JP2020132850A - Resin composition for molding and molded body - Google Patents
Resin composition for molding and molded body Download PDFInfo
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- JP2020132850A JP2020132850A JP2019150889A JP2019150889A JP2020132850A JP 2020132850 A JP2020132850 A JP 2020132850A JP 2019150889 A JP2019150889 A JP 2019150889A JP 2019150889 A JP2019150889 A JP 2019150889A JP 2020132850 A JP2020132850 A JP 2020132850A
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- 238000000465 moulding Methods 0.000 title claims abstract description 31
- 239000011342 resin composition Substances 0.000 title claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 87
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 229920000098 polyolefin Polymers 0.000 claims abstract description 40
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 isostearyl group Chemical group 0.000 claims description 79
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000003367 polycyclic group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 6
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 60
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 38
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 24
- 150000002430 hydrocarbons Chemical group 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000004594 Masterbatch (MB) Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000010526 radical polymerization reaction Methods 0.000 description 9
- 238000004898 kneading Methods 0.000 description 8
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 8
- 239000012989 trithiocarbonate Substances 0.000 description 8
- RYWGNBFHIFRNEP-UHFFFAOYSA-N (4-benzoylphenyl) 2-methylprop-2-enoate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 RYWGNBFHIFRNEP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 241000408655 Dispar Species 0.000 description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 6
- HNBDRPTVWVGKBR-UHFFFAOYSA-N methyl pentanoate Chemical compound CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 4
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- LTYBJDPMCPTGEE-UHFFFAOYSA-N (4-benzoylphenyl) prop-2-enoate Chemical compound C1=CC(OC(=O)C=C)=CC=C1C(=O)C1=CC=CC=C1 LTYBJDPMCPTGEE-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 3
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 3
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000012987 RAFT agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 238000010550 living polymerization reaction Methods 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- UPPUJFRSINZXTE-UHFFFAOYSA-N (2,2,3,3,4-pentamethylpiperidin-1-yl) 2-methylprop-2-enoate Chemical compound CC1CCN(OC(=O)C(C)=C)C(C)(C)C1(C)C UPPUJFRSINZXTE-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920003355 Novatec® Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- GIIUJJXXMYYQQD-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-1-yl) prop-2-enoate Chemical compound CC1(C)CCCC(C)(C)N1OC(=O)C=C GIIUJJXXMYYQQD-UHFFFAOYSA-N 0.000 description 1
- XMCLXVNPGNYTRE-VOTSOKGWSA-N (2,2,6,6-tetramethylpiperidin-4-yl) (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC1CC(C)(C)NC(C)(C)C1 XMCLXVNPGNYTRE-VOTSOKGWSA-N 0.000 description 1
- KKMCJEPDHKUQRC-UHFFFAOYSA-N (2-benzoylphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1C(=O)C1=CC=CC=C1 KKMCJEPDHKUQRC-UHFFFAOYSA-N 0.000 description 1
- BSUKKOMNQGNSGP-QPJJXVBHSA-N (2e)-2-ethylidenehexanoic acid Chemical compound CCCC\C(=C/C)C(O)=O BSUKKOMNQGNSGP-QPJJXVBHSA-N 0.000 description 1
- FBOKNOQEFIMYLY-RUDMXATFSA-N (2e)-2-ethylideneoctanoic acid Chemical compound CCCCCC\C(=C/C)C(O)=O FBOKNOQEFIMYLY-RUDMXATFSA-N 0.000 description 1
- IMNBHNRXUAJVQE-UHFFFAOYSA-N (4-benzoyl-3-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound OC1=CC(OC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 IMNBHNRXUAJVQE-UHFFFAOYSA-N 0.000 description 1
- LJWQJECMFUGUDV-UHFFFAOYSA-N (4-benzoyl-3-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC(OC(=O)C=C)=CC=C1C(=O)C1=CC=CC=C1 LJWQJECMFUGUDV-UHFFFAOYSA-N 0.000 description 1
- PSZLOSABHFZLDK-VOTSOKGWSA-N (e)-n-(2,2,6,6-tetramethylpiperidin-4-yl)but-2-enamide Chemical compound C\C=C\C(=O)NC1CC(C)(C)NC(C)(C)C1 PSZLOSABHFZLDK-VOTSOKGWSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- XGXDUNRFIKXMCZ-UHFFFAOYSA-N 1-(1-amino-2,2,6,6-tetramethylpiperidin-3-yl)prop-2-en-1-one Chemical compound CC1(C)CCC(C(=O)C=C)C(C)(C)N1N XGXDUNRFIKXMCZ-UHFFFAOYSA-N 0.000 description 1
- GXZPMXGRNUXGHN-UHFFFAOYSA-N 1-ethenoxy-2-methoxyethane Chemical compound COCCOC=C GXZPMXGRNUXGHN-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- HSYTWZQOHWQNAX-UHFFFAOYSA-N 2-(2,2,3,3,4-pentamethylpiperidin-1-yl)prop-2-enoic acid Chemical compound CC1CCN(C(C1(C)C)(C)C)C(=C)C(=O)O HSYTWZQOHWQNAX-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- IKWGMGMZWODWEO-UHFFFAOYSA-N 2-(2-carboxyethylsulfanylcarbothioylsulfanyl)propanoic acid Chemical compound OC(=O)C(C)SC(=S)SCCC(O)=O IKWGMGMZWODWEO-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- DRLRGHZJOQGQEC-UHFFFAOYSA-N 2-(2-methoxypropoxy)propyl acetate Chemical compound COC(C)COC(C)COC(C)=O DRLRGHZJOQGQEC-UHFFFAOYSA-N 0.000 description 1
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- 238000010552 living cationic polymerization reaction Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HNWDFLSODFEDIT-UHFFFAOYSA-N n-(1,2,2,6,6-pentamethylpiperidin-3-yl)prop-2-enamide Chemical compound CN1C(C)(C)CCC(NC(=O)C=C)C1(C)C HNWDFLSODFEDIT-UHFFFAOYSA-N 0.000 description 1
- ZKECVHXIVHRIIA-UHFFFAOYSA-N n-(2,2,6,6-tetramethylpiperidin-1-yl)prop-2-enamide Chemical compound CC1(C)CCCC(C)(C)N1NC(=O)C=C ZKECVHXIVHRIIA-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、紫外線吸収性ポリマーを含有する成形用樹脂組成物に関する。 The present invention relates to a molding resin composition containing an ultraviolet absorbing polymer.
従来から樹脂成形体(以下、成形体という)は、医薬用薬剤や化粧品等の包装材料として使用されていた。医薬用薬剤や化粧品等の内容物は、紫外線で劣化しやすいため、紫外線吸収剤を配合すると、紫外線吸収剤が移行して内容物を汚染する場合があった。
そこで、特許文献1および2では、ポリオレフィン、および紫外線吸収剤を組み込んだ樹脂を含む組成物が開示されている。また、特許文献3では紫外線吸収モノマーを共重合した共重合体が開示されている。
Conventionally, resin molded articles (hereinafter referred to as molded articles) have been used as packaging materials for pharmaceutical drugs and cosmetics. Since the contents of medicinal agents and cosmetics are easily deteriorated by ultraviolet rays, when an ultraviolet absorber is added, the ultraviolet absorbers may migrate and contaminate the contents.
Therefore, Patent Documents 1 and 2 disclose compositions containing polyolefins and resins incorporating an ultraviolet absorber. Further, Patent Document 3 discloses a copolymer obtained by copolymerizing an ultraviolet absorbing monomer.
しかし、ポリオレフィン製の成形体を作製する場合、紫外線吸収剤を組み込んだ樹脂は、ポリオレフィンとの相溶性が悪く、通常の混合では、成形体の強度が保持できなかった。また、紫外線吸収剤を分子に組み込んだ紫外線吸収ポリマーは、低分子量成分に起因するマイグレーションや臭気が問題となっていた。そのため従来の組成物は、ポリオレフィン中で樹脂を合成することでしか所望の相溶性を確保できない問題があった。 However, when a molded product made of polyolefin is produced, the resin incorporating the ultraviolet absorber has poor compatibility with polyolefin, and the strength of the molded product cannot be maintained by ordinary mixing. Further, the ultraviolet absorbing polymer in which the ultraviolet absorber is incorporated into the molecule has a problem of migration and odor due to the low molecular weight component. Therefore, the conventional composition has a problem that a desired compatibility can be secured only by synthesizing a resin in polyolefin.
本発明は、ポリオレフィンとの相溶性が良好で、内容物の紫外線による劣化が少なく、かつ内容物を汚染し難い成形体を作製できる成形用樹脂組成物の提供を目的とする。 An object of the present invention is to provide a molding resin composition capable of producing a molded product having good compatibility with polyolefin, less deterioration of the content due to ultraviolet rays, and less likely to contaminate the content.
本発明の成形用樹脂組成物は、ポリオレフィン(A)、および紫外線吸収性ポリマー(B)を含み、
前記紫外線吸収性ポリマー(B)は、ベンゾフェノン骨格を有する単量体単位、および下記一般式(1)で示す単量体単位を有し、
前記紫外線吸収性ポリマー(B)の重量平均分子量は、5,000〜100,000であり、かつ前記紫外線吸収性ポリマー(B)全体に占める重量平均分子量1,000以下のポリマーは、1%以下である。
The molding resin composition of the present invention contains a polyolefin (A) and an ultraviolet absorbing polymer (B).
The ultraviolet-absorbing polymer (B) has a monomer unit having a benzophenone skeleton and a monomer unit represented by the following general formula (1).
The weight average molecular weight of the ultraviolet absorbing polymer (B) is 5,000 to 100,000, and 1% or less of the polymer having a weight average molecular weight of 1,000 or less in the entire ultraviolet absorbing polymer (B). Is.
一般式(1)
ただし、一般式(1)中、R16は、水素原子又はメチル基を表す。Zは、炭素数が10以上の炭化水素基を表す。 However, in the general formula (1), R 16 represents a hydrogen atom or a methyl group. Z represents a hydrocarbon group having 10 or more carbon atoms.
上記の本発明によれば、ポリオレフィンとの相溶性が良好で、内容物の紫外線による劣化が少なく、かつ内容物を汚染し難い成形体を作製できる成形用樹脂組成物を提供できる。 According to the above invention, it is possible to provide a molding resin composition which has good compatibility with polyolefin, is less deteriorated by ultraviolet rays of the content, and can produce a molded product which is less likely to contaminate the content.
本明細書の成形用樹脂組成物(以下、組成物という)は、ポリオレフィン(A)、および特定構造の単量体単位を有する紫外線吸収性ポリマー(B)(以下、ポリマー(B)ともいう)を含む。なお、単量体は、エチレン性不飽和基含有単量体である。
紫外線吸収性ポリマー(B)は、ポリオレフィン(A)との相溶性が良好であるため、従来のようにポリオレフィン(A)中でポリマーを合成せずに所望の相溶性が得られる。別途、合成した紫外線吸収性ポリマー(B)とポリオレフィン(A)を溶融混練し、所望の形状に成形し、成形体を作製できる。得られた成形体は、例えば、容器として作製すると機械強度が良好で、内容物の汚染を抑制できる。
The molding resin composition (hereinafter, referred to as a composition) of the present specification is an ultraviolet-absorbing polymer (B) having a polyolefin (A) and a monomer unit having a specific structure (hereinafter, also referred to as a polymer (B)). including. The monomer is an ethylenically unsaturated group-containing monomer.
Since the ultraviolet-absorbing polymer (B) has good compatibility with the polyolefin (A), the desired compatibility can be obtained without synthesizing the polymer in the polyolefin (A) as in the conventional case. Separately, the synthesized ultraviolet-absorbing polymer (B) and polyolefin (A) can be melt-kneaded and molded into a desired shape to prepare a molded product. When the obtained molded product is produced as a container, for example, it has good mechanical strength and can suppress contamination of the contents.
<ポリオレフィン(A)>
ポリオレフィン(A)は、組成物の主原料であり、例えば、ポリエチレン、ポリプロピレンポリエチレン、ポリプロピレン、ポリブテン−1、およびポリ−4−メチルペンテン、ならびにこれらの共重合体が挙げられる。
ポリエチレンは、例えば、低密度ポリエチレン、高密度ポリエチレンが挙げられる。
ポリプロピレンは、例えば、結晶性または非晶性ポリプロピンが挙げられる。
これらの共重合体は、例えば、エチレン−プロピレンのランダム、ブロックあるいはグラフト共重合体、α−オレフィンとエチレンあるいはプロピレンの共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸メチル共重合体、エチレン−アクリル酸エチル共重合体およびエチレン−アクリル酸共重合体等が挙げられる。
これらの中でも結晶性または非晶性ポリプロピレン、エチレン−プロピレンのランダム、ブロックあるいはグラフト共重合体が好ましく、プロピレン−エチレンブロック共重合体がより好ましい。また安価で、比重が小さいために成形品を軽量化できる観点からはポリプロピレンが好ましい。
<Polyolefin (A)>
Polyolefin (A) is the main raw material of the composition, and examples thereof include polyethylene, polypropylene polyethylene, polypropylene, polybutene-1, and poly-4-methylpentene, and copolymers thereof.
Examples of polyethylene include low-density polyethylene and high-density polyethylene.
Polypropylene includes, for example, crystalline or amorphous polypropines.
These copolymers include, for example, ethylene-propylene random, block or graft copolymers, α-olefin and ethylene or propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers. , Ethylene-ethyl acrylate copolymer, ethylene-acrylate copolymer and the like.
Among these, crystalline or amorphous polypropylene, ethylene-propylene random, block or graft copolymers are preferable, and propylene-ethylene block copolymers are more preferable. Further, polypropylene is preferable from the viewpoint of being inexpensive and having a small specific gravity, so that the weight of the molded product can be reduced.
ポリオレフィン(A)のメルトフローレイト(MFR)は、1〜100(g/10分)が好ましい。なお、MFRはJISK−7210に準拠して求めた数値である。 The melt flow rate (MFR) of the polyolefin (A) is preferably 1 to 100 (g / 10 minutes). The MFR is a numerical value obtained in accordance with JIS K-7210.
<紫外線吸収性ポリマー(B)>
紫外線吸収性ポリマー(B)は、紫外線を吸収可能な樹脂である。また、紫外線吸収性ポリマー(B)は、樹脂であることで、成形体から内容物へのマイグレーションが抑制される。また、紫外線吸収性ポリマー(B)は、特定構造の単量体単位を有するためオレフィン(A)と相溶性が良好であり、成形体は高い透明性が得られる。
<Ultraviolet absorbing polymer (B)>
The ultraviolet-absorbing polymer (B) is a resin capable of absorbing ultraviolet rays. Further, since the ultraviolet absorbing polymer (B) is a resin, migration from the molded product to the contents is suppressed. Further, since the ultraviolet-absorbing polymer (B) has a monomer unit having a specific structure, it has good compatibility with the olefin (A), and the molded product can obtain high transparency.
より詳しく説明すると、紫外線吸収性ポリマー(B)は、ベンゾフェノン骨格を有する単量体単位、および下記一般式(1)で示す単量体単位を有する。紫外線吸収性ポリマー(B)は、ベンゾフェノン骨格を有する単量体を使用しているため紫外線を吸収できる。特に290nm付近の透過率を抑える効果がある。なお、例えば、ベンゾフェノン骨格を有する単量体単位は、ベンゾフェノン骨格を有する単量体を重合して形成される、ポリマー(B)を構成する構造単位である。 More specifically, the ultraviolet-absorbing polymer (B) has a monomer unit having a benzophenone skeleton and a monomer unit represented by the following general formula (1). Since the ultraviolet-absorbing polymer (B) uses a monomer having a benzophenone skeleton, it can absorb ultraviolet rays. In particular, it has the effect of suppressing the transmittance near 290 nm. For example, the monomer unit having a benzophenone skeleton is a structural unit constituting the polymer (B) formed by polymerizing a monomer having a benzophenone skeleton.
ベンゾフェノン骨格を有する単量体は、ベンゾフェノン骨格とエチレン性不飽和二重結
合を有する化合物であれば、特に限定されない。
ベンゾフェノン骨格を有する単量体は、例えば、4−アクリロイルオキシベンゾフェノン、4−メタクリロイルオキシベンゾフェノン、2−ヒドロキシ−4−アクリロイルオキシベンゾフェノン、2−ヒドロキシ−4−メタクリロイルオキシベンゾフェノン、2−ヒドロキシ−4−(2−アクリロイルオキシ)エトキシベンゾフェノン、2−ヒドロキシ−4−(2−メタクリロイルオキシ)エトキシベンゾフェノン、2−ヒドロキシ−4−(2−メチル−2−アクリロイルオキシ)エトキシベンゾフェノン、2,2’−ジヒドロキシ−4−メタクリロイルオキシベンゾフェノン等が挙げられる。
The monomer having a benzophenone skeleton is not particularly limited as long as it is a compound having an ethylenically unsaturated double bond with the benzophenone skeleton.
The monomer having a benzophenone skeleton is, for example, 4-acryloyloxybenzophenone, 4-methacryloyloxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-4- ( 2-Acryloyloxy) ethoxybenzophenone, 2-hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone, 2-hydroxy-4- (2-methyl-2-acryloyloxy) ethoxybenzophenone, 2,2'-dihydroxy-4 − Examples include methacryloyloxybenzophenone.
ベンゾフェノン骨格を有する単量体は、単独または2種類以上を併用して使用できる。 The monomer having a benzophenone skeleton can be used alone or in combination of two or more.
ベンゾフェノン骨格を有する単量体は、ポリマー(B)を構成する単量体単位中、0.1〜30質量%が好ましく、1〜30質量%がより好ましい。適量含有すると他の物性の低下を抑制しつつ紫外線吸収性がより向上できる。 The monomer having a benzophenone skeleton is preferably 0.1 to 30% by mass, more preferably 1 to 30% by mass, based on the monomer unit constituting the polymer (B). When an appropriate amount is contained, the ultraviolet absorption can be further improved while suppressing the deterioration of other physical properties.
<一般式(1)で示す単量体>
一般式(1)
General formula (1)
式中、R16は、水素原子又はメチル基を表す。Zは、炭素数が10以上の炭化水素基を表す。
一般式(1)で示す単量体のZは、炭素数10以上の炭化水素基であることで、紫外線吸収性ポリマー(B)は、長鎖の疎水性ユニットを有する。これにより紫外線吸収性ポリマー(B)は、主鎖に長鎖の炭化水素鎖を有し、疎水性の高いポリオレフィン(A)との親和性が向上することで両者の相溶性が向上する。なお、Zの炭素数の上限は、ベンゾフェノン骨格を有する単量体と共重合できればよく限定されないところ、強いて挙げれば22以下が好ましく、20以下がより好ましい。
In the formula, R 16 represents a hydrogen atom or a methyl group. Z represents a hydrocarbon group having 10 or more carbon atoms.
The monomer Z represented by the general formula (1) is a hydrocarbon group having 10 or more carbon atoms, and the ultraviolet absorbing polymer (B) has a long-chain hydrophobic unit. As a result, the ultraviolet-absorbing polymer (B) has a long-chain hydrocarbon chain in the main chain, and the affinity with the highly hydrophobic polyolefin (A) is improved, so that the compatibility between the two is improved. The upper limit of the number of carbon atoms of Z is not limited as long as it can be copolymerized with a monomer having a benzophenone skeleton, and is preferably 22 or less, more preferably 20 or less.
一般式(1)中、Zの炭素数10以上の炭化水素基は、直鎖構造、分岐構造、環状構造が挙げられる。
直鎖構造および分岐構造の炭化水素基は、例えば、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基、トリコシル基、テトラコシル基のアルキル基等が挙げられる。
直鎖構造および分岐構造の炭化水素基は、分岐構造が好ましく、イソステアリル基がより好ましい。なお、直鎖構造および分岐構造の炭化水素基の炭素数は、14以上が好ましい。
In the general formula (1), examples of the hydrocarbon group having 10 or more carbon atoms in Z include a linear structure, a branched structure, and a cyclic structure.
The hydrocarbon groups having a linear structure and a branched structure include, for example, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an icosyl group, a henicosyl group, Examples thereof include a docosyl group, a tricosyl group, and an alkyl group of a tetracosyl group.
As the hydrocarbon group having a linear structure and a branched structure, a branched structure is preferable, and an isostearyl group is more preferable. The number of carbon atoms of the hydrocarbon groups having a linear structure and a branched structure is preferably 14 or more.
環状構造の炭化水素基(環状炭化水素基ともいう)は、脂環式炭化水素基、多環式炭化水素基が挙げられる。
脂環式炭化水素基は、例えば、シクロドデシル基等が挙げられる。
多環式炭化水素基は、例えば、イソボルニル基、ジシクロペンタニル基、ジシクロペンテニル基、2−メチル−2−アダマンチル基、2−エチル−2−アダマンチル基等が挙げら
れる。これらの脂環式炭化水素基および多環式炭化水素基は、多環式炭化水素基が好ましく、ジシクロペンタニル基がより好ましい。
Examples of the hydrocarbon group having a cyclic structure (also referred to as a cyclic hydrocarbon group) include an alicyclic hydrocarbon group and a polycyclic hydrocarbon group.
Examples of the alicyclic hydrocarbon group include a cyclododecyl group and the like.
Examples of the polycyclic hydrocarbon group include an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group and the like. As these alicyclic hydrocarbon group and polycyclic hydrocarbon group, a polycyclic hydrocarbon group is preferable, and a dicyclopentanyl group is more preferable.
一般式(1)で示す単量体は、例えば、ラウリル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、ベヘニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、2−メチルー2−アダマンチル(メタ)アクリレート、2−エチルー2−アダマンチル(メタ)アクリレート等が挙げられる。これらの中でも、イソステアリル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、イソボルニル(メタ)アクリレートが好ましく、ジシクロペンタニル(メタ)アクリレートがさらに好ましい。 The monomer represented by the general formula (1) is, for example, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, dicyclopentanyl ( Examples thereof include meta) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, and 2-ethyl-2-adamantyl (meth) acrylate. Among these, isostearyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate are preferable, and dicyclopentanyl (meth) acrylate is more preferable.
一般式(1)で示す単量体は、単独または2種類以上を併用して使用できる。 The monomer represented by the general formula (1) can be used alone or in combination of two or more.
一般式(1)で示す単量体の含有量は、ポリマー(B)を構成する単量体単位中、30〜97質量%が好ましく、40〜80質量%がより好ましい。適量含有することで紫外線吸収性、およびポリオレフィン(A)との相溶性が両立しやすい。 The content of the monomer represented by the general formula (1) is preferably 30 to 97% by mass, more preferably 40 to 80% by mass, based on the monomer unit constituting the polymer (B). By containing an appropriate amount, it is easy to achieve both ultraviolet absorption and compatibility with the polyolefin (A).
単量体単位として、さらに一般式(2)で示す単量体単位を有することが好ましい。これにより紫外線吸収性ポリマー(B)の紫外線吸収性がより向上する。 As the monomer unit, it is preferable to further have the monomer unit represented by the general formula (2). As a result, the ultraviolet absorption of the ultraviolet absorbing polymer (B) is further improved.
一般式(2)
式中、R1は、水素原子又は炭素数1〜8の炭化水素基を表す。R2は、炭素数1〜6のアルキレン基、もしくは-O-R5を表し、R5は、炭素数1〜6のアルキレン基を表す。R3は、水素原子又はメチル基を表す。X1は、水素原子、ハロゲン原子、炭素数1〜8の炭化水素基、炭素数1〜6のアルコキシ基、シアノ基又はニトロ基を表す。 In the formula, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. R 2 represents an alkylene group having 1 to 6 carbon atoms or -O-R 5 , and R 5 represents an alkylene group having 1 to 6 carbon atoms. R 3 represents a hydrogen atom or a methyl group. X 1 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group.
一般式(2)中、炭素数1〜8の炭化水素基は、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の鎖式炭化水素基;シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等の脂環式炭化水素基;フェニル基、トリル基、キシリル基、ベンジル基、フェネチル基等の芳香族炭化水素基等が挙げられる。 In the general formula (2), the hydrocarbon group having 1 to 8 carbon atoms is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, or a heptyl. Chain hydrocarbon groups such as groups and octyl groups; alicyclic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; phenyl group, trill group, xsilyl group, benzyl group, Examples include an aromatic hydrocarbon group such as a phenethyl group.
炭素数1〜6のアルキレン基は、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基等の直鎖状アルキレン基;プロピレン基、2−メチルトリメチレン基、2−メチルテトラメチレン基等の分枝鎖状アルキレン基等が挙げられる。また、上記炭素
数2又は3のアルキレン基は、例えば、これらの中から炭素数2又は3のものが挙げられる。
ハロゲン原子は、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
炭素数1〜6のアルコキシ基は、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基、ヘプトキシ基等が挙げられる。
The alkylene group having 1 to 6 carbon atoms is, for example, a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group or a tetramethylene group; a propylene group, a 2-methyltrimethylene group, a 2-methyltetramethylene group or the like. Examples thereof include a branched alkylene group. Further, as the alkylene group having 2 or 3 carbon atoms, for example, those having 2 or 3 carbon atoms can be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a heptoxy group and the like.
一般式(2)で示す単量体は、例えば、2−[2’−ヒドロキシ−5’−(メタクリロイルオキシメチル)フェニル]−2H−ベンゾトリアゾール、2−[2−ヒドロキシ−5
−[2−(メタクリロイルオキシ)エチル]フェニル]−2H−ベンゾトリアゾール、2−[2’−ヒドロキシ−5’−(メタクリロイルオキシプロピル)フェニル]−2H−ベンゾトリアゾール、2−[2’−ヒドロキシ−3’−tert−ブチル−5’−(メタクリロイルオキシエチル)フェニル]−2H−ベンゾトリアゾール、2−[2’−ヒドロキシ−5’−tert−ブチル−3’−(メタクリロイルオキシエチル)フェニル]−2H−ベンゾトリアゾール、2−〔2’−ヒドロキシ−5’−(β−メタクリロイルオキシエトキシ)−3’−tert−ブチルフェニル〕−4−tert−ブチル−2H−ベンゾトリアゾール等が挙げられる。
The monomer represented by the general formula (2) is, for example, 2- [2'-hydroxy-5'-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5.
-[2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy- 3'-tert-butyl-5'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3'-(methacryloyloxyethyl) phenyl] -2H -Benzotriazole, 2- [2'-hydroxy-5'-(β-methacryloyloxyethoxy) -3'-tert-butylphenyl] -4-tert-butyl-2H-benzotriazole and the like can be mentioned.
一般式(2)で示す単量体は、単独または2種類以上を併用して使用できる。 The monomer represented by the general formula (2) can be used alone or in combination of two or more.
一般式(2)で示す単量体の含有量は、ポリマー(B)を構成する単量体単位中、1〜30質量%が好ましく、5〜25質量%がより好ましい。適量含有することで紫外線吸収性、およびポリオレフィン(A)との相溶性を両立しやすい。 The content of the monomer represented by the general formula (2) is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, based on the monomer unit constituting the polymer (B). By containing an appropriate amount, it is easy to achieve both ultraviolet absorption and compatibility with the polyolefin (A).
紫外線吸収性ポリマー(B)は、一般式(3)で示す単量体単位を有することが好ましい。これにより紫外線吸収性ポリマー(B)の光安定性がより向上する。 The ultraviolet-absorbing polymer (B) preferably has a monomer unit represented by the general formula (3). As a result, the light stability of the ultraviolet absorbing polymer (B) is further improved.
一般式(3)
式中、R9は水素原子またはシアノ基を表し、R10、R11はそれぞれ独立して水素原子
またはメチル基を表し、R12は水素原子または炭化水素基を表し、Y1は酸素原子またはイミノ基を表す。
In the formula, R 9 represents a hydrogen atom or a cyano group, R 10 and R 11 independently represent a hydrogen atom or a methyl group, R 12 represents a hydrogen atom or a hydrocarbon group, and Y 1 represents an oxygen atom or a hydrocarbon group. Represents an imino group.
一般式(3)で示す単量体は、例えば、4−(メタ)アクリロイルオキシ−2,2,6,6−テトラメチルピペリジン、4−(メタ)アクリロイルアミノ−2,2,6,6−テトラメチルピペリジン、ペンタメチルピペリジニルメタクリレート、ペンタメチルピペリジニルアクリレート、4−(メタ)アクリロイルアミノ−1,2,2,6,6−ペンタメチルピペリジン、4−シアノ−4−(メタ)アクリロイルアミノ−2,2,6,6−テトラメチルピペリジン、4−クロトノイルオキシ−2,2,6,6−テトラメチルピペリジン、4−クロトノイルアミノ−2,2,6,6−テトラメチルピペリジン等が挙げられる。 The monomer represented by the general formula (3) is, for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6- Tetramethylpiperidin, pentamethylpiperidinyl methacrylate, pentamethylpiperidinylacrylate, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidin, 4-cyano-4- (meth) acryloyl Amino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, etc. Can be mentioned.
一般式(3)で示す単量体は、単独または2種類以上を併用して使用できる。 The monomer represented by the general formula (3) can be used alone or in combination of two or more.
一般式(3)で示す単量体の含有量は、ポリマー(B)を構成する単量体単位中、1〜30質量%が好ましく、5〜25質量%がより好ましい。適量含有することで光安定性、およびポリオレフィン(A)との相溶性がより向上する。 The content of the monomer represented by the general formula (3) is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, based on the monomer unit constituting the polymer (B). By containing an appropriate amount, photostability and compatibility with polyolefin (A) are further improved.
紫外線吸収性ポリマー(B)は、単量体単位に芳香族ビニル単量体を有することが好ましい。これにより、ポリオレフィン(A)との相溶性がより向上する。芳香族ビニル単量体は、例えば、スチレン、α−メチルスチレン、安息香酸ビニル、ビニルトルエン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、イソプロピルスチレン、ブチルスチレン、ヒドロキシスチレン、メトキシスチレン、ブトキシスチレン、アセトキシスチレン、クロロスチレン、ジクロロスチレン、ブロモスチレン、クロロメチルスチレン、酸性物質により脱保護可能な基(例えばt−Bocなど)で保護されたヒドロキシスチレン等が挙げられる。特に、単量体に芳香族ビニル単量体と多環式炭化水素基を併用することが好ましい。これにより、ポリオレフィン(A)との相溶性がさらに向上する。 The ultraviolet-absorbing polymer (B) preferably has an aromatic vinyl monomer as a monomer unit. As a result, the compatibility with the polyolefin (A) is further improved. Aromatic vinyl monomers include, for example, styrene, α-methylstyrene, vinyl benzoate, vinyltoluene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene. , Chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected by a group deprotectable by an acidic substance (for example, t-Boc) and the like. In particular, it is preferable to use an aromatic vinyl monomer and a polycyclic hydrocarbon group together as the monomer. As a result, the compatibility with the polyolefin (A) is further improved.
芳香族ビニル単量体は、単独または2種類以上を併用して使用できる。 The aromatic vinyl monomer can be used alone or in combination of two or more.
芳香族ビニル単量体の含有量は、ポリマー(B)を構成する単量体単位中、10〜80質量%が好ましく、20〜70質量%がより好ましい。適量含有することでポリオレフィン(A)との相溶性がより向上する。 The content of the aromatic vinyl monomer is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, based on the monomer unit constituting the polymer (B). By containing an appropriate amount, the compatibility with the polyolefin (A) is further improved.
紫外線吸収性ポリマー(B)は、単量体単位にその他単量体単位を含有できる。その他単量体は、これまでに例示した以外の単量体である。 The ultraviolet-absorbing polymer (B) can contain other monomer units in the monomer unit. Other monomers are monomers other than those exemplified so far.
その他単量体は、例えば、(メタ)アクリル酸エステル、クロトン酸エステル、ビニルエステル、マレイン酸ジエステル、フマル酸ジエステル、イタコン酸ジエステル、(メタ)アクリルアミド、ビニルエーテル、ビニルアルコールのエステル、スチレン、(メタ)アクリロニトリル、酸性基含有モノマーが挙げられる。 Other monomers include, for example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth) acrylamide, vinyl ether, vinyl alcohol ester, styrene, (meth). ) Examples include acrylonitrile and an acidic group-containing monomer.
(メタ)アクリル酸エステルは、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n−プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸n−ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸t−ブチルシクロヘキシル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸t−オクチル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸オクタデシル、(メタ)アクリル酸アセトキシエチル、(メタ)アクリル酸フェニル、(メタ)アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸2−メトキシエチル、(メタ)アクリル酸2−エトキシエチル、(メタ)アクリル酸2−(2−メトキシエトキシ)エチル、(メタ)アクリル酸3−フェノキシ−2−ヒドロキシプロピル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸ジエチレングリコールモノメチルエーテル、(メタ)アクリル酸ジエチレングリコールモノエチルエーテル、(メタ)アクリル酸トリエチレングリコールモノメチルエーテル、(メタ)アクリル酸トリエチレングリコールモノエチルエーテル、(メタ)アクリル酸ポリエチレングリコールモノメチルエーテル、(メタ)アクリル酸ポリエチレングリコールモノエチルエーテル、(メタ)アクリル酸β−フェノキシエトキシエチル、(メタ)アクリル酸ノニルフェノキシポリエチレングリコール、(メタ)アクリル酸ジシクロペンテニル、(メタ)アクリル酸ジシクロペンテニルオキシエチル、(メタ)アクリル酸トリフロロエチル、(メタ)アクリル酸オクタフロロペンチル、(メタ)アクリル酸パーフロロオクチルエチル、(メタ)アクリル酸ジシクロペンタニル、(メタ)アクリル酸トリブロモフェニル、(メタ)アクリル酸トリブロモフェニルオキシエチル等が挙げられる。 The (meth) acrylic acid ester is, for example, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, n-butyl (meth) acrylic acid, ( Isobutyl acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, T-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) ) 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, (meth) Benzyl acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, (meth) acrylic Polyethylene Glycolic Acid Monomethyl Ether, (Meta) Polyethylene Glycol Acrylate Monoethyl Ether, (Meta) β-Phenoxyethoxyethyl Acrylic Acid, Nonyl Phenoxy Polyethylene Glycol (Meta) Acrylic Acid, Dicyclopentenyl (Meta) Acrylic Acid, (Meta) Dicyclopentenyloxyethyl acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) acrylic Examples thereof include tribromophenyl acid and tribromophenyloxyethyl (meth) acrylate.
クロトン酸エステルは、例えば、クロトン酸ブチル、及びクロトン酸ヘキシル等が挙げられる。 Examples of the crotonic acid ester include butyl crotonic acid and hexyl crotonic acid.
ビニルエステルは、例えば、ビニルアセテート、ビニルプロピオネート、ビニルブチレート、ビニルメトキシアセテート等が挙げられる。マレイン酸ジエステルは、例えば、マレイン酸ジメチル、マレイン酸ジエチル、及びマレイン酸ジブチル等が挙げられる。 Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate and the like. Examples of the maleic acid diester include dimethyl maleate, diethyl maleate, and dibutyl maleate.
フマル酸ジエステルは、例えば、フマル酸ジメチル、フマル酸ジエチル、及びフマル酸ジブチル等が挙げられる。 Examples of the fumaric acid diester include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.
イタコン酸ジエステルは、例えば、イタコン酸ジメチル、イタコン酸ジエチル、イタコン酸ジブチル等が挙げられる。 Examples of the itaconic acid diester include dimethyl itaconic acid, diethyl itaconic acid, and dibutyl itaconic acid.
(メタ)アクリルアミドは、例えば、(メタ)アクリルアミド、N−メチル(メタ)アクリルアミド、N−エチル(メタ)アクリルアミド、N−プロピル(メタ)アクリルアミド、N−イソプロピル(メタ)アクリルアミド、N−n−ブチルアクリル(メタ)アミド、N−t−ブチル(メタ)アクリルアミド、N−シクロヘキシル(メタ)アクリルアミド、N−(2−メトキシエチル)(メタ)アクリルアミド、N,N−ジメチル(メタ)アクリルアミド、N,N−ジエチル(メタ)アクリルアミド、N−フェニル(メタ)アクリルアミド、N−ベンジル(メタ)アクリルアミド、(メタ)アクリロイルモルホリン、ジアセトンアクリルアミド等が挙げられる。 (Meta) acrylamide includes, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-n-butyl. Acrylic (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N Examples thereof include -diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholin, and diacetoneacrylamide.
ビニルエーテルは、例えば、メチルビニルエーテル、ブチルビニルエーテル、ヘキシルビニルエーテル、及びメトキシエチルビニルエーテル等が挙げられる。 Examples of the vinyl ether include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and the like.
酸性基含有モノマーは、例えば、アクリル酸、メタクリル酸、クロトン酸、α−クロルアクリル酸、けい皮酸等の不飽和モノカルボン酸;マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸、シトラコン酸、無水シトラコン酸、メサコン酸等の不飽和ジカルボン酸またはその酸無水物;3価以上の不飽和多価カルボン酸またはその酸無水物;こはく酸モノ(2−アクリロイロキシエチル)、こはく酸モノ(2−メタクリロイロキシエチル)、フタル酸モノ(2−アクリロイロキシエチル)、フタル酸モノ(2−メタクリロイロキシエチル)等の2価以上の多価カルボン酸のモノ〔(メタ)アクリロイロキシアルキル〕エステル;ω−カルボキシ−ポリカプロラクトンモノアクリレート、ω−カルボキシ−ポリカプロラクトンモノメタクリレート等の両末端カルボキシポリマーのモノ(メタ)アクリレート類等を挙げられる。 Acidic group-containing monomers include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and citraconic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride. , Citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or acid anhydrides thereof; trivalent or higher unsaturated polycarboxylic acids or acid anhydrides thereof; monosuccinate (2-acryloyloxyethyl), Mono- (2-methacryloyloxyethyl) mono-succinic acid (2-methacryloyloxyethyl), mono-mono (2-acryloyloxyethyl) phthalate, mono- (2-methacryloyloxyethyl) monovalent or higher valent carboxylic acids. ) Acryloyloxyalkyl] ester; mono (meth) acrylates of both terminal carboxypolymers such as ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate can be mentioned.
その他単量体は、単独または2種類以上を併用して使用できる。 Other monomers can be used alone or in combination of two or more.
紫外線吸収性ポリマー(B)の合成は、アニオン重合、リビングアニオン重合、カチオ
ン重合、リビングカチオン重合、フリーラジカル重合、及びリビングラジカル重合等が挙げられる。これらの中でもフリーラジカル重合、リビングラジカル重合が好ましい。
Examples of the synthesis of the ultraviolet absorbing polymer (B) include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, living radical polymerization and the like. Of these, free radical polymerization and living radical polymerization are preferable.
フリーラジカル重合は、重合開始剤を使用するのが好ましい。重合開始剤は、例えば、アゾ系化合物、過酸化物が好ましい。アゾ系化合物は、例えば、2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス(2−メチルブチロニトリル)、2、2’−アゾビス(イソ酪酸メチル)、1,1’−アゾビス(シクロヘキサン1−カルボニトリル)、2,2’−アゾビス(2,4−ジメチルバレロニトリル)、2,2’−アゾビス(2,4−ジメチル−4−メトキシバレロニトリル)、ジメチル2,2’−アゾビス(2−メチルプロピオネート)、4,4’−アゾビス(4−シアノバレリック酸)、2,2’−アゾビス(2−ヒドロキシメチルプロピオニトリル)、または2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]等が挙げられる。過酸化物は、例えば、過酸化ベンゾイル、t−ブチルパーベンゾエイト、クメンヒドロパーオキシド、ジイソプロピルパーオキシジカーボネート、ジ−n−プロピルパーオキシジカーボネート、ジ(2−エトキシエチル)パーオキシジカーボネート、t−ブチルパーオキシネオデカノエート、t−ブチルパーオキシビバレート、(3,5,5−トリメチルヘキサノイル)パーオキシド、ジプロピオニルパーオキシド、またはジアセチルパーオキシド等が挙げられる。 For free radical polymerization, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound or a peroxide is preferable. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (methyl isobutyrate), 1,1'. -Azobis (cyclohexane1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl2,2 '-Azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), or 2,2'-azobis [2- (2-Imidazolin-2-yl) propane] and the like can be mentioned. Peroxides include, for example, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate. , T-Butylperoxyneodecanoate, t-Butylperoxyvivarate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
重合開始剤は、単独または2種類以上を併用して使用できる。 The polymerization initiator can be used alone or in combination of two or more.
合成の反応温度は、40〜150℃が好ましく、50〜110℃がより好ましい。反応時間は、3〜30時間が好ましく、5〜20時間がより好ましい。 The reaction temperature of the synthesis is preferably 40 to 150 ° C, more preferably 50 to 110 ° C. The reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.
紫外線吸収性ポリマー(B)の合成は、リビングラジカル重合が好ましい。これにより一般的なラジカル重合に起こる副反応が抑制され、更には、重合の成長が均一に起こる為、容易にブロックポリマーや分子量の揃った樹脂を合成できる。 Living radical polymerization is preferable for the synthesis of the ultraviolet-absorbing polymer (B). As a result, side reactions that occur in general radical polymerization are suppressed, and further, the growth of the polymerization occurs uniformly, so that a block polymer or a resin having a uniform molecular weight can be easily synthesized.
リビングラジカル重合(以下、単に「リビング重合」という)は、例えば、可逆的付加開裂連鎖移動重合(以下、RAFT重合)、原子移動ラジカル重合(以下、ATRP)、ヨウ素化合物を用いたリビング重合、有機テルル化合物を用いたリビング重合(以下、TERP)等の方法が挙げられる。これらの中でも反応操作が容易で重金属を含む化合物を必要としない点でRAFT重合が好ましい。また、RAFT重合に使用するRAFT剤は、紫外線を吸収する効果があるため、紫外線吸収性ポリマーの紫外線吸収性がより向上する。 Living radical polymerization (hereinafter, simply referred to as “living polymerization”) includes, for example, reversible addition cleavage chain transfer polymerization (hereinafter, RAFT polymerization), atom transfer radical polymerization (hereinafter, ATRP), living polymerization using iodine compounds, and organic. Examples thereof include a method such as living polymerization (hereinafter referred to as TERP) using a tellurium compound. Among these, RAFT polymerization is preferable because the reaction operation is easy and a compound containing a heavy metal is not required. Further, since the RAFT agent used for RAFT polymerization has an effect of absorbing ultraviolet rays, the ultraviolet absorption of the ultraviolet absorbing polymer is further improved.
RAFT剤は、連鎖移動効果、および重合開始効果を有する化合物であり、例えば、ジチオベンゾエート型、トリチオカーボネート型、ジチオカルバメート型、およびキサンテート型等、ならびにこれらの前駆体であるジスルフィド型が挙げられる。
ジチオベンゾエート型は、例えば、ジチオ安息香酸2−シアノ−2−プロピル、4−シアノ−4−(チオベンゾイルチオ)ペンタン酸、ベンゾジチオ酸2−フェニル−2−プロピル等が挙げられる。
トリチオカーボネート型は、例えば、4−[(2−カルボキシエチルスルファニルチオカルボニル)スルファニル]−4−シアノペンタン酸、2−{[(2−カルボキシエチル)スルファニルチオカルボニル]スルファニル}プロパン酸、4−シアノ−4−[(ドデシルスルファニルチオカルボニル)スルファニル]ペンタン酸、2−シアノ−2−[(ドデシルスルファニルチオカルボニル)スルファニル]プロパン、2−[(ドデシルスルファニルチオカルボニル)スルファニル]プロパン酸、4−シアノ−4−[(ドデシルスルファニルチオカルボニル)スルファニル]ペンタン酸メチル、2−メチル−2−[(ドデシルスルファニルチオカルボニル)スルファニル]プロパン酸、S,S−ジベンジルトリチオ炭酸、トリチオ炭酸=ビス[4−(アリルオキシカルボニル)ベンジル]、トリチオ炭酸=ビス[4−(2,3−ジヒドロキシプロポキシカルボニル)ベンジル]、トリチオ炭酸=ビス{4−[エチル−(2−アセチルオキシエチル)カルバモイル]ベンジル}、トリチオ炭酸ビス{4−[エチル−(2−ヒドロキシエチル)カルバモイル]ベンジル}、トリチオ炭酸=ビス[4−(2−ヒドロキシエトキシカルボニル)ベンジル]等が挙げられる。
ジチオカルバメート型は、例えば、4−クロロ−3,5−ジメチルピラゾ−ル−1−カルボジチオ酸2'−シアノブタン−2'−イル、3,5−ジメチルピラゾ−ル−1−カルボジチオ酸2'−シアノブタン−2'−イル、3,5−ジメチルピラゾ−ル−1−カルボジチオ酸シアノメチル、N−メチル−N−フェニルジチオカルバミン酸シアノメチル等が挙げられる。
ジスルフィド型としては、ビス(ドデシルスルファニルチオカルボニル)ジスルフィド、ビス(チオベンゾイル)ジスルフィド等が挙げられる。これらはA−Bブロックポリマーの製造に好ましい。
The RAFT agent is a compound having a chain transfer effect and a polymerization initiation effect, and examples thereof include a dithiobenzoate type, a trithiocarbonate type, a dithiocarbamate type, a xanthate type, and the like, and a disulfide type which is a precursor thereof. ..
Examples of the dithiobenzoate type include 2-cyano-2-propyl dithiobenzoate, 4-cyano-4- (thiobenzoylthio) pentanoic acid, 2-phenyl-2-propyl benzodithioate and the like.
The trithiocarbonate type is, for example, 4-[(2-carboxyethyl sulfanylthiocarbonyl) sulfanyl] -4-cyanopentanoic acid, 2-{[(2-carboxyethyl) sulfanylthiocarbonyl] sulfanyl} propanoic acid, 4- Cyan-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, 2-cyano-2-[(dodecylsulfanylthiocarbonyl) sulfanyl] propane, 2-[(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid, 4-cyano -4-[(Dodecylsulfanylthiocarbonyl) sulfanyl] methylpentanoate, 2-methyl-2-[(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid, S, S-dibenzyltrithiocarbonate, trithiocarbonate = bis [4 -(Allyloxycarbonyl) benzyl], trithiocarbonate = bis [4- (2,3-dihydroxypropoxycarbonyl) benzyl], trithiocarbonate = bis {4- [ethyl- (2-acetyloxyethyl) carbamoyl] benzyl}, Examples thereof include trithiocarbonate bis {4- [ethyl- (2-hydroxyethyl) carbamoyl] benzyl} and trithiocarbonate = bis [4- (2-hydroxyethoxycarbonyl) benzyl].
The dithiocarbamate type is, for example, 4-chloro-3,5-dimethylpyrazol-1-carbodithioic acid 2'-cyanobutane-2'-yl, 3,5-dimethylpyrazole-1-carbodithioic acid 2'-cyanobutane-. Examples thereof include cyanomethyl 2,5-dimethylpyrazol-1-carbodithioate and cyanomethyl N-methyl-N-phenyldithiocarbamate.
Examples of the disulfide type include bis (dodecylsulfanilthiocarbonyl) disulfide and bis (thiobenzoyl) disulfide. These are preferred for the production of AB block polymers.
これらの中でも、合成時の反応制御が容易なトリチオカーボネート型化合物が好ましく、4−シアノ−4−[(ドデシルスルファニルチオカルボニル)スルファニル]ペンタン酸、2−シアノ−2−[(ドデシルスルファニルチオカルボニル)スルファニル]プロパン、4−シアノ−4−[(ドデシルスルファニルチオカルボニル)スルファニル]ペンタン酸メチル、トリチオ炭酸ビス{4−[エチル−(2−ヒドロキシエチル)カルバモイル]ベンジル}、ビス(ドデシルスルファニルチオカルボニル)ジスルフィドがより好ましい。 Among these, a trithiocarbonate-type compound whose reaction can be easily controlled during synthesis is preferable, 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, 2-cyano-2-[(dodecylsulfanylthiocarbonyl). ) Sulfanyl] Propane, 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] methylpentanoate, trithiocarbonate bis {4- [ethyl- (2-hydroxyethyl) carbamoyl] benzyl}, bis (dodecylsulfanylthiocarbonyl) ) Disulfide is more preferred.
RAFT剤の使用量は、単量体100質量部に対して、0.1〜10質量部が好ましい。 The amount of the RAFT agent used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the monomer.
紫外線吸収性ポリマー(B)の合成には、有機溶剤を用いることが好ましい。有機溶剤は、例えば、酢酸エチル、酢酸n−ブチル、酢酸イソブチル、トルエン、キシレン、アセトン、ヘキサン、メチルエチルケトン、シクロヘキサノン、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、またはジエチレングリコールモノブチルエーテルアセテート等が挙げられる。 It is preferable to use an organic solvent for the synthesis of the ultraviolet absorbing polymer (B). The organic solvent is, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene. Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like can be mentioned.
有機溶剤は、単独または2種類以上を併用して使用できる。 The organic solvent can be used alone or in combination of two or more.
紫外線吸収性ポリマー(B)の重量平均分子量は、5,000〜100,000が好ましく、6,000〜50,000がより好ましい。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定した数値である。 The weight average molecular weight of the ultraviolet-absorbing polymer (B) is preferably 5,000 to 100,000, more preferably 6,000 to 50,000. The weight average molecular weight is a numerical value measured by gel permeation chromatography (GPC).
本明細書で紫外線吸収ポリマー(B)は、その全体に占める重量平均分子量1,000以下の成分(ポリマー)が1%以下である。これにより、本明細書の組成物を使用して作成する成形体は、マイグレーションを抑制しつつ、良好な紫外線吸収効果が得られる。なお、重量平均分子量1,000以下の成分の量は、紫外線吸収性ポリマー(B)をGPCで測定して得られる重量平均分子量チャートを基に算出する。 In the present specification, the ultraviolet absorbing polymer (B) contains 1% or less of a component (polymer) having a weight average molecular weight of 1,000 or less in the whole. As a result, the molded product produced by using the composition of the present specification can obtain a good ultraviolet absorbing effect while suppressing migration. The amount of the component having a weight average molecular weight of 1,000 or less is calculated based on a weight average molecular weight chart obtained by measuring the ultraviolet absorbing polymer (B) with GPC.
紫外線吸収ポリマー(B)全体に占める重量平均分子量1,000以下の成分を1%以下にする方法としては、例えば、(1)リビングラジカル重合を用いて、分子量分布がシャープなポリマーを合成して、重量平均分子量1,000以下の成分を抑制する方法。(2)紫外線吸収ポリマー(B)溶液に貧溶媒を加えて分液し、重量平均分子量1,000以下の成分を抑制する方法。(3)貧溶媒に紫外線吸収ポリマー(B)溶液を滴下して再沈殿後ろ過、乾燥を行い重量平均分子量1,000以下の成分を抑制する方法等が挙げられる。なお、本明細書において紫外線吸収性ポリマー(B)全体に占める重量平均分子量1,000以下のポリマーを1%以下にする方法は、上記の方法に限定されないことは言うまでもない。 As a method of reducing the component having a weight average molecular weight of 1,000 or less in the entire ultraviolet absorbing polymer (B) to 1% or less, for example, (1) living radical polymerization is used to synthesize a polymer having a sharp molecular weight distribution. , A method for suppressing a component having a weight average molecular weight of 1,000 or less. (2) A method in which a poor solvent is added to a solution of an ultraviolet absorbing polymer (B) to separate the solutions to suppress components having a weight average molecular weight of 1,000 or less. (3) Examples thereof include a method in which a solution of an ultraviolet absorbing polymer (B) is added dropwise to a poor solvent, reprecipitated, filtered, and dried to suppress components having a weight average molecular weight of 1,000 or less. Needless to say, the method for reducing the weight average molecular weight of a polymer having a weight average molecular weight of 1,000 or less to 1% or less in the entire ultraviolet absorbing polymer (B) in the present specification is not limited to the above method.
紫外線吸収性ポリマー(B)の配合量は、ポリオレフィン(A)100質量部に対して、0.01〜10質量部が好ましい。 The blending amount of the ultraviolet absorbing polymer (B) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyolefin (A).
本明細書の組成物は、ワックスを含有できる。 The compositions herein can contain wax.
ワックスは、例えば、ポリエチレンワックス、ポリプロピレンワックス等が挙げられる。ワックスの融点は、50〜180℃が好ましく、80〜170℃がより好ましい。なお、ワックスの融点は、示差走査熱量計を用いて窒素雰囲気下で測定する。 Examples of the wax include polyethylene wax and polypropylene wax. The melting point of the wax is preferably 50 to 180 ° C, more preferably 80 to 170 ° C. The melting point of the wax is measured in a nitrogen atmosphere using a differential scanning calorimeter.
ワックスの数平均分子量は、500〜25,000が好ましく、1,000〜15,000がより好ましい。なお、数平均分子量はJIS K2207:1996(日本工業規格)に準拠して測定した数値である。 The number average molecular weight of the wax is preferably 500 to 25,000, more preferably 1,000 to 15,000. The number average molecular weight is a numerical value measured in accordance with JIS K2207: 1996 (Japanese Industrial Standards).
ワックスの配合量は、ポリオレフィン(A)100質量部に対して、0.1〜10質量部が好ましい。 The blending amount of the wax is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyolefin (A).
本明細書の組成物は、たとえば、紫外線吸収性ポリマー(B)を高濃度で配合したマスターバッチとして製造することが好ましい。マスターバッチは、例えば、紫外線吸収性ポリマー(B)とポリオレフィン(A)を溶融混練し、ペレタイザーを使用してペレット状に製造できる。なお、紫外線吸収性ポリマー(B)の凝集を防ぐため、予め、紫外線吸収性ポリマー(B)とワックスを溶融混練した分散体を作製した後、ポリオレフィン(A)と共に、溶融混錬してマスターバッチを作製することが好ましい。ここで、分散体の作製は、ブレンドミキサーや3本ロールミル等を用いることが好ましい。
紫外線吸収性ポリマー(B)は、成形体が含む相当量を成形時に配合するよりも、一旦、マスターバッチとして着色成形用樹脂組成物に予備分散した後に、希釈樹脂の熱可塑性樹脂と配合(溶融混錬)して所望の成形体を製造すると、紫外線吸収性ポリマー(B)を成形体内に均一に分散しやすくなる。
組成物をマスターバッチとして作製する場合、ポリオレフィン(A)100質量部に対して、紫外線吸収性ポリマー(B)を1〜200質量部配合することが好ましい。マスターバッチ(X)と、成形体の母材樹脂となる希釈用樹脂(Y)との質量比は、X/Y=10/1〜1/100が好ましく、X/Y=1/5〜1/100がより好ましい。この範囲にすると成形品は、良好な光特性が得やすい。
The composition of the present specification is preferably produced as, for example, a masterbatch containing a high concentration of the ultraviolet absorbing polymer (B). The masterbatch can be produced, for example, by melt-kneading the ultraviolet-absorbing polymer (B) and the polyolefin (A) and using a pelletizer to produce pellets. In order to prevent aggregation of the ultraviolet-absorbing polymer (B), a dispersion in which the ultraviolet-absorbing polymer (B) and wax are melt-kneaded in advance is prepared, and then melt-kneaded together with the polyolefin (A) in a masterbatch. It is preferable to prepare. Here, it is preferable to use a blend mixer, a three-roll mill, or the like for producing the dispersion.
The ultraviolet-absorbing polymer (B) is first pre-dispersed in a colored molding resin composition as a masterbatch and then blended (melted) with a thermoplastic resin of a diluted resin, rather than blending a considerable amount contained in the molded product at the time of molding. When a desired molded product is produced by kneading), the ultraviolet-absorbing polymer (B) can be easily uniformly dispersed in the molded product.
When the composition is prepared as a masterbatch, it is preferable to mix 1 to 200 parts by mass of the ultraviolet absorbing polymer (B) with respect to 100 parts by mass of the polyolefin (A). The mass ratio of the master batch (X) to the dilution resin (Y) used as the base resin of the molded product is preferably X / Y = 10/1 to 1/100, and X / Y = 1/5 to 1. / 100 is more preferable. Within this range, the molded product can easily obtain good optical characteristics.
希釈用樹脂は、ポリオレフィンに限定されず、ポリオレフィン(A)と相溶性の良い熱可塑性樹脂を適宜選択して使用できる。 The dilution resin is not limited to polyolefin, and a thermoplastic resin having good compatibility with polyolefin (A) can be appropriately selected and used.
溶融混練は、例えば単軸混練押出機、二軸混練押出機、タンデム式二軸混練押出機等を用が好ましい。溶融混錬温度は、ポリオレフィン(A)の種類により異なるが、通常150〜250℃程度である。 For melt kneading, for example, a single-screw kneading extruder, a twin-screw kneading extruder, a tandem twin-screw kneading extruder, or the like is preferably used. The melt-kneading temperature varies depending on the type of polyolefin (A), but is usually about 150 to 250 ° C.
本明細書の組成物は、さらに酸化防止剤、光安定剤、分散剤等を含むことができる。 The compositions herein can further include antioxidants, light stabilizers, dispersants and the like.
本明細書の成形体は、組成物を含む。具体的には、組成物を成形して作製する。
成形方法は、例えば、押出成形、射出成形、ブロー成形等が挙げられる。押出成形は、例えばコンプレッション成形、パイプ押出成形、ラミネート成形、Tダイ成形、インフレーション成形、溶融紡糸等が挙げられる。
The molded article of the present specification includes a composition. Specifically, it is produced by molding a composition.
Examples of the molding method include extrusion molding, injection molding, blow molding and the like. Examples of the extrusion molding include compression molding, pipe extrusion molding, laminate molding, T-die molding, inflation molding, melt spinning and the like.
成形温度は、希釈樹脂の軟化点によるところ、通常160〜240℃である。 The molding temperature is usually 160 to 240 ° C., depending on the softening point of the diluted resin.
本明細書の成形体は、通常の押出成形よりも成形速度が速い高速押出成形(成形機スクリュー回転数:150rpm程度)や、無剪断領域が長いコンプレッション成形で製造する場合にも配合のばらつきが生じ難い。特に射出成形の約10倍の成形速度である高速コンプレッション成形(生産速度500個/分以上、場合によっては700〜900個/分)においても成形品に配合のばらつきが生じ難く、内容物を汚染し難い。 The molded product of the present specification varies in composition even when it is manufactured by high-speed extrusion molding (molding machine screw rotation speed: about 150 rpm), which has a faster molding speed than normal extrusion molding, or compression molding, which has a long shear-free region. Hard to occur. In particular, even in high-speed compression molding (production speed of 500 pieces / minute or more, in some cases 700 to 900 pieces / minute), which is about 10 times faster than injection molding, it is difficult for the molded product to vary in composition and contaminate the contents. It's hard to do.
本明細書の成形体の製造方法の1例としてコンプレッション成形の説明をする。まず、本発明の着色成形用樹脂組成物を溶融混合し、圧縮成型機に投入し、当該圧縮成型機内で剪断力を加えず、圧縮による押し出す力を加えることで成型品を得る工程を含む、成型品の製造方法である。ここで剪断力を加えず、圧縮による押し出す力を加えることは、着色成形用樹脂組成物には混合する力が加わっていない状態、すなわち無剪断領域に着色成形用樹脂組成物が存在している。なお本発明で成型品は型に樹脂を投入し物品を得るものである。また成形品は、プラスチックフィルムなど型を使用せずに得た物品と成型品を含むものである。 Compression molding will be described as an example of the method for producing a molded product of the present specification. First, it comprises a step of melt-mixing the resin composition for coloring molding of the present invention, putting it into a compression molding machine, and obtaining a molded product by applying a pushing force by compression without applying a shearing force in the compression molding machine. This is a method for manufacturing a molded product. Here, applying a pressing force by compression without applying a shearing force means that the colored molding resin composition exists in a state where no mixing force is applied to the colored molding resin composition, that is, in the shear-free region. .. In the present invention, the molded product is obtained by putting a resin into a mold to obtain an article. Further, the molded product includes an article obtained without using a mold such as a plastic film and a molded product.
本明細書の成形品は、例えば、医療用薬剤、化粧品、食品用容器および包装材、雑貨、繊維製品、医薬品用容器、各種産業用被覆材、自動車用部品、家電製品、住宅等の建材、トイレタリー用品などの用途で幅広く使用できる。 The molded products described in the present specification include, for example, medical agents, cosmetics, food containers and packaging materials, miscellaneous goods, textile products, pharmaceutical containers, various industrial coating materials, automobile parts, home appliances, building materials for houses, etc. It can be widely used for toiletry products.
以下、本発明をさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。なお、「質量部」は、「部」、「質量%」は「%」と記載する。 Hereinafter, the present invention will be described in more detail, but the present invention is not limited to these examples. In addition, "part by mass" is described as "part", and "mass%" is described as "%".
(分子量)
数平均分子量(Mn)、重量平均分子量(Mw)は、RI検出器を装備したゲルパーミエーションクロマトグラフィー(GPC)で測定した。装置としてHLC−8320GPC(東ソー社製)を用い、分離カラムを2本直列に繋ぎ、両方の充填剤には「TSK−GEL SUPER HZM−N」を2連でつなげて使用し、オーブン温度40℃、溶離液としてTHF溶液を用い、流速0.35ml/minで測定した。サンプルは1wt%の
上記溶離液からなる溶剤に溶解し、20マイクロリットル注入した。分子量はいずれもポリスチレン換算値である。
(Molecular weight)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is connected in two for both fillers, and the oven temperature is 40 ° C. , THF solution was used as an eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected in 20 microliters. All molecular weights are polystyrene-equivalent values.
実施例で使用したポリオレフィンを以下に示す。
(A−1)ポリエチレン(サンテックLD M2270、MFR=7g/10min、旭化成ケミカルズ社製)
(A−2)ポリエチレン(ノバテックUJ790、MFR=50g/10min、日本ポリエチレン社製)
(A−3)ポリプロピレン(ノバテックPP FA3EB、MFR=10.5g/10min、日本ポリプロ社製)
(A−4)ポリプロピレン(プライムポリプロJ226T、MFR=20g/10min、プライムポリマー社製)
(A−5)ポリエチレン(エボリューH SP65051B、MFR= 0.45g/10min、プライムポリマー社製)
The polyolefins used in the examples are shown below.
(A-1) Polyethylene (Suntech LD M2270, MFR = 7g / 10min, manufactured by Asahi Kasei Chemicals)
(A-2) Polyethylene (Novatec UJ790, MFR = 50g / 10min, manufactured by Japan Polyethylene Corporation)
(A-3) Polypropylene (Novatec PP FA3EB, MFR = 10.5g / 10min, manufactured by Japan Polypropylene Corporation)
(A-4) Polypropylene (Prime Polypro J226T, MFR = 20g / 10min, manufactured by Prime Polymer Co., Ltd.)
(A-5) Polyethylene (Evolu H SP65051B, MFR = 0.45 g / 10 min, manufactured by Prime Polymer Co., Ltd.)
また実施例で使用したワックスを以下に示す。
(D−1)ポリエチレンワックス(サンワックス131−P 平均分子量3500、融点105℃、三洋化成工業社製)
(D−2)ポリエチレンワックス(ハイワックス405MP 平均分子量4500、融点120℃、三井化学社製)
(D−3)ポリプロピレンワックス(ハイワックスNP056 数平均分子量7200、融点130℃、三井化学社製)
The wax used in the examples is shown below.
(D-1) Polyethylene wax (Sunwax 131-P average molecular weight 3500, melting point 105 ° C, manufactured by Sanyo Chemical Industries, Ltd.)
(D-2) Polyethylene wax (High wax 405MP, average molecular weight 4500, melting point 120 ° C., manufactured by Mitsui Chemicals, Inc.)
(D-3) Polypropylene wax (High wax NP056, number average molecular weight 7200, melting point 130 ° C, manufactured by Mitsui Chemicals, Inc.)
[紫外線吸収性ポリマー(B)の製造例]
<製造例1(ポリマーB−1)>
温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコに、メチルエチルケトン61.4部を仕込み窒素気流下で75℃に昇温した。別途、4−メタクリロイルオキシベンゾフェノン(MCCユニテック社製、MBP)を5.0部、一般式(1)で示す単量体としてジシクロペンタニルメタクリレート(日立化成社製、FA−513M)を47.5部、スチレンを47.5部、2,2’−アゾビス(イソ酪酸メチル)を10.0部、およびメチルエチルケトン75.0部を均一に混合した後、滴下ロートに仕込んだ。次いで滴下ロートの内容物を2時間かけて滴下した。滴下終了後、2時間反応を継続した。その後、サンプリングを行い重合収率が98%以上である事を確認し、メチルエチルケトンで不揮発分が35%になるように希釈し、室温に冷却し、樹脂溶液b−1を得た。
次に温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコにメチルエチルケトン500部、メタノール500部を仕込んでおき、ディスパーで1,000回転させたところに上記樹脂溶液b−1、250部を1時間かけて滴下した。生成してきた白色沈殿物をろ過で取出し、真空乾燥機で50℃12時間乾燥し、ポリマー(B−1)を得た。
[Production example of ultraviolet-absorbing polymer (B)]
<Production Example 1 (Polymer B-1)>
61.4 parts of methyl ethyl ketone was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 5.0 parts of 4-methacryloyloxybenzophenone (MBP, manufactured by MCC Unitech) and dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) as a monomer represented by the general formula (1) were added to 47. After uniformly mixing 5 parts, 47.5 parts of styrene, 10.0 parts of 2,2'-azobis (methyl isobutyrate), and 75.0 parts of methyl ethyl ketone, the mixture was charged into a dropping funnel. Then, the contents of the dropping funnel were dropped over 2 hours. After completion of the dropping, the reaction was continued for 2 hours. Then, sampling was performed to confirm that the polymerization yield was 98% or more, diluted with methyl ethyl ketone so that the non-volatile content was 35%, and cooled to room temperature to obtain a resin solution b-1.
Next, 500 parts of methyl ethyl ketone and 500 parts of methanol were placed in a four-neck separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, and the resin solution b-1 was rotated 1,000 times with a dispar. , 250 parts were added dropwise over 1 hour. The white precipitate formed was taken out by filtration and dried in a vacuum dryer at 50 ° C. for 12 hours to obtain a polymer (B-1).
<製造例2,3,5,9>
単量体の種類と量を表1の通り変更した以外は、製造例1と同様に合成し、ポリマー(B−2、B−3,B−5,B−9)を得た。
<Manufacturing Examples 2, 3, 5, 9>
Polymers (B-2, B-3, B-5, B-9) were obtained by synthesizing in the same manner as in Production Example 1 except that the type and amount of the monomer were changed as shown in Table 1.
<製造例4>
単量体の種類と量を表1の通り変更し、樹脂溶液b−4を得た。不揮発分35%のb−4、250部にアセトン250部を添加し、ディスパーで1,000回転で30分間攪拌したあと、攪拌を止め、1時間放置すると2層に分かれた。下層の樹脂層を取出し、メチルエチルケトンで35%に希釈し、樹脂溶液b−4‘を得た。
得られた樹脂溶液を真空乾燥機で50℃12時間乾燥し、ポリマー(B−4)を得た。
<Manufacturing example 4>
The type and amount of the monomer were changed as shown in Table 1 to obtain a resin solution b-4. 250 parts of acetone was added to 250 parts of b-4 having a non-volatile content of 35%, and the mixture was stirred with Dispar at 1,000 rpm for 30 minutes, and then the stirring was stopped and left for 1 hour to separate into two layers. The lower resin layer was taken out and diluted with methyl ethyl ketone to 35% to obtain a resin solution b-4'.
The obtained resin solution was dried in a vacuum dryer at 50 ° C. for 12 hours to obtain a polymer (B-4).
<製造例6>
温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコにメチルエチルケトン250部、メタノール250部を仕込んでおき、ディスパーで1,000回転させたところに製造例4で得られた樹脂溶液b−4‘、125部を1時間かけて滴下した。生成してきた白色沈殿物をろ過で取出し、真空乾燥機で50℃12時間乾燥し、ポリマー(B−6)を得た。
<Manufacturing example 6>
The resin obtained in Production Example 4 was prepared by charging 250 parts of methyl ethyl ketone and 250 parts of methanol into a four-necked separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, and rotating the flask 1,000 times with a dispar. 125 parts of the solution b-4'was added dropwise over 1 hour. The white precipitate formed was taken out by filtration and dried in a vacuum dryer at 50 ° C. for 12 hours to obtain a polymer (B-6).
<製造例7,12>
単量体の種類と量を表1の通り変更し、製造例4,6と同様の操作を行いポリマー(B−7、B−12)を得た。
<Manufacturing Examples 7 and 12>
The types and amounts of the monomers were changed as shown in Table 1, and the same operations as in Production Examples 4 and 6 were carried out to obtain polymers (B-7, B-12).
<製造例8>
温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコに、メチルエチルケトン38.0部、4−メタクリロイルオキシベンゾフェノンを3.0部、一般式(1)で示す単量体としてジシクロペンタニルメタクリレートを41.0部、スチレンを41.0部、一般式(2)で示す単量体として2−[2−ヒドロキシ−5−[2−(メタク
リロイルオキシ)エチル]フェニル]−2H−ベンゾトリアゾール(大塚化学社製、RUVA−93)を15.0部、チオグリコール酸オクチル(淀化学社製、OTG)を2.0gを仕込み窒素気流下で75℃に昇温した。そこに2,2’−アゾビス(イソ酪酸メチル)を1.0部、チオグリコール酸オクチル(淀化学社製、OTG)を2.0gおよびメチルエチルケトン17.0部を8時間かけて滴下した。滴下終了後、2時間反応を継続した。その後、サンプリングを行い重合収率が98%以上である事を確認し、メチルエチルケトンで希釈し、不揮発分35%の樹脂溶液b−8を得た。b−8、250部にアセトン250部を添加し、ディスパーで1,000回転で30分間攪拌したあと、攪拌を止め、1時間放置すると2層に分かれた。下層の樹脂層を取出し、メチルエチルケトンで35%に希釈し、樹脂溶液b−8‘を得た。
温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコにメチルエチルケトン250部、メタノール250部を仕込んでおき、ディスパーで1,000回転させたところに樹脂溶液b−8‘、125部を1時間かけて滴下した。生成してきた白色沈殿物をろ過で取出し、真空乾燥機で50℃12時間乾燥し、ポリマー(B−8)を得た。
<Manufacturing example 8>
In a four-neck separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, 38.0 parts of methyl ethyl ketone and 3.0 parts of 4-methacryloyloxybenzophenone were added as a monomer represented by the general formula (1). 41.0 parts of cyclopentanyl methacrylate, 41.0 parts of styrene, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H as the monomer represented by the general formula (2) -Benzotriazole (manufactured by Otsuka Chemical Co., Ltd., RUVA-93) was charged in 15.0 parts, and octyl thioglycolate (manufactured by Yodo Chemical Co., Ltd., OTG) was charged in 2.0 g, and the temperature was raised to 75 ° C. under a nitrogen stream. 1.0 part of 2,2'-azobis (methyl isobutyrate), 2.0 g of octyl thioglycolate (manufactured by Yodo Chemical Co., Ltd., OTG) and 17.0 parts of methyl ethyl ketone were added dropwise thereto over 8 hours. After completion of the dropping, the reaction was continued for 2 hours. Then, sampling was performed to confirm that the polymerization yield was 98% or more, and the mixture was diluted with methyl ethyl ketone to obtain a resin solution b-8 having a non-volatile content of 35%. 250 parts of acetone was added to 250 parts of b-8, and after stirring with a dispar at 1,000 rpm for 30 minutes, the stirring was stopped and the mixture was left for 1 hour to separate into two layers. The lower resin layer was taken out and diluted with methyl ethyl ketone to 35% to obtain a resin solution b-8'.
250 parts of methyl ethyl ketone and 250 parts of methanol were placed in a 4-port separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, and the resin solution b-8', 125 was placed at 1,000 rpm with a dispar. The portion was added dropwise over 1 hour. The white precipitate formed was taken out by filtration and dried in a vacuum dryer at 50 ° C. for 12 hours to obtain a polymer (B-8).
<製造例10>
温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコに、メチルエチルケトン38.0部、4−メタクリロイルオキシベンゾフェノン(MCCユニテック株式会社製、MBP)を3.0部、一般式(1)で示す単量体としてジシクロペンタニルメタクリレートを41.0部、スチレンを41.0部、一般式(2)で示す単量体として2−[2−ヒドロキシ−5−[2−(メタクリロイルオキシ)エチル]フェニル]−2H−ベンゾトリアゾールを15.0部、4−シアノ−4−[(ドデシルスルファニルチオカルボニル)スルファニル]ペンタン酸メチルを4.4gを仕込み窒素気流下で75℃に昇温した。そこに2,2’−アゾビス(イソ酪酸メチル)を2.5部およびメチルエチルケトン17.0部を8時間かけて滴下した。滴下終了後、24時間反応を継続した。その後、サンプリングを行い重合収率が99%以上である事を確認し、50℃へ冷却、テフロン(登録商標)バットに取り出した。さらに、真空乾燥機で50℃12時間乾燥し、ポリマー(B−10)を得た。
<Manufacturing example 10>
38.0 parts of methyl ethyl ketone, 3.0 parts of 4-methacryloyloxybenzophenone (MBP manufactured by MCC Unitech Co., Ltd.) in a four-neck separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler. As the monomer represented by 1), 41.0 parts of dicyclopentanyl methacrylate, 41.0 parts of styrene, and 2- [2-hydroxy-5- [2- (2) as the monomer represented by the general formula (2)). 15.0 parts of methacryloyloxy) ethyl] phenyl] -2H-benzotriazole and 4.4 g of 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] methylpentanoate were added and the temperature was raised to 75 ° C. under a nitrogen stream. It was warm. 2.5 parts of 2,2'-azobis (methyl isobutyrate) and 17.0 parts of methyl ethyl ketone were added dropwise thereto over 8 hours. After completion of the dropping, the reaction was continued for 24 hours. Then, sampling was performed to confirm that the polymerization yield was 99% or more, the mixture was cooled to 50 ° C., and the mixture was taken out into a Teflon (registered trademark) vat. Further, it was dried in a vacuum dryer at 50 ° C. for 12 hours to obtain a polymer (B-10).
<製造例11>
温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコに、メチルエチルケトン43.0部、ビス(ドデシルスルファニルチオカルボニル)ジスルフィドを1.77部、ジメチル2,2’−アゾビス(2−メチルプロピオネート)を0.88部仕込み窒素気流下で70℃に昇温し、2時間反応させた。そこに4−アクリロイルオキシベンゾフェノンを10.0部、一般式(2)で示す単量体として2−[2−ヒドロキシ−5−[2−(メタクリロイルオキシ)エチル]フェニル]−2H−ベンゾトリアゾールを40.0部仕込み窒素気流下で75℃に昇温した。そこにジメチル2,2’−アゾビス(2−メチルプロピオネート)を0.15部およびメチルエチルケトン10.0部を8時間かけて滴下し、Aブロックを合成した。その後、ジシクロペンタニルメタクリレートを45.0部、2−メトキシエチルアクリレートを5.0部、メチルエチルケトンを40.1部仕込み、ジメチル2,2’−アゾビス(2−メチルプロピオネート)を0.15部およびメチルエチルケトン10.0部を8時間かけて滴下し、Bブロックを合成した。滴下終了後、24時間反応を継続した。その後、サンプリングを行い重合収率が99%以上である事を確認し、樹脂溶液b−11を得た。
次に温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコにメタノール500部を仕込んでおき、ディスパーで1,000回転させたところに上記樹脂溶液b−11、100部を1時間かけて滴下した。生成してきた白色沈殿物をろ過で取出し、真空乾燥機で50℃12時間乾燥し、ABブロックポリマー(B−11)を得た。得られたポリマーの重量平均分子量(Mw)15,200、Mw/Mn 1.23であった。
<Manufacturing example 11>
43.0 parts of methyl ethyl ketone, 1.77 parts of bis (dodecylsulfanilthiocarbonyl) disulfide, dimethyl 2,2'-azobis (2) in a four-neck separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler. -Methylpropionate) was charged in 0.88 parts, heated to 70 ° C. under a nitrogen stream, and reacted for 2 hours. There, 10.0 parts of 4-acryloyloxybenzophenone was added, and 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole was added as a monomer represented by the general formula (2). The temperature was raised to 75 ° C. under a nitrogen stream charged with 40.0 parts. 0.15 part of dimethyl 2,2'-azobis (2-methylpropionate) and 10.0 parts of methyl ethyl ketone were added dropwise thereto over 8 hours to synthesize A block. Then, 45.0 parts of dicyclopentanyl methacrylate, 5.0 parts of 2-methoxyethyl acrylate, 40.1 parts of methyl ethyl ketone were charged, and dimethyl 2,2'-azobis (2-methylpropionate) was added to 0. 15 parts and 10.0 parts of methyl ethyl ketone were added dropwise over 8 hours to synthesize a B block. After completion of the dropping, the reaction was continued for 24 hours. Then, sampling was performed to confirm that the polymerization yield was 99% or more, and a resin solution b-11 was obtained.
Next, 500 parts of methanol was placed in a 4-port separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, and 100 parts of the above resin solution b-11 was placed in a place where the mixture was rotated 1,000 times with a dispar. It was added dropwise over 1 hour. The white precipitate formed was taken out by filtration and dried in a vacuum dryer at 50 ° C. for 12 hours to obtain an AB block polymer (B-11). The weight average molecular weight (Mw) of the obtained polymer was 15,200 and Mw / Mn 1.23.
<製造例12>
温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコに、酢酸エチル25.4部、ビス(ドデシルスルファニルチオカルボニル)ジスルフィドを1.77部、2,2’−アゾビス(2、4−ジメチルバレロニトリル)を0.95部仕込み窒素気流下で70℃に昇温し、2時間反応させた。そこに4−メタクリロイルオキシベンゾフェノン(MCCユニテック株式会社製、MBP)を10.0部、一般式(2)で示す単量体として2−[2−ヒドロキシ−5−[2−(メタクリロイルオキシ)エチル]フェニル]−2H−ベンゾトリアゾールを40.0部仕込み窒素気流下で75℃に昇温した。そこに2,2’−アゾビス(2、4−ジメチルバレロニトリル)を0.16部および酢酸エチル10.0部を8時間かけて滴下し、Aブロックを合成した。その後、ジシクロペンタニルメタクリレートを45.0部、2−メトキシエチルアクリレートを5.0部、酢酸エチルを23.4部仕込み、2,2’−アゾビス(2、4−ジメチルバレロニトリル)を0.16部および酢酸エチル10.0部を8時間かけて滴下し、Bブロックを合成した。滴下終了後、24時間反応を継続した。その後、サンプリングを行い重合収率が99%以上である事を確認し、樹脂溶液b−12を得た。
次に温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコにメタノール500部を仕込んでおき、ディスパーで1,000回転させたところに上記樹脂溶液b−12、100部を1時間かけて滴下した。生成してきた白色沈殿物をろ過で取出し、真空乾燥機で50℃12時間乾燥し、ABブロックポリマー(B−12)を得た。得られたポリマーの重量平均分子量(Mw)13,600、Mw/Mn 1.20であった。
<Manufacturing example 12>
25.4 parts of ethyl acetate, 1.77 parts of bis (dodecylsulfanylthiocarbonyl) disulfide, 2,2'-azobis (2) in a 4-neck separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler. , 4-Dimethylvaleronitrile) was charged in 0.95 parts, heated to 70 ° C. under a nitrogen stream, and reacted for 2 hours. There, 10.0 parts of 4-methacryloyloxybenzophenone (MBP manufactured by MCC Unitech Co., Ltd.) was added as a monomer represented by the general formula (2), 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl). ] Phenyl] -2H-benzotriazole was charged in 40.0 parts and heated to 75 ° C. under a nitrogen stream. 0.16 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 10.0 parts of ethyl acetate were added dropwise thereto over 8 hours to synthesize A block. After that, 45.0 parts of dicyclopentanyl methacrylate, 5.0 parts of 2-methoxyethyl acrylate, 23.4 parts of ethyl acetate were charged, and 2,2'-azobis (2,4-dimethylvaleronitrile) was 0. .16 parts and 10.0 parts of ethyl acetate were added dropwise over 8 hours to synthesize B block. After completion of the dropping, the reaction was continued for 24 hours. Then, sampling was performed to confirm that the polymerization yield was 99% or more, and a resin solution b-12 was obtained.
Next, 500 parts of methanol was placed in a 4-port separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, and 100 parts of the above resin solution b-12 was placed in a place where it was rotated 1,000 times with a dispar. It was added dropwise over 1 hour. The white precipitate formed was taken out by filtration and dried in a vacuum dryer at 50 ° C. for 12 hours to obtain an AB block polymer (B-12). The weight average molecular weight (Mw) of the obtained polymer was 13,600 and Mw / Mn 1.20.
<製造例13>
温度計、攪拌機、滴下ロート、冷却器を具備した4つ口セパラブルフラスコに、メチルエチルケトン61.4部を仕込み窒素気流下で75℃に昇温した。別途、4−メタクリロイルオキシベンゾフェノンを3.0部、一般式(1)で示す単量体としてジシクロペンタニルメタクリレートを41.0部、スチレンを41.0部、一般式(2)で示す単量体として2−[2−ヒドロキシ−5−[2−(メタクリロイルオキシ)エチル]フェニル]−2H−ベンゾトリアゾールを15.0部、2,2’−アゾビス(イソ酪酸メチル)を10.0部、およびメチルエチルケトン75.0部、を均一に混合した後、滴下ロートに仕込んだ。次いで滴下ロートの内容物を2時間かけて滴下した。滴下終了後、2時間反応を継続した。その後、サンプリングを行い重合収率が98%以上である事を確認し、50℃へ冷却、テフロン(登録商標)バットに取り出した。さらに、真空乾燥機で50℃12時間乾燥し、ポリマー(B−13)を得た。
<Manufacturing example 13>
61.4 parts of methyl ethyl ketone was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 3.0 parts of 4-methacryloyloxybenzophenone, 41.0 parts of dicyclopentanyl methacrylate as the monomer represented by the general formula (1), 41.0 parts of styrene, and simply represented by the general formula (2). As a metric, 15.0 parts of 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole and 10.0 parts of 2,2'-azobis (methyl isobutyrate). , And 75.0 parts of methyl ethyl ketone were uniformly mixed and then charged into a dropping funnel. Then, the contents of the dropping funnel were dropped over 2 hours. After completion of the dropping, the reaction was continued for 2 hours. Then, sampling was performed to confirm that the polymerization yield was 98% or more, the mixture was cooled to 50 ° C., and the mixture was taken out into a Teflon (registered trademark) vat. Further, it was dried in a vacuum dryer at 50 ° C. for 12 hours to obtain a polymer (B-13).
表1中の用語の詳細は以下の通りである。
・MBP:4−メタクリロイルオキシベンゾフェノン(MCCユニテック社製)
・4ABP:4−アクリロイルオキシベンゾフェノン
・RUVA−93:
2−[2−ヒドロキシ−5−[2−(メタクリロイルオキシ)エチル]フェニル]−2H−ベン
ゾトリアゾール(大塚化学社製)
・FA−711MM:
ペンタメチルピペリジニルメタクリレート(日立化成社製)
・2−MTA:2−メトキシエチルアクリレート
The details of the terms in Table 1 are as follows.
・ MBP: 4-methacryloyloxybenzophenone (manufactured by MCC Unitech)
・ 4ABP: 4-acryloyloxybenzophenone ・ RUVA-93:
2- [2-Hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd.)
・ FA-711MM:
Pentamethylpiperidinyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
2-MTA: 2-Methoxyethyl acrylate
(実施例1)
〔マスターバッチの製造〕
ワックス(D−1)100部、およびポリマー(B−1)100部を混合し、3本ロールミルを使用して160℃で混練を行いポリマー(B−1)の分散体を得た。次いで、ポリオレフィン(A−3)100部と共に得られた上記分散体100部をヘンシェルミキサーで混合した。次いで、スクリュー径30mmの単軸押出機にて180℃で溶融混練した後、冷却し、ペレタイザーを用いてペレット状にカッティングしてマスターバッチを得た。
(Example 1)
[Manufacturing of masterbatch]
100 parts of wax (D-1) and 100 parts of polymer (B-1) were mixed and kneaded at 160 ° C. using a 3-roll mill to obtain a dispersion of polymer (B-1). Next, 100 parts of the above dispersion obtained together with 100 parts of polyolefin (A-3) was mixed with a Henschel mixer. Next, after melt-kneading at 180 ° C. with a single-screw extruder having a screw diameter of 30 mm, the mixture was cooled and cut into pellets using a pelletizer to obtain a masterbatch.
[フィルム成形]
希釈樹脂としてポリオレフィン(A−3)100部に対して、得られたマスターバッチ50部を混合した。次いで、T−ダイ成形機(東洋精機社製)を用いて、温度180℃で溶融混合し成形を行い厚さ250μmのフィルムを得た。
[Film molding]
50 parts of the obtained masterbatch was mixed with 100 parts of polyolefin (A-3) as a diluted resin. Next, using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.), melt mixing was performed at a temperature of 180 ° C. and molding was performed to obtain a film having a thickness of 250 μm.
(実施例2〜17、比較例1〜3)
実施例1の材料を表2に示す材料および配合量に変更した以外は、実施例1と同様にして、マスターバッチを製造し、次いでそれぞれ実施例2〜17、比較例1〜3のフィルム
を成形した。
(Examples 2 to 17, Comparative Examples 1 to 3)
A masterbatch was produced in the same manner as in Example 1 except that the materials of Example 1 were changed to the materials and blending amounts shown in Table 2, and then the films of Examples 2 to 17 and Comparative Examples 1 to 3, respectively. Molded.
表2中の用語の詳細は以下の通りである。 Details of the terms in Table 2 are as follows.
アデカスタブLA−29(ADEKA社製)
[紫外線吸収性]
得られたフィルムの透過率を、紫外可視近赤外分光光度計(島津製作所社製)を用いて測定した。透過率は白色標準板に対しての分光透過率を測定した。なお、評価基準は、以下に示す。
〇:波長290〜360nmの光透過率が全領域にわたって0.3%未満 良好
△:波長290〜360nmの範囲で一部光透過率が0.3%%以上の領域がある 実用域
×:波長290〜360nmの光透過率が全領域にわたって0.3%%以上 実用不可
[UV absorption]
The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). As for the transmittance, the spectral transmittance with respect to the white standard plate was measured. The evaluation criteria are shown below.
〇: Light transmittance of wavelength 290 to 360 nm is less than 0.3% over the entire region Good Δ: There is a region where light transmittance is 0.3% or more in a range of wavelength 290 to 360 nm Practical range ×: Wavelength Light transmittance of 290 to 360 nm is 0.3% or more over the entire region, impractical
[フィルムの透過性]
ポリオレフィンとの相溶性を確認するために得られたフィルムの透過性を目視評価した。なお、評価基準は、以下の通りである。
◎:濁りが全く認められない。非常に良好
〇:濁りがほとんど認められない。良好
△:濁りが若干認められる。実用域
×:明らかに濁りが認められる。実用不可
[Film permeability]
The permeability of the obtained film was visually evaluated to confirm the compatibility with the polyolefin. The evaluation criteria are as follows.
⊚: No turbidity is observed. Very good 〇: Almost no turbidity is observed. Good Δ: Some turbidity is observed. Practical range ×: Clearly turbidity is observed. Not practical
[耐光性試験]
得られたフィルムをキセノンウェザーメーターで、300〜400nmが60W/m2の照度で1500時間暴露した。
〇:黄変が全く認められない。良好
△:黄変がわずかに認められる。実用域
×:明らかに黄変が認められる。実用不可
[Light resistance test]
The resulting film was exposed on a xenon weather meter at 300-400 nm with an illuminance of 60 W / m2 for 1500 hours.
〇: No yellowing is observed. Good Δ: Slight yellowing is observed. Practical range ×: Yellowing is clearly observed. Not practical
[マイグレーション評価]
得られたフィルムを酸化チタンを配合した軟質塩化ビニルシートで挟み、熱プレス機を使用して圧力100g/cm2・温度170℃30秒間の条件で加熱圧着した。次いで、直ちにフィルムを外して酸化チタンを配合した軟質塩化ビニルシートへのマイグレーションを紫外可視近赤外分光光度計(島津製作所社製)を用いて評価した。評価は、上記の処理を行った軟質塩化ビニルシート上の場所5点を選び、紫外領域の吸光度を測定し、その平均を算出することで行った。
○:380〜480nmにおける吸光度が検出されない(0.05未満)。良好
△:380〜480nmにおける吸光度が0.05以上0.2以下。実用域
×:380〜480nmにおける吸光度が0.2を超える。実用不可
[Migration evaluation]
The obtained film was sandwiched between soft vinyl chloride sheets containing titanium oxide, and heat-pressed using a hot press under the conditions of a pressure of 100 g / cm 2 and a temperature of 170 ° C. for 30 seconds. Then, the film was immediately removed and migration to a soft vinyl chloride sheet containing titanium oxide was evaluated using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The evaluation was carried out by selecting 5 points on the soft vinyl chloride sheet subjected to the above treatment, measuring the absorbance in the ultraviolet region, and calculating the average thereof.
◯: Absorbance at 380 to 480 nm is not detected (less than 0.05). Good Δ: Absorbance at 380 to 480 nm is 0.05 or more and 0.2 or less. Practical range ×: Absorbance at 380 to 480 nm exceeds 0.2. Not practical
[臭気評価]
得られたフィルムの臭気を官能試験で確認し、ポリオレフィンのみのフィルムとの違いの確認を5名で行った。
○:ポリオレフィンフィルムのみのフィルムと同等の臭気と5名が判定。良好
△:ポリオレフィンフィルムのみのフィルムと同等の臭気と3名が判定。実用域
×:ポリオレフィンフィルムのみのフィルムと同等の臭気と0名が判定。実用不可
[Odor evaluation]
The odor of the obtained film was confirmed by a sensory test, and the difference from the polyolefin-only film was confirmed by 5 people.
◯: 5 people judged that the odor was the same as that of the polyolefin film only film. Good Δ: 3 people judged that the odor was the same as that of the polyolefin film only film. Practical range ×: 0 people were judged to have the same odor as the film containing only polyolefin film. Not practical
(実施例2〜17、比較例1〜3)
実施例1の材料を表2に示す材料および配合量に変更した以外は、実施例1と同様にして、マスターバッチを製造し、次いでそれぞれ実施例2〜17、比較例1〜3のフィルムを成形した。なお、本明細書で実施例3は、参考例である。
(Examples 2 to 17, Comparative Examples 1 to 3)
A masterbatch was produced in the same manner as in Example 1 except that the materials of Example 1 were changed to the materials and blending amounts shown in Table 2, and then the films of Examples 2 to 17 and Comparative Examples 1 to 3, respectively. Molded. In this specification, Example 3 is a reference example.
Claims (7)
前記紫外線吸収性ポリマー(B)は、ベンゾフェノン骨格を有する単量体単位、および下記一般式(1)で示す単量体単位を有し、
前記紫外線吸収性ポリマー(B)の重量平均分子量は、5,000〜100,000であり、かつ前記紫外線吸収性ポリマー(B)全体に占める重量平均分子量1,000以下のポリマーは、1%以下である、成形用樹脂組成物。
一般式(1)
(ただし、一般式(1)中、R16は、水素原子又はメチル基を表す。Zは、炭素数が10以上の炭化水素基を表す。 Contains polyolefin (A), and UV-absorbing polymer (B)
The ultraviolet-absorbing polymer (B) has a monomer unit having a benzophenone skeleton and a monomer unit represented by the following general formula (1).
The weight average molecular weight of the ultraviolet absorbing polymer (B) is 5,000 to 100,000, and 1% or less of the polymer having a weight average molecular weight of 1,000 or less in the entire ultraviolet absorbing polymer (B). A resin composition for molding.
General formula (1)
(However, in the general formula (1), R 16 represents a hydrogen atom or a methyl group. Z represents a hydrocarbon group having 10 or more carbon atoms.
一般式(2)
(ただし、一般式(2)中、R1は、水素原子又は炭素数1〜8の炭化水素基を表す。
R2は、炭素数1〜6のアルキレン基、もしくは-O-R5を表し、R5は、炭素数1〜6のアルキレン基を表す。R3は、水素原子又はメチル基を表す。X1は、水素原子、ハロゲン原子、炭素数1〜8の炭化水素基、炭素数1〜6のアルコキシ基、シアノ基又はニトロ基を表す。) The molding resin composition according to any one of claims 1 to 3, wherein the ultraviolet-absorbing polymer (B) contains a monomer unit represented by the following general formula (2).
General formula (2)
(However, in the general formula (2), R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
R 2 represents an alkylene group having 1 to 6 carbon atoms or -O-R 5 , and R 5 represents an alkylene group having 1 to 6 carbon atoms. R 3 represents a hydrogen atom or a methyl group. X 1 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group. )
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PCT/JP2020/006299 WO2020171071A1 (en) | 2019-02-20 | 2020-02-18 | Ultraviolet ray-absorbing polymer, molding resin composition, and molded body |
CN202080015324.6A CN113454132B (en) | 2019-02-20 | 2020-02-18 | Ultraviolet-absorbing polymer, molding resin composition, and molded article |
KR1020217028962A KR20210132082A (en) | 2019-02-20 | 2020-02-18 | UV-absorbing polymer, resin composition for molding, and molded article |
US17/405,036 US20210380743A1 (en) | 2019-02-20 | 2021-08-18 | Ultraviolet-ray absorbing polymer, formation resin composition, and formed body |
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WO2023210758A1 (en) * | 2022-04-28 | 2023-11-02 | 東洋紡エムシー株式会社 | Polyethylene nonwoven fabric and method for producing same |
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JPH03281685A (en) * | 1990-03-30 | 1991-12-12 | Ipposha Oil Ind Co Ltd | Ultraviolet absorber for plastic |
JPH05170941A (en) * | 1991-01-24 | 1993-07-09 | Mitsubishi Rayon Co Ltd | Acrylic resin film having improved weather resistance |
JPH0790184A (en) * | 1993-07-27 | 1995-04-04 | Otsuka Chem Co Ltd | Light-and chemical-resistant resin composition |
JP2001139924A (en) * | 1999-08-30 | 2001-05-22 | Ipposha Oil Ind Co Ltd | Silicone-containing polymeric ultraviolet absorber and coating agent composition |
JP2003129033A (en) * | 2001-10-23 | 2003-05-08 | Otsuka Chem Co Ltd | Ultraviolet-absorbing polymer, polyolefinic material, sheet and film produced from the same material |
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JPH03281685A (en) * | 1990-03-30 | 1991-12-12 | Ipposha Oil Ind Co Ltd | Ultraviolet absorber for plastic |
JPH05170941A (en) * | 1991-01-24 | 1993-07-09 | Mitsubishi Rayon Co Ltd | Acrylic resin film having improved weather resistance |
JPH0790184A (en) * | 1993-07-27 | 1995-04-04 | Otsuka Chem Co Ltd | Light-and chemical-resistant resin composition |
JP2001139924A (en) * | 1999-08-30 | 2001-05-22 | Ipposha Oil Ind Co Ltd | Silicone-containing polymeric ultraviolet absorber and coating agent composition |
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WO2023210758A1 (en) * | 2022-04-28 | 2023-11-02 | 東洋紡エムシー株式会社 | Polyethylene nonwoven fabric and method for producing same |
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