JP5433999B2 - Manufacturing method of resin for photoresist - Google Patents
Manufacturing method of resin for photoresist Download PDFInfo
- Publication number
- JP5433999B2 JP5433999B2 JP2008185288A JP2008185288A JP5433999B2 JP 5433999 B2 JP5433999 B2 JP 5433999B2 JP 2008185288 A JP2008185288 A JP 2008185288A JP 2008185288 A JP2008185288 A JP 2008185288A JP 5433999 B2 JP5433999 B2 JP 5433999B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- solvent
- polymerization
- group
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920005989 resin Polymers 0.000 title claims description 78
- 239000011347 resin Substances 0.000 title claims description 78
- 229920002120 photoresistant polymer Polymers 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 239000000178 monomer Substances 0.000 claims description 67
- 238000006116 polymerization reaction Methods 0.000 claims description 67
- 239000002904 solvent Substances 0.000 claims description 63
- -1 2-hydroxyethoxy Chemical group 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 21
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 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 claims description 3
- ZMAOPHHNBQIJOQ-UHFFFAOYSA-N (2-propan-2-yl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(C(C)C)(OC(=O)C(C)=C)C2C3 ZMAOPHHNBQIJOQ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 claims 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 78
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 19
- 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 18
- 239000000203 mixture Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- FDYDISGSYGFRJM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)(C)C2C3 FDYDISGSYGFRJM-UHFFFAOYSA-N 0.000 description 15
- 238000004821 distillation Methods 0.000 description 15
- 230000005855 radiation Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 12
- 239000003505 polymerization initiator Substances 0.000 description 11
- 239000011342 resin composition Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000006239 protecting group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical class OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 3
- YNGIFMKMDRDNBQ-UHFFFAOYSA-N 3-ethenylphenol Chemical compound OC1=CC=CC(C=C)=C1 YNGIFMKMDRDNBQ-UHFFFAOYSA-N 0.000 description 3
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 150000002596 lactones Chemical group 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- VLSRKCIBHNJFHA-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C(F)(F)F VLSRKCIBHNJFHA-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- JNMDSVAPEKNHQF-UHFFFAOYSA-N [3-(2-hydroxyethoxy)-1-adamantyl] 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2(OCCO)CC1(OC(=O)C(=C)C)C3 JNMDSVAPEKNHQF-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-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
- 238000000746 purification Methods 0.000 description 2
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical group C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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 1
- RYJXBOAUROTLHI-UHFFFAOYSA-N (5-oxo-4-oxatricyclo[5.2.1.03,8]decan-2-yl) 2-methylprop-2-enoate Chemical compound C1C(=O)OC2C(OC(=O)C(=C)C)C3CC2C1C3 RYJXBOAUROTLHI-UHFFFAOYSA-N 0.000 description 1
- YGTDGBOXXLHPPC-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-(1-methyl-2-bicyclo[2.2.1]hept-2-enyl)propan-2-ol Chemical compound OC(C(F)(F)F)(C(F)(F)F)C=1C2(CCC(C1)C2)C YGTDGBOXXLHPPC-UHFFFAOYSA-N 0.000 description 1
- OJRIMKKGHYINJA-UHFFFAOYSA-N 1,1,1-trifluoro-5-sulfanyl-2-(trifluoromethyl)pentan-2-ol Chemical compound FC(F)(F)C(C(F)(F)F)(O)CCCS OJRIMKKGHYINJA-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- RHDPTOIUYREFCO-UHFFFAOYSA-N 2-(4-ethenylphenyl)-1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(C(F)(F)F)(O)C1=CC=C(C=C)C=C1 RHDPTOIUYREFCO-UHFFFAOYSA-N 0.000 description 1
- GWFCWZQFUSJPRE-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]cyclohexane-1-carboxylic acid Chemical compound CC(=C)C(=O)OCCOC(=O)C1CCCCC1C(O)=O GWFCWZQFUSJPRE-UHFFFAOYSA-N 0.000 description 1
- ZCSSLICRCYXAKF-UHFFFAOYSA-N 3-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C(C(F)(F)F)=CC1C2 ZCSSLICRCYXAKF-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 1
- IVQQRSCSISNRNA-UHFFFAOYSA-N 5-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)(C(F)(F)F)CC1C=C2 IVQQRSCSISNRNA-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLQQUUPVSXIM-UHFFFAOYSA-N DL-mevalonic acid Natural products OCCC(O)(C)CC(O)=O KJTLQQUUPVSXIM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-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
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- CILNNJGKJKUKIJ-UHFFFAOYSA-N [1,1,1,3,3,3-hexafluoro-2-[4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)cyclohexyl]propan-2-yl] prop-2-enoate Chemical compound FC(F)(F)C(C(F)(F)F)(O)C1CCC(C(OC(=O)C=C)(C(F)(F)F)C(F)(F)F)CC1 CILNNJGKJKUKIJ-UHFFFAOYSA-N 0.000 description 1
- DGTBPTXOXUGLAH-UHFFFAOYSA-N ac1ncxct Chemical compound C1CC2C3C(=O)OCC3C1C2 DGTBPTXOXUGLAH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- WFBABIZEXSULPX-UHFFFAOYSA-N decan-2-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCC(C)OC(=O)C(C)=C WFBABIZEXSULPX-UHFFFAOYSA-N 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- OGBAEJNSZKSDFD-UHFFFAOYSA-N heptan-2-yl 2-methylprop-2-enoate Chemical compound CCCCCC(C)OC(=O)C(C)=C OGBAEJNSZKSDFD-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 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
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、フォトレジスト用樹脂の製造方法に関する。更に詳しくは、本発明は、樹脂原料として用いられるモノマーのポリマーへの転化率を向上させることができるフォトレジスト用樹脂の製造方法。 The present invention relates to a method for producing a photoresist resin. More specifically, the present invention relates to a method for producing a photoresist resin, which can improve the conversion rate of a monomer used as a resin raw material into a polymer.
集積回路素子の製造に代表される微細加工の分野においては、より高い集積度を得るために、より微細な加工が可能なリソグラフィー技術が必要とされている。しかし、従来のリソグラフィープロセスでは、一般に放射線としてｉ線等の近紫外線が用いられているが、この近紫外線では、サブクオーターミクロンレベルの微細加工が極めて困難であると言われている。そこで、例えば、０．１０μｍ以下のレベルでの微細加工を可能とするために、より波長の短い放射線の利用が検討されている。このような短波長の放射線としては、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、Ｘ線、電子線等を挙げることができるが、これらのうち、特にＫｒＦエキシマレーザー（波長２４８ｎｍ）或いはＡｒＦエキシマレーザー（波長１９３ｎｍ）が注目されている。 In the field of microfabrication represented by the manufacture of integrated circuit elements, lithography technology capable of finer processing is required to obtain a higher degree of integration. However, in the conventional lithography process, near ultraviolet rays such as i rays are generally used as radiation, and it is said that fine processing at the subquarter micron level is extremely difficult with this near ultraviolet rays. Therefore, for example, in order to enable fine processing at a level of 0.10 μm or less, use of radiation having a shorter wavelength is being studied. Examples of such short-wavelength radiation include an emission line spectrum of a mercury lamp, far-ultraviolet rays typified by an excimer laser, an X-ray, an electron beam, and the like. Among these, a KrF excimer laser (wavelength 248 nm) is particularly preferable. ) Or ArF excimer laser (wavelength 193 nm) has been attracting attention.
このような放射線による照射に適した、レジスト形成用の感放射線性樹脂組成物、多層レジストにおける上層膜や下層膜（反射防止膜等）を形成するための樹脂組成物等のフォトリソグラフィに使用される樹脂組成物が数多く提案されている。 Used for photolithography such as a radiation-sensitive resin composition for resist formation suitable for irradiation with such radiation, and a resin composition for forming an upper layer film or a lower layer film (antireflection film, etc.) in a multilayer resist. Many resin compositions have been proposed.
そして、このような樹脂組成物に用いられるフォトレジスト用樹脂の製造方法としては、例えば、重合性モノマーを含有する溶液と、重合開始剤を含有する溶液とを、重合系内に連続的又は断続的に供給して重合させる方法（特許文献１及び２参照）や、減圧且つ還流条件下で重合させる方法（特許文献３参照）等が知られている。 And as a manufacturing method of the resin for photoresists used for such a resin composition, for example, a solution containing a polymerizable monomer and a solution containing a polymerization initiator are continuously or intermittently contained in the polymerization system. For example, there are known a method in which the polymer is supplied and polymerized (see Patent Documents 1 and 2), a method in which the polymerization is performed under reduced pressure and reflux conditions (see Patent Document 3), and the like.
しかしながら、従来のレジスト用樹脂の製造方法においては、樹脂原料として用いられるモノマーのポリマーへの転化率は未だ十分であるとはいえず、残留する未反応モノマーが最終製品の露光特性を悪化させる原因となる恐れがある。特に、固体状のモノマー等の重合溶媒に対する溶解性が低いモノマーが用いられる場合には、多量のモノマー溶解用の溶媒が必要となり、重合反応の際におけるモノマー濃度を十分に高めることができず、モノマーのポリマーへの転化率を十分に高められていないのが現状である。
以上のことから、得られる樹脂の更なる性能及び生産性等の向上の観点から、樹脂原料として用いられるモノマーのポリマーへの転化率をより高くすることができるフォトレジスト用樹脂の製造方法が求められているのが現状である。
However, in the conventional method for producing a resist resin, the conversion rate of the monomer used as a resin raw material into a polymer is still not sufficient, and the remaining unreacted monomer causes the exposure characteristics of the final product to deteriorate. There is a risk of becoming. In particular, when a monomer having low solubility in a polymerization solvent such as a solid monomer is used, a large amount of solvent for dissolving the monomer is required, and the monomer concentration in the polymerization reaction cannot be sufficiently increased. The present situation is that the conversion rate of the monomer into the polymer is not sufficiently increased.
From the above, from the viewpoint of improving the performance and productivity of the obtained resin, there is a demand for a method for producing a resin for photoresist that can further increase the conversion rate of the monomer used as the resin raw material to the polymer. This is the current situation.
本発明は、樹脂原料として用いられるモノマーのポリマーへの転化率を向上させることができるフォトレジスト用樹脂の製造方法を提供することを目的とする。 An object of this invention is to provide the manufacturing method of the resin for photoresists which can improve the conversion rate to the polymer of the monomer used as a resin raw material.
本発明は、以下のとおりである。
［１］溶媒の存在下で重合性化合物を重合させることにより、フォトレジスト用樹脂を製造するフォトレジスト用樹脂の製造方法であって、
前記重合性化合物は、エチレン性不飽和結合を有する単量体であり、
前記重合性化合物のうちの少なくとも１種は、常温において固体状の化合物であり、
重合反応中に、溶媒を留去することを特徴とするフォトレジスト用樹脂の製造方法。
［２］常温において固体状の前記化合物は、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン、２−エチル−２−アダマンチルメタクリレート、５−オキソ−４−オキサ−トリシクロ［５．２．１．０３，８］デカ−２−イルメタクリレート、３−（２−ヒドロキシエトキシ）−１−アダマンチルメタクリレート、２−イソプロピル−２−アダマンチルメタクリレート、２−［〔（トリフルオロメチル）スルホニル〕アミノ］エチルメタクリレート、１，２−シクロヘキサンジカルボン酸モノ［２−〔（２−メチル−１−オキソ−２−プロペニル）オキシ〕エチル］エステル、５−［３，３，３−トリフルオロ−２−ヒドロキシ−２−（トリフルオロメチル）プロピル］ビシクロ［２．２．１］ヘプタン−２−イルメタクリレート、又は、６−［３，３，３−トリフルオロ−２−ヒドロキシ−２−（トリフルオロメチル）プロピル］ビシクロ［２．２．１］ヘプタン−２−イルメタクリレートである前記［１］に記載のフォトレジスト用樹脂の製造方法。
［３］重合反応中における前記溶媒の留去量が、重合の際に使用される溶媒の総量を１００質量％とした場合に、２５〜６５質量％である前記［１］又は［２］に記載のフォトレジスト用樹脂の製造方法。
［４］前記反応溶媒の留去を連続的又は間欠的に行う前記［１］乃至［３］のいずれかに記載のフォトレジスト用樹脂の製造方法。
［５］重合反応中における前記溶媒の留去速度が、重合の際に使用される溶媒の初期の総量を１００質量％とした場合に、５〜４４質量％／ｈである前記［１］乃至［４］のいずれかに記載のフォトレジスト用樹脂の製造方法。
［６］前記重合反応を加圧下で行う前記［１］乃至［５］のいずれかに記載のフォトレジスト用樹脂の製造方法。
The present invention is as follows.
[1] A method for producing a photoresist resin, which comprises producing a photoresist resin by polymerizing a polymerizable compound in the presence of a solvent,
The polymerizable compound is a monomer having an ethylenically unsaturated bond,
At least one of the polymerizable compounds is a solid compound at room temperature,
A method for producing a photoresist resin, wherein a solvent is distilled off during a polymerization reaction.
[2] The compound that is solid at room temperature includes 5-methacryloyloxy-2,6-norbornanecarbolactone, 2-ethyl-2-adamantyl methacrylate, 5-oxo-4-oxa-tricyclo [5.2.1. 0 3,8 ] dec-2-yl methacrylate, 3- (2-hydroxyethoxy) -1-adamantyl methacrylate, 2-isopropyl-2-adamantyl methacrylate, 2-[[(trifluoromethyl) sulfonyl] amino] ethyl methacrylate 1,2-cyclohexanedicarboxylic acid mono [2-[(2-methyl-1-oxo-2-propenyl) oxy] ethyl] ester, 5- [3,3,3-trifluoro-2-hydroxy-2- (Trifluoromethyl) propyl] bicyclo [2.2.1] heptan-2-ylmetac In the above [1], which is a rate or 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] bicyclo [2.2.1] heptan-2-yl methacrylate The manufacturing method of resin for description of description.
[3] In the above [1] or [2], the amount of the solvent distilled off during the polymerization reaction is 25 to 65% by mass when the total amount of the solvent used in the polymerization is 100% by mass. The manufacturing method of resin for description of description.
[4] The method for producing a photoresist resin according to any one of [1] to [3], wherein the reaction solvent is distilled off continuously or intermittently.
[5] The above-mentioned [1] to [44], wherein the evaporation rate of the solvent during the polymerization reaction is 5 to 44% by mass / h when the initial total amount of the solvent used in the polymerization is 100% by mass. [4] The method for producing a photoresist resin according to any one of [4].
[6] The method for producing a photoresist resin according to any one of [1] to [5], wherein the polymerization reaction is performed under pressure.
本発明のフォトレジスト用樹脂の製造方法によれば、重合反応中に溶媒を留去（蒸発留去）することによって、重合溶液中における固形分濃度（特に単量体の濃度）を従来よりも高濃度に維持することができ、即ち従来よりも固形分が濃縮された状態で重合させることができ、樹脂原料として用いられるモノマー（単量体）のポリマー（重合体）への転化率を大幅に向上させることができる。また、重合溶媒に対する溶解性が低く、モノマー溶解用の溶媒が多量に必要な固体状のモノマー等を用いる場合であっても、上述のように固形分濃度を従来よりも高濃度に維持して重合可能であるため、ポリマーへの転化率を向上させることができる。更に、ポリマーへの転化率が向上することによって、最終製品の露光特性を悪化させる原因となる未反応モノマー等の不純物の含有量が少ない高純度の樹脂溶液が得られ、高品質なフォトレジスト用樹脂を得ることができる。更には、重合に必要な高価なモノマーの使用量を従来よりも少なくすることができ、フォトレジスト用樹脂の生産性を向上させることができる。 According to the method for producing a resin for a photoresist of the present invention, the solid content concentration (particularly the monomer concentration) in the polymerization solution is made higher than before by distilling off the solvent during the polymerization reaction (evaporation distillation). It can be maintained at a high concentration, that is, it can be polymerized in a state where the solid content is more concentrated than before, and the conversion rate of the monomer (monomer) used as a resin raw material to a polymer (polymer) is greatly increased. Can be improved. In addition, even when using solid monomers that have low solubility in the polymerization solvent and require a large amount of solvent for dissolving the monomer, the solid content concentration is maintained higher than the conventional concentration as described above. Since it can polymerize, the conversion rate to a polymer can be improved. Furthermore, by improving the conversion rate to polymer, a high-purity resin solution with a low content of impurities such as unreacted monomers that cause the exposure characteristics of the final product to deteriorate can be obtained. A resin can be obtained. Furthermore, the amount of expensive monomers required for polymerization can be reduced as compared with the conventional amount, and the productivity of the photoresist resin can be improved.
以下、本発明を詳細に説明する。
本発明のフォトレジスト用樹脂の製造方法は、溶媒の存在下で重合性化合物を重合させることにより、フォトレジスト用樹脂を製造するものであって、重合性化合物のうちの少なくとも１種は、常温において固体状の化合物であり、重合反応中に、溶媒を留去することを特徴とする。
Hereinafter, the present invention will be described in detail.
The method for producing a photoresist resin of the present invention is a method for producing a photoresist resin by polymerizing a polymerizable compound in the presence of a solvent, and at least one of the polymerizable compounds is at room temperature. In which the solvent is distilled off during the polymerization reaction.
前記重合性化合物は、レジスト形成用の感放射線性樹脂組成物、多層レジストにおける上層膜や下層膜（反射防止膜等）を形成するための樹脂組成物等のフォトリソグラフィに使用される樹脂組成物に含まれるフォトレジスト用樹脂の製造に用いられるエチレン性不飽和結合を有する重合性化合物（単量体）である。 The polymerizable compound is a resin composition used for photolithography, such as a radiation-sensitive resin composition for resist formation, a resin composition for forming an upper layer film or a lower layer film (antireflection film, etc.) in a multilayer resist. a polymerizable compound having an ethylenically unsaturated bond used in the production of a photoresist resin contained in the (monomeric).
ここで、例えば、レジスト形成用のポジ型感放射線性樹脂組成物に含まれる樹脂は、少なくとも、酸によって分解してアルカリ現像液に可溶となる化学構造を有する繰り返し単位、より具体的には、非極性置換基が酸によって解離してアルカリ現像液に可溶な極性基が発現する化学構造を有する繰り返し単位（１）と、半導体基板等の基板に対する密着性を高めるための極性基を有する繰り返し単位（２）とを必須成分としており、必要に応じて、溶剤やアルカリ現像液への溶解性を調節するための非極性の置換基を有する繰り返し単位（３）を含んで構成されている。 Here, for example, the resin contained in the positive-type radiation-sensitive resin composition for resist formation is at least a repeating unit having a chemical structure that is decomposed by an acid and becomes soluble in an alkali developer, more specifically, And a repeating unit (1) having a chemical structure in which a non-polar substituent is dissociated by an acid and a polar group soluble in an alkali developer is expressed, and a polar group for enhancing adhesion to a substrate such as a semiconductor substrate The repeating unit (2) is an essential component, and includes a repeating unit (3) having a non-polar substituent for adjusting the solubility in a solvent or an alkali developer as necessary. .
前記酸によって分解してアルカリ可溶性となる繰り返し単位（１）は、従来レジストとして一般的に用いられている化学構造を意味し、酸によって分解してアルカリ可溶性になる化学構造を有する単量体を重合させるか、或いは、アルカリ可溶性の化学構造を有する単量体を重合させた後、アルカリ可溶性の化学構造におけるアルカリ可溶性基を有する置換基（アルカリ可溶性基）を、アルカリに溶解せず酸によって解離する基（酸解離性保護基）で保護することにより得ることができる。 The repeating unit (1) that is decomposed by an acid and becomes alkali-soluble means a chemical structure generally used as a conventional resist, and a monomer having a chemical structure that is decomposed by an acid and becomes alkali-soluble. After polymerizing or polymerizing a monomer having an alkali-soluble chemical structure, the substituent having an alkali-soluble group (alkali-soluble group) in the alkali-soluble chemical structure is dissociated by an acid without being dissolved in the alkali. It can be obtained by protecting with a group (acid-dissociable protecting group).
酸によって分解してアルカリ可溶性になる化学構造を有する単量体としては、アルカリ可溶性置換基を含有する重合性化合物に、酸解離性保護基が結合した化合物を挙げることができ、例えば、非極性の酸解離性保護基で保護されたフェノール性水酸基、カルボキシル基やヒドロキシフルオロアルキル基を有する化合物等が挙げられる。具体的には、例えば、ｐ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン、ｐ−ヒドロキシ−α−メチルスチレン等のヒドロキシスチレン類；アクリル酸、メタクリル酸、マレイン酸、フマル酸、α−トリフルオロメチルアクリル酸、５−ノルボルネン−２−カルボン酸、２−トリフルオロメチル−５−ノルボルネン−２−カルボン酸、カルボキシテトラシクロ［４．４．０．１２，５．１７，１０］ドデシルメタクリレート等のエチレン性二重結合を有するカルボン酸類；ｐ−（２−ヒドロキシ−１，１，１，３，３，３−ヘキサフルオロ−２−プロピル）スチレン、２−（４−（２−ヒドロキシ−１，１，１，３，３，３−ヘキサフルオロ−２−プロピル）シクロヘキシル）−１，１，１，３，３，３−ヘキサフルオロプロピルアクリレート、２−（４−（２−ヒドロキシ−１，１，１，３，３，３−ヘキサフルオロ−２−プロピル）シクロヘキシル）−１，１，１，３，３，３−ヘキサフルオロプロピルトリフルオロメチルアクリレート、５−（２−ヒドロキシ−１，１，１，３，３，３−ヘキサフルオロ−２−プロピル）メチル−２−ノルボルネン等のヒドロキシフルオロアルキル基を有する重合性化合物等が挙げられる。 Examples of the monomer having a chemical structure that becomes alkali-soluble when decomposed by an acid include compounds in which an acid-dissociable protecting group is bonded to a polymerizable compound containing an alkali-soluble substituent. And compounds having a phenolic hydroxyl group, a carboxyl group or a hydroxyfluoroalkyl group protected with an acid dissociable protecting group. Specifically, for example, hydroxystyrenes such as p-hydroxystyrene, m-hydroxystyrene, p-hydroxy-α-methylstyrene; acrylic acid, methacrylic acid, maleic acid, fumaric acid, α-trifluoromethylacrylic acid , 5-norbornene-2-carboxylic acid, 2-trifluoromethyl-5-norbornene-2-carboxylic acid, carboxytetracyclo [4.4.0.1 2,5 . 1 7,10 ] carboxylic acids having an ethylenic double bond such as dodecyl methacrylate; p- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) styrene, 2- ( 4- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl) -1,1,1,3,3,3-hexafluoropropyl acrylate, 2- (4 -(2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl) -1,1,1,3,3,3-hexafluoropropyltrifluoromethyl acrylate, 5- Polymerizable compounds having a hydroxyfluoroalkyl group such as (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) methyl-2-norbornene That.
また、前記酸解離性の保護基としては、例えば、ｔｅｒｔ−ブチル基、ｔｅｒｔ−アミル基、１−メチル−１−シクロペンチル基、１−エチル−１−シクロペンチル基、１−メチル−１−シクロヘキシル基、１−エチル−１−シクロヘキシル基、２−メチル−２−アダマンチル基、２−エチル−２−アダマンチル基、２−プロピル−２−アダマンチル基、２−（１−アダマンチル）−２−プロピル基、８−メチル−８−トリシクロ［５．２．１．０２，６］デカニル基、８−エチル−８−トリシクロ［５．２．１．０２，６］デカニル基、８−メチル−８−テトラシクロ［４．４．０．１２，５．１７，１０］ドデカニル基、８−エチル−８−テトラシクロ［４．４．０．１２，５．１７，１０］ドデカニル基等の飽和炭化水素基；１−メトキシエチル基、２−エトキシエチル基、１−ｉｓｏ−プロポキシエチル基、１−ｎ−ブトキシエチル基、１−ｔｅｒｔ−ブトキシエチル基、１−シクロペンチルオキシエチル基、１−シクロヘキシルオキシエチル基、１−トリシクロ［５．２．１．０２，６］デカニルオキシエチル基、メトキシメチル基、エトキシメチル基、ｉｓｏ−プロポキシメチル基、ｎ−ブトキシメチル基、ｔｅｒｔ−ブトキシメチル基、シクロペンチルオキシメチル基、シクロヘキシルオキシメチル基、トリシクロ［５．２．１．０２，６］デカニルオキシメチル基、ｔｅｒｔ−ブトキシカルボニル基等の含酸素炭化水素基等が挙げられる。 Examples of the acid dissociable protecting group include a tert-butyl group, a tert-amyl group, a 1-methyl-1-cyclopentyl group, a 1-ethyl-1-cyclopentyl group, and a 1-methyl-1-cyclohexyl group. 1-ethyl-1-cyclohexyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 2-propyl-2-adamantyl group, 2- (1-adamantyl) -2-propyl group, 8-methyl-8-tricyclo [5.2.1.0 2,6 ] decanyl group, 8-ethyl-8-tricyclo [5.2.1.0 2,6 ] decanyl group, 8-methyl-8- Tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodecanyl group, 8-ethyl-8-tetracyclo [4.4.0.1 2,5 . 1 7, 10 ] saturated hydrocarbon group such as dodecanyl group; 1-methoxyethyl group, 2-ethoxyethyl group, 1-iso-propoxyethyl group, 1-n-butoxyethyl group, 1-tert-butoxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-tricyclo [5.2.1.0 2,6 ] decanyloxyethyl group, methoxymethyl group, ethoxymethyl group, iso-propoxymethyl group, n Oxygenated carbon such as -butoxymethyl group, tert-butoxymethyl group, cyclopentyloxymethyl group, cyclohexyloxymethyl group, tricyclo [5.2.1.0 2,6 ] decanyloxymethyl group, tert-butoxycarbonyl group A hydrogen group etc. are mentioned.
アルカリ可溶性の化学構造を有する単量体を重合させた後、アルカリ可溶性の化学構造におけるアルカリ可溶性基を、酸解離性保護基で保護する場合は、前記のアルカリ可溶性基を有する化合物をそのまま重合反応に用い、その後、酸触媒のもとでビニルエーテルやハロゲン化アルキルエーテル等のアルカリに溶解しない置換基を与える化合物と反応させることにより、酸解離性保護基を導入することができる。反応に用いる酸触媒としては、ｐ−トルエンスルホン酸、トリフルオロ酢酸、強酸性イオン交換樹脂等が挙げられる。 After polymerizing a monomer having an alkali-soluble chemical structure and then protecting the alkali-soluble group in the alkali-soluble chemical structure with an acid-dissociable protecting group, the compound having the alkali-soluble group is directly polymerized. Then, an acid-dissociable protecting group can be introduced by reacting with a compound that gives a substituent that does not dissolve in an alkali such as vinyl ether or halogenated alkyl ether under an acid catalyst. Examples of the acid catalyst used in the reaction include p-toluenesulfonic acid, trifluoroacetic acid, and strongly acidic ion exchange resin.
また、基板に対する密着性を高めるための極性基を有する繰り返し単位（２）を与える単量体としては、例えば、極性基としてフェノール性水酸基、カルボキシル基やヒドロキシフルオロアルキル基を有する化合物等を挙げることができ、具体的には、例えば、アルカリ可溶性基を含有する重合性化合物として前記説明したヒドロキシスチレン類やエチレン性二重結合を有するカルボン酸類、ヒドロキシフルオロアルキル基を有する重合性化合物、及び、これらに更に極性基が置換した単量体のほか、ノルボルネン環、テトラシクロドデセン環等の脂環構造に極性基が結合した単量体等を挙げることができる。 Examples of the monomer that gives the repeating unit (2) having a polar group for improving adhesion to the substrate include compounds having a phenolic hydroxyl group, a carboxyl group, or a hydroxyfluoroalkyl group as the polar group. Specifically, for example, as the polymerizable compound containing an alkali-soluble group, hydroxystyrenes described above, carboxylic acids having an ethylenic double bond, polymerizable compounds having a hydroxyfluoroalkyl group, and these In addition to the monomer further substituted with a polar group, a monomer having a polar group bonded to an alicyclic structure such as a norbornene ring or a tetracyclododecene ring can be used.
置換基として繰り返し単位（２）に導入される前記極性基としては、ラクトン構造を含むものが特に好ましく、例えば、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、１，３−シクロヘキサンカルボラクトン、２，６−ノルボルナンカルボラクトン、４−オキサトリシクロ［５．２．１．０２，６］デカン−３−オン、メバロン酸δ−ラクトン等のラクトン構造を含む置換基が挙げられる。
また、ラクトン構造以外の極性基としては、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、３−ヒドロキシ−１−アダマンチル基等のヒドロキシアルキル基等が挙げられる。
The polar group introduced into the repeating unit (2) as a substituent is particularly preferably one containing a lactone structure, such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, 1,3-cyclohexanecarbolactone. , 2,6-norbornanecarbolactone, 4-oxatricyclo [5.2.1.0 2,6 ] decan-3-one, and a substituent containing a lactone structure such as mevalonic acid δ-lactone.
Examples of polar groups other than the lactone structure include hydroxyalkyl groups such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a 3-hydroxy-1-adamantyl group.
更に、必要に応じて含有される、レジスト溶剤やアルカリ現像液への溶解性を調節するための非極性の置換基を有する繰り返し単位（３）を与える単量体としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、インデン等のエチレン性二重結合を有する芳香族化合物；アクリル酸、メタクリル酸、トリフルオロメチルアクリル酸、ノルボルネンカルボン酸、２−トリフルオロメチルノルボルネンカルボン酸、カルボキシテトラシクロ［４．４．０．１２，５．１７，１０］ドデシルメタクリレート等のエチレン性二重結合を有するカルボン酸に酸安定性非極性基が置換したエステル化合物；ノルボルネン、テトラシクロドデセン等のエチレン性二重結合を有する脂環式炭化水素化合物等が挙げられる。
また、前記カルボン酸にエステル置換する酸安定性非極性置換基の例としては、メチル基、エチル基、シクロペンチル基、シクロヘキシル基、イソボルニル基、トリシクロ［５．２．１．０２，６］デカニル基、２−アダマンチル基、テトラシクロ［４．４．０．１２，５．１７，１０］ドデシル基等が挙げられる。
Furthermore, as a monomer which gives the repeating unit (3) having a nonpolar substituent for adjusting the solubility in a resist solvent or an alkali developer, which is contained as necessary, styrene, α-methyl Aromatic compounds having an ethylenic double bond such as styrene, p-methylstyrene, and indene; acrylic acid, methacrylic acid, trifluoromethyl acrylic acid, norbornene carboxylic acid, 2-trifluoromethyl norbornene carboxylic acid, carboxytetracyclo [ 4.4.0.1 2,5 . 1 7,10 ] ester compound in which acid-stable nonpolar group is substituted for carboxylic acid having ethylenic double bond such as dodecyl methacrylate; alicyclic carbonization having ethylenic double bond such as norbornene and tetracyclododecene A hydrogen compound etc. are mentioned.
Examples of acid-stable nonpolar substituents that are ester-substituted for the carboxylic acid include methyl, ethyl, cyclopentyl, cyclohexyl, isobornyl, and tricyclo [5.2.1.0 2,6 ] decanyl. Group, 2-adamantyl group, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodecyl group and the like.
これらの単量体は、繰り返し単位（１）、（２）及び（３）のそれぞれにおいて、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
レジスト形成用のポジ型感放射線性樹脂組成物に含まれる樹脂中の各繰り返し単位の組成比は、レジストとしての基本性能を損なわない範囲で選択することができる。即ち、一般に、繰り返し単位（１）は１０〜７０モル％であることが好ましく、より好ましくは１０〜６０モル％である。また、繰り返し単位（２）の組成比は３０〜９０モル％であることが好ましく、より好ましくは４０〜９０モル％であるが、同一の極性基を有する単量体単位については、７０モル％以下とすることが好ましい。更に、繰り返し単位（３）の組成比は、５０モル％以下であることが好ましく、より好ましくは４０モル％以下である。
These monomers may be used individually by 1 type in each of repeating unit (1), (2), and (3), and may be used in combination of 2 or more type.
The composition ratio of each repeating unit in the resin contained in the positive-type radiation-sensitive resin composition for resist formation can be selected within a range that does not impair the basic performance as a resist. That is, in general, the repeating unit (1) is preferably 10 to 70 mol%, more preferably 10 to 60 mol%. The composition ratio of the repeating unit (2) is preferably 30 to 90 mol%, more preferably 40 to 90 mol%, but for the monomer unit having the same polar group, 70 mol% The following is preferable. Furthermore, the composition ratio of the repeating unit (3) is preferably 50 mol% or less, more preferably 40 mol% or less.
一方、多層レジストにおける上層膜や下層膜（反射防止膜等）を形成するための樹脂組成物に含まれる樹脂は、前述のレジスト形成用のポジ型感放射線性樹脂組成物に含まれる樹脂の化学構造から、酸で分解してアルカリ可溶性になる繰り返し単位（１）を除いた化学構造のポリマーが使用される。樹脂中の各繰り返し単位の組成比は特に限定されず、塗膜の使用目的により適宜調整される。一般には、繰り返し単位（２）の組成比は１０〜１００モル％の範囲から選択され、繰り返し単位（３）の組成比は０〜９０モル％の範囲から選択される。 On the other hand, the resin contained in the resin composition for forming the upper layer film and the lower layer film (antireflection film, etc.) in the multilayer resist is the same as the chemistry of the resin contained in the positive type radiation sensitive resin composition for resist formation described above. A polymer having a chemical structure in which the repeating unit (1) which is decomposed with an acid and becomes alkali-soluble is removed from the structure. The composition ratio of each repeating unit in the resin is not particularly limited, and is appropriately adjusted depending on the intended use of the coating film. Generally, the composition ratio of the repeating unit (2) is selected from the range of 10 to 100 mol%, and the composition ratio of the repeating unit (3) is selected from the range of 0 to 90 mol%.
更に、前記多層レジストにおける上層膜や下層膜を反射防止膜として使用する場合には、前記樹脂は、架橋点と、フォトリソグラフィにおいて照射される放射線を吸収する化学構造とを含む必要があり、架橋点としては、水酸基、アミノ基、カルボキシル基、エポキシ基等の、エステル結合やウレタン結合等により架橋可能な反応性の置換基が挙げられる。架橋点となる反応性置換基を含有する単量体としては、ｐ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン等のヒドロキシスチレン類の他、これまで例示してきた重合性化合物に前記水酸基、アミノ基、カルボキシル基、エポキシ基等の反応性置換基が置換した単量体を適宜用いることができる。 Further, when the upper layer film or the lower layer film in the multilayer resist is used as an antireflection film, the resin needs to include a crosslinking point and a chemical structure that absorbs radiation irradiated in photolithography. The point includes reactive substituents that can be cross-linked by an ester bond, a urethane bond, or the like, such as a hydroxyl group, an amino group, a carboxyl group, or an epoxy group. Examples of the monomer containing a reactive substituent serving as a crosslinking point include hydroxystyrenes such as p-hydroxystyrene and m-hydroxystyrene, and the above-described polymerizable compounds such as the hydroxyl group, amino group, and carboxyl. A monomer substituted with a reactive substituent such as a group or an epoxy group can be appropriately used.
放射線を吸収する化学構造は、使用する放射線の波長により異なるが、例えばＡｒＦエキシマレーザー光に対しては、ベンゼン環及びその類縁体を含む化学構造が好適に用いられる。この様な化学構造を含む単量体としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン等のスチレン類及びその誘導体；置換又は非置換のフェニル（メタ）アクリレート、置換又は非置換のナフタレン（メタ）アクリレート、置換又は非置換のアントラセンメチル（メタ）アクリレート等のエチレン性二重結合を有する芳香族含有エステル類等が挙げられる。この放射線を吸収する化学構造を有する単量体は、極性基の有無により前記繰り返し単位（２）又は（３）のどちらとして導入されてもよいが、放射線を吸収する化学構造を有する単量体としての組成比は１０〜１００モル％の範囲から選択されることが好ましい。尚、本明細書において、「（メタ）アクリレート」とは、アクリレート及びメタクリレートを意味する。 The chemical structure that absorbs radiation varies depending on the wavelength of the radiation used. For example, for ArF excimer laser light, a chemical structure containing a benzene ring and its analogs is preferably used. Examples of the monomer having such a chemical structure include styrenes such as styrene, α-methylstyrene, p-methylstyrene, p-hydroxystyrene, m-hydroxystyrene, and derivatives thereof; substituted or unsubstituted phenyl (meta And aromatic-containing esters having an ethylenic double bond such as acrylate, substituted or unsubstituted naphthalene (meth) acrylate, substituted or unsubstituted anthracenemethyl (meth) acrylate, and the like. The monomer having a chemical structure that absorbs radiation may be introduced as either the repeating unit (2) or (3) depending on the presence or absence of a polar group, but the monomer having a chemical structure that absorbs radiation. Is preferably selected from the range of 10 to 100 mol%. In the present specification, “(meth) acrylate” means acrylate and methacrylate.
また、本発明のフォトレジスト用樹脂の製造方法は、後述の重合溶媒に対する溶解性が低く、モノマー溶解用の溶媒が多量に必要な固体状のモノマー等を用いる場合であっても、モノマーのポリマーへの転化率を向上させることができる。
本発明において用いられる、常温において固体状の具体的な重合性化合物としては、例えば、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン、２−エチル−２−アダマンチルメタクリレート、５−オキソ−４−オキサ−トリシクロ［５．２．１．０３，８］デカ−２−イルメタクリレート、３−（２−ヒドロキシエトキシ）−１−アダマンチルメタクリレート、２−イソプロピル−２−アダマンチルメタクリレート、２−［〔（トリフルオロメチル）スルホニル〕アミノ］エチルメタクリレート、１，２−シクロヘキサンジカルボン酸モノ［２−〔（２−メチル−１−オキソ−２−プロペニル）オキシ〕エチル］エステル、５−［３，３，３−トリフルオロ−２−ヒドロキシ−２−（トリフルオロメチル）プロピル］ビシクロ［２．２．１］ヘプタン−２−イルメタクリレート、６−［３，３，３−トリフルオロ−２−ヒドロキシ−２−（トリフルオロメチル）プロピル］ビシクロ［２．２．１］ヘプタン−２−イルメタクリレート等が挙げられる。
In addition, the method for producing a photoresist resin of the present invention has a low solubility in a polymerization solvent described later, and even when a solid monomer or the like that requires a large amount of a solvent for dissolving a monomer is used, the monomer polymer The conversion rate to can be improved.
Specific examples of the polymerizable compound that is solid at room temperature used in the present invention include, for example, 5-methacryloyloxy-2,6-norbornanecarbolactone, 2-ethyl-2-adamantyl methacrylate, 5-oxo-4- Oxa-tricyclo [5.2.1.0 3,8 ] dec-2-yl methacrylate, 3- (2-hydroxyethoxy) -1-adamantyl methacrylate, 2-isopropyl-2-adamantyl methacrylate, 2-[[( Trifluoromethyl) sulfonyl] amino] ethyl methacrylate, 1,2-cyclohexanedicarboxylic acid mono [2-[(2-methyl-1-oxo-2-propenyl) oxy] ethyl] ester, 5- [3,3,3 -Trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] bi Chro [2.2.1] heptan-2-yl methacrylate, 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] bicyclo [2.2.1] heptane- Examples include 2-yl methacrylate.
また、前記重合性化合物の重合方法は特に限定されず、溶液重合等の公知の方法を用いることができる。
前記フォトレジスト用樹脂を含有する樹脂溶液は、例えば、重合開始剤を使用し、更には必要に応じて連鎖移動剤を使用し、前述の重合性化合物を適当な溶媒中で重合させることにより得ることができる。
具体的には、例えば、（１）溶媒の入った反応容器に、単量体（重合性化合物）及び重合開始剤を含有する溶液を滴下して重合させる方法、（２）溶媒の入った反応容器に、単量体を含む溶液及び重合開始剤を含む溶液を、それぞれ滴下して重合させる方法、（３）反応容器に、単量体、重合開始剤及び溶媒を仕込み、バッチ方式で重合させる方法等が挙げられる。
Moreover, the polymerization method of the said polymeric compound is not specifically limited, Well-known methods, such as solution polymerization, can be used.
The resin solution containing the photoresist resin is obtained, for example, by using a polymerization initiator and, if necessary, using a chain transfer agent, and polymerizing the polymerizable compound in an appropriate solvent. be able to.
Specifically, for example, (1) a method of polymerizing a solution containing a monomer (polymerizable compound) and a polymerization initiator in a reaction vessel containing a solvent, and (2) a reaction containing a solvent. A method in which a solution containing a monomer and a solution containing a polymerization initiator are dropped into a container and polymerized, and (3) a monomer, a polymerization initiator and a solvent are charged in a reaction vessel and polymerized in a batch system. Methods and the like.
前記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−メチルブチロニトリル）、２，２’−アゾビスイソ酪酸ジメチル、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、４，４’−アゾビス（４−シアノ吉草酸）等のアゾ化合物、デカノイルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、ビス（３，５，５−トリメチルヘキサノイル）パーオキサイド、コハク酸パーオキサイド、ｔｅｒｔ−ブチルパーオキシ−２−エチルへキサノエート等の有機過酸化物等のラジカル重合開始剤が挙げられる。これらの重合開始剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobisisobutyrate, 1,1′- Azo compounds such as azobis (cyclohexane-1-carbonitrile), 4,4′-azobis (4-cyanovaleric acid), decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, bis (3,5,5-trimethyl) Hexanoyl) peroxide, succinic acid peroxide, radical polymerization initiators such as organic peroxides such as tert-butylperoxy-2-ethylhexanoate. These polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.
前記連鎖移動剤としては、例えば、ドデシルメルカプタン、メルカプトエタノール、メルカプトプロパノール、メルカプト酢酸、メルカプトプロピオン酸、４，４−ビス（トリフルオロメチル）−４−ヒドロキシ−１−メルカプトブタン等のチオール化合物を挙げることができる。これらの連鎖移動剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the chain transfer agent include thiol compounds such as dodecyl mercaptan, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, and 4,4-bis (trifluoromethyl) -4-hydroxy-1-mercaptobutane. be able to. These chain transfer agents may be used individually by 1 type, and may be used in combination of 2 or more type.
前記重合開始剤及び連鎖移動剤の使用量は、重合反応に用いる原料モノマー（重合性化合物）や重合開始剤、連鎖移動剤の種類、重合温度、重合溶媒、精製条件等の製造条件により適宜調整することができる。
一般に、樹脂の重量平均分子量が高すぎると、塗膜形成時に使用される溶媒やアルカリ現像液への溶解性が低くなる傾向にある。一方、重量平均分子量が低すぎると、塗膜性能が悪くなる傾向にある。そのため、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレン換算重量平均分子量（以下、「Ｍｗ」ともいう。）は、２０００〜４００００の範囲になるよう調整することが好ましく、より好ましくは３０００〜３００００である。
The amount of the polymerization initiator and chain transfer agent used is appropriately adjusted according to the production conditions such as the raw material monomer (polymerizable compound) used in the polymerization reaction, the polymerization initiator, the type of chain transfer agent, the polymerization temperature, the polymerization solvent, and the purification conditions. can do.
In general, if the weight average molecular weight of the resin is too high, the solubility in a solvent or an alkali developer used for forming a coating film tends to be low. On the other hand, when the weight average molecular weight is too low, the coating film performance tends to deteriorate. Therefore, the polystyrene-reduced weight average molecular weight (hereinafter also referred to as “Mw”) by gel permeation chromatography (GPC) is preferably adjusted to be in the range of 2000 to 40000, more preferably 3000 to 30000.
また、重合反応に用いられる溶媒（重合溶媒）は特に限定されないが、例えば、水、アセトン、メチルエチルケトン、メチルアミルケトン、シクロヘキサノン、メチルイソブチルケトン、テトロヒドロフラン、ジオキサン、プロピレングリコールモノメチルエーテル、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、ベンゼン及びトルエンのうちの少なくとも一種を用いることが好ましい。これらの重合溶媒を用いた場合、高収率で、不純物のより少ないフォトレジスト用樹脂を得ることができる。更には、得られたフォトレジスト用樹脂の分子量分布を狭くでき、レジスト膜や反射防止膜に求められる光学的性質、化学的性質、塗布性や基板或いは下層膜に対する密着性等の物理的な性質を向上させることができる。 Further, the solvent (polymerization solvent) used in the polymerization reaction is not particularly limited. For example, water, acetone, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, methyl isobutyl ketone, tetrohydrofuran, dioxane, propylene glycol monomethyl ether, ethyl lactate, It is preferable to use at least one of propylene glycol monomethyl ether acetate, benzene and toluene. When these polymerization solvents are used, a photoresist resin with a high yield and fewer impurities can be obtained. Furthermore, the molecular weight distribution of the obtained photoresist resin can be narrowed, and physical properties such as optical properties, chemical properties, coating properties and adhesion to the substrate or lower layer film required for resist films and antireflection films. Can be improved.
前記重合溶媒の使用量は特に限定されないが、通常、単量体１質量部に対して０．５〜２０質量部、好ましくは１〜１０質量部である。溶媒の使用量が少なすぎる場合には、単量体が析出したり高粘度になりすぎて重合系を均一に保てなくなるおそれがある。一方、溶媒の使用量が多すぎる場合には、原料モノマーの転化率が不十分であったり、得られる重合体（樹脂）の分子量を所望の値まで高めることができないおそれがある。 Although the usage-amount of the said polymerization solvent is not specifically limited, Usually, it is 0.5-20 mass parts with respect to 1 mass part of monomers, Preferably it is 1-10 mass parts. If the amount of the solvent used is too small, the monomer may precipitate or become too viscous to keep the polymerization system uniform. On the other hand, when the amount of the solvent used is too large, the conversion rate of the raw material monomer may be insufficient, or the molecular weight of the polymer (resin) obtained may not be increased to a desired value.
また、本発明におけるフォトレジスト用樹脂の製造方法においては、重合反応中に、溶媒が留去される。このように、溶媒を留去することで、重合溶液中における固形分濃度（特に単量体の濃度）を従来よりも高濃度に維持することができ、樹脂原料として用いられるモノマーのポリマーへの転化率を大幅に向上させることができる。
前記溶媒の留去方法は、蒸発留去が可能な限り特に限定されるものではない。例えば、重合容器に還流される反応溶媒の一部を、クライゼン型連結管等を用いることによって留去することができる。
Moreover, in the manufacturing method of the resin for photoresists in this invention, a solvent is distilled off during a polymerization reaction. In this way, by distilling off the solvent, the solid content concentration (particularly the monomer concentration) in the polymerization solution can be maintained at a higher concentration than before, and the monomer used as the resin raw material is converted into a polymer. The conversion rate can be greatly improved.
The method for distilling off the solvent is not particularly limited as far as evaporation can be carried out. For example, a part of the reaction solvent refluxed to the polymerization vessel can be distilled off by using a Claisen type connecting tube or the like.
前記溶媒の重合反応中における留去量は特に限定されず、適宜調整することができる。例えば、前記留去量は、重合の際に使用される溶媒の総量を１００質量％とした場合に、２５〜６５質量％であることが好ましく、より好ましくは２８〜４５質量％、更に好ましくは３０〜４０質量％である。この留去量が、２５〜６５質量％である場合には、モノマー等の固形分を十分に溶解させたまま濃縮でき、且つ固形分濃度を高めて重合できるため、ポリマーへの転化率が向上し、高収率となるため好ましい。 The amount of the solvent distilled off during the polymerization reaction is not particularly limited and can be adjusted as appropriate. For example, the distillation amount is preferably 25 to 65% by mass, more preferably 28 to 45% by mass, further preferably 100% by mass when the total amount of the solvent used in the polymerization is 100% by mass. 30 to 40% by mass. When the amount of this distillation is 25 to 65% by mass, it can be concentrated while sufficiently dissolving the solids such as monomers, and the polymerization can be performed by increasing the solids concentration, so that the conversion rate to the polymer is improved. However, it is preferable because of high yield.
また、前記溶媒の重合反応中における留去速度は特に限定されず、適宜調整することができる。例えば、前記留去速度は、重合の際に使用される溶媒の初期の総量を１００質量％とした場合に、５〜４４質量％／ｈであることが好ましく、より好ましくは５〜３０質量％／ｈ、更に好ましくは８〜２２質量％／ｈ、特に好ましくは１０〜１７質量％／ｈである。この留去速度が、５〜４４質量％／ｈである場合には、急激な濃縮による固形分（モノマー等）の析出を防止できるため好ましい。また、本発明においては、このように留去速度を調整することにより、反応生成する樹脂の重合度や分子量分布を所定の範囲内に制御することができる。 Further, the distillation rate of the solvent during the polymerization reaction is not particularly limited, and can be appropriately adjusted. For example, the distillation rate is preferably 5 to 44% by mass, more preferably 5 to 30% by mass, when the initial total amount of the solvent used in the polymerization is 100% by mass. / H, more preferably 8 to 22% by mass / h, particularly preferably 10 to 17% by mass / h. A distillation rate of 5 to 44% by mass / h is preferable because precipitation of solids (monomer and the like) due to rapid concentration can be prevented. In the present invention, the degree of polymerization and the molecular weight distribution of the reaction-generated resin can be controlled within a predetermined range by adjusting the distillation rate in this way.
前記溶媒の留去は、重合反応中において、連続的に行われてもよいし、間欠的に行われてもよい。具体的には、例えば、モノマー溶液の滴下等による重合時間がＸ時間である場合、（１）所定の留去量となるように、Ｘ時間連続で溶媒の留去を行ってもよいし（連続的留去）、（２）所定の留去量となるように、Ｘ時間未満の範囲で溶媒の留去を行ってもよいし（間欠的留去）、（３）所定の留去量となるように、合計Ｘ時間以下の範囲で、数回に分けて、溶媒の留去を行ってもよい（間欠的留去）。 The solvent may be distilled off continuously or intermittently during the polymerization reaction. Specifically, for example, when the polymerization time by dropping of the monomer solution or the like is X hours, (1) the solvent may be distilled off continuously for X hours so as to obtain a predetermined distillation amount ( (Continuous distillation), (2) the solvent may be distilled off for less than X hours (intermittent distillation), or (3) the predetermined amount The solvent may be distilled off several times within a range of not more than X hours in total (intermittent distillation).
前記重合における反応条件は特に限定されず、用いられる単量体、重合溶媒等に応じて適宜調整できる。例えば、反応温度は、通常４０〜１２０℃、好ましくは５０〜１００℃である。また、反応時間は、通常１〜４８時間、好ましくは１〜２４時間である。
また、この重合の際の圧力は特に限定されないが、再現性よくポリマーが得られるという観点から、圧力を調節し、一定の圧力下で行うことが好ましく、常圧下（大気圧下）又は加圧下で行うことがより好ましい。特に、加圧下の条件であれば、真空ポンプ等の装置を使用することなく、窒素等の不活性ガスにより容易に圧力コントロールを行うことができるため好ましい。
具体的な加圧条件［圧力（ｈＰａ）］としては、例えば、常圧（１０１３．２５）を超え、１３００ｈＰａ以下が好ましく、より好ましくは１０２０〜１１００ｈＰａ、更に好ましくは１０２０〜１０８０ｈＰａである。
The reaction conditions in the polymerization are not particularly limited, and can be appropriately adjusted according to the monomer used, the polymerization solvent, and the like. For example, the reaction temperature is usually 40 to 120 ° C, preferably 50 to 100 ° C. The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours.
The pressure during the polymerization is not particularly limited, but from the viewpoint that a polymer can be obtained with good reproducibility, it is preferable to adjust the pressure and perform the reaction under a constant pressure, under normal pressure (atmospheric pressure) or under pressure. It is more preferable to carry out with. In particular, the condition under pressure is preferable because the pressure can be easily controlled with an inert gas such as nitrogen without using a device such as a vacuum pump.
The specific pressurizing condition [pressure (hPa)] exceeds, for example, normal pressure (101.25) and is preferably 1300 hPa or less, more preferably 1020 to 1100 hPa, still more preferably 1020 to 1080 hPa.
この重合反応により得られる樹脂溶液の濃度（固形分濃度）は、１〜８０質量％であることが好ましく、より好ましくは５〜５０質量％、更に好ましくは１０〜５０質量％である。 It is preferable that the density | concentration (solid content density | concentration) of the resin solution obtained by this polymerization reaction is 1-80 mass%, More preferably, it is 5-50 mass%, More preferably, it is 10-50 mass%.
また、本発明のフォトレジスト用樹脂の製造方法においては、前述の重合反応により得られたフォトレジスト用樹脂を含有する樹脂溶液に対して、公知の精製処理等を行い、乾燥することによって、樹脂分（固形分）を分離することができる。 In the method for producing a photoresist resin of the present invention, the resin solution containing the photoresist resin obtained by the above-described polymerization reaction is subjected to a known purification treatment and dried to obtain a resin. Minutes (solid content) can be separated.
以下、実施例を挙げて、本発明を更に具体的に説明する。但し、本発明は、これらの実施例に何ら制約されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
［１］フォトレジスト用樹脂を含有する樹脂溶液の製造（実施例１〜３、比較例１〜４）
（実施例１）
８１０ｍＬの四口フラスコに、ジムロート管と、受器を装着したクライゼン型連結管と、温度計と、を装着し、メチルエチルケトン４０ｇを入れ十分に窒素置換した後、スリーワンモーターで攪拌しながら８０℃まで昇温した。
その後、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン（ＮＬＭ）６２ｇ、２−メチル−２−アダマンチルメタクリレート（ＭＡｄＭＡ）９８ｇ、及びアゾビスイソブチロニトリル１１．５ｇをメチルエチルケトン２００ｇに溶かした溶液を滴下漏斗により３時間かけて一定速度で滴下した。尚、この重合反応は、前記ジムロート管により、重合溶媒（メチルエチルケトン）を還流しながら行った。また、滴下開始と同時に、３時間かけてフラスコ内のメチルエチルケトン８０ｇ（溶媒総量を１００質量％とした場合に、３３．３質量％）を、前記クライゼン型連結管を通じて、１０４０ｈＰａの圧力下で留去させた。また、留去速度は時間当たり２６．７ｇ（初期の溶媒総量を１００質量％とした場合に、１１．１質量％／ｈ）と一定を保った。
滴下終了後、更に３時間熟成させた後、室温まで冷却し、実施例１のフォトレジスト用樹脂を含有する樹脂溶液を得た。
そして、モノマーのポリマーへの転化率を測定した結果、９７．９質量％であった。尚、この転化率は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定で得られた値（面積１００分率）を予め作成しておいた検量線に当てはめて重量比に換算したものである。また、ＧＰＣ測定及びモノマー転化率の算出方法の詳細を以下に示す。
[1] Production of a resin solution containing a resin for photoresist (Examples 1 to 3, Comparative Examples 1 to 4)
Example 1
A 810 mL four-necked flask is equipped with a Dimroth tube, a Claisen type connecting tube equipped with a receiver, and a thermometer. After 40 g of methyl ethyl ketone is fully substituted with nitrogen, the mixture is heated to 80 ° C. while stirring with a three-one motor. The temperature rose.
Thereafter, 62 g of 5-methacryloyloxy-2,6-norbornanecarbolactone (NLM), 98 g of 2-methyl-2-adamantyl methacrylate (MAdMA), and 11.5 g of azobisisobutyronitrile were dissolved in 200 g of methyl ethyl ketone. It was dripped at a constant speed by a dropping funnel over 3 hours. This polymerization reaction was performed while refluxing a polymerization solvent (methyl ethyl ketone) through the Dimroth tube. Simultaneously with the start of dropping, 80 g of methyl ethyl ketone (33.3% by mass when the total amount of the solvent is 100% by mass) in the flask is distilled out for 3 hours through the Claisen type connecting tube under a pressure of 1040 hPa. I let you. The distillation rate was kept constant at 26.7 g per hour (11.1% by mass / h when the initial total amount of solvent was 100% by mass).
After completion of dropping, the mixture was further aged for 3 hours, and then cooled to room temperature to obtain a resin solution containing the photoresist resin of Example 1.
And as a result of measuring the conversion rate of the monomer to the polymer, it was 97.9 mass%. In addition, this conversion rate is converted into a weight ratio by applying a value (area fraction of 100) obtained by gel permeation chromatography (GPC) measurement to a calibration curve prepared in advance. Moreover, the detail of the calculation method of GPC measurement and a monomer conversion rate is shown below.
<ＧＰＣの測定方法>
重合後の樹脂溶液０．０５ｇをテトラヒドロフランで希釈し、全体量を５．００ｇとする。これを０．４５μｍのフィルターでろ過した後、専用のガラス製小瓶に詰め込み、測定を開始する。未反応モノマー成分は溶出時間より判断した。
装置：東ソー社製ＨＬＣ８２２０
カラム：ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＨ−Ｌ、ＴＳＫｇｅｌ ＳｕｐｅｒＨ４０００、ＴＳＫｇｅｌ ＳｕｐｅｒＨ２０００の組み合わせ
カラム温度：４０℃
注入量：１０μ?
測定流量：０．６ｍ?／ｍｉｎ
<GPC measurement method>
Dilute 0.05 g of the resin solution after polymerization with tetrahydrofuran to a total amount of 5.00 g. After filtering this with a 0.45 μm filter, it is packed in a special glass vial and measurement is started. The unreacted monomer component was judged from the elution time.
Apparatus: HLC8220 manufactured by Tosoh Corporation
Column: Combination of TSKguardcolumn SuperH-L, TSKgel SuperH4000, TSKgel SuperH2000 Column temperature: 40 ° C
Injection volume: 10μ?
Measurement flow rate: 0.6 m? / Min
<モノマー転化率の算出方法>
未反応モノマー成分を十分に除去した樹脂をテトラヒドロフランに溶解し、検量線用の試料とした。試料はテトラヒドロフランに溶解させる樹脂量を変量した数種類を準備し、ＧＰＣ測定に供した。カラムに供された樹脂量と面積の関係より回帰式を求め、検量線を作成した。測定条件は上述のＧＰＣの測定方法に従った。
<Method for calculating monomer conversion>
The resin from which the unreacted monomer component was sufficiently removed was dissolved in tetrahydrofuran to obtain a sample for a calibration curve. Several types of samples with varying amounts of resin dissolved in tetrahydrofuran were prepared and subjected to GPC measurement. A regression equation was obtained from the relationship between the amount of resin applied to the column and the area, and a calibration curve was prepared. The measurement conditions followed the GPC measurement method described above.
（実施例２）
８１０ｍＬの四口フラスコに、ジムロート管と、受器を装着したクライゼン型連結管と、温度計と、を装着し、メチルエチルケトン４０ｇを入れ十分に窒素置換した後、スリーワンモーターで攪拌しながら８０℃まで昇温した。
その後、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン（ＮＬＭ）６２ｇ、２−メチル−２−アダマンチルメタクリレート（ＭＡｄＭＡ）９８ｇ、及びアゾビスイソブチロニトリル１１．５ｇをメチルエチルケトン２００ｇに溶かした溶液を滴下漏斗により３時間かけて一定速度で滴下した。尚、この重合反応は、前記ジムロート管により、重合溶媒（メチルエチルケトン）を還流しながら行った。また、滴下開始と同時に、１．５時間かけてフラスコ内のメチルエチルケトン８０ｇ［溶媒総量〔４０（ｇ）＋２００（ｇ）＝２４０（ｇ）〕を１００質量％とした場合に、３３．３質量％］を、前記クライゼン型連結管を通じて、１０４０ｈＰａの圧力下で留去させた。また、留去速度は時間当たり５３．３ｇ（初期の溶媒総量を１００質量％とした場合に、２２．２質量％／ｈ）と一定を保った。
滴下終了後、更に３時間熟成させた後、室温まで冷却し、実施例２のフォトレジスト用樹脂を含有する樹脂溶液を得た。
そして、実施例１と同様にしてモノマーの転化率を測定した結果、９７．４質量％であった。
(Example 2)
A 810 mL four-necked flask is equipped with a Dimroth tube, a Claisen type connecting tube equipped with a receiver, and a thermometer. After 40 g of methyl ethyl ketone is fully substituted with nitrogen, the mixture is heated to 80 ° C. while stirring with a three-one motor. The temperature rose.
Thereafter, 62 g of 5-methacryloyloxy-2,6-norbornanecarbolactone (NLM), 98 g of 2-methyl-2-adamantyl methacrylate (MAdMA), and 11.5 g of azobisisobutyronitrile were dissolved in 200 g of methyl ethyl ketone. It was dripped at a constant speed by a dropping funnel over 3 hours. This polymerization reaction was performed while refluxing a polymerization solvent (methyl ethyl ketone) through the Dimroth tube. In addition, at the same time as the start of dropping, 80 g of methyl ethyl ketone [total amount of solvent [40 (g) +200 (g) = 240 (g)] in the flask over 100 hours was set to 33.3% by mass. ] Was distilled off through the Claisen type connecting tube under a pressure of 1040 hPa. The distillation rate was kept constant at 53.3 g per hour (22.2% by mass / h when the initial total amount of solvent was 100% by mass).
After completion of the dropwise addition, the mixture was further aged for 3 hours and then cooled to room temperature to obtain a resin solution containing the photoresist resin of Example 2.
And as a result of measuring the conversion rate of a monomer like Example 1, it was 97.4 mass%.
（実施例３）
８１０ｍＬの四口フラスコに、ジムロート管と、受器を装着したクライゼン型連結管と、温度計と、を装着し、メチルエチルケトン４０ｇを入れ十分に窒素置換した後、スリーワンモーターで攪拌しながら８０℃まで昇温した。
その後、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン（ＮＬＭ）６２ｇ、２−メチル−２−アダマンチルメタクリレート（ＭＡｄＭＡ）９８ｇ、及びアゾビスイソブチロニトリル１１．５ｇをメチルエチルケトン２００ｇに溶かした溶液を滴下漏斗により３時間かけて一定速度で滴下した。尚、この重合反応は、前記ジムロート管により、重合溶媒（メチルエチルケトン）を還流しながら行った。また、滴下開始１．５時間後から、１．５時間かけてフラスコ内のメチルエチルケトン８０ｇ［溶媒総量〔４０（ｇ）＋２００（ｇ）＝２４０（ｇ）〕を１００質量％とした場合に、３３．３質量％］を、前記クライゼン型連結管を通じて、１０４０ｈＰａの圧力下で留去させた。また、留去速度は時間当たり５３．３ｇ（初期の溶媒総量を１００質量％とした場合に、２２．２質量％／ｈ）と一定を保った。
滴下終了後、更に３時間熟成させた後、室温まで冷却し、実施例３のフォトレジスト用樹脂を含有する樹脂溶液を得た。
そして、実施例１と同様にしてモノマーの転化率を測定した結果、９７．４質量％であった。
(Example 3)
A 810 mL four-necked flask is equipped with a Dimroth tube, a Claisen type connecting tube equipped with a receiver, and a thermometer. After 40 g of methyl ethyl ketone is fully substituted with nitrogen, the mixture is heated to 80 ° C. while stirring with a three-one motor. The temperature rose.
Thereafter, 62 g of 5-methacryloyloxy-2,6-norbornanecarbolactone (NLM), 98 g of 2-methyl-2-adamantyl methacrylate (MAdMA), and 11.5 g of azobisisobutyronitrile were dissolved in 200 g of methyl ethyl ketone. It was dripped at a constant speed by a dropping funnel over 3 hours. This polymerization reaction was performed while refluxing a polymerization solvent (methyl ethyl ketone) through the Dimroth tube. Further, from 1.5 hours after the start of dropping, when 80 g of methyl ethyl ketone [total amount of solvent [40 (g) +200 (g) = 240 (g)] in the flask was taken as 100% by mass over a period of 1.5 hours, 33 .3% by mass] was distilled off through the Claisen type connecting tube under a pressure of 1040 hPa. The distillation rate was kept constant at 53.3 g per hour (22.2% by mass / h when the initial total amount of solvent was 100% by mass).
After completion of the dropwise addition, the mixture was further aged for 3 hours and then cooled to room temperature to obtain a resin solution containing the photoresist resin of Example 3.
And as a result of measuring the conversion rate of a monomer like Example 1, it was 97.4 mass%.
（比較例１）
８１０ｍＬの四口フラスコに、ジムロート管と、温度計と、を装着し、メチルエチルケトン４０ｇを入れ十分に窒素置換した後、スリーワンモーターで攪拌しながら８０℃まで昇温した。
その後、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン（ＮＬＭ）６２ｇ、２−メチル−２−アダマンチルメタクリレート（ＭＡｄＭＡ）９８ｇ、及びアゾビスイソブチロニトリル５．７ｇをメチルエチルケトン２００ｇに溶かした溶液を滴下漏斗により３時間かけて一定速度で滴下した。尚、この重合反応は、前記ジムロート管により、重合溶媒（メチルエチルケトン）を還流しながら行った。
滴下終了後、更に３時間熟成させた後、室温まで冷却し、比較例１のフォトレジスト用樹脂を含有する樹脂溶液を得た。
そして、実施例１と同様にしてモノマーの転化率を測定した結果、９４．４質量％であった。
(Comparative Example 1)
A 810 mL four-necked flask was equipped with a Dimroth tube and a thermometer. After 40 g of methyl ethyl ketone was added and sufficiently purged with nitrogen, the temperature was raised to 80 ° C. while stirring with a three-one motor.
Thereafter, 62 g of 5-methacryloyloxy-2,6-norbornanecarbolactone (NLM), 98 g of 2-methyl-2-adamantyl methacrylate (MAdMA) and 5.7 g of azobisisobutyronitrile were dissolved in 200 g of methyl ethyl ketone. It was dripped at a constant speed by a dropping funnel over 3 hours. This polymerization reaction was performed while refluxing a polymerization solvent (methyl ethyl ketone) through the Dimroth tube.
After completion of dropping, the mixture was further aged for 3 hours, and then cooled to room temperature to obtain a resin solution containing the photoresist resin of Comparative Example 1.
And as a result of measuring the conversion rate of a monomer like Example 1, it was 94.4 mass%.
（比較例２）
８１０ｍＬの四口フラスコに、ジムロート管と、温度計と、を装着し、メチルエチルケトン４０ｇを入れ十分に窒素置換した後、スリーワンモーターで攪拌しながら８０℃まで昇温した。
その後、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン（ＮＬＭ）６２ｇ、２−メチル−２−アダマンチルメタクリレート（ＭＡｄＭＡ）９８ｇ、及びアゾビスイソブチロニトリル１１．５ｇをメチルエチルケトン２００ｇに溶かした溶液を滴下漏斗により３時間かけて一定速度で滴下した。尚、この重合反応は、前記ジムロート管により、重合溶媒（メチルエチルケトン）を還流しながら行った。
滴下終了後、更に３時間熟成させた後、室温まで冷却し、比較例２のフォトレジスト用樹脂を含有する樹脂溶液を得た。
そして、実施例１と同様にしてモノマーの転化率を測定した結果、９５．４質量％であった。
(Comparative Example 2)
A 810 mL four-necked flask was equipped with a Dimroth tube and a thermometer. After 40 g of methyl ethyl ketone was added and sufficiently purged with nitrogen, the temperature was raised to 80 ° C. while stirring with a three-one motor.
Thereafter, 62 g of 5-methacryloyloxy-2,6-norbornanecarbolactone (NLM), 98 g of 2-methyl-2-adamantyl methacrylate (MAdMA), and 11.5 g of azobisisobutyronitrile were dissolved in 200 g of methyl ethyl ketone. It was dripped at a constant speed by a dropping funnel over 3 hours. This polymerization reaction was performed while refluxing a polymerization solvent (methyl ethyl ketone) through the Dimroth tube.
After completion of dropping, the mixture was further aged for 3 hours, and then cooled to room temperature to obtain a resin solution containing the photoresist resin of Comparative Example 2.
And as a result of measuring the conversion rate of a monomer like Example 1, it was 95.4 mass%.
（比較例３）
８１０ｍＬの四口フラスコに、ジムロート管と、温度計と、を装着し、メチルエチルケトン４０ｇを入れ十分に窒素置換した後、スリーワンモーターで攪拌しながら８０℃まで昇温した。
その後、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン（ＮＬＭ）６２ｇ、２−メチル−２−アダマンチルメタクリレート（ＭＡｄＭＡ）９８ｇ、及びアゾビスイソブチロニトリル８．６ｇをメチルエチルケトン２００ｇに溶かした溶液を滴下漏斗により３時間かけて一定速度で滴下した。尚、この重合反応は、前記ジムロート管により、重合溶媒（メチルエチルケトン）を還流しながら行った。
滴下終了後、更に３時間熟成させた後、室温まで冷却し、比較例３のフォトレジスト用樹脂を含有する樹脂溶液を得た。
そして、実施例１と同様にしてモノマーの転化率を測定した結果、９５．０質量％であった。
(Comparative Example 3)
A 810 mL four-necked flask was equipped with a Dimroth tube and a thermometer. After 40 g of methyl ethyl ketone was added and sufficiently purged with nitrogen, the temperature was raised to 80 ° C. while stirring with a three-one motor.
Thereafter, 62 g of 5-methacryloyloxy-2,6-norbornanecarbolactone (NLM), 98 g of 2-methyl-2-adamantyl methacrylate (MAdMA), and 8.6 g of azobisisobutyronitrile were dissolved in 200 g of methyl ethyl ketone. It was dripped at a constant speed by a dropping funnel over 3 hours. This polymerization reaction was performed while refluxing a polymerization solvent (methyl ethyl ketone) through the Dimroth tube.
After completion of dropping, the mixture was further aged for 3 hours, and then cooled to room temperature to obtain a resin solution containing the photoresist resin of Comparative Example 3.
And as a result of measuring the conversion rate of a monomer like Example 1, it was 95.0 mass%.
（比較例４）
８１０ｍＬの四口フラスコに、ジムロート管と、温度計と、を装着し、メチルエチルケトン８０ｇを入れ十分に窒素置換した後、スリーワンモーターで攪拌しながら８０℃まで昇温した。
その後、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン（ＮＬＭ）３１ｇ、２−メチル−２−アダマンチルメタクリレート（ＭＡｄＭＡ）４９ｇ、及びアゾビスイソブチロニトリル２．９ｇをメチルエチルケトン１６０ｇに溶かした溶液を滴下漏斗により３時間かけて一定速度で滴下した。尚、この重合反応は、前記ジムロート管により、重合溶媒（メチルエチルケトン）を還流しながら行った。
滴下終了後、更に３時間熟成させた後、室温まで冷却し、比較例４のフォトレジスト用樹脂を含有する樹脂溶液を得た。
そして、実施例１と同様にしてモノマーの転化率を測定した結果、８４．７質量％であった。
(Comparative Example 4)
A 810 mL four-necked flask was equipped with a Dimroth tube and a thermometer. After 80 g of methyl ethyl ketone was added and sufficiently purged with nitrogen, the temperature was raised to 80 ° C. while stirring with a three-one motor.
Thereafter, a solution of 31 g of 5-methacryloyloxy-2,6-norbornanecarbolactone (NLM), 49 g of 2-methyl-2-adamantyl methacrylate (MAdMA) and 2.9 g of azobisisobutyronitrile in 160 g of methyl ethyl ketone was prepared. It was dripped at a constant speed by a dropping funnel over 3 hours. This polymerization reaction was performed while refluxing a polymerization solvent (methyl ethyl ketone) through the Dimroth tube.
After completion of dropping, the mixture was further aged for 3 hours, and then cooled to room temperature to obtain a resin solution containing the photoresist resin of Comparative Example 4.
And as a result of measuring the conversion rate of a monomer like Example 1, it was 84.7 mass%.
これらの実施例１〜３及び比較例１〜４のフォトレジスト用樹脂を含有する樹脂溶液の調製における原料組成（単量体、重合開始剤及び溶媒）、重合条件、溶剤の留去速度、留去時間、留去量、モノマーのポリマーへの転化率を表１にまとめて示した。尚、表１における「単量体Ａ」は「５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン」を示し、「単量体Ｂ」は「２−メチル−２−アダマンチルメタクリレート」を示し、「重合開始剤」は「アゾビスイソブチロニトリル」を示し、「溶媒」は「重合に用いたメチルエチルケトンの総量」を示す。また、表１における実施例１〜３の「固形分濃度（初期）」は、仕込み段階の固形分の濃度を示し、「固形分濃度（重合後）」は、重合後の固形分の濃度を示す。 Raw material composition (monomer, polymerization initiator and solvent), polymerization conditions, solvent evaporation rate, distillation in the preparation of resin solutions containing the photoresist resins of Examples 1 to 3 and Comparative Examples 1 to 4 Table 1 summarizes the last time, the amount of distillation, and the conversion ratio of the monomer to the polymer. In Table 1, “monomer A” represents “5-methacryloyloxy-2,6-norbornanecarbolactone”, “monomer B” represents “2-methyl-2-adamantyl methacrylate”, “ “Polymerization initiator” indicates “azobisisobutyronitrile”, and “solvent” indicates “total amount of methyl ethyl ketone used for polymerization”. In Table 1, “Solid Concentration (Initial)” in Examples 1 to 3 indicates the solid content concentration in the charging stage, and “Solid Concentration (After Polymerization)” indicates the solid content concentration after polymerization. Show.
［２］実施例の効果
表１によれば、重合反応中に溶剤を留去した実施例１〜３では、原料モノマーのポリマーへの転化率が優れていることが分かった。
[2] Effect of Examples According to Table 1, in Examples 1 to 3 in which the solvent was distilled off during the polymerization reaction, it was found that the conversion rate of the raw material monomer to the polymer was excellent.
Claims (6)
前記重合性化合物は、エチレン性不飽和結合を有する単量体であり、
前記重合性化合物のうちの少なくとも１種は、常温において固体状の化合物であり、
重合反応中に、溶媒を留去することを特徴とするフォトレジスト用樹脂の製造方法。 A method for producing a photoresist resin, which comprises producing a photoresist resin by polymerizing a polymerizable compound in the presence of a solvent,
The polymerizable compound is a monomer having an ethylenically unsaturated bond,
At least one of the polymerizable compounds is a solid compound at room temperature,
A method for producing a photoresist resin, wherein a solvent is distilled off during a polymerization reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008185288A JP5433999B2 (en) | 2008-07-16 | 2008-07-16 | Manufacturing method of resin for photoresist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008185288A JP5433999B2 (en) | 2008-07-16 | 2008-07-16 | Manufacturing method of resin for photoresist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010024298A JP2010024298A (en) | 2010-02-04 |
| JP5433999B2 true JP5433999B2 (en) | 2014-03-05 |
Family
ID=41730419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008185288A Active JP5433999B2 (en) | 2008-07-16 | 2008-07-16 | Manufacturing method of resin for photoresist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5433999B2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05310837A (en) * | 1992-05-14 | 1993-11-22 | Japan Synthetic Rubber Co Ltd | Production of oxygen-permeable polymeric material |
| JP2004323688A (en) * | 2003-04-25 | 2004-11-18 | Mitsubishi Rayon Co Ltd | Amphiphilic polymer and method for producing the same |
| US20070105040A1 (en) * | 2005-11-10 | 2007-05-10 | Toukhy Medhat A | Developable undercoating composition for thick photoresist layers |
| JP5103568B2 (en) * | 2006-07-24 | 2012-12-19 | エンカレッジ・テクノロジ株式会社 | Personal authentication device |
| DE102007052412A1 (en) * | 2006-11-29 | 2008-06-05 | Basf Se | Process for the preparation of water-soluble haze-free copolymers of at least one water-soluble N-vinyl lactam and at least one hydrophobic comonomer |
-
2008
- 2008-07-16 JP JP2008185288A patent/JP5433999B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010024298A (en) | 2010-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3720827B2 (en) | Method for producing resist polymer | |
| KR101081776B1 (en) | Novel thiol compound, copolymer and method for producing the copolymer | |
| KR20060051697A (en) | Positive photosensitive resin and novel dithiol compound | |
| KR101124184B1 (en) | A preparation process of copolymer for semiconductor lithography and a copolymer for semiconductor lithography available by this process | |
| JP4808485B2 (en) | Manufacturing method of resin for photoresist | |
| JP5192120B2 (en) | Method for preventing increase of particles in copolymer for semiconductor resist | |
| JPWO2009063726A1 (en) | Manufacturing method of resin for photoresist | |
| JP5024203B2 (en) | Method for producing resin solution for photoresist | |
| JP5092721B2 (en) | Manufacturing method of resin for photoresist | |
| JP4488906B2 (en) | Method for producing polymer compound for photoresist | |
| JP3694685B2 (en) | Resist polymer and radiation-sensitive resist composition | |
| US9023982B2 (en) | Method for purifying resin for photolithography | |
| JP5433999B2 (en) | Manufacturing method of resin for photoresist | |
| JP2010013531A (en) | Method of purifying photoresist resin | |
| JP5298549B2 (en) | Method for producing polymer for photoresist | |
| JP5206065B2 (en) | Method for producing photoresist polymer and distillation can used therefor | |
| JP6051651B2 (en) | Method for producing resin solution for photoresist | |
| JP2010204306A (en) | Method for producing resin solution for photoresist | |
| JP3679404B2 (en) | Chain transfer agent, copolymer and method for producing copolymer using novel thiol compound | |
| JP5298550B2 (en) | Method for producing polymer for photoresist | |
| JP3803932B1 (en) | Method for producing resin solution for photoresist | |
| JP5309660B2 (en) | Method for producing polymer for photoresist | |
| JP3818454B1 (en) | Method for producing resin solution for photoresist | |
| JP4344212B2 (en) | Copolymer, production method of copolymer and novel thiol compound | |
| JP2006124716A (en) | Preparation process of copolymer for semiconductor lithography |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110128 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20111215 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120921 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120925 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121106 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130903 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131007 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131112 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131125 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5433999 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |