JP4626955B2 - Method for producing p-hydroxystyrene-based polymer - Google Patents
Method for producing p-hydroxystyrene-based polymer Download PDFInfo
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- JP4626955B2 JP4626955B2 JP2004293655A JP2004293655A JP4626955B2 JP 4626955 B2 JP4626955 B2 JP 4626955B2 JP 2004293655 A JP2004293655 A JP 2004293655A JP 2004293655 A JP2004293655 A JP 2004293655A JP 4626955 B2 JP4626955 B2 JP 4626955B2
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- ethoxyethoxy
- styrene
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- 229920000642 polymer Polymers 0.000 title claims description 43
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000178 monomer Substances 0.000 claims description 33
- DTNCNFLLRLHPNJ-UHFFFAOYSA-N 1-ethenyl-4-(1-ethoxyethoxy)benzene Chemical compound CCOC(C)OC1=CC=C(C=C)C=C1 DTNCNFLLRLHPNJ-UHFFFAOYSA-N 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- -1 1-ethoxyethoxy group Chemical group 0.000 claims description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 24
- 238000010511 deprotection reaction Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 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 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 6
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 5
- 125000006239 protecting group Chemical group 0.000 description 5
- 239000000243 solution Substances 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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- ONMLAAZEQUPQSE-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)CO ONMLAAZEQUPQSE-UHFFFAOYSA-N 0.000 description 1
- WQIWJMDSYYXWJB-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) prop-2-enoate 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C.OCC(C)(C)COC(=O)C=C WQIWJMDSYYXWJB-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- VMOQKKFBYIBJOJ-UHFFFAOYSA-N 1-ethenyl-4-(2-ethoxyethoxy)benzene Chemical compound CCOCCOC1=CC=C(C=C)C=C1 VMOQKKFBYIBJOJ-UHFFFAOYSA-N 0.000 description 1
- CQUFSHRIMFCUBU-UHFFFAOYSA-N 1-ethenyl-4-(methoxymethoxy)benzene Chemical compound COCOC1=CC=C(C=C)C=C1 CQUFSHRIMFCUBU-UHFFFAOYSA-N 0.000 description 1
- HGOUNPXIJSDIKV-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl 2-methylprop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C(C)=C HGOUNPXIJSDIKV-UHFFFAOYSA-N 0.000 description 1
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- YGTVWCBFJAVSMS-UHFFFAOYSA-N 5-hydroxypentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCO YGTVWCBFJAVSMS-UHFFFAOYSA-N 0.000 description 1
- INRQKLGGIVSJRR-UHFFFAOYSA-N 5-hydroxypentyl prop-2-enoate Chemical compound OCCCCCOC(=O)C=C INRQKLGGIVSJRR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- AKSYMJYVYJGVBW-UHFFFAOYSA-N C(C(=C)C)(=O)OCC1CO1.C(C(=C)C)(=O)OCC(CO)(CO)CO Chemical compound C(C(=C)C)(=O)OCC1CO1.C(C(=C)C)(=O)OCC(CO)(CO)CO AKSYMJYVYJGVBW-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 1
- DQVUUGHMHQPVSI-UHFFFAOYSA-N [chloro(phenyl)methyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(Cl)C1=CC=CC=C1 DQVUUGHMHQPVSI-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- FCSHDIVRCWTZOX-DVTGEIKXSA-N clobetasol Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)CCl)(O)[C@@]1(C)C[C@@H]2O FCSHDIVRCWTZOX-DVTGEIKXSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- DWXAVNJYFLGAEF-UHFFFAOYSA-N furan-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CO1 DWXAVNJYFLGAEF-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はp−ヒドロキシスチレン系重合体の製造方法に関する。より詳しくは、p−(1−エトキシエトキシ)スチレンを使用することにより、酸でp−(1−エトキシエトキシ)スチレン由来の構成単位のみを選択的に脱保護することが可能であるp−ヒドロキシスチレン系重合体の製造方法に関する。 The present invention relates to a method for producing a p-hydroxystyrene polymer. More specifically, by using p- (1-ethoxyethoxy) styrene, it is possible to selectively deprotect only the structural unit derived from p- (1-ethoxyethoxy) styrene with an acid. The present invention relates to a method for producing a styrene polymer.
近年のLSIの高集積化と高速化に伴い、リソグラフイー工程に使用されるフォトレジストは微細なパターン形成が必要になっている。リソグラフイー工程に使用されるポリ−p−ヒドロキシスチレンなどのアルケニルフェノール類の重合物は、化学増幅型レジスト材料として有用なものとして使用されているが、アクリレートやスチレンなど種々のモノマーと共重合することで、より高解像度および現像性を高める検討がなされている。
従来、p−ヒドロキシスチレン系重合体の製造に際しては、p−ヒドロキシスチレンが不安定、且つフェノール性水酸基が重合の阻害となるため予め水酸基を保護基で保護したモノマーを重合する必要がある。具体的には、(1)p−(t−ブトキシ)スチレン、(2)p−アセトキシスチレンなどの保護モノマーを用い、これら単量体を重合して重合体を得た後、保護基を脱保護する方法が採用されてきた(特許文献1、2参照)。
With the recent high integration and high speed of LSI, fine pattern formation is required for the photoresist used in the lithographic process. Polymers of alkenylphenols such as poly-p-hydroxystyrene used in the lithographic process are used as useful chemical amplification resist materials, but copolymerize with various monomers such as acrylate and styrene. Thus, studies have been made to increase the resolution and developability.
Conventionally, in the production of a p-hydroxystyrene polymer, since p-hydroxystyrene is unstable and a phenolic hydroxyl group inhibits polymerization, it is necessary to polymerize a monomer in which the hydroxyl group is previously protected with a protecting group. Specifically, (1) p- (t-butoxy) styrene, (2) p-acetoxystyrene and other protective monomers are used to polymerize these monomers to obtain a polymer, and then the protective group is removed. A protection method has been employed (see Patent Documents 1 and 2).
上記(1)の方法において、p−(t−ブトキシ)スチレン単位の保護基を脱保護させるには酸触媒の下、50〜70℃で5〜10時間反応させる必要があり、この条件では酸解離性基を有するモノマーとを共重合させた共重合体の場合、その酸解離性基も脱保護してしまうという欠点がある。
また(2)の方法では、p−アセトキシスチレン単位の保護基を塩基触媒で脱保護させるため(1)のように酸解離性基も脱保護することはないが、50〜70℃でアルコール存在下5〜15時間反応させる必要がある。また、重合系に(メタ)アクリル酸単位を含有する場合、塩基触媒が塩を作ってしまうという欠点がある。
一方、p−メトキシメトキシスチレンをリビングアニオン重合した後、メトキシメトキシ基を脱保護させることを特徴とするポリ(p−ヒドロキシスチレン)の製造方法も提案されている(特許文献3)。しかし当該明細書中の実施例においては、塩酸を使用したメトキシメトキシ基の脱保護反応に60℃で8時間撹拌すると記載されているように、工業上は必ずしも有利なものであるとは言えない。
さらに、特許文献4において、p−エトキシエトキシスチレンを使用した共重合体を得た後、シュウ酸により脱保護反応する例が記載されているが、こちらも当該反応を完結させるために20時間もの時間を要しており、やはり工業上有利なものであるとは言えない。
In the method of (1) above, in order to deprotect the protecting group of p- (t-butoxy) styrene unit, it is necessary to react at 50 to 70 ° C. for 5 to 10 hours under an acid catalyst. In the case of a copolymer obtained by copolymerizing a monomer having a dissociable group, there is a drawback that the acid dissociable group is also deprotected.
In the method (2), since the protecting group of the p-acetoxystyrene unit is deprotected with a base catalyst, the acid-dissociable group is not deprotected as in (1), but alcohol exists at 50 to 70 ° C. It is necessary to react for the next 5 to 15 hours. Moreover, when a (meth) acrylic acid unit is contained in a polymerization system, there exists a fault that a base catalyst will make a salt.
On the other hand, a method for producing poly (p-hydroxystyrene) is also proposed in which p-methoxymethoxystyrene is subjected to living anion polymerization and then the methoxymethoxy group is deprotected (Patent Document 3). However, in the examples in this specification, it is not necessarily industrially advantageous as it is described that the deprotection reaction of methoxymethoxy group using hydrochloric acid is stirred at 60 ° C. for 8 hours. .
Furthermore, Patent Document 4 describes an example in which a deprotection reaction is performed with oxalic acid after obtaining a copolymer using p-ethoxyethoxystyrene, but this also takes 20 hours to complete the reaction. It takes time and cannot be said to be industrially advantageous.
上述のような理由から、本発明の目的は、脱保護により副反応を起こさず、短時間で脱保護反応が完了し、且つ脱保護後の後処理が簡便なp−ヒドロキシスチレン系重合体の製造方法を提供することにある。 For the reasons described above, an object of the present invention is to provide a p-hydroxystyrene-based polymer that does not cause a side reaction by deprotection, completes the deprotection reaction in a short time, and is simple in post-treatment after deprotection. It is to provide a manufacturing method.
本発明者らは上記課題を解決するため鋭意研究した結果、p−(1−エトキシエトキシ)スチレン由来の構成単位を含有する重合体をアルコールを90重量%以上含有する有機溶媒中で、水と塩酸を用いることにより1−エトキシエトキシ基のみを選択的に脱保護することが可能であることを見出し、そのため酸解離性基を有するモノマーを脱保護することなくp−ヒドロキシスチレン系重合体を製造できることを見出し、本発明を完成するに至った。
すなわち本発明は、p−(1−エトキシエトキシ)スチレン由来の構成単位を含有する重合体を、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテルから選ばれる少なくとも1種を主成分とするアルコールを90重量%以上含有
する有機溶媒中に溶解または分散し、p−(1−エトキシエトキシ)スチレン由来の構成単位1当量に対し1〜4当量である水と、p−(1−エトキシエトキシ)スチレン由来の構成単位1当量に対し0.01〜0.1当量である塩酸を用いることにより1−エトキシエトキシ基を脱保護することを特徴とするp−ヒドロキシスチレン由来の構成単位を含有する重合体の製造方法、である。
As a result of diligent research to solve the above problems, the present inventors have found that a polymer containing a structural unit derived from p- (1-ethoxyethoxy) styrene is mixed with water in an organic solvent containing 90% by weight or more of alcohol. It has been found that it is possible to selectively deprotect only the 1-ethoxyethoxy group by using hydrochloric acid, and therefore a p-hydroxystyrene polymer is produced without deprotecting the monomer having an acid dissociable group. The present inventors have found that this can be done and have completed the present invention.
That is, in the present invention, the polymer containing a structural unit derived from p- (1-ethoxyethoxy) styrene is at least selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. Water dissolved or dispersed in an organic solvent containing 90% by weight or more of an alcohol mainly composed of one kind, and 1 to 4 equivalents of water equivalent to 1 equivalent of a structural unit derived from p- (1-ethoxyethoxy) styrene ; 1-ethoxyethoxy group is deprotected by using 0.01 to 0.1 equivalent of hydrochloric acid with respect to 1 equivalent of structural unit derived from p- (1-ethoxyethoxy) styrene A method for producing a polymer containing a structural unit derived from .
p−ヒドロキシスチレンの保護基として1−エトキシエトキシ基を採用し、アルコール中で加水分解することにより、少量の塩酸で脱保護を短時間に完了させることができ、且つ他の酸解離性基を有するモノマーを脱保護することなくp−ヒドロキシスチレン系重合体を得ることが可能となった。 By adopting 1-ethoxyethoxy group as a protecting group for p-hydroxystyrene and hydrolyzing in alcohol, deprotection can be completed in a short time with a small amount of hydrochloric acid, and other acid-dissociable groups can be removed. It has become possible to obtain a p-hydroxystyrene-based polymer without deprotecting the monomer having it.
以下、本発明を詳細に説明する。
本発明に係わるp−(1−エトキシエトキシ)スチレン由来の構成単位を含有する重合体として、具体的には例えば、下記一般式(I)で表される単量体と、下記一般式(II)で表される単量体の1種または2種以上とを主成分とする単量体の混合物を重合することにより得られる重合体が挙げられる。
Specific examples of the polymer containing a structural unit derived from p- (1-ethoxyethoxy) styrene according to the present invention include, for example, a monomer represented by the following general formula (I), and the following general formula (II): The polymer obtained by superposing | polymerizing the mixture of the monomer which has 1 type, or 2 or more types of the monomer represented by this as a main component is mentioned.
更に、本発明の上記重合体として、一般式(I)で表される単量体、一般式(II)で表される単量体、並びに下記一般式(III )で表される単量体の1種または2種以上からなる単量体の混合物を重合することにより得られた重合体が挙げられる。
本発明に係わるp−(1−エトキシエトキシ)スチレン由来の構成単位を含有する重合体の製造に用いることができる上記一般式(II)で表される単量体の例としては、スチレン、p−(t−ブトキシ)スチレン、p−アセトキシスチレンが挙げられるが、特にこれらに限定されるものではない。 Examples of the monomer represented by the general formula (II) that can be used in the production of a polymer containing a structural unit derived from p- (1-ethoxyethoxy) styrene according to the present invention include styrene, p Examples include-(t-butoxy) styrene and p-acetoxystyrene, but are not particularly limited thereto.
本発明に係わるp−(1−エトキシエトキシ)スチレン由来の構成単位を含有する重合体の製造に用いることができる上記一般式(III)で表される単量体の例としては、例えば、アクリル酸、メタクリル酸;メチルアクリレート、エチルアクリレート、プロピルアクリレート、n−ブチルアクリレート、t−ブチルアクリレート、n−ヘキシルアクリレート、シクロヘキシルアクリレート、オクチルアクリレート、2−ヒドロキシエチルアクリレート、クロルエチルアクリレート、2−ヒドロキシエチルアクリレート、2,2−ジメチルヒドロキシプロピルアクリレート、5−ヒドロキシペンチルアクリレート、トリメチロールプロパンモノアクリレート、ペンタエリスリトールモノアクリレート、グリシジルアクリレート、ベンジルアクリレート、フルフリルアクリレート、テトラヒドロフルフリルアクリレート等のアルキルアクリレート;フェニルアクリレート等のアリールアクリレート;メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、n−ブチルメタクリレート、t−ブチルメタクリレート、n−ヘキシルメタクリレート、シクロヘキシルメタクリレート、ベンジルメタクリレート、クロルベンジルメタクリレート、オクチルメタクリレート、2−ヒドロキシエチルメタクリレート、4−ヒドロキシブチルメタクリレート、5−ヒドロキシペンチルメタクリレート、2,2−ジメチル−3−ヒドロキシプロピルメタクリレート、トリメチロールプロパンモノメタクリレート、ペンタエリスリトールモノメタクリレート、グリシジルメタクリレート、フルフリルメタクリレート、テトラヒドロフルフリルメタクリレート等のアルキルメタクリレート;等が挙げられるが、特にこれらに限定されるものではない。これらは一種若しくは二種以上を用いることができる。 Examples of the monomer represented by the general formula (III) that can be used for the production of a polymer containing a structural unit derived from p- (1-ethoxyethoxy) styrene according to the present invention include, for example, acrylic Acid, methacrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, octyl acrylate, 2-hydroxyethyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate Alkyl acrylates such as phenyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate; aryl acrylates such as phenyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate Glycidyl methacrylate Furfuryl methacrylate, alkyl methacrylates, such as tetrahydrofurfuryl methacrylate; but like, but is not particularly limited thereto. These can be used alone or in combination of two or more.
本発明におけるp−(1−エトキシエトキシ)スチレン由来の構成単位を含有する重合体の好ましい態様は、p−(1−エトキシエトキシ)スチレンに由来する構成単位を5重量%以上含有する重合体である。また、該重合体は上記一般式(I)、(II)並びに(III )で表される単量体に加え、他の単量体を共重合させたものでもよく、3元以上の多元共重合物であっても差し支えはない。また、その重合体の重合方法については公知の方法を採用することができ、ラジカル重合、アニオン重合、カチオン重合等、重合方法については特に制限はない。
重合開始剤としては、例えば、2,2’−アゾビス(イソブチロニトリル)、2,2’−アゾビス(2,4−ジメチルバレロニトリル)、ジメチル2,2’−アゾビス(2−メチルプロピオネート)等のアゾ化合物、および過酸化ベンゾイル等の有機過酸化物、さらにはn−ブチルリチウム等の有機アルキル化合物等が使用できる。また、開始剤の添加量は、目標とする重合体の分子量に応じ適宜選択することができる。
本発明での重合体の重合は、テトラヒドロフラン、アセトン、トルエン、プロピレングリコールモノメチルエーテル、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、種々の溶剤中で行うことが可能であるが、後の脱保護反応の促進を考慮するとイソプロピルアルコール、プロピレングリコールモノメチルエーテルなどのアルコール系溶媒が好ましい。重合時のモノマー濃度は、10〜60重量%の範囲から選択することが好ましく、目標とする分子量によりモノマー濃度を適宜変化させることができる。
A preferred embodiment of the polymer containing structural units derived from p- (1-ethoxyethoxy) styrene in the present invention is a polymer containing 5% by weight or more of structural units derived from p- (1-ethoxyethoxy) styrene. is there. In addition to the monomers represented by the general formulas (I), (II) and (III), the polymer may be a copolymer of other monomers, and may be a ternary or multi-component copolymer. Even a polymer may be used. Moreover, a well-known method can be employ | adopted about the polymerization method of the polymer, There is no restriction | limiting in particular about polymerization methods, such as radical polymerization, anion polymerization, and cationic polymerization.
Examples of the polymerization initiator include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropio). Azo compounds such as nate), organic peroxides such as benzoyl peroxide, and organic alkyl compounds such as n-butyllithium. Moreover, the addition amount of an initiator can be suitably selected according to the molecular weight of the target polymer.
The polymerization of the polymer in the present invention can be carried out in various solvents such as tetrahydrofuran, acetone, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc., but considering the promotion of the subsequent deprotection reaction. Then, alcohol solvents such as isopropyl alcohol and propylene glycol monomethyl ether are preferable. The monomer concentration at the time of polymerization is preferably selected from the range of 10 to 60% by weight, and the monomer concentration can be appropriately changed depending on the target molecular weight.
本発明において、1−エトキシエトキシ基の脱保護反応は、アルコールを90重量%以上含有する有機溶媒中に上記重合体を溶解または分散させて行うことを特徴とする。当該アルコールとしては、例えば、メタノール、エタノール、1−プロパノール、イソプロピルアルコール、ブチルアルコール等の1級アルコール;ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等のグリコールエーテルモノアルキルエーテル類;が挙げられるが、中でも脱保護基反応の点でプロピレングリコールモノメチルエーテルが好ましい。 In the present invention, the deprotection reaction of the 1-ethoxyethoxy group is performed by dissolving or dispersing the polymer in an organic solvent containing 90% by weight or more of an alcohol. Examples of the alcohol include primary alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, and butyl alcohol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene. Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, glycol ether monoalkyl ethers such as propylene glycol monobutyl ether; but the like, propylene glycol monomethyl ether is preferred in view of inter alia deprotection reaction.
本発明はまた、1−エトキシエトキシ基の脱保護反応に、水と塩酸を使用することをも特徴とする。シュウ酸等の弱酸を使用しても脱保護反応を進めることができるが、反応の進行に長時間を要するため、工業的に有利ではない。また、アルコールを90重量%以上含有する有機溶媒中では、塩酸のような強酸を使用しても、他の酸解離性基を加水分解することなく短時間で1−エトキシエトキシ基を脱保護することができる。
塩酸の使用量は、1−エトキシエトキシ基の脱保護が十分に短時間で完了し、かつ他の酸解離性基を加水分解しない程度の量であればよく、1−エトキシエトキシ基1当量に対し0.01〜0.1当量が好ましく、0.02〜0.10当量がさらに好ましい。また、水の使用量は、1−エトキシエトキシ基1当量に対し1〜4当量が好ましく、2〜4当量がさらに好ましい。
以上の条件を採用することにより、25〜40℃程度の穏やかな温度で1−エトキシエトキシ基の脱保護反応を進めることができる。反応系のスケールにもよるが概ね1〜3時間程度で反応を終了させることができ、目的のp−ヒドロキシスチレン由来の構成単位を含有する重合体を得ることができる。脱保護の終了はプロトン核磁気共鳴スペクトル(1H−NMR)測定により5.3ppm付近に見られるp−(1−エトキシエトキシ)スチレンのメチンのピークが消失することで確認することができる。
The present invention is also characterized in that water and hydrochloric acid are used for the deprotection reaction of the 1-ethoxyethoxy group. Although the deprotection reaction can proceed even if a weak acid such as oxalic acid is used, it takes a long time for the reaction to proceed, which is not industrially advantageous. Further, in an organic solvent containing 90% by weight or more of alcohol, even if a strong acid such as hydrochloric acid is used, the 1-ethoxyethoxy group is deprotected in a short time without hydrolyzing other acid dissociable groups. be able to.
The amount of hydrochloric acid used may be an amount such that deprotection of 1-ethoxyethoxy group is completed in a sufficiently short time and does not hydrolyze other acid-dissociable groups. The amount is preferably 0.01 to 0.1 equivalent, more preferably 0.02 to 0.10 equivalent. Moreover, 1-4 equivalent is preferable with respect to 1 equivalent of 1-ethoxyethoxy groups, and, as for the usage-amount of water, 2-4 equivalent is more preferable.
By adopting the above conditions, the deprotection reaction of the 1-ethoxyethoxy group can proceed at a moderate temperature of about 25 to 40 ° C. Although depending on the scale of the reaction system, the reaction can be completed in about 1 to 3 hours, and a polymer containing the target structural unit derived from p-hydroxystyrene can be obtained. The completion of the deprotection can be confirmed by disappearance of the methine peak of p- (1-ethoxyethoxy) styrene, which is seen in the vicinity of 5.3 ppm by proton nuclear magnetic resonance spectrum ( 1 H-NMR) measurement.
以下に、実施例などにより本発明をより具体的に説明するが、本発明はこれらの実施例などによって何ら限定されるものではない。
なお、分子量、分子量分布、重合率については、RI検出器を備えたゲルパーミエイションクロマトグラフィー(GPC)により以下に示す条件により測定し、その結果により算出した。また、1−エトキシエトキシ基の脱離の完了については 1H−NMRにより、他のエステル部位の脱保護の有無については赤外線吸スペクトル(IR)測定によりそれぞれ以下に示す条件により確認を行った。
[GPC]
使用装置:Shodex GPC−101〔昭和電工(株)製〕
カラム :KF−G−KF−805−KF−803−KF−802〔昭和電工(株)製〕
溶離液 :テトラヒドロフラン(THF)
流量 :1ml/min.
液温 :35℃
[NMR]
使用装置:日本電子(株)製、AL−400 400MHz
溶媒 :d−DMSO
[IR]
KBr法
使用装置:日本分光(株)製、FT/IR−420
Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to these examples and the like.
The molecular weight, molecular weight distribution, and polymerization rate were measured by gel permeation chromatography (GPC) equipped with an RI detector under the following conditions, and calculated from the results. The completion of elimination of the 1-ethoxyethoxy group was confirmed by 1 H-NMR, and the presence or absence of deprotection of other ester sites was confirmed by the infrared absorption spectrum (IR) measurement under the following conditions.
[GPC]
Equipment used: Shodex GPC-101 [manufactured by Showa Denko KK]
Column: KF-G-KF-805-KF-803-KF-802 [manufactured by Showa Denko KK]
Eluent: Tetrahydrofuran (THF)
Flow rate: 1 ml / min.
Liquid temperature: 35 ° C
[NMR]
Equipment used: AL-400 400 MHz, manufactured by JEOL Ltd.
Solvent: d-DMSO
[IR]
KBr method Device used: JASCO Corporation, FT / IR-420
〔実施例1〕
撹拌器、冷却管、窒素バブリング管付き1リットル反応容器に、重合モノマーとしてのp−(1−エトキシエトキシ)スチレン50.0gとp−(t−ブトキシ)スチレン45.8g、t−ブチルメタクリレート73.9g、溶媒としてのプロピレングリコールモノメチルエーテル254.6gおよび重合開始剤としての2,2’−アゾビス(イソブチロニトリル)10.2g仕込み窒素バブリング下にて80℃まで昇温し、6時間重合を行った。その結果、得られた共重合体は重量平均分子量11000、分子量分布2.31であった。
得られた重合液にプロピレングリコールモノメチルエーテルを254.6gと水17.7gを加え30℃で、35%塩酸1.4g(p−(1−エトキシエトキシ)スチレンに対し0.05モル等量)を滴下した。
滴下1時間後、プロトン核磁気共鳴スペクトル測定により5.3ppm付近に見られるp−(1−エトキシエトキシ)スチレンのメチンのピークが消失しており脱保護反応が終了していること、およびt−ブトキシおよびt−ブチル基が脱離していないことを確認した。
[Example 1]
In a 1 liter reaction vessel equipped with a stirrer, a cooling tube and a nitrogen bubbling tube, 50.0 g of p- (1-ethoxyethoxy) styrene as a polymerization monomer, 45.8 g of p- (t-butoxy) styrene, and t-butyl methacrylate 73 .9 g, 254.6 g of propylene glycol monomethyl ether as a solvent and 10.2 g of 2,2′-azobis (isobutyronitrile) as a polymerization initiator, heated to 80 ° C. under nitrogen bubbling, and polymerized for 6 hours Went. As a result, the obtained copolymer had a weight average molecular weight of 11,000 and a molecular weight distribution of 2.31.
254.6 g of propylene glycol monomethyl ether and 17.7 g of water were added to the resulting polymerization solution, and 1.4 g of 35% hydrochloric acid (0.05 mol equivalent to p- (1-ethoxyethoxy) styrene) at 30 ° C. Was dripped.
One hour after the dropping, the methine peak of p- (1-ethoxyethoxy) styrene seen in the vicinity of 5.3 ppm by proton nuclear magnetic resonance spectrum measurement disappeared, and the deprotection reaction was completed, and t- It was confirmed that butoxy and t-butyl groups were not eliminated.
〔実施例2〕
撹拌器、冷却管、窒素バブリング管付き1リットル反応容器に、重合モノマーとしてのp−(1−エトキシエトキシ)スチレン50.0g、p−(t−ブトキシ)スチレン45.8g、t−ブチルメタクリレート37.0g、メタクリル酸11.2g、溶媒としてのプロピレングリコールモノメチルエーテル216.0g、および重合開始剤としての2,2’−アゾビス(イソブチロニトリル)8.6g仕込み窒素バブリング下にて80℃まで昇温し、6時間重合を行った。その結果、得られた共重合体は重量平均分子量12900、分子量分布2.33であった。
得られた重合液にプロピレングリコールモノメチルエーテル164.2gとメタノール95.1g、及び水17.7gを加え30℃で、35%塩酸1.4g(p−(1−エトキシエトキシ)スチレンに対し0.05モル等量)を滴下した。滴下1時間後、プロトン核磁気共鳴スペクトル測定により5.3ppm付近に見られるp−(1−エトキシエトキシ)スチレンのメチンのピークが消失しており脱保護反応が終了していること、t−ブトキシおよびt−ブチル基が脱離していないことを確認した。
[Example 2]
In a 1 liter reaction vessel equipped with a stirrer, a cooling tube, and a nitrogen bubbling tube, 50.0 g of p- (1-ethoxyethoxy) styrene as a polymerization monomer, 45.8 g of p- (t-butoxy) styrene, and t-butyl methacrylate 37 0.0 g, 11.2 g of methacrylic acid, 216.0 g of propylene glycol monomethyl ether as a solvent, and 8.6 g of 2,2′-azobis (isobutyronitrile) as a polymerization initiator up to 80 ° C. under nitrogen bubbling The temperature was raised and polymerization was carried out for 6 hours. As a result, the obtained copolymer had a weight average molecular weight of 12900 and a molecular weight distribution of 2.33.
Propylene glycol monomethyl ether (164.2 g), methanol (95.1 g), and water (17.7 g) were added to the resulting polymerization solution, and at 30 ° C., 35% hydrochloric acid (1.4 g) (p- (1-ethoxyethoxy) styrene was reduced to 0.000). 05 mole equivalent) was added dropwise. One hour after the dropping, the methine peak of p- (1-ethoxyethoxy) styrene, which was observed at around 5.3 ppm by proton nuclear magnetic resonance spectrum measurement, disappeared, and the deprotection reaction was completed, t-butoxy It was confirmed that the t-butyl group was not eliminated.
〔実施例3〕
撹拌子入り1リットル反応容器に、溶媒としてのテトラヒドロフラン450.0g仕込み、−60℃まで冷却した後、反応開始剤としてのブチルリチウムを8.6g仕込み、重合モノマーとしてのp−(1−エトキシエトキシ)スチレン120.5g、p−(t−ブトキシ)スチレン25.73g、およびスチレン4.22gの混合液を滴下した。滴下10分後メタノール0.5g仕込み反応を終了した。その結果、得られた共重合体は、重量平均分子量12400、分子量分布1.08であった。得られた重合液を40℃にて減圧留去を行い、テトラヒドロフランを300g留去し、プロピレングリコールモノメチルエーテル450.0g仕込んだ。再び40℃にて減圧留去を行い、テトラヒドロフランを150g留去し、この置換重合液に水34.0g仕込み30℃で、35%塩酸5.2g(p−(1−エトキシエトキシ)スチレンに対し0.1モル等量)を滴下した。滴下1時間後、プロトン核磁気共鳴スペクトル測定により5.3ppm付近に見られるp−(1−エトキシエトキシ)スチレンのメチンのピークが消失しており脱保護反応が終了していること、t−ブトキシが脱離していないことを確認した。
Example 3
In a 1 liter reaction vessel containing a stirrer, 450.0 g of tetrahydrofuran as a solvent was charged and cooled to −60 ° C., and then 8.6 g of butyl lithium as a reaction initiator was charged, and p- (1-ethoxyethoxy as a polymerization monomer). ) A mixed liquid of 120.5 g of styrene, 25.73 g of p- (t-butoxy) styrene, and 4.22 g of styrene was dropped. Ten minutes after the dropping, 0.5 g of methanol was charged and the reaction was terminated. As a result, the obtained copolymer had a weight average molecular weight of 12400 and a molecular weight distribution of 1.08. The obtained polymerization liquid was distilled off under reduced pressure at 40 ° C., 300 g of tetrahydrofuran was distilled off, and 450.0 g of propylene glycol monomethyl ether was charged. Again, 40 g of the solvent was distilled off under reduced pressure, 150 g of tetrahydrofuran was distilled off, and 34.0 g of water was added to this substitution polymerization solution, and at 30 ° C., 5.2 g of 35% hydrochloric acid (based on p- (1-ethoxyethoxy) styrene). 0.1 molar equivalent) was added dropwise. One hour after the dropping, the methine peak of p- (1-ethoxyethoxy) styrene, which was observed at around 5.3 ppm by proton nuclear magnetic resonance spectrum measurement, disappeared, and the deprotection reaction was completed, t-butoxy It was confirmed that was not detached.
〔実施例4〕
撹拌子入り1リットル反応容器に、溶媒としてのテトラヒドロフラン450.0g仕込み、−40℃まで冷却した後、重合開始剤としてのブチルリチウムを8.6g仕込み、重合モノマーとしてのp−(1−エトキシエトキシ)スチレン93.10g、p−(t−ブトキシ)スチレン56.90gの混合液を滴下した。滴下10分後、メタノールを0.5g仕込み反応を終了した。その結果、得られた共重合体は重量平均分子量12400、分子量分布1.08であった。
得られた重合液を40℃にて減圧留去を行い、テトラヒドロフランを300g留去し、プロピレングリコールモノメチルエーテルを600.0g仕込んだ。再び40℃にて減圧留去を行い、テトラヒドロフランを150g留去し、この置換重合液に水34.0g仕込み、30℃で35%塩酸5.05g(p−(1−エトキシエトキシ)スチレンに対し0.1モル等量)を滴下した。滴下1時間後プロトン核磁気共鳴スペクトル測定により5.3ppm付近に見られるp−(1−エトキシエトキシ)スチレンのメチンのピークが消失しており脱保護反応が終了していること、t−ブトキシが脱離していないことを確認した。
得られた重合体の組成比(モル比)は、p−ヒドロキシスチレン:スチレン=60:40であり、仕込み組成比と一致した。
Example 4
In a 1 liter reaction vessel containing a stirrer, 450.0 g of tetrahydrofuran as a solvent was charged and cooled to −40 ° C., and then 8.6 g of butyl lithium as a polymerization initiator was charged, and p- (1-ethoxyethoxy as a polymerization monomer). ) A mixed solution of 93.10 g of styrene and 56.90 g of p- (t-butoxy) styrene was dropped. Ten minutes after the dropping, 0.5 g of methanol was added to complete the reaction. As a result, the obtained copolymer had a weight average molecular weight of 12400 and a molecular weight distribution of 1.08.
The obtained polymerization liquid was distilled off under reduced pressure at 40 ° C., 300 g of tetrahydrofuran was distilled off, and 600.0 g of propylene glycol monomethyl ether was charged. Distillation under reduced pressure was again performed at 40 ° C., 150 g of tetrahydrofuran was distilled off, 34.0 g of water was charged into this substitution polymerization solution, and 5.05 g of 35% hydrochloric acid at 30 ° C. (based on p- (1-ethoxyethoxy) styrene). 0.1 molar equivalent) was added dropwise. One hour after the dropping, the methine peak of p- (1-ethoxyethoxy) styrene seen in the vicinity of 5.3 ppm by proton nuclear magnetic resonance spectrum measurement disappeared, and the deprotection reaction was completed. It was confirmed that it was not detached.
The composition ratio (molar ratio) of the obtained polymer was p-hydroxystyrene: styrene = 60: 40, which was consistent with the charged composition ratio.
〔比較例1〕
撹拌器、冷却管、窒素バブリング管付き1リットル反応容器に、重合モノマーとしてのp−(t−ブトキシ)スチレン140.8g、t−ブチルメタクリレート28.4g、溶媒としてのプロピレングリコールモノメチルエーテル253.6g、および重合開始剤としての2,2’−アゾビス(イソブチロニトリル)9.7g仕込み、窒素バブリング下にて80℃まで昇温し、6時間重合を行った。その結果、得られた共重合体は、重量平均分子量12100、分子量分布2.21であった。得られた重合液にプロピレングリコールモノメチルエーテル403.5g、および35%塩酸91.8g仕込み密閉下60℃にて6時間後にIRにて900cm-1付近のブトキシ基のエーテル結合のピークが完全に消失したことにより反応の終了を確認した。しかしプロトン核磁気共鳴スペクトル測定によりt−ブチルメタクリレートのt−ブチル基のピークが減りt−ブチル基の脱離が確認された。
[Comparative Example 1]
In a 1 liter reaction vessel equipped with a stirrer, a cooling tube and a nitrogen bubbling tube, 140.8 g of p- (t-butoxy) styrene as a polymerization monomer, 28.4 g of t-butyl methacrylate, and 253.6 g of propylene glycol monomethyl ether as a solvent Then, 9.7 g of 2,2′-azobis (isobutyronitrile) as a polymerization initiator was charged, the temperature was raised to 80 ° C. under nitrogen bubbling, and polymerization was performed for 6 hours. As a result, the obtained copolymer had a weight average molecular weight of 12100 and a molecular weight distribution of 2.21. The obtained polymerization solution was charged with 403.5 g of propylene glycol monomethyl ether and 91.8 g of 35% hydrochloric acid, and after 6 hours at 60 ° C. in a sealed state, the peak of the butoxy group ether bond near 900 cm −1 disappeared completely by IR. This confirmed the completion of the reaction. However, the proton nuclear magnetic resonance spectrum measurement reduced the t-butyl group peak of t-butyl methacrylate and confirmed the elimination of the t-butyl group.
〔比較例2〕
撹拌子入り1リットル反応容器に、溶媒としてのテトラヒドロフラン450.0g仕込み、−40℃まで冷却した後、反応開始剤としてのブチルリチウムを8.6g仕込み、重合モノマーとしてのp−(1−エトキシエトキシ)スチレン93.10gとp−(t−ブトキシ)スチレン56.90gとの混合液を滴下した。滴下10分後メタノールを0.5g仕込み反応を終了した。その結果、得られた共重合体は、重量平均分子量12400、分子量分布1.08であった。得られた重合液を40℃にて減圧留去を行い、テトラヒドロフランを300g留去し、プロピレングリコールモノメチルエーテルを600.0g仕込んだ。この置換重合液(溶媒重量比率;テトラヒドロフラン:20%、プロピレングリコールモノメチルエーテル:80%)に水34.0g仕込み、30℃で35%塩酸5.05g(p−(1−エトキシエトキシ)スチレンに対し0.1モル等量)を滴下した。滴下1時間後プロトン核磁気共鳴スペクトル測定により5.3ppm付近に見られるp−(1−エトキシエトキシ)スチレンのメチンのピークが消失せず、脱保護反応が終了していなかった。
[Comparative Example 2]
In a 1 liter reaction vessel containing a stirrer, 450.0 g of tetrahydrofuran as a solvent was charged and cooled to −40 ° C., and then 8.6 g of butyl lithium as a reaction initiator was charged, and p- (1-ethoxyethoxy as a polymerization monomer). ) A mixed liquid of 93.10 g of styrene and 56.90 g of p- (t-butoxy) styrene was dropped. Ten minutes after the dropping, 0.5 g of methanol was added to complete the reaction. As a result, the obtained copolymer had a weight average molecular weight of 12400 and a molecular weight distribution of 1.08. The obtained polymerization liquid was distilled off under reduced pressure at 40 ° C., 300 g of tetrahydrofuran was distilled off, and 600.0 g of propylene glycol monomethyl ether was charged. Into this substitution polymerization liquid (solvent weight ratio: tetrahydrofuran: 20%, propylene glycol monomethyl ether: 80%), 34.0 g of water was charged, and at 30 ° C., 5.05 g of 35% hydrochloric acid (based on p- (1-ethoxyethoxy) styrene). 0.1 molar equivalent) was added dropwise. One hour after the dropping, the methine peak of p- (1-ethoxyethoxy) styrene, which was observed at around 5.3 ppm by proton nuclear magnetic resonance spectrum measurement, did not disappear, and the deprotection reaction was not completed.
本発明により、p−(1−エトキシエトキシ)スチレン由来の構成単位を含有する重合体を、アルコールを90重量%以上含有する溶媒中に溶解または分散し、水と塩酸を用いることにより1−エトキシエトキシ基を選択的に脱保護してp−ヒドロキシスチレン由来の構成単位を含有する重合体の製造方法を提供することができ、該重合体はリソグラフィー工程における化学増幅型フォトレジストとして有用である。 According to the present invention, a polymer containing a structural unit derived from p- (1-ethoxyethoxy) styrene is dissolved or dispersed in a solvent containing 90% by weight or more of alcohol, and 1-ethoxy is obtained by using water and hydrochloric acid. A method for producing a polymer containing a structural unit derived from p-hydroxystyrene by selectively deprotecting an ethoxy group can be provided, and the polymer is useful as a chemically amplified photoresist in a lithography process.
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JPH0247109A (en) * | 1988-08-08 | 1990-02-16 | Hoechst Celanese Corp | Method for manufacturing a poly(vinyl phenol) by ester-exchanging of poly(acetoxy styrene) with an acid catalyst |
JPH11255820A (en) * | 1998-03-12 | 1999-09-21 | Mitsui Chem Inc | Preparation of narrow distribution poly(p-yydroxy-styrene) |
JP2002049156A (en) * | 2000-08-02 | 2002-02-15 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JP2002348328A (en) * | 2001-05-23 | 2002-12-04 | Nippon Soda Co Ltd | Alkenylphenol-based copolymer and process for preparation thereof |
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JPH0247109A (en) * | 1988-08-08 | 1990-02-16 | Hoechst Celanese Corp | Method for manufacturing a poly(vinyl phenol) by ester-exchanging of poly(acetoxy styrene) with an acid catalyst |
JPH11255820A (en) * | 1998-03-12 | 1999-09-21 | Mitsui Chem Inc | Preparation of narrow distribution poly(p-yydroxy-styrene) |
JP2002049156A (en) * | 2000-08-02 | 2002-02-15 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JP2002348328A (en) * | 2001-05-23 | 2002-12-04 | Nippon Soda Co Ltd | Alkenylphenol-based copolymer and process for preparation thereof |
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