JP2024102539A - Method for producing polymer, composition containing polymer obtainable by production method, resist composition, and resist pattern - Google Patents
Method for producing polymer, composition containing polymer obtainable by production method, resist composition, and resist pattern Download PDFInfo
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- JP2024102539A JP2024102539A JP2023006498A JP2023006498A JP2024102539A JP 2024102539 A JP2024102539 A JP 2024102539A JP 2023006498 A JP2023006498 A JP 2023006498A JP 2023006498 A JP2023006498 A JP 2023006498A JP 2024102539 A JP2024102539 A JP 2024102539A
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- acid
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- 229920000642 polymer Polymers 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims description 40
- 239000000178 monomer Substances 0.000 claims abstract description 80
- -1 copper (II) compound Chemical class 0.000 claims abstract description 74
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 18
- 150000004045 organic chlorine compounds Chemical class 0.000 claims abstract description 16
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 143
- 125000000217 alkyl group Chemical group 0.000 claims description 88
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 70
- 239000002253 acid Substances 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 28
- 125000002723 alicyclic group Chemical group 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 150000002430 hydrocarbons Chemical group 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 150000003606 tin compounds Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 230000002401 inhibitory effect Effects 0.000 claims description 9
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000005907 alkyl ester group Chemical group 0.000 claims description 7
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 6
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 125000005670 ethenylalkyl group Chemical group 0.000 claims description 3
- 150000003512 tertiary amines Chemical group 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- 239000002904 solvent Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 5
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 5
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 5
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 4
- GTLWADFFABIGAE-UHFFFAOYSA-N 1-chloroethylbenzene Chemical compound CC(Cl)C1=CC=CC=C1 GTLWADFFABIGAE-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([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
- 238000000034 method Methods 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
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 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 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- 239000004793 Polystyrene Substances 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000003982 chlorocarboxylic acids Chemical class 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
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 125000004043 oxo group Chemical group O=* 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 125000005504 styryl group Chemical group 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- JNAYPRPPXRWGQO-UHFFFAOYSA-N 2-chloropropanenitrile Chemical compound CC(Cl)C#N JNAYPRPPXRWGQO-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 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
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- VSYDNHCEDWYFBX-UHFFFAOYSA-N (1-methylcyclopentyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCC1 VSYDNHCEDWYFBX-UHFFFAOYSA-N 0.000 description 1
- DCTVCFJTKSQXED-UHFFFAOYSA-N (2-ethyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(CC)(OC(=O)C(C)=C)C2C3 DCTVCFJTKSQXED-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FMGGHNGKHRCJLL-UHFFFAOYSA-N 1,2-bis(chloromethyl)benzene Chemical group ClCC1=CC=CC=C1CCl FMGGHNGKHRCJLL-UHFFFAOYSA-N 0.000 description 1
- GRFNSWBVXHLTCI-UHFFFAOYSA-N 1-ethenyl-4-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=C(C=C)C=C1 GRFNSWBVXHLTCI-UHFFFAOYSA-N 0.000 description 1
- VGUWFGWZSVLROP-UHFFFAOYSA-N 1-pyridin-2-yl-n,n-bis(pyridin-2-ylmethyl)methanamine Chemical compound C=1C=CC=NC=1CN(CC=1N=CC=CC=1)CC1=CC=CC=N1 VGUWFGWZSVLROP-UHFFFAOYSA-N 0.000 description 1
- HRMLMRIORGNUSV-UHFFFAOYSA-N 2-amino-2-(1-benzothiophen-3-yl)acetic acid Chemical compound C1=CC=C2C(C(C(O)=O)N)=CSC2=C1 HRMLMRIORGNUSV-UHFFFAOYSA-N 0.000 description 1
- NUJHTYRNHYOUKO-UHFFFAOYSA-N 2-chloro-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(Cl)C(=O)C1=CC=CC=C1 NUJHTYRNHYOUKO-UHFFFAOYSA-N 0.000 description 1
- MYCXCBCDXVFXNE-UHFFFAOYSA-N 2-chloro-2-methylpropanoic acid Chemical compound CC(C)(Cl)C(O)=O MYCXCBCDXVFXNE-UHFFFAOYSA-N 0.000 description 1
- KPJKMUJJFXZGAX-UHFFFAOYSA-N 2-chloropropan-2-ylbenzene Chemical compound CC(C)(Cl)C1=CC=CC=C1 KPJKMUJJFXZGAX-UHFFFAOYSA-N 0.000 description 1
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- PRIUALOJYOZZOJ-UHFFFAOYSA-L 2-ethylhexyl 2-[dibutyl-[2-(2-ethylhexoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCC(CC)CCCC PRIUALOJYOZZOJ-UHFFFAOYSA-L 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- NJMWXCOSLAUOGE-UHFFFAOYSA-N 4,11-dimethyl-1,4,8,11-tetrazabicyclo[6.6.2]hexadecane Chemical compound C1CN(C)CCCN2CCN(C)CCCN1CC2 NJMWXCOSLAUOGE-UHFFFAOYSA-N 0.000 description 1
- VHJFWJXYEWHCGD-UHFFFAOYSA-N 4-nonyl-2-(4-nonylpyridin-2-yl)pyridine Chemical group CCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCC)C=2)=C1 VHJFWJXYEWHCGD-UHFFFAOYSA-N 0.000 description 1
- OAAGDVLVOKMRCQ-UHFFFAOYSA-N 5-piperidin-4-yl-3-pyridin-4-yl-1,2,4-oxadiazole Chemical compound C1CNCCC1C1=NC(C=2C=CN=CC=2)=NO1 OAAGDVLVOKMRCQ-UHFFFAOYSA-N 0.000 description 1
- CQFWAYQEJLDONT-UHFFFAOYSA-N CN(C)CCCN(C)CCN(C)CCN(C)C Chemical compound CN(C)CCCN(C)CCN(C)CCN(C)C CQFWAYQEJLDONT-UHFFFAOYSA-N 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CVRXLMUYFMERMJ-UHFFFAOYSA-N N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine Chemical compound C=1C=CC=NC=1CN(CC=1N=CC=CC=1)CCN(CC=1N=CC=CC=1)CC1=CC=CC=N1 CVRXLMUYFMERMJ-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- HKRYOHNBGZLDSH-UHFFFAOYSA-N butyl 3-[2-[bis[2-[bis(3-butoxy-3-oxopropyl)amino]ethyl]amino]ethyl-(3-butoxy-3-oxopropyl)amino]propanoate Chemical compound CCCCOC(=O)CCN(CCC(=O)OCCCC)CCN(CCN(CCC(=O)OCCCC)CCC(=O)OCCCC)CCN(CCC(=O)OCCCC)CCC(=O)OCCCC HKRYOHNBGZLDSH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- RWHJATFJJVMKGR-UHFFFAOYSA-L dibutyltin(2+);methanethioate Chemical compound [O-]C=S.[O-]C=S.CCCC[Sn+2]CCCC RWHJATFJJVMKGR-UHFFFAOYSA-L 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNYIUBKOOFMIBM-UHFFFAOYSA-L dioctyltin(2+);methanethioate Chemical compound [O-]C=S.[O-]C=S.CCCCCCCC[Sn+2]CCCCCCCC HNYIUBKOOFMIBM-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- IWYBVQLPTCMVFO-UHFFFAOYSA-N ethyl 2,2-dichloroacetate Chemical compound CCOC(=O)C(Cl)Cl IWYBVQLPTCMVFO-UHFFFAOYSA-N 0.000 description 1
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 description 1
- ARQNAXVQDYBTEE-UHFFFAOYSA-N ethyl 2-chloro-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Cl ARQNAXVQDYBTEE-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- HKMLRUAPIDAGIE-UHFFFAOYSA-N methyl 2,2-dichloroacetate Chemical compound COC(=O)C(Cl)Cl HKMLRUAPIDAGIE-UHFFFAOYSA-N 0.000 description 1
- JLEJCNOTNLZCHQ-UHFFFAOYSA-N methyl 2-chloropropanoate Chemical compound COC(=O)C(C)Cl JLEJCNOTNLZCHQ-UHFFFAOYSA-N 0.000 description 1
- BUFDMFWOASMLTE-UHFFFAOYSA-N methyl 3-[2-[bis[2-[bis(3-methoxy-3-oxopropyl)amino]ethyl]amino]ethyl-(3-methoxy-3-oxopropyl)amino]propanoate Chemical compound COC(=O)CCN(CCC(=O)OC)CCN(CCN(CCC(=O)OC)CCC(=O)OC)CCN(CCC(=O)OC)CCC(=O)OC BUFDMFWOASMLTE-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- URKRYOHZWVRTIL-UHFFFAOYSA-N n',n'-bis[2-(diethylamino)ethyl]-n,n-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CCN(CC)CC)CCN(CC)CC URKRYOHZWVRTIL-UHFFFAOYSA-N 0.000 description 1
- DTSDBGVDESRKKD-UHFFFAOYSA-N n'-(2-aminoethyl)propane-1,3-diamine Chemical compound NCCCNCCN DTSDBGVDESRKKD-UHFFFAOYSA-N 0.000 description 1
- JKCHLHLFXZUVDS-UHFFFAOYSA-N n,n'-bis[2-(dimethylamino)ethyl]-n,n'-dimethylpropane-1,3-diamine Chemical compound CN(C)CCN(C)CCCN(C)CCN(C)C JKCHLHLFXZUVDS-UHFFFAOYSA-N 0.000 description 1
- RPHOHIVITQPVKC-UHFFFAOYSA-N n-(pyridin-2-ylmethyl)octan-1-amine Chemical compound CCCCCCCCNCC1=CC=CC=N1 RPHOHIVITQPVKC-UHFFFAOYSA-N 0.000 description 1
- OXWGLVVRVXFLHN-UHFFFAOYSA-N n-(pyridin-2-ylmethyl)propan-1-amine Chemical compound CCCNCC1=CC=CC=N1 OXWGLVVRVXFLHN-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001902 propagating effect Effects 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
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- NCELKGDJMASKSV-UHFFFAOYSA-N tert-butyl 5-ethenyl-2-hydroxybenzoate Chemical compound C(C)(C)(C)OC(=O)C1=C(C=CC(=C1)C=C)O NCELKGDJMASKSV-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
Description
本発明は、重合体の製造方法、当該製造方法により得られる重合体を含有する組成物、レジスト組成物およびレジストパターンに関する。 The present invention relates to a method for producing a polymer, a composition containing the polymer obtained by the method, a resist composition, and a resist pattern.
リビングラジカル重合は開始反応および成長反応からなり、連鎖移動反応、停止反応等の成長末端を失活させる副反応を伴わない重合である。当該リビングラジカル重合を用いることで特定の構造をブロック化したポリマー、分子量の揃ったポリマーなどの特徴あるポリマーが製造可能になることから、用途を問わず広く採用されている。 Living radical polymerization consists of an initiation reaction and a propagation reaction, and is not accompanied by side reactions that deactivate the propagation end, such as chain transfer reactions and termination reactions. Living radical polymerization is widely used regardless of the application, as it makes it possible to produce distinctive polymers, such as polymers with specific blocked structures and polymers with uniform molecular weights.
リビングラジカル重合のなかでも原子移動ラジカル重合（ＡＴＲＰ）はモノマーの汎用性が高く、多様な構造を有するポリマーの合成が可能であるため、近年注目を集めている（例えば特許文献１）。 Among living radical polymerizations, atom transfer radical polymerization (ATRP) has been attracting attention in recent years because of its high monomer versatility and the ability to synthesize polymers with diverse structures (e.g., Patent Document 1).
反応性の異なる２種以上のモノマーを用いて原子移動ラジカル重合する場合、重合条件の設定が通常は厳しくなる。例えば重合成分にスチレン系モノマーと酸解離性基を有する重合性モノマーとを用いて原子移動ラジカル重合する場合においては、スチレン系モノマーの重合には重合温度１００℃以上に通常設定されるが、１００℃以上の重合温度では酸解離性基を有する重合性モノマーの分解が生じるおそれがある。その一方で、酸解離性基を有する重合性モノマーの分解が生じないように重合温度を低温に設定した場合、スチレン系モノマーの重合が十分に進まない問題があった。 When atom transfer radical polymerization is performed using two or more monomers with different reactivities, the polymerization conditions must usually be set stricter. For example, when atom transfer radical polymerization is performed using a styrene-based monomer and a polymerizable monomer having an acid-dissociable group as polymerization components, the polymerization temperature for the polymerization of the styrene-based monomer is usually set to 100°C or higher, but at a polymerization temperature of 100°C or higher, there is a risk of decomposition of the polymerizable monomer having an acid-dissociable group. On the other hand, if the polymerization temperature is set low so as not to cause decomposition of the polymerizable monomer having an acid-dissociable group, there is a problem that the polymerization of the styrene-based monomer does not proceed sufficiently.
本発明が解決しようとする課題は、スチレン系モノマーと酸解離性基を有する重合性モノマーとを低温で重合できる重合体の製造方法を提供することである。 The problem that the present invention aims to solve is to provide a method for producing a polymer that can polymerize a styrene-based monomer and a polymerizable monomer having an acid-dissociable group at a low temperature.
本発明者らは、上記課題を解決するため鋭意検討を行った結果、特定の化合物を用いることで重合温度６０℃以下であってもスチレン系モノマーと酸解離性基を有する重合性モノマーとを原子移動ラジカル重合が可能であることを見出し、本発明を完成させた。 As a result of intensive research to solve the above problems, the present inventors discovered that atom transfer radical polymerization of a styrene-based monomer and a polymerizable monomer having an acid-dissociable group is possible even at polymerization temperatures of 60°C or less by using a specific compound, and thus completed the present invention.
すなわち、本発明は、以下の重合体の製造方法等に関するものである。
１．酸解離性基を有する重合性モノマーおよびスチレン系モノマーを含有する重合成分を原子移動ラジカル重合する重合体の製造方法であって、
前記原子移動ラジカル重合を、有機塩素化合物であるラジカル重合開始剤、銅（II）化合物およびアミン化合物の存在下において、重合温度６０℃以下で行う重合体の製造方法。
２．前記ラジカル重合開始剤が、シアン化アルキルクロライド（アルキル基は炭素原子数１～６のアルキル基）、ビニルアルキルクロライド（アルキル基は炭素原子数１～６のアルキル基）、フェニルアルキルクロライド（アルキル基は炭素原子数１～６のアルキル基）、炭素原子数１～６のクロロカルボン酸および前記クロロカルボン酸のアルキルエステル（アルキル基は炭素原子数１～６のアルキル基）から選択される１種以上である１に記載の重合体の製造方法。
３．前記銅（II）化合物の使用量を前記ラジカル重合開始剤１モル当量に対して０．１～０．５モル当量の範囲とする１又は２に記載の重合体の製造方法。
４．前記銅（II）化合物が、ハロゲン化銅（II）である１～３のいずれかに記載の重合体の製造方法。
５．前記アミン化合物が、３級アミン構造および／又はピリジン環を有する化合物である１～４のいずれかに記載の重合体の製造方法。
６．前記アミン化合物が、２，２’－ビピリジル、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’－ペンタメチルジエチレントリアミン、トリスピリジルメチルアミンおよびトリス［２－（ジメチルアミノ）エチル］アミンからなる群から選択される１種以上である１～５のいずれかに記載の重合体の製造方法。
７．前記原子移動ラジカル重合を、前記ラジカル重合開始剤、前記銅（II）化合物、前記アミン化合物およびスズ化合物の存在下で行う１～６のいずれかに記載の重合体の製造方法。
８．前記酸解離性基を有する重合性モノマーが、下記一般式（ａ－１）、（ａ－２）又は（ａ－３）で表されるモノマーである１～７のいずれかに記載の重合体の製造方法。
Ｒ１１は、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり、
Ｖａ１は、エーテル結合を有しててもよい２価の炭化水素基であり、
ｎａ１は、０～２の範囲の整数であり、
Ｒａ１は、酸解離性基であり、
Ｒ１２は、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり、
Ｗａ１は、ｎａ２＋１価の炭化水素基であり、
ｎａ２は、１～３の範囲の整数であり、
Ｒａ２は、酸解離性基であり、
Ｙａ１は、単結合又はエーテル結合を有しててもよい２価の炭化水素基であり、
Ｚは重合性基を含む基であり、
Ｒａ３は、酸解離性基であり、
ｎａ３１は、０～３の範囲の整数であり、
ｎａ３２は、０以上の整数である。但し、ｎａ３２はｎａ３２≦ｎａ３１×２＋４を満たす。）
９．前記酸解離性基が、下記一般式（ａｄ－１）、（ａｄ－２）、（ａｄ－３）又は（ａｄ－４）で表される基である１～８のいずれかに記載の重合体の製造方法。
Ｒａ１０は、炭素原子数１～１２のアルキル基又は炭素原子数１～１２のエーテル結合を有するアルキル基であり、
Ｒａ１１、Ｒａ１２およびＲａ１３は、それぞれ独立に、水素原子又は炭素原子数１～１０のアルキル基であり、
Ｒａ１１、Ｒａ１２およびＲａ１３のうち少なくとも２つが互いに結合して環を形成してもよく、
Ａｒａ１は、環形成炭素原子数６～１２のアリール基又は環形成炭素原子数６～１２のアルキルアリール基であり、
Ｒａ１４およびＲａ１５は、それぞれ独立に、水素原子又は炭素原子数１～１０のアルキル基であり、
Ｒａ１６は、環形成炭素原子数６～１２のアリール基、環形成炭素原子数５～１２の脂環式炭化水素基又は、炭素原子数１～１０のアルキル基であり、
Ｘａは環形成炭素原子数５～１２の脂環式炭化水素基である。）
１０．前記スチレン系モノマーが下記一般式（ｂ）で表されるスチレン化合物である１～９のいずれかに記載の重合体の製造方法。
Ｒ２１は、水素原子又はメチル基であり、
Ｒ２２は、ハロゲン原子、炭素原子数１～５のアルキル基、炭素原子数２～１５のアルキルカルボニルオキシ基、水酸基、カルボキシル基、又は水酸基もしくはカルボキシル基の水素原子が酸解離性溶解抑制基で置換された基あり、
ｎｂは０～５の範囲の整数である）
１１．前記酸解離性溶解抑制基が、下記一般式（ｂｐ－１）又は（ｂｐ－２）で表される基である１０に記載の重合体の製造方法。
Ｒｂ１０は、水素原子又はメチル基であり、
Ｒｂ１２は、炭素原子数１～５のアルキル基であり、
Ｘｂは、環形成炭素原子数５～１２の脂環式炭化水素基であり、
ｎｂ１は０又は１であり、
Ｒｂ１３は、水素原子又は炭素原子数１～５のアルキル基であり、
Ｒｂ１４は、ハロゲン原子、炭素原子数１～５のアルキル基又は環形成炭素原子数５～１２の脂環式炭化水素基である。
ｎｂ２は０～３の範囲の整数である。）
１２．前記酸解離性基を有する重合性モノマーと前記スチレン系モノマーを、酸解離性基を有する重合性モノマー：スチレン系モノマー（質量比）＝９５：５～３０：７０で使用する１～１１のいずれかに記載の重合体の製造方法。
１３．１～１２のいずれかに記載の製造方法で得た酸解離性基を有する重合性モノマーとスチレン系モノマーのランダム共重合体を含有する組成物。
１４．レジスト組成物である１３に記載の組成物。
１５．１４のレジスト組成物を用いたレジストパターン。
That is, the present invention relates to the following method for producing a polymer, etc.
1. A method for producing a polymer by atom transfer radical polymerization of a polymerization component containing a polymerizable monomer having an acid-dissociable group and a styrene-based monomer, comprising the steps of:
The method for producing a polymer comprises carrying out the atom transfer radical polymerization in the presence of a radical polymerization initiator which is an organic chlorine compound, a copper (II) compound, and an amine compound at a polymerization temperature of 60° C. or lower.
2. The method for producing a polymer according to 1, wherein the radical polymerization initiator is at least one selected from the group consisting of cyanide alkyl chloride (wherein the alkyl group has 1 to 6 carbon atoms), vinyl alkyl chloride (wherein the alkyl group has 1 to 6 carbon atoms), phenyl alkyl chloride (wherein the alkyl group has 1 to 6 carbon atoms), chlorocarboxylic acid having 1 to 6 carbon atoms, and alkyl ester of the chlorocarboxylic acid (wherein the alkyl group has 1 to 6 carbon atoms).
3. The method for producing a polymer according to 1 or 2, wherein the amount of the copper (II) compound used is in the range of 0.1 to 0.5 molar equivalents per molar equivalent of the radical polymerization initiator.
4. The method for producing a polymer according to any one of 1 to 3, wherein the copper(II) compound is a copper(II) halide.
5. The method for producing a polymer according to any one of 1 to 4, wherein the amine compound is a compound having a tertiary amine structure and/or a pyridine ring.
6. The method for producing a polymer according to any one of 1 to 5, wherein the amine compound is one or more selected from the group consisting of 2,2'-bipyridyl, N,N,N',N'',N''-pentamethyldiethylenetriamine, trispyridylmethylamine and tris[2-(dimethylamino)ethyl]amine.
7. The method for producing a polymer according to any one of 1 to 6, wherein the atom transfer radical polymerization is carried out in the presence of the radical polymerization initiator, the copper (II) compound, the amine compound, and a tin compound.
8. The method for producing a polymer according to any one of 1 to 7, wherein the polymerizable monomer having an acid-dissociable group is a monomer represented by the following general formula (a-1), (a-2) or (a-3):
R 11 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms;
Va1 is a divalent hydrocarbon group which may have an ether bond,
n a1 is an integer ranging from 0 to 2;
Ra1 is an acid dissociable group,
R 12 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms;
Wa1 is a hydrocarbon group having a valence of n a2 +1;
n a2 is an integer ranging from 1 to 3;
Ra2 is an acid dissociable group,
Ya 1 is a divalent hydrocarbon group which may have a single bond or an ether bond;
Z is a group containing a polymerizable group,
Ra3 is an acid dissociable group,
n a31 is an integer ranging from 0 to 3;
n a32 is an integer equal to or greater than 0. However, n a32 satisfies n a32 ≦n a31 × 2 + 4.
9. The method for producing a polymer according to any one of 1 to 8, wherein the acid-dissociable group is a group represented by the following general formula (ad-1), (ad-2), (ad-3) or (ad-4):
Ra 10 is an alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms and an ether bond,
Ra 11 , Ra 12 and Ra 13 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
At least two of Ra 11 , Ra 12 and Ra 13 may be bonded to each other to form a ring;
Ara 1 is an aryl group having 6 to 12 ring carbon atoms or an alkylaryl group having 6 to 12 ring carbon atoms;
Ra 14 and Ra 15 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
Ra 16 is an aryl group having 6 to 12 ring carbon atoms, an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms, or an alkyl group having 1 to 10 carbon atoms,
Xa is an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms.
10. The method for producing a polymer according to any one of 1 to 9, wherein the styrene-based monomer is a styrene compound represented by the following general formula (b):
R 21 is a hydrogen atom or a methyl group;
R 22 represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyloxy group having 2 to 15 carbon atoms, a hydroxyl group, a carboxyl group, or a group in which the hydrogen atom of a hydroxyl group or a carboxyl group has been substituted with an acid dissociable, dissolution inhibiting group;
n b is an integer ranging from 0 to 5.
11. The method for producing a polymer according to 10, wherein the acid dissociable, dissolution inhibiting group is a group represented by the following general formula (bp-1) or (bp-2):
Rb10 is a hydrogen atom or a methyl group;
Rb12 is an alkyl group having 1 to 5 carbon atoms;
Xb is an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms,
n b1 is 0 or 1;
Rb13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
Rb 14 is a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms.
n b2 is an integer ranging from 0 to 3.
12. The method for producing a polymer according to any one of 1 to 11, wherein the polymerizable monomer having an acid-dissociable group and the styrene-based monomer are used in a ratio (mass ratio) of polymerizable monomer having an acid-dissociable group:styrene-based monomer=95:5 to 30:70.
13. A composition containing a random copolymer of a polymerizable monomer having an acid-labile group and a styrene-based monomer, obtained by the production method according to any one of 1 to 12.
14. The composition according to 13, which is a resist composition.
15. A resist pattern was formed using the resist composition of 14.
本発明により、スチレン系モノマーと酸解離性基を有する重合性モノマーとを低温で原子移動ラジカル重合できる重合体の製造方法が提供できる。 The present invention provides a method for producing a polymer that can perform atom transfer radical polymerization at low temperatures between a styrene-based monomer and a polymerizable monomer having an acid-dissociable group.
以下、本発明の一実施形態について説明する。本発明は、以下の実施形態に限定されるものではなく、本発明の効果を損なわない範囲で適宜変更を加えて実施することができる。 One embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be modified as appropriate without impairing the effects of the present invention.
［重合体の製造方法］
本発明の重合体の製造方法は、酸解離性基を有する重合性モノマーおよびスチレン系モノマーを含有する重合成分を原子移動ラジカル重合する重合体の製造方法であって、原子移動ラジカル重合を、有機塩素化合物であるラジカル重合開始剤、銅（II）化合物およびアミン化合物の存在下において、重合温度６０℃以下で行う。
[Method of producing polymer]
The method for producing a polymer of the present invention is a method for producing a polymer by atom transfer radical polymerization of polymerization components containing a polymerizable monomer having an acid dissociable group and a styrene-based monomer, and the atom transfer radical polymerization is carried out in the presence of a radical polymerization initiator which is an organic chlorine compound, a copper (II) compound, and an amine compound at a polymerization temperature of 60° C. or less.
リビングラジカル重合は、活性重合末端が原子又は原子団により保護されたドーマント種が可逆的にラジカルを発生させてモノマーと反応することにより生長反応が進行し、第一のモノマーが消費されても生長末端が活性を失うことなく、逐次的に追加される第二モノマーと反応してブロックポリマーを得ることができる。
本発明の重合体の製造方法では、ラジカル重合開始剤として有機塩素化合物を用いることで、生長途中で起こる副反応を抑制し、高い収率で狭分散な重合体を得ることができる。また、銅（II）化合物およびアミン化合物を用いることで、不安定な高活性触媒の失活を防ぐことができる。
以下、本発明の重合体の製造方法に用いる各成分について説明する。
In living radical polymerization, a dormant species, in which an active polymerization end is protected by an atom or atomic group, reversibly generates radicals and reacts with a monomer, thereby causing a propagation reaction to proceed. Even when the first monomer is consumed, the propagating end does not lose its activity, and can react with a second monomer that is successively added to obtain a block polymer.
In the method for producing a polymer of the present invention, by using an organic chlorine compound as a radical polymerization initiator, side reactions occurring during the polymerization can be suppressed, and a polymer with a narrow dispersion can be obtained in a high yield. In addition, by using a copper (II) compound and an amine compound, deactivation of an unstable highly active catalyst can be prevented.
Each component used in the process for producing the polymer of the present invention will be described below.
（有機塩素化合物）
有機塩素化合物は分子内に塩素を有する有機化合物であり、ラジカル重合開始剤として機能する。活性末端をＢｒではなくＣｌとすることで、生長途中で起こる副反応を抑制し、高い収率で狭分散な重合体を得ることができる。
有機塩素化合物は、塩素以外のハロゲン原子を含まないと好ましい。
(Organochlorine compounds)
An organic chlorine compound is an organic compound that has chlorine in the molecule and functions as a radical polymerization initiator. By making the active end Cl instead of Br, it is possible to suppress side reactions that occur during the growth and obtain a narrowly dispersed polymer in high yield.
The organic chlorine compound preferably does not contain any halogen atoms other than chlorine.
有機塩素化合物は、好ましくはシアン化アルキルクロライド（アルキル基は炭素原子数１～６のアルキル基）、ビニルアルキルクロライド（アルキル基は炭素原子数１～６のアルキル基）、フェニルアルキルクロライド（アルキル基は炭素原子数１～６のアルキル基）、炭素原子数１～６のクロロカルボン酸および前記クロロカルボン酸のアルキルエステル（アルキル基は炭素原子数１～６のアルキル基）から選択される１種以上である。
前記クロロカルボン酸のアルキルエステルは、クロロカルボン酸にフェニル基がさらに置換したフェニルクロロカルボン酸のアルキルエステルも使用できる。
The organic chlorine compound is preferably one or more selected from cyanide alkyl chlorides (wherein the alkyl group has 1 to 6 carbon atoms), vinyl alkyl chlorides (wherein the alkyl group has 1 to 6 carbon atoms), phenyl alkyl chlorides (wherein the alkyl group has 1 to 6 carbon atoms), chlorocarboxylic acids having 1 to 6 carbon atoms, and alkyl esters of the chlorocarboxylic acids (wherein the alkyl group has 1 to 6 carbon atoms).
The alkyl ester of chlorocarboxylic acid may be an alkyl ester of phenylchlorocarboxylic acid, which is a chlorocarboxylic acid further substituted with a phenyl group.
有機塩素化合物の具体例としては、フェニルメチルクロライド、１－フェニルエチルクロライド、１－フェニルイソプロピルクロライド等のフェニルアルキルクロライド（アルキル基は炭素原子数１～６のアルキル基）；２－クロロプロピオン酸、２－クロロイソ酪酸、２－クロロプロピオン酸メチル、２－クロロプロピオン酸エチル、２－クロロイソ酪酸エチル、２，３－ジクロロプロピオン酸メチルなどの炭素原子数１～６のクロロカルボン酸およびそのアルキルエステル（アルキルエステルのアルキル基は炭素原子数１～６のアルキル基）；クロロホルム、四塩化炭素等のハロゲン化アルキル（アルキル基は炭素原子数１～６のアルキル基）；クロロアセトフェノン、クロロアセトン、クロロイソプロピルフェニルケトン、ｐ－トルエンスルフォニルクロリド、２－クロロプロピオニトリル、α，α’－ジクロロキシレン、クロロアセトニトリル（シアン化メチルクロライド）、ビニルメチルクロライド、等が挙げられる。 Specific examples of organic chlorine compounds include phenyl alkyl chlorides such as phenyl methyl chloride, 1-phenyl ethyl chloride, and 1-phenyl isopropyl chloride (where the alkyl group has 1 to 6 carbon atoms); chlorocarboxylic acids having 1 to 6 carbon atoms and their alkyl esters (where the alkyl group of the alkyl ester has 1 to 6 carbon atoms), such as 2-chloropropionic acid, 2-chloroisobutyric acid, methyl 2-chloropropionate, ethyl 2-chloropropionate, ethyl 2-chloroisobutyrate, and methyl 2,3-dichloropropionate; alkyl halides such as chloroform and carbon tetrachloride (where the alkyl group has 1 to 6 carbon atoms); chloroacetophenone, chloroacetone, chloroisopropyl phenyl ketone, p-toluenesulfonyl chloride, 2-chloropropionitrile, α,α'-dichloroxylene, chloroacetonitrile (methyl chloride cyanide), and vinyl methyl chloride.
有機塩素化合物は１種単独で用いてもよく、２種以上を併用してもよい。 The organic chlorine compounds may be used alone or in combination of two or more.
有機塩素化合物の使用量は特に限定されないが、重合成分（例えばスチレン系モノマーと（メタ）アクリル系モノマーの合計）１００ｍｏｌに対して例えば０．０５～２０ｍｏｌであり、好ましくは０．１～１０ｍｏｌであり、より好ましくは０．５～１０ｍｏｌである。 The amount of the organic chlorine compound used is not particularly limited, but is, for example, 0.05 to 20 mol, preferably 0.1 to 10 mol, and more preferably 0.5 to 10 mol per 100 mol of the polymerization components (e.g., the total of the styrene-based monomer and the (meth)acrylic monomer).
（銅（II）化合物）
活性種として銅（Ｉ）化合物ではなく銅（II）化合物を使用する。
(Copper (II) Compounds)
A copper(II) compound is used as the active species rather than a copper(I) compound.
銅（II）化合物は、Ｃｕ２＋Ｘ２で表される化合物であり、Ｘは、ハロゲン原子、炭素原子数１～６のアルコキシル基、（ＳＯ４）１／２、（ＰＯ４）１／３、（ＨＰＯ４）１／２、（Ｈ２ＰＯ４）、トリフラート、ヘキサフルオロホスフェート、メタンスルホネート、アリールスルホネート（好ましくはベンゼンスルホネート又はトルエンスルホネート）、ＳｅＲ１１、ＣＮ及びＲ１２ＣＯＯからなる群から選択することができる。ここで、Ｒ１１は、アリール基、直鎖状又は分岐状の炭素原子数１～２０（好ましくは炭素原子数１～１０）のアルキル基を表し、Ｒ１２は、水素原子、ハロゲンで１～５回（好適にはフッ素もしくは塩素で１～３回）置換されていてもよい直鎖状又は分岐状の炭素原子数１～６のアルキル基（好ましくはメチル基）を表す。 The copper (II) compound is a compound represented by Cu 2+ X 2 , where X can be selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO 4 ) 1/2 , (PO 4 ) 1/3 , (HPO 4 ) 1/2 , (H 2 PO 4 ), triflate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 11 , CN, and R 12 COO, where R 11 represents an aryl group, or a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 12 represents a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted 1 to 5 times with a halogen (preferably 1 to 3 times with fluorine or chlorine).
入手の容易さ等も考慮すると、銅（II）化合物はハロゲン化銅（II）であると好ましい。 Considering the ease of availability, it is preferable that the copper(II) compound is a copper(II) halide.
銅（II）化合物は１種単独で用いてもよく、２種以上を併用してもよい。 The copper(II) compound may be used alone or in combination of two or more types.
銅（II）化合物の使用量は特に限定されないが、ラジカル重合開始剤（有機塩素化合物）１モル当量に対して例えば０．１～１．０モル当量であり、好ましくは０．１～０．８モル当量であり、より好ましくは０．１～０．５モル当量である。 The amount of copper (II) compound used is not particularly limited, but is, for example, 0.1 to 1.0 molar equivalents, preferably 0.1 to 0.8 molar equivalents, and more preferably 0.1 to 0.5 molar equivalents relative to 1 molar equivalent of the radical polymerization initiator (organic chlorine compound).
（アミン化合物）
アミン化合物は、銅（II）化合物と配位結合可能な配位子化合物であればよく、例えば銅（II）とσ結合を介して配位できる１つ以上の窒素原子を含む配位子を有する化合物である。
(Amine Compound)
The amine compound may be any ligand compound capable of forming a coordinate bond with a copper(II) compound, and is, for example, a compound having a ligand containing one or more nitrogen atoms capable of forming a coordinate bond with copper(II) via a σ bond.
アミン化合物は、好ましくは３級アミン構造および／又はピリジン環を有する化合物であり、より好ましくは下記一般式（ｃ－１）又は（ｃ－２）で表される化合物である The amine compound is preferably a compound having a tertiary amine structure and/or a pyridine ring, and more preferably a compound represented by the following general formula (c-1) or (c-2):
Ｒｃ１、Ｒｃ２、Ｒｃ３およびＲｃ４は、それぞれ独立に、アミノ結合（－Ｎ－）を有してもよい炭素原子数１～１２のアルキル基であり、
Ｒｃ５およびＲｃ６は、それぞれ独立に、アミノ結合（－Ｎ－）および／又はビニル結合を有してもよい炭素原子数２～１２のアルキル基であり、
Ｘｃは２価の連結基であり、
ｎｃ１およびｎｃ１は、それぞれ独立に、０～４の範囲の整数であり、
ｎｃ３は０又は１の整数である。）
R c1 , R c2 , R c3 and R c4 each independently represent an alkyl group having 1 to 12 carbon atoms which may have an amino bond (—N—),
R c5 and R c6 each independently represent an alkyl group having 2 to 12 carbon atoms which may have an amino bond (—N—) and/or a vinyl bond;
Xc is a divalent linking group;
n and n are each independently an integer ranging from 0 to 4;
nc3 is an integer of 0 or 1.
Ｒｃ１～Ｒｃ６において、アミノ結合（－Ｎ－）を有する炭素原子数１～１２のアルキル基とは、アルキル基の少なくとも１つの炭素原子が窒素原子に置き換わった基を意味する。
Ｒｃ５およびＲｃ６において、ビニル結合を有する炭素原子数２～１２のアルキル基とは、アルキル基の少なくとも１組の炭素原子がビニル結合を形成していることを意味する。
In R c1 to R c6 , the alkyl group having 1 to 12 carbon atoms and having an amino bond (—N—) means a group in which at least one carbon atom of the alkyl group is replaced with a nitrogen atom.
In R c5 and R c6 , the alkyl group having 2 to 12 carbon atoms and a vinyl bond means that at least one pair of carbon atoms in the alkyl group forms a vinyl bond.
Ｒｃ１～Ｒｃ６のアルキル基の構造は、直鎖状および分岐鎖状のいずれでもよく、環構造を含んでもよい。
また、Ｒｃ１～Ｒｃ６のアルキル基は、さらに置換基を有してもよく、当該置換基としては、水酸基、オキソ基、エーテル結合（－Ｏ－）、カルボキシル基、シアノ基等が挙げれる。
The structure of the alkyl groups of R c1 to R c6 may be either linear or branched, and may contain a ring structure.
Moreover, the alkyl groups of R c1 to R c6 may further have a substituent, and examples of the substituent include a hydroxyl group, an oxo group, an ether bond (—O—), a carboxyl group, and a cyano group.
Ｘｃの２価の連結基は、例えば単結合又はアミノ結合（－Ｎ－）を有してもよい炭素原子数１～１２のアルキレン基である。 The divalent linking group for Xc is, for example, an alkylene group having 1 to 12 carbon atoms which may have a single bond or an amino bond (-N-).
アミン化合物の具体例としては、２，２’－ビピリジル及びその誘導体、１，１０－フェナントロリン及びその誘導体、テトラメチルエチレンジアミン、ペンタメチルジエチレントリアミン、ヘキサメチルトリス（２－アミノエチル）アミン、トリス［２－（ジメチルアミノ）エチル］アミン、トリス［２－（ジエチルアミノ）エチル］アミン、トリス［２－（ジ－（２－（メトキシカルボニル）エチル）アミノ）エチル］アミン、トリス［２－（ジ－（２－（ｎ－ブトキシカルボニル）エチル）アミノ）エチル］アミン、２，５，９，１２－テトラメチル－２，５，９，１２－テトラアザトリデカン、２，６，９，１３－テトラメチル－２，６，９，１３－テトラアザテトラデカン、４，１１－ジメチル－１，４，８，１１－テトラアザビシクロ［６．６．２］ヘキサデカン、Ｎ’－Ｎ”－ジメチル－Ｎ’，Ｎ”－ビス（（ピリジン－２－イル）メチル）アミン、２，５，８，１２－テトラメチル－２，５，８，１２－テトラアザトリデカン、トリス（２－ピリジルメチル）アミン、Ｎ，Ｎ，Ｎ‘，Ｎ’－テトラ［（２－ピリジル）メチル］エチレンジアミン、Ｎ－［２－（ジメチルアミノ）エチル］－Ｎ，Ｎ’，Ｎ”－トリメチル－１，３－プロパンジアミン、Ｎ－（２－アミノエチル）－１，３－プロパンジアミン、Ｎ－（ｎ－プロピル）ピリジルメチルアミン、Ｎ－（ｎ－オクチル）ピリジルメチルアミン等のポリアミンが挙げられる。 Specific examples of amine compounds include 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris(2-aminoethyl)amine, tris[2-(dimethylamino)ethyl]amine, tris[2-(diethylamino)ethyl]amine, tris[2-(di-(2-(methoxycarbonyl)ethyl)amino)ethyl]amine, tris[2-(di-(2-(n-butoxycarbonyl)ethyl)amino)ethyl]amine, 2,5,9,12-tetramethyl-2,5,9,12-tetraazatridecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetate, Examples of polyamines include ladecane, 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane, N'-N"-dimethyl-N',N"-bis((pyridin-2-yl)methyl)amine, 2,5,8,12-tetramethyl-2,5,8,12-tetraazatridecane, tris(2-pyridylmethyl)amine, N,N,N',N'-tetra[(2-pyridyl)methyl]ethylenediamine, N-[2-(dimethylamino)ethyl]-N,N',N"-trimethyl-1,3-propanediamine, N-(2-aminoethyl)-1,3-propanediamine, N-(n-propyl)pyridylmethylamine, and N-(n-octyl)pyridylmethylamine.
アミン化合物は１種単独で用いてもよく、２種以上を併用してもよい。 The amine compounds may be used alone or in combination of two or more.
アミン化合物の使用量は、銅（II）化合物１モル当量に対して例えば０．５～４モル当量であり、好ましくは０．７５～３モル当量であり、より好ましくは１～２モル当量である。 The amount of the amine compound used is, for example, 0.5 to 4 molar equivalents, preferably 0.75 to 3 molar equivalents, and more preferably 1 to 2 molar equivalents, per molar equivalent of the copper(II) compound.
（スズ化合物）
本発明の製造方法では原子移動ラジカル重合を、好ましくは前記ラジカル重合開始剤、前記銅（II）化合物、前記アミン化合物およびスズ化合物の存在下で行う。
スズ化合物は、銅（II）化合物とアミン化合物の錯体化合物の還元剤として機能する化合物であり、スズ化合物をさらに用いることで銅（II）化合物の高活性触媒の失活を防ぐことができる。
(Tin compounds)
In the production method of the present invention, atom transfer radical polymerization is preferably carried out in the presence of the radical polymerization initiator, the copper (II) compound, the amine compound and the tin compound.
The tin compound functions as a reducing agent for a complex compound of a copper (II) compound and an amine compound, and the use of the tin compound in addition can prevent the deactivation of the highly active catalyst of the copper (II) compound.
スズ化合物としては、例えば有機スズ化合物が使用でき、当該有機スズ化合物としては、ジブチルスズジアセテート、ジブチルスズジラウレート、ジブチルスズメルカプチド、ジブチルスズチオカルボキシレート、ジブチルスズジマレエート、ジオクチルスズチオカルボキシレート等のジアルキルスズ化合物；オクチル酸スズ、２－エチルヘキサン酸スズ等のカルボン酸スズ塩が挙げられる。 As the tin compound, for example, an organic tin compound can be used, and examples of the organic tin compound include dialkyltin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate; and tin carboxylates such as tin octoate and tin 2-ethylhexanoate.
スズ化合物は１種単独で用いてもよく、２種以上を併用してもよい。 The tin compounds may be used alone or in combination of two or more.
スズ化合物の使用量は、銅（II）化合物１モル当量に対して例えば０．１～１０モル当量であり、好ましくは０．２～５モル当量であり、より好ましくは０．３～１モル当量である。 The amount of the tin compound used is, for example, 0.1 to 10 molar equivalents, preferably 0.2 to 5 molar equivalents, and more preferably 0.3 to 1 molar equivalent, per molar equivalent of the copper(II) compound.
（酸解離性基を有する重合性モノマー）
重合成分である酸解離性基を有する重合性モノマーにおいて、「重合性モノマー」とは、重合性基を有するモノマーを意味し、当該重合性基としては例えばビニル基、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、（メタ）アクリロイルアミノ基、ビニルエーテル基、アリル基、スチリル基、マレイミド基等が挙げられる。
(Polymerizable monomer having an acid-dissociable group)
With regard to the polymerizable monomer having an acid-dissociable group, which is a polymerization component, the term "polymerizable monomer" means a monomer having a polymerizable group, and examples of the polymerizable group include a vinyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl ether group, an allyl group, a styryl group, and a maleimide group.
本発明の製造方法で得られる重合体を例えば化学増幅型レジスト組成物のベース樹脂とする場合、酸解離性基を有する重合性モノマーは、好ましくは下記一般式（ａ－１）、（ａ－２）又は（ａ－３）で表されるモノマーである。 When the polymer obtained by the manufacturing method of the present invention is used as the base resin of a chemically amplified resist composition, the polymerizable monomer having an acid-dissociable group is preferably a monomer represented by the following general formula (a-1), (a-2) or (a-3).
Ｒ１１は、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり、
Ｖａ１は、エーテル結合を有しててもよい２価の炭化水素基であり、
ｎａ１は、０～２の範囲の整数であり、
Ｒａ１は、酸解離性基であり、
Ｒ１２は、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり、
Ｗａ１は、ｎａ２＋１価の炭化水素基であり、
ｎａ２は、１～３の範囲の整数であり、
Ｒａ２は、酸解離性基であり、
Ｙａ１は、単結合又はエーテル結合を有しててもよい２価の炭化水素基であり、
Ｚは重合性基を含む基であり、
Ｒａ３は、酸解離性基であり、
ｎａ３１は、０～３の範囲の整数であり、
ｎａ３２は、０以上の整数である。但し、ｎａ３２はｎａ３２≦ｎａ３１×２＋４を満たす。）
R 11 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms;
Va1 is a divalent hydrocarbon group which may have an ether bond,
n a1 is an integer ranging from 0 to 2;
Ra1 is an acid dissociable group,
R 12 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms;
Wa1 is a hydrocarbon group having a valence of n a2 +1;
n a2 is an integer ranging from 1 to 3;
Ra2 is an acid dissociable group,
Ya 1 is a divalent hydrocarbon group which may have a single bond or an ether bond;
Z is a group containing a polymerizable group,
Ra3 is an acid dissociable group,
n a31 is an integer ranging from 0 to 3;
n a32 is an integer equal to or greater than 0. However, n a32 satisfies n a32 ≦n a31 × 2 + 4.
Ｒ１１およびＲ１２の炭素原子数１～５のアルキル基の構造は、直鎖状および分岐鎖状のいずれでもよく、環構造を含んでもよい。
Ｒ１１およびＲ１２の炭素原子数１～５のアルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。
The structure of the alkyl group having 1 to 5 carbon atoms for R 11 and R 12 may be either linear or branched, and may contain a ring structure.
Specific examples of the alkyl group having 1 to 5 carbon atoms for R 11 and R 12 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
Ｒ１１およびＲ１２の炭素原子数１～５のハロゲン化アルキル基は、前記炭素原子数１～５のアルキル基の水素原子の一部または全部がハロゲン原子で置換された基であり、当該ハロゲン原子としては、好ましくはフッ素原子である。 The halogenated alkyl group having 1 to 5 carbon atoms for R 11 and R 12 is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms, and the halogen atoms are preferably fluorine atoms.
Ｒ１１およびＲ１２は、好ましくは水素原子又はメチル基である。 R 11 and R 12 are preferably a hydrogen atom or a methyl group.
Ｖａ１およびＹａ１のエーテル結合を有しててもよい２価の炭化水素基は、脂肪族炭化水素基および芳香族炭化水素基のいずれでもよく、好ましくは脂肪族炭化水素基である。
当該脂肪族炭化水素基は、飽和でもよく不飽和でもよい。また、当該脂肪族炭化水素基の構造は、直鎖状および分岐鎖状のいずれもよく、環構造を含んでもよい。
The divalent hydrocarbon group which may have an ether bond represented by Va1 and Ya1 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group.
The aliphatic hydrocarbon group may be saturated or unsaturated. The structure of the aliphatic hydrocarbon group may be either linear or branched, and may include a ring structure.
Ｖａ１およびＹａ１のエーテル結合を有しててもよい２価の炭化水素基は、好ましくは炭素原子数１～１０のアルキレン基であり、より好ましくは炭素原子数１～６のアルキレン基であり、さらに好ましくは炭素原子数１～４のアルキレン基である。 The divalent hydrocarbon group which may have an ether bond for Va1 and Ya1 is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
Ｗａ１のｎａ２＋１価の炭化水素基は、脂肪族炭化水素基および芳香族炭化水素基のいずれでもよく、好ましくは脂肪族炭化水素基である。
当該脂肪族炭化水素基は、飽和でもよく不飽和でもよい。また、当該脂肪族炭化水素基の構造は、直鎖状および分岐鎖状のいずれもよく、環構造を含んでもよい。
The n a2 +1 valent hydrocarbon group of Wa 1 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group.
The aliphatic hydrocarbon group may be saturated or unsaturated. The structure of the aliphatic hydrocarbon group may be either linear or branched, and may include a ring structure.
ｎａ２＋１価は、好ましくは２～４価であり、より好ましくは２価又は３価である。 The n a2 +1 valency is preferably divalent to tetravalent, and more preferably divalent or trivalent.
Ｚの「重合性基を含む基」は、重合性基のみから構成される基でもよいし、重合性基と当該重合性基以外の他の基とから構成される基でもよい。「重合性基以外の他の基」としては、エーテル結合を有しててもよい２価の炭化水素基が挙げられる。
上記エーテル結合を有しててもよい２価の炭化水素基は、好ましくは炭素原子数１～１０のアルキレン基であり、より好ましくは炭素原子数１～６のアルキレン基であり、さらに好ましくは炭素原子数１～４のアルキレン基である。
The "group containing a polymerizable group" of Z may be a group composed only of a polymerizable group, or may be a group composed of a polymerizable group and a group other than the polymerizable group. Examples of the "group other than the polymerizable group" include a divalent hydrocarbon group which may have an ether bond.
The divalent hydrocarbon group which may have an ether bond is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
Ｚの重合性基を含む基としては、例えば、ビニル基、アリル基、アクリロイル基、メタクリロイル基、フルオロビニル基、ジフルオロビニル基、トリフルオロビニル基、ジフルオロトリフルオロメチルビニル基、トリフルオロアリル基、パーフルオロアリル基、トリフルオロメチルアクリロイル基、ノニルフルオロブチルアクリロイル基、ビニルエーテル基、含フッ素ビニルエーテル基、アリルエーテル基、含フッ素アリルエーテル基、スチリル基、ビニルナフチル基、含フッ素スチリル基、含フッ素ビニルナフチル基、ノルボルニル基、含フッ素ノルボルニル基、シリル基等が挙げられ、好ましくはビニル基である。 Examples of groups containing a polymerizable group for Z include vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, fluorovinyl groups, difluorovinyl groups, trifluorovinyl groups, difluorotrifluoromethylvinyl groups, trifluoroallyl groups, perfluoroallyl groups, trifluoromethylacryloyl groups, nonylfluorobutylacryloyl groups, vinyl ether groups, fluorine-containing vinyl ether groups, allyl ether groups, fluorine-containing allyl ether groups, styryl groups, vinyl naphthyl groups, fluorine-containing styryl groups, fluorine-containing vinyl naphthyl groups, norbornyl groups, fluorine-containing norbornyl groups, and silyl groups, with vinyl groups being preferred.
Ｒａ１、Ｒａ２およびＲａ３の酸解離性基は、光酸発生剤、熱酸発生剤などの酸発生剤から発生する酸の作用により解離可能な置換基であり、好ましくは下記一般式（ａｄ－１）、（ａｄ－２）、（ａｄ－３）又は（ａｄ－４）で表される基である。 The acid-dissociable groups of Ra 1 , Ra 2 and Ra 3 are substituents which can be dissociated by the action of an acid generated from an acid generator such as a photoacid generator or a thermal acid generator, and are preferably groups represented by the following general formula (ad-1), (ad-2), (ad-3) or (ad-4).
Ｒａ１０は、炭素原子数１～１２のアルキル基又は炭素原子数１～１２のエーテル結合を有するアルキル基であり、
Ｒａ１１、Ｒａ１２およびＲａ１３は、それぞれ独立に、水素原子又は炭素原子数１～１２のアルキル基であり、
Ｒａ１１、Ｒａ１２およびＲａ１３のうち少なくとも２つが互いに結合して環を形成してもよく、
Ａｒａ１は、環形成炭素原子数６～１２のアリール基又は環形成炭素原子数６～１２のアルキルアリール基であり、
Ｒａ１４およびＲａ１５は、それぞれ独立に、水素原子又は炭素原子数１～１２のアルキル基であり、
Ｒａ１６は、環形成炭素原子数６～１２のアリール基、環形成炭素原子数５～１２の脂環式炭化水素基又は炭素原子数１～１０のアルキル基であり、
Ｘａは環形成炭素原子数５～１５の脂環式炭化水素基であり、
＊は結合手である。）
Ra 10 is an alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms and an ether bond,
Ra 11 , Ra 12 and Ra 13 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms;
At least two of Ra 11 , Ra 12 and Ra 13 may be bonded to each other to form a ring;
Ara 1 is an aryl group having 6 to 12 ring carbon atoms or an alkylaryl group having 6 to 12 ring carbon atoms;
Ra 14 and Ra 15 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms;
Ra 16 is an aryl group having 6 to 12 ring carbon atoms, an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms, or an alkyl group having 1 to 10 carbon atoms,
Xa is an alicyclic hydrocarbon group having 5 to 15 ring carbon atoms,
* is a bond.)
Ｒａ１０の炭素原子数１～１２のアルキル基の構造は、直鎖状および分岐鎖状のいずれでもよく、環構造を含んでもよい。
Ｒａ１０の炭素原子数１～１２のアルキル基は、好ましくは炭素原子数１～１０のアルキル基であり、より好ましくは炭素原子数１～５のアルキル基である。
The structure of the alkyl group having 1 to 12 carbon atoms represented by Ra 10 may be either linear or branched, and may contain a ring structure.
The alkyl group having 1 to 12 carbon atoms for Ra 10 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
Ｒａ１０の炭素原子数１～１２のアルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。 Specific examples of the alkyl group having 1 to 12 carbon atoms for Ra 10 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
Ｒａ１０の炭素原子数１～１２のエーテル結合を有するアルキル基は、上記アルキル基の炭素炭素間にエーテル結合（－Ｏ－）を含む基である。 The alkyl group having 1 to 12 carbon atoms and an ether bond for Ra 10 is a group containing an ether bond (—O—) between carbon atoms of the alkyl group.
Ｒａ１１、Ｒａ１２およびＲａ１３の炭素原子数１～１２のアルキル基は、Ｒａ１０の炭素原子数１～１２のアルキル基と同じである。 The alkyl group having 1 to 12 carbon atoms for Ra 11 , Ra 12 and Ra 13 is the same as the alkyl group having 1 to 12 carbon atoms for Ra 10 .
Ｒａ１１、Ｒａ１２およびＲａ１３のうち少なくとも２つが互いに結合して環を形成してもよい。
例えばＲａ１１およびＲａ１２が互いに結合してシクロヘキセン環又はシクロペンテン環を形成してもよく、Ｒａ１２およびＲａ１３が互いに結合してシクロペンタン環を形成をしてもよい。
At least two of Ra 11 , Ra 12 and Ra 13 may be bonded to each other to form a ring.
For example, Ra 11 and Ra 12 may be bonded to each other to form a cyclohexene ring or a cyclopentene ring, and Ra 12 and Ra 13 may be bonded to each other to form a cyclopentane ring.
Ａｒａ１の環形成炭素原子数６～１２のアリール基としては、フェニル基、ナフタレニル基、アントラセニル基、フェナントレニル基等が挙げられる。 Examples of the aryl group having 6 to 12 ring carbon atoms for Ara 1 include a phenyl group, a naphthalenyl group, an anthracenyl group, and a phenanthrenyl group.
Ａｒａ１の環形成炭素原子数６～１２のアルキルアリール基は、上記アリール基にさらにアルキル基が置換した基である。 The alkylaryl group having 6 to 12 ring carbon atoms for Ara 1 is the above-mentioned aryl group further substituted with an alkyl group.
Ｒａ１４、Ｒａ１５およびＲａ１５の炭素原子数１～１２のアルキル基は、Ｒａ１０の炭素原子数１～１２のアルキル基と同じである。 The alkyl group having 1 to 12 carbon atoms for Ra 14 , Ra 15 and Ra 15 is the same as the alkyl group having 1 to 12 carbon atoms for Ra 10 .
Ｒａ１６の環形成炭素原子数６～１２のアリール基は、Ａｒａ１の環形成炭素原子数６～１２のアリール基と同じである。 The aryl group having 6 to 12 ring carbon atoms for Ra 16 is the same as the aryl group having 6 to 12 ring carbon atoms for Ara 1 .
Ｒａ１６の環形成炭素原子数５～１２の脂環式炭化水素基は、単環式脂環式炭化水素基および多環式脂環式炭化水素基のいずれもでよい。
Ｒａ１６の環形成炭素原子数５～１２の脂環式炭化水素基の具体例としては、シクロペンチル基、シクロヘキシル基、ジシクロペンタニル基、アダマンチル基、ノルボルニル基、イソボルニル基、トリシクロデカニル基、テトラシクロドデカニル基等が挙げられる。
The alicyclic hydrocarbon group having 5 to 12 ring carbon atoms for Ra 16 may be either a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group.
Specific examples of the alicyclic hydrocarbon group having 5 to 12 ring carbon atoms for Ra 16 include a cyclopentyl group, a cyclohexyl group, a dicyclopentanyl group, an adamantyl group, a norbornyl group, an isobornyl group, a tricyclodecanyl group, and a tetracyclododecanyl group.
Ｘａの環形成炭素原子数５～１５の脂環式炭化水素基は、単環式脂環式炭化水素基および多環式脂環式炭化水素基のいずれもでよい。
Ｘａの環形成炭素原子数５～１５の脂環式炭化水素基の具体例としては、シクロペンチル基、シクロヘキシル基、ジシクロペンタニル基、アダマンチル基、ノルボルニル基、イソボルニル基、トリシクロデカニル基、テトラシクロドデカニル基等が挙げられる。
The alicyclic hydrocarbon group having 5 to 15 ring carbon atoms represented by Xa may be either a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group.
Specific examples of the alicyclic hydrocarbon group of Xa having 5 to 15 ring carbon atoms include a cyclopentyl group, a cyclohexyl group, a dicyclopentanyl group, an adamantyl group, a norbornyl group, an isobornyl group, a tricyclodecanyl group, and a tetracyclododecanyl group.
Ｘａの環形成炭素原子数５～１５の脂環式炭化水素基はさらに置換基を有してもよく、当該置換基としては、水酸基、オキソ基、カルボキシル基、炭素原子数１～６のアルキル基、炭素原子数１～６のアルコキシ基、炭素原子数１～６のヒドロキシアルキル基、炭素原子数１～６のカルボキシアルキル基、炭素原子数１～６のアシルアルコキシ基等が挙げれる。 The alicyclic hydrocarbon group of Xa having 5 to 15 ring carbon atoms may further have a substituent, and examples of the substituent include a hydroxyl group, an oxo group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a carboxyalkyl group having 1 to 6 carbon atoms, and an acylalkoxy group having 1 to 6 carbon atoms.
一般式（ａｄ－１）で表される酸解離性基の具体例を以下に示す。 Specific examples of the acid-dissociable group represented by general formula (ad-1) are shown below.
一般式（ａｄ－２）で表される酸解離性基の具体例を以下に示す。 Specific examples of the acid-dissociable group represented by general formula (ad-2) are shown below.
一般式（ａｄ－３）で表される酸解離性基の具体例を以下に示す。 Specific examples of the acid-dissociable group represented by general formula (ad-3) are shown below.
一般式（ａｄ－３）で表される酸解離性基の具体例を以下に示す。 Specific examples of the acid-dissociable group represented by general formula (ad-3) are shown below.
本発明の製造方法で得られる重合体の酸解離性基を有する重合性モノマーの繰り返し部分の具体例を以下に示す。尚、Ｒαは、水素原子、メチル基又はトリフルオロメチル基を表す。 Specific examples of the repeating portion of the polymerizable monomer having an acid-labile group in the polymer obtained by the production method of the present invention are shown below: In addition, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group.
（スチレン系モノマー）
重合成分であるスチレン系モノマーは特に限定されない。
本発明の製造方法で得られる重合体を例えば化学増幅型レジスト組成物のベース樹脂とする場合、スチレン系モノマーは、好ましくは下記一般式（ｂ）で表されるスチレン化合物である。
(styrene monomer)
The styrene monomer that is a polymerization component is not particularly limited.
When the polymer obtained by the production method of the present invention is used as the base resin of, for example, a chemically amplified resist composition, the styrene-based monomer is preferably a styrene compound represented by the following general formula (b).
Ｒ２１は、水素原子又はメチル基であり、
Ｒ２２は、ハロゲン原子、炭素原子数１～５のアルキル基、炭素原子数２～１５のアルキルカルボニルオキシ基、水酸基、カルボキシル基、又は水酸基もしくはカルボキシル基の水素原子が酸解離性溶解抑制基で置換された基あり、
ｎｂは０～５の範囲の整数である）
R 21 is a hydrogen atom or a methyl group;
R 22 represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyloxy group having 2 to 15 carbon atoms, a hydroxyl group, a carboxyl group, or a group in which the hydrogen atom of a hydroxyl group or a carboxyl group has been substituted with an acid dissociable, dissolution inhibiting group;
n b is an integer ranging from 0 to 5.
Ｒ２２の炭素原子数１～５のアルキル基の構造は、直鎖状および分岐鎖状のいずれでもよく、環構造を含んでもよい。
Ｒ２２の炭素原子数１～５のアルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。
The structure of the alkyl group having 1 to 5 carbon atoms for R 22 may be either linear or branched, and may contain a ring structure.
Specific examples of the alkyl group having 1 to 5 carbon atoms for R 22 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
Ｒ２２の炭素原子数２～１５のアルキルカルボニルオキシ基は、Ｒ－Ｃ（＝Ｏ）－Ｏ－で表される置換基であり（Ｒはアルキル基）、Ｒ２２の炭素原子数２～１５のアルキルカルボニルオキシ基のアルキル基部分の構造は、直鎖状および分岐鎖状のいずれでもよく、環構造を含んでもよい。
Ｒ２２の炭素原子数２～１５のアルキルカルボニルオキシ基の具体例としては、アセトキシ基、プロピオニルオキシ基、ブチリルオキシ基、イソブチリルオキシ基、バレリルオキシ基、イソバレリルオキシ基、ピバロイルオキシ基等が挙げられる。
The alkylcarbonyloxy group having 2 to 15 carbon atoms represented by R 22 is a substituent represented by R-C(=O)-O- (R is an alkyl group), and the structure of the alkyl group portion of the alkylcarbonyloxy group having 2 to 15 carbon atoms represented by R 22 may be either linear or branched, or may contain a ring structure.
Specific examples of the alkylcarbonyloxy group having 2 to 15 carbon atoms for R 22 include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, and a pivaloyloxy group.
Ｒ２２の酸解離性溶解抑制基は、解離前はアルカリ溶解抑制性を示すことができ、且つ、光酸発生剤、熱酸発生剤などの酸発生剤から発生する酸の作用により解離可能な置換基を意味する。
当該酸解離性溶解抑制基は、好ましくは下記一般式（ｂｐ－１）又は（ｂｐ－２）で表される基である。
Ｒｂ１０は、水素原子又はメチル基であり、
Ｒｂ１２は、炭素原子数１～５のアルキル基であり、
Ｘｂは、環形成炭素原子数５～１２の脂環式炭化水素基であり、
ｎｂ１は０又は１であり、
Ｒｂ１３は、水素原子又は炭素原子数１～５のアルキル基であり、
Ｒｂ１４は、ハロゲン原子、炭素原子数１～５のアルキル基又は環形成炭素原子数５～１２の脂環式炭化水素基である。
ｎｂ２は０～３の範囲の整数であり、
＊は結合手である。）
The acid dissociable dissolution inhibiting group for R 22 refers to a substituent which is capable of exhibiting alkali dissolution inhibiting properties before dissociation and which can be dissociated by the action of an acid generated from an acid generator such as a photoacid generator or a thermal acid generator.
The acid dissociable, dissolution inhibiting group is preferably a group represented by the following general formula (bp-1) or (bp-2).
Rb10 is a hydrogen atom or a methyl group;
Rb12 is an alkyl group having 1 to 5 carbon atoms;
Xb is an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms,
n b1 is 0 or 1;
Rb13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
Rb 14 is a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms.
n b2 is an integer ranging from 0 to 3;
* is a bond.)
Ｒｂ１２、Ｒｂ１３およびＲｂ１４の炭素原子数１～５のアルキル基の構造は、直鎖状および分岐鎖状のいずれでもよく、環構造を含んでもよい。
Ｒｂ１２、Ｒｂ１３およびＲｂ１４の炭素原子数１～５のアルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。
The structure of the alkyl group having 1 to 5 carbon atoms for Rb 12 , Rb 13 and Rb 14 may be either linear or branched, and may contain a ring structure.
Specific examples of the alkyl group having 1 to 5 carbon atoms for Rb 12 , Rb 13 and Rb 14 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group.
ＸｂおよびＲｂ１４の環形成炭素原子数５～１２の脂環式炭化水素基は、単環式脂環式炭化水素基および多環式脂環式炭化水素基のいずれもでよい。
ＸｂおよびＲｂ１４の環形成炭素原子数５～１２の脂環式炭化水素基の具体例としては、シクロペンチル基、シクロヘキシル基、ジシクロペンタニル基、アダマンチル基、ノルボルニル基、イソボルニル基、トリシクロデカニル基、テトラシクロドデカニル基等が挙げられる。
The alicyclic hydrocarbon group having 5 to 12 ring carbon atoms represented by Xb and Rb 14 may be either a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group.
Specific examples of the alicyclic hydrocarbon group having 5 to 12 ring carbon atoms for Xb and Rb 14 include a cyclopentyl group, a cyclohexyl group, a dicyclopentanyl group, an adamantyl group, a norbornyl group, an isobornyl group, a tricyclodecanyl group, and a tetracyclododecanyl group.
ＸｂおよびＲｂ１４の環形成炭素原子数５～１２の脂環式炭化水素基はさらに置換基を有してもよく、当該置換基としては、水酸基、オキソ基、カルボキシル基、炭素原子数１～６のアルキル基、炭素原子数１～６のアルコキシ基、炭素原子数１～６のヒドロキシアルキル基、炭素原子数１～６のカルボキシアルキル基、炭素原子数１～６のアシルアルコキシ基等が挙げれる。 The alicyclic hydrocarbon group having 5 to 12 ring carbon atoms of Xb and Rb 14 may further have a substituent, and examples of the substituent include a hydroxyl group, an oxo group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a carboxyalkyl group having 1 to 6 carbon atoms, and an acylalkoxy group having 1 to 6 carbon atoms.
酸解離性溶解抑制基の具体例を以下に示す。
本発明の重合体の製造方法に用いる重合成分はスチレン系モノマーおよび酸解離性基を有する重合性モノマーを含めばよく、本発明の効果を損なわない範囲で、スチレン系モノマーおよび酸解離性基を有する重合性モノマー以外のその他のモノマー成分を用いてもよい。
重合成分におけるスチレン系モノマーおよび酸解離性基を有する重合性モノマーが占める割合は、例えば８０重量％以上であり、好ましくは９０重量％以上であり、より好ましくは９５重量％以上である。
重合成分におけるスチレン系モノマーおよび酸解離性基を有する重合性モノマーが占める割合の上限は特に限定されないが、例えば１００重量％である。
The polymerization components used in the method for producing a polymer of the present invention may include a styrene-based monomer and a polymerizable monomer having an acid-dissociable group, and monomer components other than the styrene-based monomer and the polymerizable monomer having an acid-dissociable group may be used as long as the effects of the present invention are not impaired.
The proportion of the styrene-based monomer and the polymerizable monomer having an acid-dissociable group in the polymerization components is, for example, 80% by weight or more, preferably 90% by weight or more, and more preferably 95% by weight or more.
The upper limit of the proportion of the styrene-based monomer and the polymerizable monomer having an acid-dissociable group in the polymerization components is not particularly limited, but is, for example, 100% by weight.
本発明の重合体の製造方法では、スチレン系モノマーと酸解離性基を有する重合性モノマーの反応順序は特に限定されず、例えば下記２つのパターンのいずれかを採用できる。
パターン１：スチレン系モノマーと酸解離性基を有する重合性モノマーとを一括で仕込んで、有機塩素化合物であるラジカル重合開始剤、銅（II）化合物およびアミン化合物の存在下で重合する。
パターン２：スチレン系モノマーおよび酸解離性基を有する重合性モノマーの一方のモノマーを、有機塩素化合物であるラジカル重合開始剤、銅（II）化合物およびアミン化合物の存在下で重合し、当該反応系に他方のモノマーをさらに加えて重合する。
In the method for producing a polymer of the present invention, the order of reaction of the styrene-based monomer and the polymerizable monomer having an acid-labile group is not particularly limited, and for example, either of the following two patterns can be adopted.
Pattern 1: A styrene-based monomer and a polymerizable monomer having an acid-dissociable group are charged all at once, and polymerized in the presence of a radical polymerization initiator which is an organic chlorine compound, a copper (II) compound, and an amine compound.
Pattern 2: One of a styrene-based monomer and a polymerizable monomer having an acid-dissociable group is polymerized in the presence of a radical polymerization initiator which is an organic chlorine compound, a copper (II) compound and an amine compound, and the other monomer is further added to the reaction system to polymerize it.
本発明の重合体を製造する際のスチレン系モノマーと酸解離性基を有する重合性モノマーの仕込み比（質量）としては、例えばスチレン系モノマー：酸解離性基を有する重合性モノマー＝８０：２０～５：９５であり、好ましくはスチレン系モノマー：酸解離性基を有する重合性モノマー＝７０：３０～１０：９０であり、より好ましくはスチレン系モノマー：酸解離性基を有する重合性モノマー＝６０：４０～２５：７５である。 When producing the polymer of the present invention, the charge ratio (by mass) of the styrene monomer to the polymerizable monomer having an acid dissociable group is, for example, styrene monomer:polymerizable monomer having an acid dissociable group=80:20 to 5:95, preferably styrene monomer:polymerizable monomer having an acid dissociable group=70:30 to 10:90, and more preferably styrene monomer:polymerizable monomer having an acid dissociable group=60:40 to 25:75.
本発明の重合体の製造方法では、溶媒を使用することが好ましい。
使用する溶媒としては、例えば、酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶媒；ジイソプロピルエーテル、ジメトキシエタン、ジエチレングリコールジメチルエーテル等のエーテル系溶媒；ジクロロメタン、ジクロロエタン等のハロゲン系溶媒；トルエン、キシレン、アニソール等の芳香族系溶媒；メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤；メタノール、エタノール、イソプロパノール等のアルコール系溶剤；ジメチルホルムアミド、ジメチルスルホキシド等の非プロトン性極性溶媒などが挙げられる。
上記溶媒は、１種単独で用いてもよく２種以上を併用してもよい。
In the method for producing a polymer of the present invention, it is preferable to use a solvent.
Examples of the solvent to be used include ester-based solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether-based solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen-based solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene, xylene, and anisole; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol-based solvents such as methanol, ethanol, and isopropanol; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.
The above solvents may be used alone or in combination of two or more kinds.
重合温度は６０℃以下とする。重合温度を６０℃以下とすることで酸解離性基を有する重合性モノマーの分解を防ぎ、得られる重合体の収率を高めることができる。
重合温度は好ましくは５０℃以下である。また、重合温度の下限は特に限定されないが、例えば２５℃である。
The polymerization temperature is set to 60° C. or lower. By setting the polymerization temperature to 60° C. or lower, decomposition of the polymerizable monomer having an acid-dissociable group can be prevented, and the yield of the obtained polymer can be increased.
The polymerization temperature is preferably 50° C. or lower. The lower limit of the polymerization temperature is not particularly limited, but is, for example, 25° C.
重合反応時の重合雰囲気は特に限定されず、例えば窒素ガス雰囲気、アルゴンガス雰囲気などの不活性ガス雰囲気とするとよい。 The polymerization atmosphere during the polymerization reaction is not particularly limited, but may be, for example, an inert gas atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.
本発明の重合体の製造方法により重合体を製造した場合、得られた重合体中に、重合で用いた銅（II）化合物などに起因する金属が残留する場合がある。得られた重合体中に残留した金属は、重合終了後に活性アルミナ等を用いて除去するとよい。 When a polymer is produced by the method of the present invention, metals resulting from the copper (II) compound used in the polymerization may remain in the resulting polymer. Metals remaining in the resulting polymer may be removed using activated alumina or the like after the polymerization is completed.
［レジスト組成物］
本発明の重合体の製造方法により得らえる重合体は、レジスト組成物のベースポリマーとして好適に用いることができる。
スチレン系モノマーおよび酸解離性基を有する重合性モノマーを重合成分とする重合体は、酸の作用により現像液に対する溶解性を変化させることができ、酸発生剤と組み合わせることでレジスト組成物とすることができる。
[Resist Composition]
The polymer obtained by the method for producing a polymer of the present invention can be suitably used as a base polymer for a resist composition.
A polymer having a styrene-based monomer and a polymerizable monomer having an acid-dissociable group as polymerization components can change its solubility in a developer by the action of acid, and can be made into a resist composition by combining it with an acid generator.
レジスト組成物が含有する酸発生剤は公知のものが使用できる。 The resist composition may contain an acid generator that is known in the art.
レジストパターンの製造は、基板上にレジスト組成物を用いてレジスト膜を形成する工程（１）、レジスト膜を露光する工程（２）、および露光後のレジスト膜を現像してレジストパターンを形成する工程（３）を経て製造することができる。
レジスト膜を露光する工程（２）において、前記レジスト膜の露光をＥＵＶ（極端紫外線）で行うことによってナノメートルオーダーの微細なレジストパターンを形成することができる。
The resist pattern can be produced through a step (1) of forming a resist film on a substrate using a resist composition, a step (2) of exposing the resist film to light, and a step (3) of developing the exposed resist film to form a resist pattern.
In the step (2) of exposing the resist film, the resist film is exposed to EUV (extreme ultraviolet) light, whereby a fine resist pattern on the order of nanometers can be formed.
以下、実施例と比較例とにより、本発明を具体的に説明する。
尚、本発明は下記実施例に限定されない。
The present invention will be specifically described below with reference to examples and comparative examples.
However, the present invention is not limited to the following examples.
実施例および比較例において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）はゲルパーミエージョンクロマトグラフィー（ＧＰＣ）測定に基づきポリスチレン換算した値である。
ＧＰＣの測定条件は以下の通りである。
In the examples and comparative examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values calculated in terms of polystyrene based on gel permeation chromatography (GPC).
The measurement conditions for GPC are as follows.
［ＧＰＣ測定条件］
測定装置：東ソー株式会社製高速ＧＰＣ装置「ＨＬＣ－８４２０ＧＰＣ」
カラム：東ソー株式会社製「ＴＳＫ ＧＵＡＲＤＣＯＬＵＭＮ ＳｕｐｅｒＨＺ－Ｌ」＋東ソー株式会社製「ＴＳＫ ｇｅｌ ＳｕｐｅｒＨＺＭ－Ｎ」＋東ソー株式会社製「ＴＳＫ ｇｅｌ ＳｕｐｅｒＨＺＭ－Ｎ」＋東ソー株式会社製「ＴＳＫ ｇｅｌ ＳｕｐｅｒＨＺＭ－Ｎ」＋東ソー株式会社製「ＴＳＫ ｇｅｌ ＳｕｐｅｒＨＺＭ－Ｎ」
検出器：ＲＩ（示差屈折計）
データ処理：東ソー株式会社製「ＥｃｏＳＥＣ Ｄａｔａ Ａｎａｌｙｓｉｓ バージョン１．０７」
カラム温度：４０℃
展開溶媒：テトラヒドロフラン
流速：０．３５ｍＬ／分
測定試料：試料７．５ｍｇを１０ｍｌのテトラヒドロフランに溶解し、得られた溶液をマイクロフィルターでろ過したものを測定試料とした。
試料注入量：２０μｌ
標準試料：前記「ＨＬＣ－８４２０ＧＰＣ」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
[GPC measurement conditions]
Measurement equipment: Tosoh Corporation's high-speed GPC equipment "HLC-8420GPC"
Column: "TSK GUARDCOLUMN SuperHZ-L" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation + "TSK gel SuperHZM-N" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation's "EcoSEC Data Analysis Version 1.07"
Column temperature: 40°C
Developing solvent: tetrahydrofuran Flow rate: 0.35 mL/min Measurement sample: 7.5 mg of a sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered through a microfilter to prepare a measurement sample.
Sample injection volume: 20 μl
Standard sample: In accordance with the measurement manual for the above-mentioned "HLC-8420GPC," the following monodisperse polystyrene with known molecular weight was used.
（単分散ポリスチレン）
東ソー株式会社製「Ａ－３００」
東ソー株式会社製「Ａ－５００」
東ソー株式会社製「Ａ－１０００」
東ソー株式会社製「Ａ－２５００」
東ソー株式会社製「Ａ－５０００」
東ソー株式会社製「Ｆ－１」
東ソー株式会社製「Ｆ－２」
東ソー株式会社製「Ｆ－４」
東ソー株式会社製「Ｆ－１０」
東ソー株式会社製「Ｆ－２０」
東ソー株式会社製「Ｆ－４０」
東ソー株式会社製「Ｆ－８０」
東ソー株式会社製「Ｆ－１２８」
東ソー株式会社製「Ｆ－２８８」
(Monodisperse polystyrene)
"A-300" manufactured by Tosoh Corporation
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
"F-288" manufactured by Tosoh Corporation
（実施例１：重合体（１）の合成）
窒素置換したフラスコに、メタクリル酸ｔｅｒｔ－ブチル２２．７ｇ、４－アセトキシスチレン４８．１ｇ、塩化銅（ＩＩ）０．６ｇ、トリス［２－（ジメチルアミノ）エチル］アミン２．８ｇおよび溶剤としてメチルエチルケトン６４．８ｇを仕込み、窒素気流下にて攪拌しながら５５℃に昇温した。次いで、２－エチルヘキサン酸スズ（ＩＩ）１．０ｇ、ジクロロ酢酸エチル１．７ｇを加え、窒素気流下、５５℃で２８時間反応させた。
得られた反応物に、活性アルミナ３０ｇを加えて攪拌した。活性アルミナを濾過後、溶媒を減圧留去して重合体（１）を得た。
(Example 1: Synthesis of polymer (1))
In a nitrogen-purged flask, 22.7 g of tert-butyl methacrylate, 48.1 g of 4-acetoxystyrene, 0.6 g of copper(II) chloride, 2.8 g of tris[2-(dimethylamino)ethyl]amine, and 64.8 g of methyl ethyl ketone as a solvent were charged, and the mixture was heated to 55° C. with stirring under a nitrogen stream. Next, 1.0 g of tin(II) 2-ethylhexanoate and 1.7 g of ethyl dichloroacetate were added, and the mixture was reacted at 55° C. for 28 hours under a nitrogen stream.
To the reaction mixture was added 30 g of activated alumina, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a polymer (1).
得られた重合体（１）の分子量をＧＰＣで測定した結果、重量平均分子量（Ｍｗ）５，７００、数平均分子量（Ｍｎ）４，６３０、分子量分布（Ｍｗ／Ｍｎ）１．２３であった。 The molecular weight of the obtained polymer (1) was measured by GPC, and the weight average molecular weight (Mw) was 5,700, the number average molecular weight (Mn) was 4,630, and the molecular weight distribution (Mw/Mn) was 1.23.
（実施例２：重合体（２）の合成）
窒素置換したフラスコに、２－エチル－２－アダマンチルメタクリレート４７．３ｇ、スチレン３４．７ｇ、塩化銅（ＩＩ）０．１ｇ、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’－ペンタメチルジエチレントリアミン０．５ｇおよび溶剤として酢酸ブチル７９．３ｇを仕込み、窒素気流下にて攪拌しながら４５℃に昇温した。次いで、２－エチルヘキサン酸スズ（ＩＩ）０．９ｇ、ジクロロ酢酸メチル１．２ｇを加え、窒素気流下、４５℃で３５時間反応させた。
得られた反応物に、活性アルミナ３０ｇを加えて攪拌した。活性アルミナを濾過後、溶媒を減圧留去して重合体（２）を得た。
(Example 2: Synthesis of polymer (2))
A flask purged with nitrogen was charged with 47.3 g of 2-ethyl-2-adamantyl methacrylate, 34.7 g of styrene, 0.1 g of copper(II) chloride, 0.5 g of N,N,N',N'',N''-pentamethyldiethylenetriamine, and 79.3 g of butyl acetate as a solvent, and the mixture was heated to 45°C with stirring under a nitrogen stream. Next, 0.9 g of tin(II) 2-ethylhexanoate and 1.2 g of methyl dichloroacetate were added, and the mixture was reacted at 45°C for 35 hours under a nitrogen stream.
To the reaction mixture was added 30 g of activated alumina, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a polymer (2).
得られた重合体（２）の分子量をＧＰＣで測定した結果、重量平均分子量（Ｍｗ）８，４００、数平均分子量（Ｍｎ）７，０６０、分子量分布（Ｍｗ／Ｍｎ）１．１９であった。 The molecular weight of the resulting polymer (2) was measured by GPC, and the weight average molecular weight (Mw) was 8,400, the number average molecular weight (Mn) was 7,060, and the molecular weight distribution (Mw/Mn) was 1.19.
（実施例３：重合体（３）の合成）
窒素置換したフラスコに、メタクリル酸１－メチルシクロペンチル１６８．２３ｇ、スチレン１３．４ｇ、塩化銅（ＩＩ）０．３ｇ、トリス［２－（ジメチルアミノ）エチル］アミン１．７４ｇおよび溶剤として酢酸ブチル１４２．５ｇを仕込み、窒素気流下にて攪拌しながら４０℃に昇温した。次いで、２－エチルヘキサン酸スズ（ＩＩ）１．８ｇ、（１－クロロエチル）ベンゼン２．８ｇを加え、窒素気流下、４０℃で２４時間反応させた。
得られた反応物に、活性アルミナ３０ｇを加えて攪拌した。活性アルミナを濾過後、溶媒を減圧留去して重合体（３）を得た。
(Example 3: Synthesis of polymer (3))
In a nitrogen-purged flask, 168.23 g of 1-methylcyclopentyl methacrylate, 13.4 g of styrene, 0.3 g of copper(II) chloride, 1.74 g of tris[2-(dimethylamino)ethyl]amine, and 142.5 g of butyl acetate as a solvent were charged, and the mixture was heated to 40° C. with stirring under a nitrogen stream. Next, 1.8 g of tin(II) 2-ethylhexanoate and 2.8 g of (1-chloroethyl)benzene were added, and the mixture was reacted at 40° C. for 24 hours under a nitrogen stream.
To the reaction mixture was added 30 g of activated alumina, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a polymer (3).
得られた重合体（３）の分子量をＧＰＣで測定した結果、重量平均分子量（Ｍｗ）３，１００、数平均分子量（Ｍｎ）２，３８０、分子量分布（Ｍｗ／Ｍｎ）１．３０であった。 The molecular weight of the resulting polymer (3) was measured by GPC, and the weight average molecular weight (Mw) was 3,100, the number average molecular weight (Mn) was 2,380, and the molecular weight distribution (Mw/Mn) was 1.30.
（実施例４：重合体（４）の合成）
窒素置換したフラスコに、メタクリル酸ｔｅｒｔ－ブチル４８．３ｇ、４－ｔｅｒｔ－ブトキシスチレン２５．７ｇ、塩化銅（ＩＩ）０．３ｇ、トリスピリジルメチルアミン１．０ｇおよび溶剤としてアニソール２６．６ｇを仕込み、窒素気流下にて攪拌しながら６０℃に昇温した。次いで、２－エチルヘキサン酸スズ（ＩＩ）０．４ｇ、（１－クロロエチル）ベンゼン０．７ｇを加え、窒素気流下、６０℃で２０時間反応させた。
得られた反応物に、活性アルミナ３０ｇを加えて攪拌した。活性アルミナを濾過後、溶媒を減圧留去して重合体（４）を得た。
(Example 4: Synthesis of polymer (4))
In a nitrogen-purged flask, 48.3 g of tert-butyl methacrylate, 25.7 g of 4-tert-butoxystyrene, 0.3 g of copper(II) chloride, 1.0 g of trispyridylmethylamine, and 26.6 g of anisole as a solvent were charged, and the mixture was heated to 60° C. with stirring under a nitrogen stream. Next, 0.4 g of tin(II) 2-ethylhexanoate and 0.7 g of (1-chloroethyl)benzene were added, and the mixture was reacted at 60° C. for 20 hours under a nitrogen stream.
To the reaction mixture was added 30 g of activated alumina, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a polymer (4).
得られた重合体（４）の分子量をＧＰＣで測定した結果、重量平均分子量（Ｍｗ）１５，２００、数平均分子量（Ｍｎ）１２，５６０、分子量分布（Ｍｗ／Ｍｎ）１．２１であった。 The molecular weight of the resulting polymer (4) was measured by GPC, and the weight average molecular weight (Mw) was 15,200, the number average molecular weight (Mn) was 12,560, and the molecular weight distribution (Mw/Mn) was 1.21.
（実施例５：重合体（５）の合成）
窒素置換したフラスコに、５－ビニル－２－ヒドロキシ安息香酸ｔｅｒｔ－ブチル６２．９ｇ、４－アセトキシスチレン５．２ｇ、塩化銅（ＩＩ）１．４ｇ、トリス［２－（ジメチルアミノ）エチル］アミン２．３ｇおよび溶剤として酢酸ｎ－ブチル１８．８ｇを仕込み、窒素気流下にて攪拌しながら５０℃に昇温した。次いで、２－エチルヘキサン酸スズ（ＩＩ）１．５ｇ、（１－クロロエチル）ベンゼン２．４ｇを加え、窒素気流下、５０℃で３４時間反応させた。
得られた反応物に、活性アルミナ３０ｇを加えて攪拌した。活性アルミナを濾過後、溶媒を減圧留去して重合体（５）を得た。
(Example 5: Synthesis of polymer (5))
Into a nitrogen-purged flask, 62.9 g of tert-butyl 5-vinyl-2-hydroxybenzoate, 5.2 g of 4-acetoxystyrene, 1.4 g of copper(II) chloride, 2.3 g of tris[2-(dimethylamino)ethyl]amine, and 18.8 g of n-butyl acetate as a solvent were charged, and the mixture was heated to 50° C. with stirring under a nitrogen stream. Next, 1.5 g of tin(II) 2-ethylhexanoate and 2.4 g of (1-chloroethyl)benzene were added, and the mixture was reacted at 50° C. for 34 hours under a nitrogen stream.
To the reaction mixture was added 30 g of activated alumina, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a polymer (5).
得られた重合体（５）の分子量をＧＰＣで測定した結果、重量平均分子量（Ｍｗ）４，２００、数平均分子量（Ｍｎ）３，７２０、分子量分布（Ｍｗ／Ｍｎ）１．１３であった。 The molecular weight of the resulting polymer (5) was measured by GPC, and the weight average molecular weight (Mw) was 4,200, the number average molecular weight (Mn) was 3,720, and the molecular weight distribution (Mw/Mn) was 1.13.
（実施例６：重合体（６）の合成）
窒素置換したフラスコに、メタクリル酸ｔｅｒｔ－ブチル５５．７ｇ、４－アセトキシスチレン３２．３ｇ、塩化銅（ＩＩ）０．７ｇ、トリス［２－（ジメチルアミノ）エチル］アミン１．２ｇおよび溶剤として酢酸ブチル４４．９ｇを仕込み、窒素気流下にて攪拌しながら５５℃に昇温した。次いで、２－エチルヘキサン酸スズ（ＩＩ）０．８ｇ、２－クロロプロピオニトリル０．８ｇを加え、窒素気流下、５５℃で４０時間反応させた。
得られた反応物に、活性アルミナ３０ｇを加えて攪拌した。活性アルミナを濾過後、溶媒を減圧留去して重合体（６）を得た。
(Example 6: Synthesis of polymer (6))
In a nitrogen-purged flask, 55.7 g of tert-butyl methacrylate, 32.3 g of 4-acetoxystyrene, 0.7 g of copper(II) chloride, 1.2 g of tris[2-(dimethylamino)ethyl]amine, and 44.9 g of butyl acetate as a solvent were charged, and the mixture was heated to 55° C. with stirring under a nitrogen stream. Next, 0.8 g of tin(II) 2-ethylhexanoate and 0.8 g of 2-chloropropionitrile were added, and the mixture was reacted at 55° C. for 40 hours under a nitrogen stream.
To the reaction mixture was added 30 g of activated alumina, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a polymer (6).
得られた重合体（６）の分子量をＧＰＣで測定した結果、重量平均分子量（Ｍｗ）９，８００、数平均分子量（Ｍｎ）８，１００、分子量分布（Ｍｗ／Ｍｎ）１．２１であった。 The molecular weight of the resulting polymer (6) was measured by GPC, and the weight average molecular weight (Mw) was 9,800, the number average molecular weight (Mn) was 8,100, and the molecular weight distribution (Mw/Mn) was 1.21.
（実施例７：重合体（７）の合成）
窒素置換したフラスコに、メタクリル酸ｔｅｒｔ－ブチル４９．０ｇ、４－アセトキシスチレン１４．０ｇ、塩化銅（ＩＩ）０．５ｇ、トリス［２－（ジメチルアミノ）エチル］アミン１．９ｇおよび溶剤として酢酸ブチル２８．４ｇを仕込み、窒素気流下にて攪拌しながら４０℃に昇温した。次いで、２－エチルヘキサン酸スズ（ＩＩ）１．２ｇ、塩化アリル１．１ｇを加え、窒素気流下、４０℃で３６時間反応させた。
得られた反応物に、活性アルミナ３０ｇを加えて攪拌した。活性アルミナを濾過後、溶媒を減圧留去して重合体（７）を得た。
(Example 7: Synthesis of polymer (7))
In a nitrogen-purged flask, 49.0 g of tert-butyl methacrylate, 14.0 g of 4-acetoxystyrene, 0.5 g of copper(II) chloride, 1.9 g of tris[2-(dimethylamino)ethyl]amine, and 28.4 g of butyl acetate as a solvent were charged, and the mixture was heated to 40° C. with stirring under a nitrogen stream. Next, 1.2 g of tin(II) 2-ethylhexanoate and 1.1 g of allyl chloride were added, and the mixture was reacted at 40° C. for 36 hours under a nitrogen stream.
To the reaction mixture was added 30 g of activated alumina, and the mixture was stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a polymer (7).
得られた重合体（７）の分子量をＧＰＣで測定した結果、重量平均分子量（Ｍｗ）４，６２０、数平均分子量（Ｍｎ）３，６１０、分子量分布（Ｍｗ／Ｍｎ）１．２８であった。 The molecular weight of the resulting polymer (7) was measured by GPC, and the weight average molecular weight (Mw) was 4,620, the number average molecular weight (Mn) was 3,610, and the molecular weight distribution (Mw/Mn) was 1.28.
（比較例１：重合体（１’）の合成）
窒素置換したフラスコに、メタクリル酸ｔｅｒｔ－ブチル１４．５ｇ、スチレン１０．５ｇ、塩化銅（Ｉ）２９．３ｍｇおよび４，４’－ジノニル－２，２’－ビピリジル（ｄＮｂｉｐｙ）１７８．２ｍｇを仕込んだ。トルエン中のエチルブロモイソブチレート（２９．７μｌ，２０．３×１０－２ｍｍｏｌ）のパージングされた溶液を加え、その密封したフラスコを、４０℃で２４時間反応させた。
しかしながら反応は進行せず、重合体を得ることはできなかった。
(Comparative Example 1: Synthesis of Polymer (1'))
A nitrogen purged flask was charged with 14.5 g of tert-butyl methacrylate, 10.5 g of styrene, 29.3 mg of copper(I) chloride, and 178.2 mg of 4,4'-dinonyl-2,2'-bipyridyl (dNbipy). A purged solution of ethyl bromoisobutyrate (29.7 μl, 20.3×10 −2 mmol) in toluene was added and the sealed flask was allowed to react at 40° C. for 24 hours.
However, the reaction did not proceed and no polymer was obtained.
実施例および比較例の結果から、有機塩素化合物と銅（II）化合物とを組み合わせて用いることで、通常は６０℃以下では反応が進行しないスチレンモノマーの反応が進行したことが分かる。 The results of the Examples and Comparative Examples show that the use of a combination of an organic chlorine compound and a copper (II) compound allowed the reaction of styrene monomer, which normally does not proceed at temperatures below 60°C, to proceed.
Claims (15)
前記原子移動ラジカル重合を、有機塩素化合物であるラジカル重合開始剤、銅（II）化合物およびアミン化合物の存在下において、重合温度６０℃以下で行う重合体の製造方法。 A method for producing a polymer by atom transfer radical polymerization of a polymerization component containing a polymerizable monomer having an acid dissociable group and a styrene-based monomer, comprising the steps of:
The method for producing a polymer comprises carrying out the atom transfer radical polymerization in the presence of a radical polymerization initiator which is an organic chlorine compound, a copper (II) compound, and an amine compound at a polymerization temperature of 60° C. or lower.
Ｒ１１は、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり、
Ｖａ１は、エーテル結合を有しててもよい２価の炭化水素基であり、
ｎａ１は、０～２の範囲の整数であり、
Ｒａ１は、酸解離性基であり、
Ｒ１２は、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり、
Ｗａ１は、ｎａ２＋１価の炭化水素基であり、
ｎａ２は、１～３の範囲の整数であり、
Ｒａ２は、酸解離性基であり、
Ｙａ１は、単結合又はエーテル結合を有しててもよい２価の炭化水素基であり、
Ｚは重合性基を含む基であり、
Ｒａ３は、酸解離性基であり、
ｎａ３１は、０～３の範囲の整数であり、
ｎａ３２は、０以上の整数である。但し、ｎａ３２はｎａ３２≦ｎａ３１×２＋４を満たす。） The method for producing a polymer according to claim 1 or 2, wherein the polymerizable monomer having an acid-dissociable group is at least one selected from the group consisting of a monomer represented by the following general formula (a-1), a monomer represented by the following general formula (a-2), and a monomer represented by the following general formula (a-3):
R 11 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms;
Va1 is a divalent hydrocarbon group which may have an ether bond,
n a1 is an integer ranging from 0 to 2;
Ra1 is an acid dissociable group,
R 12 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms;
Wa1 is a hydrocarbon group having a valence of n a2 +1;
n a2 is an integer ranging from 1 to 3;
Ra2 is an acid dissociable group,
Ya 1 is a divalent hydrocarbon group which may have a single bond or an ether bond;
Z is a group containing a polymerizable group,
Ra3 is an acid dissociable group,
n a31 is an integer ranging from 0 to 3;
n a32 is an integer equal to or greater than 0. However, n a32 satisfies n a32 ≦n a31 × 2 + 4.
Ｒａ１０は、炭素原子数１～１２のアルキル基又は炭素原子数１～１２のエーテル結合を有するアルキル基であり、
Ｒａ１１、Ｒａ１２およびＲａ１３は、それぞれ独立に、水素原子又は炭素原子数１～１０のアルキル基であり、
Ｒａ１１、Ｒａ１２およびＲａ１３のうち少なくとも２つが互いに結合して環を形成してもよく、
Ａｒａ１は、環形成炭素原子数６～１２のアリール基又は環形成炭素原子数６～１２のアルキルアリール基であり、
Ｒａ１４およびＲａ１５は、それぞれ独立に、水素原子又は炭素原子数１～１０のアルキル基であり、
Ｒａ１６は、環形成炭素原子数６～１２のアリール基、環形成炭素原子数５～１２の脂環式炭化水素基又は、炭素原子数１～１０のアルキル基であり、
Ｘａは環形成炭素原子数５～１２の脂環式炭化水素基である。） The method for producing a polymer according to claim 1 or 2, wherein the acid-dissociable group is a group represented by the following general formula (ad-1), (ad-2), (ad-3) or (ad-4):
Ra 10 is an alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms and an ether bond,
Ra 11 , Ra 12 and Ra 13 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
At least two of Ra 11 , Ra 12 and Ra 13 may be bonded to each other to form a ring;
Ara 1 is an aryl group having 6 to 12 ring carbon atoms or an alkylaryl group having 6 to 12 ring carbon atoms;
Ra 14 and Ra 15 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
Ra 16 is an aryl group having 6 to 12 ring carbon atoms, an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms, or an alkyl group having 1 to 10 carbon atoms,
Xa is an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms.
Ｒ２１は、水素原子又はメチル基であり、
Ｒ２２は、ハロゲン原子、炭素原子数１～５のアルキル基、炭素原子数２～１５のアルキルカルボニルオキシ基、水酸基、カルボキシル基、又は水酸基もしくはカルボキシル基の水素原子が酸解離性溶解抑制基で置換された基あり、
ｎｂは０～５の範囲の整数である） 3. The method for producing a polymer according to claim 1, wherein the styrene-based monomer is a styrene compound represented by the following general formula (b):
R 21 is a hydrogen atom or a methyl group;
R 22 represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyloxy group having 2 to 15 carbon atoms, a hydroxyl group, a carboxyl group, or a group in which the hydrogen atom of a hydroxyl group or a carboxyl group has been substituted with an acid dissociable, dissolution inhibiting group;
n b is an integer ranging from 0 to 5.
Ｒｂ１０は、水素原子又はメチル基であり、
Ｒｂ１２は、炭素原子数１～５のアルキル基であり、
Ｘｂは、環形成炭素原子数５～１２の脂環式炭化水素基であり、
ｎｂ１は０又は１であり、
Ｒｂ１３は、水素原子又は炭素原子数１～５のアルキル基であり、
Ｒｂ１４は、ハロゲン原子、炭素原子数１～５のアルキル基又は環形成炭素原子数５～１２の脂環式炭化水素基である。
ｎｂ２は０～３の範囲の整数である。） The method for producing a polymer according to claim 10, wherein the acid dissociable, dissolution inhibiting group is a group represented by the following general formula (bp-1) or (bp-2):
Rb10 is a hydrogen atom or a methyl group;
Rb12 is an alkyl group having 1 to 5 carbon atoms;
Xb is an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms,
n b1 is 0 or 1;
Rb13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
Rb 14 is a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alicyclic hydrocarbon group having 5 to 12 ring carbon atoms.
n b2 is an integer ranging from 0 to 3.
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| KR20240115735A (en) | 2024-07-26 |
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