JP5399098B2 - Block copolymer and method for producing the same - Google Patents
Block copolymer and method for producing the same Download PDFInfo
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- JP5399098B2 JP5399098B2 JP2009047628A JP2009047628A JP5399098B2 JP 5399098 B2 JP5399098 B2 JP 5399098B2 JP 2009047628 A JP2009047628 A JP 2009047628A JP 2009047628 A JP2009047628 A JP 2009047628A JP 5399098 B2 JP5399098 B2 JP 5399098B2
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- block copolymer
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- hydrocarbon group
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- carbon atoms
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- 229920001400 block copolymer Polymers 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- -1 3,3,3-trifluoropropyl Chemical group 0.000 claims description 147
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 150000002430 hydrocarbons Chemical group 0.000 description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- VMOQKKFBYIBJOJ-UHFFFAOYSA-N 1-ethenyl-4-(2-ethoxyethoxy)benzene Chemical compound CCOCCOC1=CC=C(C=C)C=C1 VMOQKKFBYIBJOJ-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 125000000304 alkynyl group Chemical group 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000003440 styrenes Chemical class 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000005024 alkenyl aryl group Chemical group 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000005018 aryl alkenyl group Chemical group 0.000 description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000005025 alkynylaryl group Chemical group 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 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 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- 125000006039 1-hexenyl group Chemical group 0.000 description 2
- JQCSUVJDBHJKNG-UHFFFAOYSA-N 1-methoxy-ethyl Chemical group C[CH]OC JQCSUVJDBHJKNG-UHFFFAOYSA-N 0.000 description 2
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 2
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 2
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000005015 aryl alkynyl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 125000004407 fluoroaryl group Chemical group 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000004401 m-toluyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1[H])C([H])([H])[H])C(*)=O 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 125000006178 methyl benzyl group Chemical group 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000005441 o-toluyl group Chemical group [H]C1=C([H])C(C(*)=O)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- DTNCNFLLRLHPNJ-UHFFFAOYSA-N 1-ethenyl-4-(1-ethoxyethoxy)benzene Chemical compound CCOC(C)OC1=CC=C(C=C)C=C1 DTNCNFLLRLHPNJ-UHFFFAOYSA-N 0.000 description 1
- OBRYRJYZWVLVLF-UHFFFAOYSA-N 1-ethenyl-4-ethoxybenzene Chemical compound CCOC1=CC=C(C=C)C=C1 OBRYRJYZWVLVLF-UHFFFAOYSA-N 0.000 description 1
- HYKOKFYURVJHKT-UHFFFAOYSA-N 1-ethenyl-4-propoxybenzene Chemical compound CCCOC1=CC=C(C=C)C=C1 HYKOKFYURVJHKT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 1
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 description 1
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 description 1
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- DCEGHEFYVNDALO-UHFFFAOYSA-N 3,3,3-trifluoropropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)F DCEGHEFYVNDALO-UHFFFAOYSA-N 0.000 description 1
- 125000004361 3,4,5-trifluorophenyl group Chemical group [H]C1=C(F)C(F)=C(F)C([H])=C1* 0.000 description 1
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- 238000011088 calibration curve Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000004581 coalescence Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
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- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- AFFZTFNQQHNSEG-UHFFFAOYSA-N trifluoromethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)F AFFZTFNQQHNSEG-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Description
本発明は酸素含有炭化水素基置換スチレンの骨格を持つ繰り返し単位と弗素含有α置換アクリル酸エステルの骨格を持つ繰り返し単位とからなるブロック共重合体に関するものである。 The present invention relates to a block copolymer comprising a repeating unit having a skeleton of an oxygen-containing hydrocarbon group-substituted styrene and a repeating unit having a skeleton of a fluorine-containing α-substituted acrylate ester.
近年、半導体製造プロセスのリソグラフィー微細加工技術としてＡｒＦ露光、ＥＶＵ露光、液浸、電子線直接描画等の技術が開発されているが、１０ｎｍ以下のパターン形成は困難な状況となっている。 In recent years, techniques such as ArF exposure, EVU exposure, immersion, and direct electron beam drawing have been developed as lithography fine processing techniques for semiconductor manufacturing processes, but pattern formation of 10 nm or less is difficult.
そこで、秩序だったミクロ相分離構造、またはナノ相分離構造を有する自己組織化ブロック共重合をリソグラフィー技術に変わる簡便で経済的なパターン形成法として、半導体デバイス製造プロセスに適用する試みが成されている。 Therefore, an attempt has been made to apply self-organized block copolymerization having an ordered microphase separation structure or nanophase separation structure to a semiconductor device manufacturing process as a simple and economical pattern formation method that replaces lithography technology. Yes.
例えば、ポリスチレンとポリメタクリル酸メチルのブロック共重合体を用いて２０ｎｍのトレンチに５ｎｍ以下の繰り返し単位を有する交互ラメラ構造を形成する方法が提案されている（例えば特許文献１参照）。 For example, a method of forming an alternating lamella structure having a repeating unit of 5 nm or less in a 20 nm trench using a block copolymer of polystyrene and polymethyl methacrylate has been proposed (see, for example, Patent Document 1).
また、重量平均分子量２００００以下のポリヒドロキシスチレンとポリメタクリル酸メチルのブロック共重合体を用いてミクロドメイン構造を２０ｎｍ未満とすることが提案されている（例えば特許文献２参照）。 In addition, it has been proposed to use a block copolymer of polyhydroxystyrene having a weight average molecular weight of 20000 or less and polymethyl methacrylate to make the microdomain structure less than 20 nm (see, for example, Patent Document 2).
しかしながら、これらの自己組織化ブロック共重合体は、分子量および分子量分布の制御が不十分であって、条件によっては、ミクロ相分離しなかったり、相分離したミクロドメインサイズが大きいといった問題や、形成パターンの均一性、再現性、制御性に関し、不十分である等の課題を抱えていた。 However, these self-assembled block copolymers have insufficient control of molecular weight and molecular weight distribution, and depending on the conditions, there are problems such as no microphase separation or large phase-separated microdomain size. There were problems such as insufficient pattern uniformity, reproducibility, and controllability.
本発明の課題は、ミクロ又はナノ相分離することでミクロ又はナノパターン形成することが可能な自己組織化ブロック共重合体を提供することにある。 An object of the present invention is to provide a self-assembled block copolymer capable of forming a micro or nano pattern by micro or nano phase separation.
本発明者らは、上記問題を解決するために酸素含有炭化水素基置換スチレンと、弗素含有α置換アクリル酸エステルとの共重合体について鋭意検討を重ねた結果、本発明を完成するに至った。 In order to solve the above problems, the present inventors have made extensive studies on a copolymer of an oxygen-containing hydrocarbon group-substituted styrene and a fluorine-containing α-substituted acrylate ester, and as a result, completed the present invention. .
本発明の態様は以下の通りである。 Aspects of the present invention are as follows.
（１）下記一般式（１）及び（２）で示される繰り返し単位からなるブロック共重合体。 (1) A block copolymer comprising repeating units represented by the following general formulas (1) and (2).
（１）
（式中、Ｒ１は、炭素数１〜２０の炭化水素基または炭素数１〜２０の酸素含有炭化水素基を表す）
(1)
(Wherein R 1 represents a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms)
（２）
（Ｒ２は、水素原子もしくは、炭素数１〜１０の炭化水素基を表し、Ｒ３は、炭素数１〜２０の弗素含有炭化水素基を表す。）
（２）Ｒ１の酸素含有炭化水素基がアルコキシアルキル基であり、Ｒ２の炭化水素基がアルキル基であり、Ｒ３の弗素含有炭化水素基がフルオロアルキル基であることを特徴とする（１）記載のブロック共重合体。
(2)
(R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 3 represents a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms.)
(2) The oxygen-containing hydrocarbon group of R 1 is an alkoxyalkyl group, the hydrocarbon group of R 2 is an alkyl group, and the fluorine-containing hydrocarbon group of R 3 is a fluoroalkyl group ( 1) The block copolymer as described.
（３）Ｒ１がエトキシエチル基であり、Ｒ２がメチル基であり、Ｒ３が２，２，２−トリフルオロエチル基であることを特徴とする（１）又は（２）に記載のブロック共重合体。 (3) R 1 is an ethoxyethyl group, R 2 is a methyl group, and R 3 is a 2,2,2-trifluoroethyl group, according to (1) or (2) Block copolymer.
（４）重量平均分子量が２００００以上かつ重量平均分子量／数平均分子量の比が２．０未満であることを特徴とする（１）〜（３）のいずれかに記載のブロック共重合体。 (4) The block copolymer according to any one of (1) to (3), wherein the weight average molecular weight is 20000 or more and the ratio of weight average molecular weight / number average molecular weight is less than 2.0.
（５）下記一般式（３） (5) The following general formula (3)
（３）
（式中、Ｒ１は前記に同じ）で示される酸素含有炭化水素基置換スチレンと下記一般式（４）
(3)
(Wherein R 1 is the same as above) and an oxygen-containing hydrocarbon group-substituted styrene represented by the following general formula (4)
（４）
（式中、Ｒ２、Ｒ３は前記に同じ）で示される弗素含有α置換アクリル酸エステルとを、リビングラジカル重合することを特徴とする、（１）〜（４）のいずれかに記載のブロック共重合体の製造方法。
(4)
(1) to (4), wherein living radical polymerization is performed on a fluorine-containing α-substituted acrylate ester represented by the formula (wherein R 2 and R 3 are the same as above): A method for producing a block copolymer.
以下、本発明の詳細について説明する。 Details of the present invention will be described below.
本発明の共重合体は下記一般式（１）、（２）で示される繰り返し単位よりなるブロック共重合体である。 The copolymer of the present invention is a block copolymer composed of repeating units represented by the following general formulas (1) and (2).
（１）
（式中、Ｒ１は前記に同じ）
(1)
(Wherein R 1 is the same as above)
（２）
（式中、Ｒ２、Ｒ３は前記に同じ）
上記一般式（１）のＲ１は、炭素数１〜２０の炭化水素基または酸素含有炭化水素基であり、特に好ましくは、炭素数１〜１０の飽和または不飽和炭化水素基であり、直鎖状、分岐鎖状、環状のいずれの構造を有してもよい。
(2)
(Wherein R 2 and R 3 are the same as above)
R 1 in the above general formula (1) is a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing hydrocarbon group, and particularly preferably a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms. It may have any structure of a chain, a branched chain, and a ring.
Ｒ１が炭化水素基である例としては、炭素数１〜２０のものであれば特に限定されるものではないが、好ましくは、炭素数１〜２０のアルキル基、アリール基、アリールアルキル基、アルキルアリール基、アルケニル基、アリールアルケニル基、アルケニルアリール基、アルキニル基、アリールアルキニル基、アルキニルアリール基等であり、酸素含有炭化水素基の例としては炭素数１〜２０のアルコキシアルキル基、アシル基等を挙げることができる。 Examples of R 1 being a hydrocarbon group are not particularly limited as long as they have 1 to 20 carbon atoms, preferably, an alkyl group having 1 to 20 carbon atoms, an aryl group, an arylalkyl group, An alkylaryl group, an alkenyl group, an arylalkenyl group, an alkenylaryl group, an alkynyl group, an arylalkynyl group, an alkynylaryl group, etc. Examples of the oxygen-containing hydrocarbon group include an alkoxyalkyl group having 1 to 20 carbon atoms, an acyl group Etc.
Ｒ１が炭化水素基であるときの具体的な例としては、メチル、エチル、ｎ−プロピル、ｉ−プロピル、シクロプロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ．−ブチル、シクロブチル、ｎ−ペンチル、ｔｅｒｔ．−アミル、シクロペンチル、ｎ−ヘキシル、シクロヘキシル、２−エチルヘキシル等のアルキル基、フェニル、ジフェニル、ナフチル等のアリール基、ベンジル、メチルベンジル等のアリールアルキル基、ｏ−トルイル、ｍ−トルイル、ｐ−トルイル、２，３−ジメチルフェニル、２，４−ジメチルフェニル、２，５−ジメチルフェニル、２，６−ジメチルフェニル、３，４−ジメチルフェニル、３，５−ジメチルフェニル、２，４，６−トリメチルフェニル、ｏ−エチルフェニル、ｍ−エチルフェニル、ｐ−エチルフェニル等のアルキルアリール基、ビニル、アリル、１−プロペニル、１−ブテニル、１，３−ブタジエニル、１−ペンテニル、１−シクロペンテニル、２−シクロペンテニル、シクロペンタジエニル、メチルシクロペンタジエニル、エチルシクロペンタジエニル、１−ヘキセニル、１−シクロヘキセニル、２，４−シクロヘキサジエニル、２，５−シクロヘキサジエニル、２，４，６−シクロヘプタトリエニル、５−ノルボルネン−２−イル等のアルケニル基、２−フェニル−１−エテニル等のアリールアルケニル基、ｏ−スチリル，ｍ−スチリル，ｐ−スチリル等のアルケニルアリール基、エチニル、１−プロピニル、２−プロピニル、１−ブチニル，２−ブチニル，３−ブチニル、１−ペンチニル、２−ペンチニル、３−ペンチニル、４−ペンチニル、１−ヘキシニル、３−ヘキシニル、５−ヘキシニル等のアルキニル基、２−フェニル−１−エチニル等のアリールアルキニル基、２−エチニル−２フェニル等のアルキニルアリール基を挙げることができる。 Specific examples when R 1 is a hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Alkyl groups such as amyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, aryl groups such as phenyl, diphenyl, naphthyl, arylalkyl groups such as benzyl, methylbenzyl, o-toluyl, m-toluyl, p-toluyl 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethyl Alkylaryl groups such as phenyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, vinyl, allyl, 1-propenyl, 1-butenyl, 1,3-butadienyl, 1-pentenyl, 1-cyclopentenyl, 2 -Cyclopentenyl, cyclopentadienyl, methylcyclopentadi Nyl, ethylcyclopentadienyl, 1-hexenyl, 1-cyclohexenyl, 2,4-cyclohexadienyl, 2,5-cyclohexadienyl, 2,4,6-cycloheptatrienyl, 5-norbornene-2- Alkenyl groups such as yl, aryl alkenyl groups such as 2-phenyl-1-ethenyl, alkenyl aryl groups such as o-styryl, m-styryl, p-styryl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, Alkynyl groups such as 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 3-hexynyl, 5-hexynyl, and aryls such as 2-phenyl-1-ethynyl Alkynyl groups such as alkynyl group and 2-ethynyl-2-phenyl can be exemplified.
また、Ｒ１が酸素含有炭化水素基であるときの具体的な例としては、メトキシメチル、エトキシメチル、プロポキシメチル、イソプロポキシメチル、１−メトキシエチル、２−メトキシエチル、１−エトキシエチル、２−エトキシエチル、１−プロポキシシエチル、２−プロポキシエチル、１−イソプロポキシシエチル、２−イソプロポキシエチル、１−メトキシプロピル、２−メトキシプロピル、３−メトキシプロピル、１−エトキシプロピル、２−エトキシプロピル、３−エトキシプロピル、１−メトキシブチル、２−メトキシブチル、３−メトキシブチル、４−メトキシブチル、１−エトキシブチル、２−エトキシブチル、３−エトキシブチル、４−エトキシブチル、１−プロポキシブチル、２−プロポキシブチル、３−プロポキシブチル、４−プロポキシブチル、１−イソプロポキシブチル、２−イソプロポキシブチル、３−イソプロポキシブチル、４−イソプロポキシブチル等のアルコキシアルキル基、アセチル基等のアシル基等を挙げることができる。 Specific examples when R 1 is an oxygen-containing hydrocarbon group include methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, 2 -Ethoxyethyl, 1-propoxyethyl, 2-propoxyethyl, 1-isopropoxyethyl, 2-isopropoxyethyl, 1-methoxypropyl, 2-methoxypropyl, 3-methoxypropyl, 1-ethoxypropyl, 2- Ethoxypropyl, 3-ethoxypropyl, 1-methoxybutyl, 2-methoxybutyl, 3-methoxybutyl, 4-methoxybutyl, 1-ethoxybutyl, 2-ethoxybutyl, 3-ethoxybutyl, 4-ethoxybutyl, 1- Propoxybutyl, 2-propoxybutyl, 3-propoxyb Examples thereof include alkoxyalkyl groups such as til, 4-propoxybutyl, 1-isopropoxybutyl, 2-isopropoxybutyl, 3-isopropoxybutyl and 4-isopropoxybutyl, and acyl groups such as acetyl group.
Ｒ１として特に好ましくは、炭素数１〜１０の炭化水素基、酸素含有炭化水素基である、メチル、エチル、ｎ−プロピル、ｉ−プロピル、シクロプロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ．−ブチル、シクロブチル、メトキシメチル、エトキシメチル、１−メトキシエチル、２−メトキシエチル、１−エトキシエチル、アセチルである。 R 1 is particularly preferably a hydrocarbon group having 1 to 10 carbon atoms and an oxygen-containing hydrocarbon group, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec- Butyl, tert. -Butyl, cyclobutyl, methoxymethyl, ethoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, acetyl.
また、ＯＲ１基はスチレン残基のｏ位、ｍ位、ｐ位のいずれの位置にあっても良い。 The OR 1 group may be located at any of the o-position, m-position and p-position of the styrene residue.
一般式（２）のＲ２は、水素原子もしくは、炭素数１〜１０の炭化水素基を表し、直鎖状、分岐鎖状、環状のいずれの構造を有してもよい。 R 2 in the general formula (2) represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may have any of a linear, branched, or cyclic structure.
Ｒ２の例としては、水素原子もしくは炭素数１〜１０の炭化水素基であれば特に限定されるものではないが、好ましくは、水素原子、炭素数１〜１０のアルキル基、アリール基、アリールアルキル基、アルキルアリール基、アルケニル基、アリールアルケニル基、アルケニルアリール基、アルキニル基、アリールアルキニル基、アルキニルアリール基等の炭化水素基を挙げることができる。 Examples of R 2 are not particularly limited as long as they are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, but preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aryl group. Examples thereof include hydrocarbon groups such as alkyl groups, alkylaryl groups, alkenyl groups, arylalkenyl groups, alkenylaryl groups, alkynyl groups, arylalkynyl groups, and alkynylaryl groups.
Ｒ２の炭化水素基であるときの具体的な例としては、メチル、エチル、ｎ−プロピル、ｉ−プロピル、シクロプロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ．−ブチル、シクロブチル、ｎ−ペンチル、ｔｅｒｔ．−アミル、シクロペンチル、ｎ−ヘキシル、シクロヘキシル、２−エチルヘキシル等のアルキル基、フェニル、ジフェニル、ナフチル等のアリール基、ベンジル、メチルベンジル等のアリールアルキル基、ｏ−トルイル、ｍ−トルイル、ｐ−トルイル、２，３−ジメチルフェニル、２，４−ジメチルフェニル、２，５−ジメチルフェニル、２，６−ジメチルフェニル、３，４−ジメチルフェニル、３，５−ジメチルフェニル、２，４，６−トリメチルフェニル、ｏ−エチルフェニル、ｍ−エチルフェニル、ｐ−エチルフェニル等のアルキルアリール基、ビニル、アリル、１−プロペニル、１−ブテニル、１，３−ブタジエニル、１−ペンテニル、１−シクロペンテニル、２−シクロペンテニル、シクロペンタジエニル、メチルシクロペンタジエニル、エチルシクロペンタジエニル、１−ヘキセニル、１−シクロヘキセニル、２，４−シクロヘキサジエニル、２，５−シクロヘキサジエニル、２，４，６−シクロヘプタトリエニル、５−ノルボルネン−２−イル等のアルケニル基、２−フェニル−１−エテニル等のアリールアルケニル基、ｏ−スチリル，ｍ−スチリル，ｐ−スチリル等のアルケニルアリール基、エチニル、１−プロピニル、２−プロピニル、１−ブチニル，２−ブチニル，３−ブチニル、１−ペンチニル、２−ペンチニル、３−ペンチニル、４−ペンチニル、１−ヘキシニル、３−ヘキシニル、５−ヘキシニル等のアルキニル基、２−フェニル−１−エチニル等のアリールアルキニル基、２−エチニル−２フェニル等のアルキニルアリール基等を挙げることができる。 Specific examples of the hydrocarbon group of R 2 include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Alkyl groups such as amyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, aryl groups such as phenyl, diphenyl, naphthyl, arylalkyl groups such as benzyl, methylbenzyl, o-toluyl, m-toluyl, p-toluyl 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethyl Alkylaryl groups such as phenyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, vinyl, allyl, 1-propenyl, 1-butenyl, 1,3-butadienyl, 1-pentenyl, 1-cyclopentenyl, 2 -Cyclopentenyl, cyclopentadienyl, methylcyclopentadi Nyl, ethylcyclopentadienyl, 1-hexenyl, 1-cyclohexenyl, 2,4-cyclohexadienyl, 2,5-cyclohexadienyl, 2,4,6-cycloheptatrienyl, 5-norbornene-2- Alkenyl groups such as yl, aryl alkenyl groups such as 2-phenyl-1-ethenyl, alkenyl aryl groups such as o-styryl, m-styryl, p-styryl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, Alkynyl groups such as 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 3-hexynyl, 5-hexynyl, and aryls such as 2-phenyl-1-ethynyl Alkynyl groups, alkynyl aryl groups such as 2-ethynyl-2-phenyl, etc. can be mentioned.
Ｒ２として特に好ましくは、水素原子、炭素数１〜６の炭化水素基である、メチル、エチル、ｎ−プロピル、ｉ−プロピル、シクロプロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ．−ブチル、シクロブチル、ｎ−ペンチル、シクロペンチル、ｎ−ヘキシル、シクロヘキシル、フェニルである。 R 2 is particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert . -Butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl and phenyl.
Ｒ３は、炭素数１〜２０の弗素含有炭化水素基を表す。好ましくは、炭素数１〜１０の飽和または不飽和の弗素含有炭化水素基であり、直鎖状、分岐鎖状、環状のいずれの構造を有してもよい。 R 3 represents a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms. Preferably, it is a C1-C10 saturated or unsaturated fluorine-containing hydrocarbon group, and may have any of a linear, branched, and cyclic structure.
Ｒ３の例としては、炭素数１〜２０の弗素含有炭化水素基であれば特に限定されるものではないが、好ましくは、炭素数１〜１０のフルオロアルキル基、フルオロアリール基、フルオロアリールアルキル基、フルオロアルケニルアリール基、フルオロアルキニルアリール基、フルオロアルキルアリール基、フルオロアルケニルアルキル基、フルオロアルキニルアルキル基等の弗素含有炭化水素基を挙げることができる。 An example of R 3 is not particularly limited as long as it is a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms. Preferably, it is a fluoroalkyl group, fluoroaryl group, or fluoroarylalkyl having 1 to 10 carbon atoms. And fluorine-containing hydrocarbon groups such as a group, a fluoroalkenylaryl group, a fluoroalkynylaryl group, a fluoroalkylaryl group, a fluoroalkenylalkyl group, and a fluoroalkynylalkyl group.
Ｒ３の具体的な例としては、フルオロメチル、ジフルオロメチル、トリフルオロメチル、２−フルオロエチル、１，２−ジフルオロエチル、２，２−ジフルオロエチル、２，２，２−トリフルオロエチル、パーフルオロエチル、１，１，２，２−テトラフルオロエチル、１，２，２，２−テトラフルオロエチル、３，３，３−トリフルオロプロピル、２，２，３，３，−テトラフルオロプロピル、２，２，３，３，３−ペンタフルオロプロピル、パーフルオロプロピル、１，１，１，３，３，３−ヘキサフルオロ−２−プロピル、パーフルオロイソプロピル、４，４，４−トリフルオロブチル、２，２，３，４，４，４−ヘキサフルオロブチル、パーフルオロブチル、５−フルオロペンチル、５，５，５−トリフルオロペンチル、４，４，５，５，５−ペンタフルオロペンチル、パーフルオロペンチル、６−フルオロヘキシル、６，６，６−トリフルオロヘキシル、パーフルオロヘキシル、７−フルオロヘプチル、７，７，７−トリフルオロヘプチル、ペーフルオロペプチル、８−フルオロオクチル、８，８，８−トリフルオロオクチル、パーフルオロオクチル、フルオロシクロヘキシキル、フルオロノルボルニル、フルオロアダマンチル等のフルオロアルキル基、２−フルオロフェニル、３−フルオロフェニル、４−フルオロフェニル、２，３−ジフルオロフェニル、２，４−ジフルオロフェニル、２，５−ジフルオロフェニル、２，６−ジフルオロフェニル、３，４−ジフルオロフェニル、３，５−ジフルオロフェニル、２，３，４−トリフルオロフェニル、２，３，５−トリフルオロフェニル、２，３，６−トリフルオロフェニル、２，４，５−トリフルオロフェニル、３，４，５−トリフルオロフェニル、２，３，４，５−テトラフルオロフェニル、２，３，５，６−テトラフルオロフェニル、２，３，４，５，６−ペンタフルオロフェニル、２，４−ジフルオロトルイル、２，５−ジフルオロトルイル、２，６−ジフルオロトルイル、３，４−ジフルオロトルイル、２，３，５，６−テトラフルオロトルイル、２，３，４，５，６−ペンタフルオロトルイル等のフルオロアリール基、４−フルオロフェネチル、２，３，４，５，６−ペンタフルオロベンシル、等のフルオロアリールアルキル基、３−フルオロ−４−エテニルフェニル等のフルオロアルケニルアリール基、３−フルオロ−４−ビニルフェニル等フルオロアルキニルアリール基、α，α，α−トリフルオロトルイル等のフルオロアルキルアリール基、３，３−ジフルオロ−２−プロペニル等のフルオロアルケニルアルキル基、３，３−ジフルオロ−２−プロピニル等のフルオロアルキニルアルキル基等を挙げることができる。 Specific examples of R 3 include fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 1,2-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, par Fluoroethyl, 1,1,2,2-tetrafluoroethyl, 1,2,2,2-tetrafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, perfluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl, perfluoroisopropyl, 4,4,4-trifluorobutyl 2,2,3,4,4,4-hexafluorobutyl, perfluorobutyl, 5-fluoropentyl, 5,5,5-trifluoropentyl, 4,4,5 , 5,5-pentafluoropentyl, perfluoropentyl, 6-fluorohexyl, 6,6,6-trifluorohexyl, perfluorohexyl, 7-fluoroheptyl, 7,7,7-trifluoroheptyl, perfluoropeptide , 8-fluorooctyl, 8,8,8-trifluorooctyl, perfluorooctyl, fluorocyclohexyl, fluoronorbornyl, fluoroadamantyl and the like, 2-fluorophenyl, 3-fluorophenyl, 4 -Fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3, 4-trifluorophenyl, 2,3,5-tri Fluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,5, 6-tetrafluorophenyl, 2,3,4,5,6-pentafluorophenyl, 2,4-difluorotoluyl, 2,5-difluorotoluyl, 2,6-difluorotoluyl, 3,4-difluorotoluyl, 2, Fluoroaryl groups such as 3,5,6-tetrafluorotoluyl, 2,3,4,5,6-pentafluorotoluyl, 4-fluorophenethyl, 2,3,4,5,6-pentafluorobenzyl, etc. Fluoroarylalkyl groups, fluoroalkenylaryl groups such as 3-fluoro-4-ethenylphenyl, 3-fluoro-4-vinylphenyl, etc. Oroalkynylaryl group, fluoroalkylaryl group such as α, α, α-trifluorotoluyl, fluoroalkenylalkyl group such as 3,3-difluoro-2-propenyl, fluoroalkynyl such as 3,3-difluoro-2-propynyl An alkyl group etc. can be mentioned.
Ｒ３として特に好ましくは、２，２，２−トリフルオロエチル、３，３，３−トリフルオロプロピル、４，４，４−トリフルオロブチル、５，５，５−トリフルオロペンチル、６，６，６−トリフルオロヘキシル、７，７，７−トリフルオロヘプチル、８，８，８−トリフルオロオクチル等の炭化水素基の末端がトリフルオロメチル基である弗素含有炭化水素基が好ましい。炭化水素基の末端がトリフルオロメチル基である弗素含有炭化水素基を有する一般式（２）の弗素含有α置換アクリル酸エステルを使用した場合、１００ｎｍ未満のドメインサイズを有する相分離ブロック共重合体をより容易に得ることができるからである。 R 3 is particularly preferably 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 5,5,5-trifluoropentyl, 6,6 Fluorine-containing hydrocarbon groups in which the end of the hydrocarbon group is a trifluoromethyl group, such as 1,6-trifluorohexyl, 7,7,7-trifluoroheptyl, 8,8,8-trifluorooctyl, etc., are preferred. A phase-separated block copolymer having a domain size of less than 100 nm when the fluorine-containing α-substituted acrylate ester of the general formula (2) having a fluorine-containing hydrocarbon group whose terminal is a trifluoromethyl group is used It is because it can obtain more easily.
本発明の一般式（１）及び（２）で示される繰り返し単位からなるブロック共重合体は３元ブロック共重合体であっても自己組織化するが、形成パターンの均一性がより優れる点から２元ブロック共重合体であることが望ましい。 The block copolymer comprising the repeating units represented by the general formulas (1) and (2) of the present invention is self-assembled even if it is a ternary block copolymer, but from the point that the uniformity of the formation pattern is more excellent A binary block copolymer is desirable.
本発明のブロック共重合体は一般式（１）の連鎖ブロック［Ａ］と一般式（２）の連鎖ブロック［Ｂ］をそれぞれ少なくとも１個以上有する構造であり、ジブロック（Ａ−Ｂ）、トリブロック（Ａ−Ｂ−Ａ）、テトラブロック（Ａ−Ｂ−Ａ−Ｂ）、ペンタブロック（Ａ−Ｂ−Ａ−Ｂ−Ａ又はＢ−Ａ−Ｂ−Ａ−Ｂ）あるいはブロック数が６個以上のものを含むが、ジブロック又はトリブロックであることが好ましい。 The block copolymer of the present invention has a structure having at least one chain block [A] of the general formula (1) and at least one chain block [B] of the general formula (2), a diblock (AB), Triblock (A-B-A), tetra-block (A-B-A-B), penta-block (A-B-A-B-A or B-A-B--A-B) or 6 blocks Although it contains more than one, it is preferably diblock or triblock.
本発明に係るブロック共重合体は式（１）の繰り返し単位と式（２）の繰り返し単位の割合は１：０．００１〜１：１０００であることが好ましく、１：０．１〜１：１００であることがより好ましい。 In the block copolymer according to the present invention, the ratio of the repeating unit of the formula (1) to the repeating unit of the formula (2) is preferably 1: 0.001 to 1: 1000, and 1: 0.1 to 1: More preferably, it is 100.
また、本発明に係るブロック共重合体はゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算重量平均分子量は２００００以上であることが好ましく、であることがより好ましい。重量平均分子量が小さすぎると自己組織化されない場合がある。 Further, the block copolymer according to the present invention preferably has a polystyrene-equivalent weight average molecular weight of 20,000 or more, more preferably, by gel permeation chromatography (GPC). If the weight average molecular weight is too small, self-organization may not occur.
更に、本発明のブロック共重合体の分子量分布（Ｍｗ／Ｍｎ）は２．０未満であることが好ましく、１．５未満であることがより好ましい。分子量分布が広い場合は低分子量や高分子量のポリマーが存在するために、自己組織化により形成されたミクロドメイン構造のパターンの均一性や規則性の悪化などの性能低下を引き起こす場合がある。 Furthermore, the molecular weight distribution (Mw / Mn) of the block copolymer of the present invention is preferably less than 2.0, and more preferably less than 1.5. When the molecular weight distribution is wide, low molecular weight or high molecular weight polymers exist, which may cause performance degradation such as uniformity of the pattern of the microdomain structure formed by self-organization or deterioration of regularity.
共重合を行う際の方法としては、ブロック共重合体製造のために通常のアニオン重合、カチオン重合、配位アニオン重合のいずれであっても使用することができるが、分子量分布が狭いブロック共重合体を製造する為には、リビングラジカル重合を用いることが好ましい。 As a method for carrying out the copolymerization, any of ordinary anionic polymerization, cationic polymerization and coordination anionic polymerization can be used for the production of the block copolymer, but the block copolymer having a narrow molecular weight distribution can be used. In order to produce the coalescence, it is preferable to use living radical polymerization.
具体的な製造方法の一例としては下記一般式（３） As an example of a specific manufacturing method, the following general formula (3)
（３）
（式中、Ｒ１は前記に同じ）で示される酸素含有炭化水素基置換スチレンと下記一般式（４）
(3)
(Wherein R 1 is the same as above) and an oxygen-containing hydrocarbon group-substituted styrene represented by the following general formula (4)
（４）
（式中、Ｒ２、Ｒ３は前記に同じ）で示される弗素含有α置換アクリル酸エステルとを、リビングラジカル重合する製造方法が挙げられる。
(4)
(Wherein R 2 and R 3 are the same as described above), and a production method of living radical polymerization of a fluorine-containing α-substituted acrylate ester.
上記一般式（３）で表される酸素含有炭化水素基置換スチレンとしては、前記したＲ１を有するＯＲ１基がベンゼン環に結合したスチレンであり、その具体例としては例えば、ｐ−メトキシスチレン、ｐ−エトキシスチレン、ｐ−プロポキシスチレン、ｐ−イソプリポキシスチレン、ｐ−ｔｅｒｔ．−ブトキシスチレン、ｐ−１−エトキシエトキシスチレン、ｐ−アセトキシスチレン等を挙げることができる。 The oxygen-containing hydrocarbon group-substituted styrene represented by the general formula (3) is a styrene in which the OR 1 group having R 1 described above is bonded to a benzene ring. Specific examples thereof include p-methoxystyrene. P-ethoxystyrene, p-propoxystyrene, p-isoprepoxystyrene, p-tert. -Butoxystyrene, p-1-ethoxyethoxystyrene, p-acetoxystyrene, etc. can be mentioned.
上記一般式（４）で表される弗素含有α置換アクリル酸エステルとしては、前記したＲ２及びＲ３を含んでなるα置換アクリル酸エステルであり、その具体例としては、１，１，１−トリフルオロメチルアクリレート、２，２，２−トリフルオロエチルアクリレート、１，１，１−トリフルオロメチルメタクリレート、２，２，２−トリフルオロエチルメタクリレート、３，３，３−トリフルオロプロピルメタクリレート等を挙げることができる。 The fluorine-containing α-substituted acrylate ester represented by the general formula (4) is an α-substituted acrylate ester containing R 2 and R 3 described above, and specific examples thereof include 1,1,1. -Trifluoromethyl acrylate, 2,2,2-trifluoroethyl acrylate, 1,1,1-trifluoromethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 3,3,3-trifluoropropyl methacrylate, etc. Can be mentioned.
共重合は、気相中または液相中で行うことができる。重合を液相中で行う場合は、一般式（３）で示される酸素含有炭化水素基置換スチレンと（４）で示される弗素含有α置換アクリル酸エステルそれ自身を反応媒体としてもよいが、不活性溶媒を反応媒体として用いることもできる。この不活性溶媒は、当該技術分野で通常用いられるものであれば使用することができるが、共重合により生成した共重合体が溶解する溶媒であることが好ましい。 Copolymerization can be carried out in the gas phase or in the liquid phase. When the polymerization is carried out in the liquid phase, the oxygen-containing hydrocarbon group-substituted styrene represented by the general formula (3) and the fluorine-containing α-substituted acrylate ester represented by (4) itself may be used as a reaction medium. An active solvent can also be used as a reaction medium. The inert solvent can be used as long as it is usually used in the technical field, but is preferably a solvent in which a copolymer formed by copolymerization dissolves.
使用できる溶媒の例としては、炭化水素系溶媒としては、４〜２０個の炭素原子を有するアルカン、シクロアルカン、例えばイソブタン、ペンタン、ヘキサン、シクロヘキサン等、芳香族系溶媒として、ベンゼン、トルエン、キシレン等が挙げられる。また、ヘテロ原子を有する溶媒としては、当該技術分野で用いられるジエチルエーテル、ターシャリーブチルメチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、シクロヘキシルメチルエーテル、テトラジドロフラン、アニソール、ジメトキシベンゼン等のエーテル類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、酢酸エチル、酢酸ブチル、ジエチル炭酸、プロピレンカーボネート等のエステル類、メタノール、エタノール、イソプロパノール、ブタノール、ターシャリーブタノール、イソアミルアルコール、２−エチルヘキサノール等のアルコール類、アセトニトリル、ベンゾニトリル等のニトリル類、トリエチルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン等のアミン類、Ｎ，Ｎ−ジメチルホルミアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類、ジメチルスルホキシド等のスルホキシド類、クロロホルム、塩化メチレン、四塩化炭素、ジクロロエタン、クロロベンゼン、ｏ−ジクロロベンゼン、臭化プロピル等のハロゲン化炭化水素類、及び、水等を挙げることができる。 Examples of solvents that can be used include hydrocarbon solvents such as alkanes having 4 to 20 carbon atoms, cycloalkanes such as isobutane, pentane, hexane, and cyclohexane, and aromatic solvents such as benzene, toluene, and xylene. Etc. Examples of the solvent having a hetero atom include diethyl ether, tertiary butyl methyl ether, diisopropyl ether, dibutyl ether, cyclohexyl methyl ether, tetradidofuran, anisole, dimethoxybenzene, and other ethers used in this technical field, acetone. , Ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate, diethyl carbonate and propylene carbonate, alcohols such as methanol, ethanol, isopropanol, butanol, tertiary butanol, isoamyl alcohol and 2-ethylhexanol , Nitriles such as acetonitrile and benzonitrile, amines such as triethylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N Amides such as dimethylformamide, N, N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, dichloroethane, chlorobenzene, o-dichlorobenzene, propyl bromide And water.
リビングラジカル共重合の際、用いる重合開始剤については、当該技術分野で通常用いられるものであれば使用することができる。 In the case of the living radical copolymerization, any polymerization initiator that is usually used in the technical field can be used.
例えば、２，２，６，６−テトラメチルピペリジン−１−オキシル（ＴＥＭＰＯ）等のニトロキシル系開始剤、フェニルチオカルボニルチオベンジル等のチオカルボニルチオエステル系開始剤、４，４’−ジヘプチル−２，２’−ビビリジル銅（Ｉ）等の遷移金属錯体系開始剤を挙げることができる。 For example, nitroxyl initiators such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), thiocarbonylthioester initiators such as phenylthiocarbonylthiobenzyl, 4,4′-diheptyl-2, A transition metal complex initiator such as 2′-bibilidyl copper (I) can be used.
なお、リビングラジカル共重合を行う場合、重合を促進する目的で上記のアゾ系ラジカル開始剤、過酸化物系ラジカル開始剤、無水酢酸、カンファースルホン酸を添加してもよい。 When living radical copolymerization is performed, the above-mentioned azo radical initiator, peroxide radical initiator, acetic anhydride, and camphorsulfonic acid may be added for the purpose of promoting polymerization.
重合反応条件は、重合体の融点未満の反応温度で行われる限り特に限定されないが、通常反応温度−８０〜１００℃、大気圧〜５０ｋｇ／ｃｍ２Ｇに選ばれる。 The polymerization reaction conditions are not particularly limited as long as the reaction is performed at a reaction temperature lower than the melting point of the polymer, but the reaction temperature is usually selected from −80 to 100 ° C. and atmospheric pressure to 50 kg / cm 2 G.
重合工程において使用する反応器は、当該技術分野で通常用いられるものであれば、適宜使用することができる。攪拌槽型反応器、流動床型反応器、または循環式反応器を用いて、重合操作を連続方式、半回分方式及び回分方式のいずれかの方式で行うことができる。更に異なる重合の反応条件で２段階以上に分けて行うことも可能である。 The reactor used in the polymerization step can be appropriately used as long as it is usually used in the technical field. Using a stirred tank reactor, a fluidized bed reactor, or a circulation reactor, the polymerization operation can be carried out by any one of a continuous system, a semi-batch system, and a batch system. Furthermore, it can be carried out in two or more stages under different polymerization reaction conditions.
本発明に係る共重合体はミクロ又はナノ相分離し、ミクロ又はナノパターン形成することが可能な自己組織化ブロック共重合体を提供できる。 The copolymer according to the present invention can provide a self-assembled block copolymer that can be micro- or nano-phase separated and micro- or nano-patterned.
以下に実施例を示すが、本発明は、これらの実施例によって何ら限定されるものではない。 Examples are shown below, but the present invention is not limited to these Examples.
なお、重合体の分子量分布（Ｑｗ＝Ｍｗ／Ｍｎ）の測定は、ＧＰＣ（東ソー社製、商品名「ＨＰＬＣ−２０１０」、カラムは同社製、商品名「ＴＳＫ−ＧＥＬ Ｇ５０００ＨＨＲ」）により、溶媒としてテトラヒドロフランを用い、３５℃で測定した。なお、標準物質としてポリスチレン（最大Ｍｗ＝８．４２×１０６）を用い、その他ポリエチレン、Ｃ３２Ｈ６６を用いて校正曲線を作成し、これを用いて測定した。 In addition, the molecular weight distribution (Qw = Mw / Mn) of the polymer was measured using GPC (trade name “HPLC-2010” manufactured by Tosoh Corporation, column manufactured by the same company, trade name “TSK-GEL G5000HHR”) as a solvent. Measurement was performed at 35 ° C. using tetrahydrofuran. In addition, a calibration curve was prepared using polystyrene (maximum Mw = 8.42 × 10 6 ) as a standard substance, and other polyethylene and C 32 H 66 , and measurement was performed using this.
（実施例１）
（１）ポリ［（ｐ−１−エトキシエトキシ）スチレン］の合成
電磁式攪拌装置を備えた３０ｍｌのシュレンク管をアルゴン置換し、ｐ−（１−エトキシエトキシ）スチレン１２．９ｇ（６７．０ｍｍｏｌ）、過酸化ベンゾイル３０．４ｍｇ（０．１２６ｍｍｏｌ）、２，２，６，６−テトラメチルピペリジン−１−オキシル２２．５ｍｇ（０．１４４ｍｍｏｌ）を仕込み、アルゴン雰囲気下、８０℃で６時間攪拌した。その後、室温まで冷却し、無水酢酸０．０７５６ｇ（０．７４１ｍｍｏｌ）を加え、アルゴン雰囲気下１２５℃で３時間攪拌した。
Example 1
(1) Synthesis of poly [(p-1-ethoxyethoxy) styrene] A 30 ml Schlenk tube equipped with an electromagnetic stirrer was replaced with argon to obtain 12.9 g (67.0 mmol) of p- (1-ethoxyethoxy) styrene. Benzoyl peroxide 30.4 mg (0.126 mmol) and 2,2,6,6-tetramethylpiperidine-1-oxyl 22.5 mg (0.144 mmol) were charged, and the mixture was stirred at 80 ° C. for 6 hours in an argon atmosphere. . Then, it cooled to room temperature, the acetic anhydride 0.0756g (0.741 mmol) was added, and it stirred at 125 degreeC under argon atmosphere for 3 hours.
反応終了後、反応溶液をヘキサン１５０ｍｌに加え、析出したポリ［（ｐ−１−エトキシエトキシ）スチレン］をろ過により回収した。回収した重合体をキシレンに溶解し、ヘキサンに加え、ポリマーを析出させる操作を３回行い、未反応のモノマーやオリゴマーを除去し、精製したポリ［（ｐ−１−エトキシエトキシ）スチレン］を得た。 After completion of the reaction, the reaction solution was added to 150 ml of hexane, and the precipitated poly [(p-1-ethoxyethoxy) styrene] was collected by filtration. The recovered polymer is dissolved in xylene, added to hexane, and the polymer is precipitated three times to remove unreacted monomers and oligomers to obtain purified poly [(p-1-ethoxyethoxy) styrene]. It was.
得られた精製ポリ［（ｐ−１−エトキシエトキシ）スチレン］は、ベンゼンに溶解させ、凍結乾燥した。乾燥した重合体の重量は、３．３３ｇであった。 The obtained purified poly [(p-1-ethoxyethoxy) styrene] was dissolved in benzene and freeze-dried. The weight of the dried polymer was 3.33 g.
単離したポリ［（ｐ−１−エトキシエトキシ）スチレン］の分子量及び分子量分布をＧＰＣにより測定した結果は、以下の通りであった。
重量平均分子量（Ｍｗ）＝３．２０×１０４
分子量分布（Ｍｗ／Ｍｎ）＝１．３７
（２）（ｐ−１−エトキシエトキシ）スチレンと２，２，２−トリフルオロエチルメタクリレートのブロック共重合体の合成
電磁式攪拌装置を備えた１００ｍｌのシュレンク管をアルゴン置換し、２，２，２−トリフルオロエチルメタクリレート７．７７ｇ（４７．２ｍｍｏｌ）、キシレン６．５８ｍｌ、上記で合成した精製したポリ［（ｐ−１−エトキシエトキシ）スチレン］１．１１ｇ、無水酢酸０．０６４８ｇ（０．６３５ｍｍｏｌ）を仕込み、アルゴン雰囲気下、１２５℃で６時間攪拌した。
The molecular weight and molecular weight distribution of the isolated poly [(p-1-ethoxyethoxy) styrene] were measured by GPC as follows.
Weight average molecular weight (Mw) = 3.20 × 10 4
Molecular weight distribution (Mw / Mn) = 1.37
(2) Synthesis of block copolymer of (p-1-ethoxyethoxy) styrene and 2,2,2-trifluoroethyl methacrylate A 100 ml Schlenk tube equipped with an electromagnetic stirrer was purged with argon, 7.77 g (47.2 mmol) of 2-trifluoroethyl methacrylate, 6.58 ml of xylene, 1.11 g of the purified poly [(p-1-ethoxyethoxy) styrene] synthesized above, 0.0648 g of acetic anhydride (0. 635 mmol), and the mixture was stirred at 125 ° C. for 6 hours under an argon atmosphere.
反応終了後、反応溶液をヘキサン１５０ｍｌに加え、析出した（ｐ−１−エトキシエトキシ）スチレンと２，２，２−トリフルオロエチルメタクリレートのブロック共重合体をろ過により回収した。回収した重合体をキシレンに溶解し、ヘキサンに加え、ポリマーを析出させる操作を３回行い、未反応のモノマーやオリゴマーを除去し、精製したｐ−１−エトキシエトキシ）スチレンと２，２，２−トリフルオロエチルメタクリレートのブロック共重合体を得た。 After completion of the reaction, the reaction solution was added to 150 ml of hexane, and the precipitated block copolymer of (p-1-ethoxyethoxy) styrene and 2,2,2-trifluoroethyl methacrylate was collected by filtration. The recovered polymer was dissolved in xylene, added to hexane, and the polymer was precipitated three times to remove unreacted monomers and oligomers, and purified p-1-ethoxyethoxy) styrene and 2,2,2 -A block copolymer of trifluoroethyl methacrylate was obtained.
得られた精製した（ｐ−１−エトキシエトキシ）スチレンと２，２，２−トリフルオロエチルメタクリレートのブロック共重合体は、ベンゼンに溶解し、凍結乾燥した。乾燥したブロック共重合体の重量は、５．４５ｇであった。 The obtained purified block copolymer of (p-1-ethoxyethoxy) styrene and 2,2,2-trifluoroethyl methacrylate was dissolved in benzene and freeze-dried. The weight of the dried block copolymer was 5.45 g.
単離した（ｐ−１−エトキシエトキシ）スチレンと２，２，２−トリフルオロエチルメタクリレートのブロック共重合体の分子量及び分子量分布をＧＰＣによりで測定し、核磁気共鳴（１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲ）により、各モノマー成分の共重合組成比を測定した。 The molecular weight and molecular weight distribution of the isolated block copolymer of (p-1-ethoxyethoxy) styrene and 2,2,2-trifluoroethyl methacrylate were measured by GPC, and nuclear magnetic resonance ( 1 H-NMR and 13 The copolymer composition ratio of each monomer component was measured by (C-NMR).
結果は、以下の通りであった。
重量平均分子量（Ｍｗ）＝７．３１×１０４
分子量分布（Ｍｗ／Ｍｎ）＝１．５４
（ｐ−１−エトキシエトキシ）スチレン：２，２，２−トリフルオロエチルメタクリレート＝１２：８８（ｍｏｌ％）
本ブロック共重合体をテトラヒドロフランに溶解後、キャスト成膜した薄膜を四酸化オスミウムにより染色し、ＴＥＭにより７５ｋＶで観察した結果を図１に示す。
The results were as follows.
Weight average molecular weight (Mw) = 7.31 × 10 4
Molecular weight distribution (Mw / Mn) = 1.54
(P-1-ethoxyethoxy) styrene: 2,2,2-trifluoroethyl methacrylate = 12: 88 (mol%)
FIG. 1 shows the result of dissolving the block copolymer in tetrahydrofuran, staining the cast thin film with osmium tetroxide, and observing the thin film with TEM at 75 kV.
１０〜３０ｎｍサイズのドメインを有する相分離が確認された。 Phase separation having domains of 10-30 nm size was confirmed.
（実施例２）
実施例１において、２，２，２−トリフルオロエチルメタクリレート４．６６ｇ（２７．８ｍｍｏｌ）、キシレン３．９５ｍｌ、上記で合成した精製したポリ［（ｐ−１−エトキシエトキシ）スチレン］２．６６ｇ、無水酢酸０．０７０２ｇ（０．６８８ｍｍｏｌ）としたこと以外、実施例１と同様にして（ｐ−１−エトキシエトキシ）スチレンと２，２，２−トリフルオロエチルメタクリレートのブロック共重合体を共重合し、精製、乾燥した。
乾燥したブロック共重合体の重量は、２．４１ｇであった。
(Example 2)
In Example 1, 4.66 g (27.8 mmol) of 2,2,2-trifluoroethyl methacrylate, 3.95 ml of xylene, 2.66 g of purified poly [(p-1-ethoxyethoxy) styrene] synthesized above. A block copolymer of (p-1-ethoxyethoxy) styrene and 2,2,2-trifluoroethyl methacrylate was prepared in the same manner as in Example 1 except that 0.0702 g (0.688 mmol) of acetic anhydride was used. Polymerized, purified and dried.
The weight of the dried block copolymer was 2.41 g.
単離した（ｐ−１−エトキシエトキシ）スチレンと２，２，２−トリフルオロエチルメタクリレートのブロック共重合体の分子量及び分子量分布、各モノマー成分の共重合組成比測定の結果は、以下の通りであった。
重量平均分子量（Ｍｗ）＝７．７４×１０４
分子量分布（Ｍｗ／Ｍｎ）＝１．４９
（ｐ−１−エトキシエトキシ）スチレン：２，２，２−トリフルオロエチルメタクリレート＝６６：３４（ｍｏｌ％）
The molecular weight and molecular weight distribution of the isolated block copolymer of (p-1-ethoxyethoxy) styrene and 2,2,2-trifluoroethyl methacrylate, and the results of measurement of the copolymer composition ratio of each monomer component are as follows. Met.
Weight average molecular weight (Mw) = 7.74 × 10 4
Molecular weight distribution (Mw / Mn) = 1.49
(P-1-ethoxyethoxy) styrene: 2,2,2-trifluoroethyl methacrylate = 66: 34 (mol%)
リソグラフィー技術に変わる簡便で経済的なパターン形成法として、半導体デバイス製造プロセスに適用できる可能性がある。 There is a possibility that it can be applied to a semiconductor device manufacturing process as a simple and economical pattern forming method that replaces the lithography technique.
Claims (5)
（式中、Ｒ１は、炭素数１〜２０の炭化水素基または炭素数１〜２０の酸素含有炭化水素基を表す）
（Ｒ２は、水素原子もしくは、炭素数１〜１０の炭化水素基を表し、Ｒ３は、２，２，２−トリフルオロエチル、３，３，３−トリフルオロプロピル、４，４，４−トリフルオロブチル、５，５，５−トリフルオロペンチル、６，６，６−トリフルオロヘキシル、７，７，７−トリフルオロヘプチル又は８，８，８−トリフルオロオクチルを表す。） A block copolymer comprising repeating units represented by the following general formulas (1) and (2).
(Wherein R 1 represents a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms)
(R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 3 represents 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 4,4,4 -Represents trifluorobutyl, 5,5,5-trifluoropentyl, 6,6,6-trifluorohexyl, 7,7,7-trifluoroheptyl or 8,8,8-trifluorooctyl)
（式中、Ｒ１は請求項１記載の一般式（１）のＲ１に同じ）で示される酸素含有炭化水素基置換スチレンと下記一般式（４）
（式中、Ｒ２、Ｒ３は請求項１記載の一般式（２）のＲ２、Ｒ３に同じ）で示される弗素含有α置換アクリル酸エステルとを、リビングラジカル重合することを特徴とする、請求項１〜４のいずれかに記載のブロック共重合体の製造方法。 The following general formula (3)
(Wherein R 1 is the same as R 1 in the general formula (1) according to claim 1) and the following general formula (4)
(Wherein, R 2, R 3 are as R 2, R 3 in the general formula of claim 1, wherein (2)) and characterized in that the fluorine-containing α-substituted acrylic acid ester represented by, for living radical polymerization The manufacturing method of the block copolymer in any one of Claims 1-4.
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| JP6402867B2 (en) * | 2013-12-06 | 2018-10-10 | エルジー・ケム・リミテッド | Block copolymer |
| EP3078691B1 (en) * | 2013-12-06 | 2018-04-18 | LG Chem, Ltd. | Block copolymer |
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| JP2007246600A (en) * | 2006-03-14 | 2007-09-27 | Shin Etsu Chem Co Ltd | Self-organizing polymeric membrane material, self-organizing pattern, and method for forming pattern |
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| JP4809378B2 (en) * | 2007-03-13 | 2011-11-09 | 信越化学工業株式会社 | Resist underlayer film material and pattern forming method using the same |
| WO2010074075A1 (en) * | 2008-12-26 | 2010-07-01 | 日産化学工業株式会社 | Additive for composition for forming resist underlayer film and composition for forming resist underlayer film comprising the same |
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