９７９号公報、特公昭４９−３６９５７号公報などに記載された方法が挙げられる。これらは、炭化水素溶剤中でアニオン重合開始剤として有機リチウム化合物等を用い、ビニル化剤としてジエチルエーテル、テトラヒドロフランの如きエーテル化合物、トリエチルアミン、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラメチルエチレンジアミンの如き第３級アミン、必要に応じカップリング剤としてエポキシ化ダイズ油、四塩化ケイ素の如き多官能性化合物を用い、ビニル芳香族化合物と共役ジエン化合物をブロック共重合する方法であり、直鎖状、分岐状あるいは放射状の構造を有するブロック共重合体として得られる。本発明においては、いかなる重合法で得られたものであっても、上記のものであれば使用可能である。 Examples of the method for producing the block copolymer include the methods described in Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-14979, Japanese Patent Publication No. 49-36957, and the like. These use organolithium compounds as anionic polymerization initiators in hydrocarbon solvents, ether compounds such as diethyl ether and tetrahydrofuran as vinylating agents, triethylamine, N, N, N ′, N′-tetramethylethylenediamine and the like. Tertiary amine, a method of block copolymerizing a vinyl aromatic compound and a conjugated diene compound using a polyfunctional compound such as epoxidized soybean oil or silicon tetrachloride as a coupling agent, if necessary, It is obtained as a block copolymer having a branched or radial structure. In the present invention, any polymer obtained by any polymerization method can be used as long as it is as described above.
上記のスチレン系ブロック共重合体を、公知の方法、例えば、特公昭４２−８７０４号公報に記載の方法で水添することによりスチレン系ブロック共重合体水素添加物は得られる。本発明は、共役ジエン部分の８０％以上を水素添加させることが好ましい。水素添加の割合が高い程、ポリオレフィン系樹脂組成物との相容性が良く、また、熱劣化を受けにくいため、優れた組成物が得られる。水素添加率は、核磁気共鳴装置（ＮＭＲ）を用いた機器分析により分析できる。 A hydrogenated styrene block copolymer can be obtained by hydrogenating the above styrene block copolymer by a known method, for example, the method described in JP-B-42-8704. In the present invention, it is preferable to hydrogenate 80% or more of the conjugated diene moiety. The higher the ratio of hydrogenation, the better the compatibility with the polyolefin resin composition and the less the composition is susceptible to thermal degradation, so that an excellent composition can be obtained. The hydrogenation rate can be analyzed by instrumental analysis using a nuclear magnetic resonance apparatus (NMR).
上記、スチレン系共重合体水素添加物は、次いで、不飽和カルボン酸及びその誘導体から選ばれた少なくとも１種の変性剤との付加反応により変性され、本発明で使用する酸変性水添ブロック共重合体が得られる。変性剤である不飽和カルボン酸及びその誘導体の例としてはマレイン酸、無水マレイン酸、マレイン酸エステル、マレイン酸アミド、マレイン酸イミド、フマル酸、フマル酸エステル、フマル酸アミド、フマル酸イミド、イタコン酸、無水イタコン酸、イタコン酸エステル、イタコン酸アミド、イタコン酸イミド、ハロゲン化マレイン酸、無水ハロゲン化マレイン酸、ハロゲン化マレイン酸エステル、ハロゲン化マレイン酸アミド、ハロゲン化マレイン酸イミド、シス−４−シクロヘキセン−１，２−ジカルボン酸、無水シス−４−シクロヘキセン−１，２−ジカルボン酸、シス−４−シクロヘキセン−１，２−ジカルボン酸エステル、シス−４−シクロヘキセン−１，２−ジカルボン酸アミド、シス−４−シクロヘキセン−１，２−ジカルボン酸イミド、エンド−シス−ビシクロ（２，２，１）−５−ヘプテン−２，３−ジカルボン酸、無水エンド−シス−ビシクロ（２，２，１）−５−ヘプテン−２，３−ジカルボン酸、エンド−シス−ビシクロ（２，２，１）−５−ヘプテン−２，３−ジカルボン酸エステル、エンド−シス−ビシクロ（２，２，１）−５−ヘプテン−２，３−ジカルボン酸アミド、エンド−シス−ビシクロ（２， ２，１）−５−ヘプテン−２，３−ジカルボン酸イミド、アクリル酸、アクリル酸エステル、アクリル酸アミド、メタクリル酸、メタクリル酸エステル及びメタクリル酸アミド等が挙げられる。これらは１種のみならず２種以上混合しても使用できる。これらの中では不飽和ジカルボン酸またはその誘導体が好ましく、とりわけ無水マレイン酸が好ましい。 The hydrogenated styrenic copolymer is then modified by an addition reaction with at least one modifier selected from unsaturated carboxylic acids and derivatives thereof, and the acid-modified hydrogenated block copolymer used in the present invention. A polymer is obtained. Examples of the unsaturated carboxylic acid and its derivatives as modifiers are maleic acid, maleic anhydride, maleic acid ester, maleic acid amide, maleic acid imide, fumaric acid, fumaric acid ester, fumaric acid amide, fumaric acid imide, itacone Acid, itaconic anhydride, itaconic acid ester, itaconic acid amide, itaconic acid imide, halogenated maleic acid, halogenated maleic anhydride, halogenated maleic acid ester, halogenated maleic acid amide, halogenated maleic acid imide, cis-4 -Cyclohexene-1,2-dicarboxylic acid, anhydrous cis-4-cyclohexene-1,2-dicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid ester, cis-4-cyclohexene-1,2-dicarboxylic acid Amido, cis-4-cyclohexene-1,2-dicar Acid imide, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid, anhydrous endo-cis-bicyclo (2,2,1) -5-heptene-2,3- Dicarboxylic acid, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid ester, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid Acid amide, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic imide, acrylic acid, acrylic acid ester, acrylic acid amide, methacrylic acid, methacrylic acid ester, methacrylic acid amide, etc. Is mentioned. These can be used not only by 1 type but by mixing 2 or more types. Among these, unsaturated dicarboxylic acids or derivatives thereof are preferable, and maleic anhydride is particularly preferable.
酸変性水添ブロック共重合体は、基体のスチレン系共重合体水素添加物に上記変性剤を溶液状態または溶融状態において、ラジカル開始剤を使用あるいは使用せずして付加せしめることによって得られる。これら酸変性水添ブロック共重合体の製造方法に関しては、本発明においては特に限定はしないが、得られた酸変性水添ブロック共重合体がゲル等の好ましくない成分を含んだり、その溶融粘度が著しく増大して加工性が悪化したりする製造方法は好ましくない。好ましい方法としては、たとえば押出機中で、ラジカル開始剤存在下で、基体のスチレン系共重合体水素添加物と上記変性剤とを反応させる方法が挙げられる。 The acid-modified hydrogenated block copolymer can be obtained by adding the above modifier to a hydrogenated styrene copolymer of a substrate in a solution state or a molten state with or without using a radical initiator. The method for producing these acid-modified hydrogenated block copolymers is not particularly limited in the present invention, but the obtained acid-modified hydrogenated block copolymer contains an undesirable component such as a gel or its melt viscosity. A manufacturing method in which the processability is remarkably increased and the workability is deteriorated is not preferable. As a preferred method, for example, a method of reacting the hydrogenation product of the styrene copolymer of the substrate with the above modifier in the presence of a radical initiator in an extruder may be mentioned.
酸変性水添ブロック共重合体に含まれるカルボン酸基またはその誘導体基を含有する分子単位の量、即ち不飽和カルボン酸またはその誘導体の付加量は、本発明において使用する酸変性水添ブロック共重合体全体の平均値として、基体のスチレン系共重合体水素添加物１００重量部あたり、０．０５〜１０重量部、より好ましくは０．１〜５重量部である。カルボン酸基またはその誘導体基を含有する分子単位が０．０５重量部未満では、未変性のスチレン系共重合体水素添加物に比して改良効果がほとんど認められず、１０重量部をこえても、それ以下の場合に比してその改良効果が顕著でない。
酸変性水添ブロック共重合体中のカルボン酸基またはその誘導体基を含有する分子単位の含有量は、赤外分光光度計や滴定等による方法により容易に把握することができる。また、本発明においては、使用する酸変性水添ブロック共重合体中の不飽和カルボン酸またはその誘導体の付加量が全体の平均値として上記範囲を満たす範囲内において未変性のスチレン系共重合体水素添加物が含まれていてもよい。前記の様に得られる（Ａ）酸変性水添ブロック共重合体成分は２種類以上を併用しても構わない。
The amount of the molecular unit containing the carboxylic acid group or derivative group thereof contained in the acid-modified hydrogenated block copolymer, that is, the amount of the unsaturated carboxylic acid or derivative thereof added is the same as the acid-modified hydrogenated block copolymer used in the present invention. The average value of the whole polymer is 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight per 100 parts by weight of the hydrogenated styrene copolymer of the base. When the molecular unit containing the carboxylic acid group or its derivative group is less than 0.05 parts by weight, the improvement effect is hardly recognized as compared with the unmodified styrene copolymer hydrogenated product, and the amount exceeds 10 parts by weight. However, the improvement effect is not remarkable as compared with the case of less than it.
The content of molecular units containing a carboxylic acid group or a derivative group thereof in the acid-modified hydrogenated block copolymer can be easily grasped by a method such as infrared spectrophotometry or titration. Further, in the present invention, an unmodified styrenic copolymer within a range in which the amount of the unsaturated carboxylic acid or its derivative added in the acid-modified hydrogenated block copolymer used satisfies the above range as an overall average value. A hydrogenated product may be contained. Two or more kinds of the (A) acid-modified hydrogenated block copolymer component obtained as described above may be used in combination.
好ましいものとしては無水マレイン酸変性スチレン共役ジエンブロック共重合水素添加物があげられる。
本発明の組成物中の（Ａ）の割合は０．１〜２５重量％、好ましくは０．１〜１５重量％である。０．１重量％未満の場合は（Ｂ）との反応または水素結合等の化学的相互作用に基づく界面の接着が不十分となり得られる組成物成形体の耐衝撃性が低くなる場合があり好ましくない。一方、２５重量％を越える場合には（Ａ）、（Ｂ）、（Ｃ）より成る組成物の（Ｂ）、（Ｃ）の相容化が過度に進行する、または（Ａ）と（Ｂ）の反応または水素結合等の化学的相互作用が進み（Ａ）＋（Ｂ）の溶融粘度が高くなる、等の理由により（Ｂ）が連続相を形成することが困難になり、その結果、組成物成形体の耐ガソリン透過性が劣る場合があり好ましくない。
また、（Ａ）の代わりにグラフト変性タイプのポリオレフィン等、例えばポリオレフィンに無水マレイン酸等を付加させたものを使用すると、組成物成形体の耐衝撃性に劣る場合があり好ましくない。
（Ａ）は、（Ｂ）、（Ｃ）の相、及び（Ｂ）、（Ｃ）の界面相に存在することができる。
Preferable examples include maleic anhydride-modified styrene conjugated diene block copolymer hydrogenation products.
The proportion of (A) in the composition of the present invention is 0.1 to 25% by weight, preferably 0.1 to 15% by weight. When the amount is less than 0.1% by weight, the impact resistance of the resulting molded article, which may result in insufficient adhesion at the interface based on the reaction with (B) or chemical interaction such as hydrogen bonding, may be reduced. Absent. On the other hand, when it exceeds 25% by weight, compatibilization of (B) and (C) of the composition comprising (A), (B) and (C) proceeds excessively, or (A) and (B ) Reaction or chemical interaction such as hydrogen bonding proceeds and the melt viscosity of (A) + (B) becomes high, and it becomes difficult for (B) to form a continuous phase. The composition molded article may be inferior in gasoline permeability resistance, which is not preferable.
In addition, it is not preferable to use a graft-modified type polyolefin or the like, for example, a product obtained by adding maleic anhydride or the like to a polyolefin, instead of (A), because the impact resistance of the molded composition may be inferior.
(A) can be present in the phases (B) and (C) and in the interfacial phases (B) and (C).
本発明の組成物における（Ｂ）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。 The (B) polyamide resin in the composition of the present invention is a polyamide resin mainly composed of amino acids, lactams, or diamines and dicarboxylic acids. Specific examples of the constituent components include ε-caprolactam, enantolactam, ω-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and other amino acids, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, and 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, metaxylylenediamine, adipic acid, suberic acid, and azelai There are dicarboxylic acids such as acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and dimer acid.
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。 These constituent components are used for polymerization alone or in the form of a mixture of two or more, 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 (metaxylylenediamine) 6 obtained by polycondensation of diamine and dicarboxylic acid, and also obtained by ring-opening polymerization of lactam. Examples thereof include polyamide 6 and polyamide 12. As polyamide copolymers, polyamide 66/6, polyamide 66/610, polyamide 66/612, polyamide 66 / 6T (T is terephthalic acid component), polyamide 66 / 6I (I is isophthalic acid component), polyamide 6T / 6I Etc. Moreover, the blended material of these polyamide resins is also mentioned. Preferred are polyamide 6 and polyamide MXD6.
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（Ａ）中のカルボン酸基またはその誘導体より成る官能基と反応する成分である。
また（Ｂ）のポリアミド系樹脂は２種以上を併用しても構わない。
本発明の組成物中の（Ｂ）の量は１〜５０重量％、好ましくは１０〜４０重量％である。１重量部未満であると耐熱性、気体／液体バリア性に劣る場合があり好ましくない。５０重量部を超えると、フィルム、シート、ブロー等の成形性が困難になる場合があり好ましくない。
These polyamide resins can be produced by a generally known method. In the case of polyamide, a melt polymerization method is generally carried out, but it may be batch polymerization or continuous polymerization. These polyamide-based resins have an amino group and / or a carboxyl group at the terminal, and this is a component that reacts with a functional group comprising a carboxylic acid group or a derivative thereof in (A).
Further, two or more kinds of the polyamide-based resin (B) may be used in combination.
The amount of (B) in the composition of the present invention is 1 to 50% by weight, preferably 10 to 40% by weight. If it is less than 1 part by weight, the heat resistance and gas / liquid barrier property may be inferior. If it exceeds 50 parts by weight, formability of a film, sheet, blow or the like may become difficult, which is not preferable.
本発明の組成物における（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。
As the (C) olefin resin in the composition of the present invention, a polyethylene resin, a polypropylene resin, or a mixture of a polyethylene resin and a polypropylene resin can be roughly used.
Polyethylene resins 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 monomers and ethylene (EVA) can be used. However, among these, high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE) are particularly preferable because they are available at low cost. These polyethylene resins may be used alone or in combination of two or more.
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、バリアー性の観点から、好ましく、その中でも密度が高いほど剛性、耐薬品性、バリアー性の観点から更に好ましい。
When a polyethylene resin is used as the olefin resin, the density is desirably 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. more desirably 3 or less, it is particularly desirable density 0.91 g / cm 3 or more 0.94 g / cm 3 or less. Even when alone or in combination of two or more, transparency is preferable if the density falls within this range.
Further, polyethylene having a density of 0.94 to 0.97 g / cm 3 is preferable from the viewpoints of rigidity, chemical resistance, and barrier properties, and among them, the higher the density, the more preferable from the viewpoints of 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 resin is used, the thermoplastic resin composition and the molded body obtained in the present invention are excellent in molding processability such as fluidity, mechanical properties such as rigidity, hinge characteristics, vibration characteristics, and rigidity.
Examples of the polypropylene-based resin include homopolypropylene, copolymer resins of propylene and other α-olefins such as ethylene, butene-1, pentene-1, and hexene-1 (including blocks and random). .
The (C) olefin resin used in the present invention includes a polyethylene resin and / or a polypropylene resin as described above, and the polypropylene resin is preferable because it has higher heat resistance than the polyethylene resin. Of these, homopolypropylene resins and block copolymerized polypropylene have the highest heat resistance and are more preferable. Moreover, when the phase which consists of (C) olefin resin exists in a thermoplastic resin composition and the molded object surface, water vapor | steam barrier property will be improved further and it is desirable.
本発明の組成物中の（Ｃ）の量は３０〜９８重量％、好ましくは４５〜８５重量％である。３０重量部未満であると成形性が困難になる場合があり、９８重量部を超えると、耐熱性、気体／液体バリア性が悪化する。
本発明においては（Ｂ）が連続相でなければならない。（Ｂ）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）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）（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）よりなる連続相である。
（Ｂ）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。
The amount of (C) in the composition of the present invention is 30 to 98% by weight, preferably 45 to 85% by weight. If it is less than 30 parts by weight, moldability may be difficult, and if it exceeds 98 parts by weight, heat resistance and gas / liquid barrier properties are deteriorated.
In the present invention, (B) must be a continuous phase. If (B) is not a continuous phase, the target heat resistance and gas barrier properties are not exhibited.
The continuous phase of “(B) is a continuous phase” refers to a phase that is not completely covered with other phases, for example, when it has two-phase separation. In the context of the present invention, a phase that is not completely covered by a phase consisting of (A), (C) (and other polymers) (excluding the thermoplastic resin composition and the surface of the molded body thereof) is (B) It is a continuous phase.
The formation of the continuous phase comprising (B) can be determined from these electron micrographs (for example, TEM).
また、本発明においては、（Ｂ）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。
また、本発明においては（Ｂ）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。
Moreover, in this invention, (B) is a continuous phase and the average thickness of a continuous phase must be 2000 nm or less. Preferably it is 1000 nm or less, More preferably, it is 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 lowered. Deformability deteriorates due to difficulties.
Moreover, in this invention, it is preferable that (B) is a continuous phase, the average thickness of a continuous phase is 2000 nm or less, and the continuous phase part whose thickness is 1000 nm or less is 40% or more. If the continuous phase portion having a thickness of 1000 nm or less is less than 40%, the moldability is deteriorated. Preferably it is 50% or more, more preferably 60% or more, and particularly preferably 70% or more. Moreover, in this invention, it is preferable that the average thickness of the continuous phase part whose thickness is 1000 nm or less is 600 nm or less. If the average thickness of the continuous phase portion having a thickness of 1000 nm or less exceeds 600 nm, the moldability deteriorates. More preferably, it is 500 nm or less, Especially preferably, it is 400 nm or less.
本発明においては、ＪＩＳ Ｋ７２１０に準拠し、（Ｂ）の融点＋３０℃以上１００℃以下、２．１６Ｋｇ荷重で測定した、（Ｂ）のメルトフローレート値（ＭＦＲＢ）と（Ｃ）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）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）の量（Ｗａ重量部）と（Ｂ）の量（Ｗｂ重量部）が以下の式を満たす場合に、（Ｂ）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 value (MFRB) of (B) and the melt flow rate of (C) measured according to JIS K7210, melting point of (B) + 30 ° C. to 100 ° C., 2.16 kg load The ratio of the value (MFRC) (MFRB / MFRC) is preferably 4 or more. If it is less than 4, it is not preferable because it becomes difficult to make (B) the continuous phase and make the thickness of the continuous phase within the scope of the present invention. More preferably, it is 17 or more, and particularly preferably 50 or more.
In addition, when the amount of (A) (Wa parts by weight) and the amount of (B) (Wb parts by weight) satisfy the following formula, (B) is a continuous phase, and the thickness of the continuous phase is within the scope of the present invention. This 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）の結晶化エンタルピー（ΔＨｃ１）と（Ｂ）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。
In the thermoplastic resin composition of the present invention and the molded product thereof, the crystallization enthalpy (ΔHc1) of (B) and the melting enthalpy (ΔHm1) of (B) satisfy the following formula at a temperature exceeding 150 ° C. (ΔHc1 and ΔHm1 can be measured by DSC method).
X = ΔHc1 / ΔHm1
Usually, 0.3 ≦ X, but 0.4 ≦ X is preferable, and 0.5 ≦ X is more preferable. From the viewpoint of heat resistance, the value of X is preferably 0.5 or more, more preferably 0.6 or more, and particularly preferably 0.7 or more.
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）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。
本発明の熱可塑性樹脂組成物及びその成形体は、（Ａ）＋（Ｂ）＋（Ｃ）＝１００重量部に対して他の熱可塑性重合体が１〜１００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。
Moreover, in the thermoplastic resin composition and its molded object of this invention, it is preferable that melting | fusing point of (B) exceeds 150 degreeC. Heat resistance deteriorates that it is 150 degrees C or less. Preferably it is 200 degreeC or more, More preferably, it is 210 degreeC or more.
The thermoplastic resin composition and molded product thereof according to the present invention may have other thermoplastic polymers added to 1 to 100 parts by weight with respect to (A) + (B) + (C) = 100 parts by weight. good. Examples of the thermoplastic polymer that can be added include styrene resins (for example, styrene homopolymer, high impact polystyrene, styrene methacrylic acid copolymer, weather resistant resin, AES resin, ASA resin (acrylonitrile-styrene-acrylic rubber). Copolymer)), polyolefin resins, polyamide resins, polyester resins, polyacetal resins, polyphenylene ether resins, acrylic resins and the like, and various compatibilizers can also be used. These may be reinforced with rubber as long as the object of the present invention is not impaired.
また、本発明の熱可塑性樹脂組成物及びその成形体は、（Ａ）＋（Ｂ）＋（Ｃ）＝１００重量部に対してゴム成分を１〜１００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。
Moreover, the thermoplastic resin composition of this invention and its molded object may add 1-100 weight part of rubber components with respect to (A) + (B) + (C) = 100 weight part.
Examples of rubber components that can be added include styrene butadiene random copolymer, styrene isoprene random copolymer, styrene-isoprene block copolymer, styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer ( SEPS), hydrogenated block copolymers such as hydrogenated styrene-butadiene block copolymer (SEBS), ethylene-α- such as ethylene-propylene copolymer, ethylene-butylene copolymer, ethylene-octene copolymer Examples include olefin copolymers (preferably those based on metallocene catalysts) and the like (polymer structures are not limited), and those modified with reactive functional groups are also included.
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。 Further, the thermoplastic resin composition and the molded body thereof according to the present invention include various compounding agents known per se, such as calcium carbonate, calcium silicate, apatite, clay, layered silicate, kaolin, talc, silica, diatomaceous earth, 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, bengara, ultramarine, bitumen, azo pigment, nitroso pigment, lake pigment, phthalocyanine pigment, phenolic, sulfite, phosphite, amine, etc. heat stabilizer, antioxidant, light stabilizer , 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）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）＋（Ｂ）＋（Ｃ）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、射出プレス成形、押出成形、ブロー成形、インジェクションブロー成形、延伸ブロー成形、回転成形、スラッシュモールド成形、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することもできる。
In particular, when the thermoplastic resin composition of the present invention and the molded product (B) thereof are dispersed in the nano-order, the above-mentioned fillers, especially clay, lamellar viscosity minerals, lamellar silicates, silica fine particles, apatite, etc., improve the gas barrier properties. can do.
The thermoplastic resin composition of the present invention comprises (A) + (B) + (C), and if necessary, the other thermoplastic polymer and / or the above various compounding agents are added to these, and an extruder or the like. It can be obtained by melt mixing with a conventional apparatus.
The molded body made of the thermoplastic resin composition of the present invention includes injection molding, injection press molding, extrusion molding, blow molding, injection blow molding, stretch blow molding, rotational molding, slush molding, film molding, sheet molding, and foam sheet. It can be obtained by ordinary molding methods such as molding and compression molding, and can be multilayer molded with other resins.
本発明の熱可塑性樹脂組成物は、その優れた気体／液体バリア性、耐衝撃性、成形性を活かし、薬液および／またはガス搬送または貯蔵用容器およびその付属部品として好ましく用いることが出来る。薬液やガスとしては例えば、ガソリン、メタノール、エタノール、イソプロピルアルコール、ブタノール、窒素、酸素、二酸化炭素、メタン、プロパン、天然ガス等の気体／液体バリア性が優れていることより、ガソリン燃料タンク、オイル用タンク、その他シャンプー、リンス、液体石鹸等の各種薬剤用ボトル等の薬液保存容器、またはそれらタンク、ボトルに付属するバルブや継手類、ホース等の燃料チューブ接続部品、オイルチューブ接続部品、ブレーキホース接続部品等の自動車材料に有用に用いることが出来る。 The thermoplastic resin composition of the present invention can be preferably used as a chemical solution and / or gas transport or storage container and its accessory parts, taking advantage of its excellent gas / liquid barrier properties, impact resistance, and moldability. Examples of chemicals and gases include gasoline fuel tanks and oils because of their excellent gas / liquid barrier properties such as gasoline, methanol, ethanol, isopropyl alcohol, butanol, nitrogen, oxygen, carbon dioxide, methane, propane, and natural gas. Tanks, other chemical storage containers such as bottles for various chemicals such as shampoos, rinses, liquid soaps, etc., or fuel tube connection parts such as valves and fittings attached to the tanks and bottles, hoses, oil tube connection parts, brake hoses It can be usefully used for automobile materials such as connecting parts.
また、本発明の熱可塑性樹脂組成物は、成形加工性、耐熱性、酸素バリア性、耐衝撃性に優れる食品包装材、食品容器及びその蓋等にも有用に用いることが出来る。
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。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 can be usefully used for food packaging materials, food containers, lids thereof, and the like that are excellent in molding processability, heat resistance, oxygen barrier properties, and impact resistance.
Furthermore, the molded product of the present invention can be easily recycled by pulverizing the molded product or molded product. The molded article of the present invention can be subjected to secondary processing such as painting, plating, silica coating, silica alumina coating, and surface treatment.
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）ガソリン透過度
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。
EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In these Examples and Comparative Examples, test methods and raw materials used for evaluation of various physical properties are as follows.
1. Test method (1) Gasoline permeability According to JIS Z0208, a gasoline permeability test (cup method: 60 ° C) of commercial gasoline was performed, and the permeability after 100 hours was measured. Can be determined.
（２）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。
（３）耐衝撃性
ＪＩＳ Ｋ７１１０に基づき、長さ１１．８ｍｍ、幅１２ｍｍ、厚み３ｍｍの射出成形体を得た。得られた成形体よりアイゾット試験片（ノッチ付き）を作成し試験を行った（単位：ｋｇ・ｃｍ／ｃｍ）。
(2) Heat resistance RHEOLOGY CO. , LTD DVE-V4 FT Rheospectr 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, the worse the heat resistance.
(3) Impact resistance Based on JIS K7110, an injection molded article having a length of 11.8 mm, a width of 12 mm, and a thickness of 3 mm was obtained. An Izod test piece (notched) was prepared from the obtained molded body and tested (unit: kg · cm / cm).
（４）連続相の観察
アイゾット試験片用成形体の断面を切り出しリンタングステン酸染色法／ルテニウム酸染色、あるいはルテニウム酸染色し、超薄切片を作成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。
（５）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、写真の短片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１μｍ下のものは６８個、１μｍを超えるものは４６個であった（計測した総数１１４個）。全体（１１４個）の平均厚みは１０６２ｎｍであった。１μｍ以下（６８個）の平均厚みは３８６ｎｍであった。
他の実施例、比較例においても同様に測定した。
(4) Observation of continuous phase A cross section of a molded article for an Izod test piece was cut out and stained with phosphotungstic acid / ruthenic acid or ruthenium acid, an ultrathin section was prepared, and an electron micrograph was measured. The thickness of the polyamide-based resin component that is a continuous phase was measured from the obtained electron micrograph, and the average thickness of the continuous phase was determined.
(5) Measurement of the thickness of the continuous phase In a transmission electron micrograph of the molded body (magnification 5000 times, measurement field range width 36 μm × length 44 μm), a straight line is drawn parallel to the short piece of the photograph as illustrated in FIG. It was. The thickness of the continuous phase portion intersecting with the straight line was measured. Further, a plurality of straight lines were drawn in parallel with the straight line at intervals of 6 μm, and the thickness of the continuous phase portion that intersected the straight line was measured. As the thickness of the continuous phase portion, 90 or more thicknesses were measured. In Example 1, 68 were those having a thickness of 1 μm or less, and 46 were over 1 μm (a total of 114 measured). The average thickness of all (114 pieces) was 1062 nm. The average thickness of 1 μm or less (68 pieces) was 386 nm.
The same measurement was performed in other examples and comparative examples.
２．原材料
［（Ａ）酸変性水添ブロック共重合］
ビニル芳香族含量２０％、水添率８０％以上の水素添加スチレンブタジエンブロック共重合体を無水マレイン酸で変性した物で、無水マレイン酸含有量が０．４重量％のもの（表中Ｈ１と略記）
ビニル芳香族含量４０％、水添率８０％以上の水素添加スチレンブタジエンブロック共重合体を無水マレイン酸で変性した物で、無水マレイン酸含有量が１．５重量％のもの（表中Ｈ２と略記）
ビニル芳香族含量３０％、水添率８０％以上の水素添加スチレンブタジエンブロック共重合体を無水マレイン酸で変性した物で、無水マレイン酸含有量が０．１重量％のもの（表中Ｈ３と略記）
2. Raw materials [(A) acid-modified hydrogenated block copolymer]
A hydrogenated styrene butadiene block copolymer having a vinyl aromatic content of 20% and a hydrogenation rate of 80% or more, modified with maleic anhydride and having a maleic anhydride content of 0.4% by weight (H1 in the table) (Abbreviation)
A hydrogenated styrene butadiene block copolymer having a vinyl aromatic content of 40% and a hydrogenation rate of 80% or more modified with maleic anhydride and having a maleic anhydride content of 1.5% by weight (in the table, H2 (Abbreviation)
A hydrogenated styrene butadiene block copolymer having a vinyl aromatic content of 30% and a hydrogenation rate of 80% or more modified with maleic anhydride and having a maleic anhydride content of 0.1% by weight (in the table, H3 and (Abbreviation)
［（Ｂ）ポリアミド樹脂］
ポリアミド６（表中１００７Ｊと略記。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、メルトフローレート２００ｇ／１０分（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ（０．２１２Ｎ）荷重で測定）
ポリアミド６（表中１０１３Ｂと略記。宇部興産株式会社製ＵＢＥナイロン１０１３Ｂメルトフローレート４０ｇ／１０分（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定）
[(B) Polyamide resin]
Polyamide 6 (abbreviated as 1007J in the table. Novamid 1007J manufactured by Mitsubishi Engineering Plastics Co., Ltd., melt flow rate 200 g / 10 min (measured according to JIS K7210 at 250 ° C. and 2.16 Kg (0.212 N) load))
Polyamide 6 (abbreviated as 1013B in the table. UBE nylon 1013B manufactured by Ube Industries, Ltd. 1013B melt flow rate 40 g / 10 min (measured in accordance with JIS K7210 at 250 ° C. and 2.16 Kg load)
［（Ｃ）オレフィン系樹脂］
ポリオレフィン系樹脂（表中Ｊ７５１と略記、旭化成株式会社製サンテックＪ７５１、メルトフローレート３．０ｇ／１０分、密度０．９５２ｇ／ｃｍ3（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定））
ポリオレフィン系樹脂（表中Ｂ１６１と略記、旭化成株式会社製サンテックＢ１６１、メルトフローレート２．０ｇ／１０分、密度０．９６６ｇ／ｃｍ3（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定））
ポリオレフィン系樹脂（表中Ｂ８７２Ａと略記、旭化成株式会社製サンテックＢ８７２Ａ、メルトフローレート０．８ｇ／１０分、密度０．９５９ｇ／ｃｍ3（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定））
ポリオレフィン系樹脂（表中Ｆ１８４と略記、旭化成株式会社製サンテックＦ１８４、メルトフローレート０．１ｇ／１０分、密度０．９５４ｇ／ｃｍ3（ＪＩＳ Ｋ７２１０に準拠し、２５０℃、２．１６Ｋｇ荷重で測定））
[(C) Olefin resin]
Polyolefin resin (abbreviated as J751 in the table, Suntec J751 manufactured by Asahi Kasei Corporation, melt flow rate 3.0 g / 10 min, density 0.952 g / cm 3 (measured at 250 ° C., 2.16 kg load according to JIS K7210) ))
Polyolefin resin (abbreviated as B161 in the table, Suntech B161 manufactured by Asahi Kasei Corporation, melt flow rate 2.0 g / 10 min, density 0.966 g / cm 3 (measured at 250 ° C., 2.16 Kg load according to JIS K7210) ))
Polyolefin resin (abbreviated as B872A in the table, Suntech B872A manufactured by Asahi Kasei Corporation, melt flow rate 0.8 g / 10 min, density 0.959 g / cm 3 (measured at 250 ° C., 2.16 Kg load according to JIS K7210) ))
Polyolefin resin (abbreviated as F184 in the table, Suntec F184 manufactured by Asahi Kasei Corporation, melt flow rate 0.1 g / 10 min, density 0.954 g / cm 3 (measured in accordance with JIS K7210 at 250 ° C., 2.16 Kg load) ))
［変性オレフィン系エラストマー］
無水マレイン酸変性ポリエチレン（表中Ｌ６１０１Ｍと略記、日本ポリオレフィン株式会社製アドテックスＬ６１０１Ｍ、メルトフローレート０．７ｇ／１０分（ＪＩＳＫ７２１０）、密度０．９２ｇ／ｃｍ3（ＪＩＳ Ｋ７１１２））
酸変性ポリオレフィン組成物（表中ＨＢ０３０と略記、三井化学株式会社製アドマーＨＢ０３０、メルトフローレート０．２ｇ／１０分（ＡＳＴＭ Ｄ１２３８ １９０℃）、密度０．９５ｇ／ｃｍ3（ＡＳＴＭ Ｄ１５０５））
[Modified olefin elastomer]
Maleic anhydride-modified polyethylene (abbreviated as L6101M in the table, Adtex L6101M manufactured by Nippon Polyolefin Co., Ltd., melt flow rate 0.7 g / 10 min (JIS K7210), density 0.92 g / cm 3 (JIS K7112))
Acid-modified polyolefin composition (abbreviated as HB030 in the table, Admer HB030 manufactured by Mitsui Chemicals, Ltd., melt flow rate 0.2 g / 10 min (ASTM D1238 190 ° C.), density 0.95 g / cm 3 (ASTM D1505))
［実施例１〜７および比較例１〜６］
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（４５ｍｍφ、Ｌ／Ｄ＝３０、混練エレメントのピッチ長＝９ミリ ニーディング部全長＝１８０ミリ 回転数＝２００ｒｐｍ）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。
得られた組成物ペレットを２５０℃に設定された射出成形機に投入し、アイゾット試験片と平板を作成し、各評価を実施した。結果を表１に示す。
[Examples 1-7 and Comparative Examples 1-6]
A composition having the composition shown in Table 1 was subjected to a co-rotating twin screw extruder set at 260 ° C. (45 mmφ, L / D = 30, pitch length of kneading elements = 9 mm, kneading part total length = 180 mm, rotation speed = 200 rpm. ), And then extruded into a strand shape and pelletized.
The obtained composition pellets were put into an injection molding machine set at 250 ° C., Izod test pieces and flat plates were prepared, and each evaluation was performed. The results are shown in Table 1.
本発明の熱可塑性樹脂組成物及びその成形体は、その優れた気体／液体バリア性、耐衝撃性、成形性を活かし、薬液および／またはガス等の各種薬剤用ボトル等の薬液保存容器、またはそれらタンク、ボトルに付属するバルブや継手類、ホース等の燃料チューブ接続部品、オイルチューブ接続部品、ブレーキホース接続部品等の自動車材料、食品包装材、食品容器およびその蓋、建材等に使用される。 The thermoplastic resin composition and molded product thereof according to the present invention, taking advantage of its excellent gas / liquid barrier properties, impact resistance, and moldability, are used for storing chemical solutions such as chemical solutions and / or bottles for various drugs such as gases, or the like. Used in tanks, valves and fittings attached to bottles, fuel tube connection parts such as hoses, oil tube connection parts, brake hose connection parts, and other automotive materials, food packaging materials, food containers and their lids, building materials, etc. .
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| KR101002050B1 (en) * | 2006-05-25 | 2010-12-17 | 주식회사 엘지화학 | Multi-layer article having barrier property |
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