JP2021144133A - Resin composition for resist and photosensitive resin composition - Google Patents
Resin composition for resist and photosensitive resin composition Download PDFInfo
- Publication number
- JP2021144133A JP2021144133A JP2020042465A JP2020042465A JP2021144133A JP 2021144133 A JP2021144133 A JP 2021144133A JP 2020042465 A JP2020042465 A JP 2020042465A JP 2020042465 A JP2020042465 A JP 2020042465A JP 2021144133 A JP2021144133 A JP 2021144133A
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- JP
- Japan
- Prior art keywords
- resin composition
- resist
- meth
- mass
- acrylate
- 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.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 53
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 30
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000126 substance Substances 0.000 abstract description 17
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 46
- -1 aromatic vinyl compound Chemical class 0.000 description 31
- 238000006116 polymerization reaction Methods 0.000 description 30
- 229920000642 polymer Polymers 0.000 description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OQSDPAMTSNMYHG-UHFFFAOYSA-N 2-cyclohexylpropan-2-yl 3,3-dimethylbutaneperoxoate Chemical compound C(CC(C)(C)C)(=O)OOC(C)(C)C1CCCCC1 OQSDPAMTSNMYHG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- VSXHKKXYCVWKFG-UHFFFAOYSA-N 2-cyclohexylpropan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C1CCCCC1 VSXHKKXYCVWKFG-UHFFFAOYSA-N 0.000 description 2
- LTDGYXDZHCEWMB-UHFFFAOYSA-N 2-hydroperoxypropan-2-ylcyclohexane Chemical compound OOC(C)(C)C1CCCCC1 LTDGYXDZHCEWMB-UHFFFAOYSA-N 0.000 description 2
- UPNZKEGXSNQEPW-UHFFFAOYSA-N 4-cyclohexyl-2,2,4-trimethylpentaneperoxoic acid Chemical compound OOC(=O)C(C)(C)CC(C)(C)C1CCCCC1 UPNZKEGXSNQEPW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LNOKVKHZEYOLIQ-UHFFFAOYSA-N 1-(2,6-diethylphenyl)pyrrole-2,5-dione Chemical compound CCC1=CC=CC(CC)=C1N1C(=O)C=CC1=O LNOKVKHZEYOLIQ-UHFFFAOYSA-N 0.000 description 1
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-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
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- CTWRMVAKUSJNBK-UHFFFAOYSA-N 2-(2,4-dimethoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class COC1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 CTWRMVAKUSJNBK-UHFFFAOYSA-N 0.000 description 1
- RXAYEPUDXSKVHS-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-bis(3-methoxyphenyl)-1h-imidazole Chemical class COC1=CC=CC(C2=C(NC(=N2)C=2C(=CC=CC=2)Cl)C=2C=C(OC)C=CC=2)=C1 RXAYEPUDXSKVHS-UHFFFAOYSA-N 0.000 description 1
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 1
- PJABOTZVAHGVAF-UHFFFAOYSA-N 2-(2-cyclohexylpropan-2-yl)-7,7-dimethyloctaneperoxoic acid Chemical compound CC(C)(C)CCCCC(C(=O)OO)C(C)(C)C1CCCCC1 PJABOTZVAHGVAF-UHFFFAOYSA-N 0.000 description 1
- UIHRWPYOTGCOJP-UHFFFAOYSA-N 2-(2-fluorophenyl)-4,5-diphenyl-1h-imidazole Chemical class FC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 UIHRWPYOTGCOJP-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
- XIOGJAPOAUEYJO-UHFFFAOYSA-N 2-(2-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class COC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 XIOGJAPOAUEYJO-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FXRQXYSJYZPGJZ-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethenylbenzene Chemical compound CC(C)(C)OC=CC1=CC=CC=C1 FXRQXYSJYZPGJZ-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- KTKKERKSKYSPOS-UHFFFAOYSA-N 2-cyclohexylpropan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)C(=O)OOC(C)(C)C1CCCCC1 KTKKERKSKYSPOS-UHFFFAOYSA-N 0.000 description 1
- PMNFBUWTEQIUHA-UHFFFAOYSA-N 2-cyclohexylpropan-2-yl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C1CCCCC1 PMNFBUWTEQIUHA-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BTZVKSVLFLRBRE-UHFFFAOYSA-N 2-methoxypropyl acetate Chemical compound COC(C)COC(C)=O BTZVKSVLFLRBRE-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-UHFFFAOYSA-N 0.000 description 1
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- Materials For Photolithography (AREA)
Abstract
Description
本発明は、レジスト用樹脂組成物および感光性樹脂組成物に関し、より詳しくは、耐薬品性および耐熱性に優れる樹脂膜を与えるレジスト用樹脂組成物および感光性樹脂組成物に関する。 The present invention relates to a resist resin composition and a photosensitive resin composition, and more particularly to a resist resin composition and a photosensitive resin composition that provide a resin film having excellent chemical resistance and heat resistance.
近年、フォトレジスト材料は広く応用されており、テレビやスマートフォンをはじめとする電子製品等の製造工程又は加工工程に不可欠な微細加工材料となっている。係るフォトレジスト材料はマスクを用いた活性エネルギー線の照射により、露光部と未露光部のアルカリ溶液への溶解性の差を発現させることによってパターン化が行われ、アルカリ溶液で未露光部を溶解させ、さらに加熱による溶剤の除去及び硬化を行い所定形状のパターン形成が行われる。 In recent years, photoresist materials have been widely applied and have become indispensable microfabrication materials in the manufacturing process or processing process of electronic products such as televisions and smartphones. The photoresist material is patterned by irradiating it with active energy rays using a mask to express the difference in solubility between the exposed part and the unexposed part in an alkaline solution, and the unexposed part is dissolved in the alkaline solution. Then, the solvent is removed and cured by heating to form a pattern having a predetermined shape.
近年では、電子製品の小型化、集積回路の微細化、表示装置の高精細化に伴い、レジスト性能の向上が一層強く望まれている。各種装置を製造するプロセスの中で、パターンに熱履歴がかかるため、加熱に対して変化が生じ難く耐熱性に優れることが要求されている。耐熱性に優れた樹脂膜を得る方法として、特許文献１には酸基含有マレイミドモノマーに由来する繰り返し単位を含む重合体を用いる方法が開示されている。 In recent years, with the miniaturization of electronic products, the miniaturization of integrated circuits, and the increase in definition of display devices, it is strongly desired to improve the resist performance. In the process of manufacturing various devices, since the pattern has a heat history, it is required that the pattern is not easily changed by heating and has excellent heat resistance. As a method for obtaining a resin film having excellent heat resistance, Patent Document 1 discloses a method using a polymer containing a repeating unit derived from an acid group-containing maleimide monomer.
さらに、パターン形成後の樹脂膜がプロセスにおいて溶剤などの薬品に接触するため、薬品に接触しても膜厚変化が生じ難く耐薬品性に優れることも要求されている。また、これまで室温下での耐薬品性が求められていたが、近年はより高温条件下での耐性も要求されるようになっている。耐薬品性に優れた樹脂膜を得る方法として、特許文献２には重合体の構成単位として２−ピロン基等の特定の官能基を有するモノマーを用いる方法が、特許文献３には重合体の構成単位としてヒドロキシフェニルマレイミドモノマーを用いる方法がそれぞれ開示されている。 Further, since the resin film after pattern formation comes into contact with a chemical such as a solvent in the process, the film thickness is unlikely to change even if it comes into contact with the chemical, and it is required to have excellent chemical resistance. In addition, chemical resistance at room temperature has been required so far, but in recent years, resistance under higher temperature conditions has also been required. As a method for obtaining a resin film having excellent chemical resistance, Patent Document 2 describes a method using a monomer having a specific functional group such as a 2-pyrone group as a constituent unit of a polymer, and Patent Document 3 describes a method of using a monomer having a specific functional group. Methods of using hydroxyphenylmaleimide monomer as a constituent unit are disclosed.
しかしながら、耐薬品性を得るためには重合体中の特定構造のモノマーの割合を多くしなければならないといった問題があり、十分に満足できるものではなかった。 However, in order to obtain chemical resistance, there is a problem that the proportion of the monomer having a specific structure in the polymer must be increased, which is not sufficiently satisfactory.
本発明の目的は、耐薬品性および耐熱性に優れる樹脂膜を与えるレジスト用樹脂組成物および感光性樹脂組成物を提供することである。 An object of the present invention is to provide a resin composition for resist and a photosensitive resin composition that provide a resin film having excellent chemical resistance and heat resistance.
本発明者らは、前記課題を解決すべく検討した結果、特定構造の有機過酸化物を用いたレジスト用樹脂組成物により上記課題を解決できることを見出した。
すなわち、本発明は、以下のものである。
［１］不飽和塩基酸モノマー（Ａ）、該不飽和塩基酸モノマー（Ａ）と共重合可能なモノマー（Ｂ）、及び重合開始剤（Ｃ）を含むレジスト用樹脂組成物であって、該重合開始剤（Ｃ）が下記一般式（１）で示される有機過酸化物を含むことを特徴とするレジスト用樹脂組成物：
As a result of studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a resin composition for resist using an organic peroxide having a specific structure.
That is, the present invention is as follows.
[1] A resin composition for a resist containing an unsaturated basic acid monomer (A), a monomer (B) copolymerizable with the unsaturated basic acid monomer (A), and a polymerization initiator (C). A resin composition for a resist, wherein the polymerization initiator (C) contains an organic peroxide represented by the following general formula (1):
（式（１）中、Ｒ１〜Ｒ３は、同一または異なって、それぞれ水素原子または炭素数１〜１０のアルキル基を示す。）。
［２］［１］に記載のレジスト用樹脂組成物から得られる樹脂、光重合開始剤、及び重合性化合物を含有することを特徴とする感光性樹脂組成物。
(In the formula (1), R 1 to R 3 represent the same or different alkyl groups having hydrogen atoms or 1 to 10 carbon atoms, respectively).
[2] A photosensitive resin composition containing a resin obtained from the resin composition for resist according to [1], a photopolymerization initiator, and a polymerizable compound.
本発明によれば、耐薬品性および耐熱性に優れる樹脂膜を与えるレジスト用樹脂組成物および感光性樹脂組成物を得ることができる。 According to the present invention, it is possible to obtain a resist resin composition and a photosensitive resin composition that provide a resin film having excellent chemical resistance and heat resistance.
以下、本発明の実施形態を説明する。なお、本発明において「（メタ）アクリル」とは、アクリル及びメタクリルを包含する総称である。 Hereinafter, embodiments of the present invention will be described. In the present invention, "(meth) acrylic" is a general term including acrylic and methacryl.
＜レジスト用樹脂組成物＞
本発明のレジスト用樹脂組成物は、不飽和塩基酸モノマー（Ａ）、該不飽和塩基酸モノマー（Ａ）と共重合可能なモノマー（Ｂ）、及び重合開始剤（Ｃ）を含む。
<Resist resin composition>
The resin composition for a resist of the present invention contains an unsaturated basic acid monomer (A), a monomer (B) copolymerizable with the unsaturated basic acid monomer (A), and a polymerization initiator (C).
＜不飽和塩基酸モノマー（Ａ）＞
本発明で用いる不飽和塩基酸モノマー（Ａ）としては、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸等が挙げられ、共重合反応性、アルカリ水溶液に対する溶解性及び入手の容易性から（メタ）アクリル酸が好ましく、メタクリル酸がより好ましい。不飽和塩基酸モノマー（Ａ）は、１種類を単独で用いてもよく、２種類以上を併用してもよい。
<Unsaturated basic acid monomer (A)>
Examples of the unsaturated basic acid monomer (A) used in the present invention include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like, and are copolymerizable and alkaline aqueous solution. (Meta) acrylic acid is preferable, and methaconic acid is more preferable, because of its solubility in and availability. As the unsaturated basic acid monomer (A), one type may be used alone, or two or more types may be used in combination.
本発明のレジスト用樹脂組成物における不飽和塩基酸モノマー（Ａ）の含有割合としては、全モノマー成分１００質量％に対して、好ましくは１〜４０質量％であり、より好ましくは５〜３０質量％であり、さらに好ましくは１０〜２５質量％である。これら範囲にすることで、レジスト特性が良好な重合体を得ることができる。 The content ratio of the unsaturated basic acid monomer (A) in the resin composition for resist of the present invention is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, based on 100% by mass of all the monomer components. %, More preferably 10 to 25% by mass. Within these ranges, a polymer having good resist properties can be obtained.
＜モノマー（Ｂ）＞
モノマー（Ｂ）としては、不飽和塩基酸モノマー（Ａ）と共重合が可能であるモノマーであれば特に限定されるものではないが、（メタ）アクリル酸エステルモノマー、芳香族ビニル化合物、マレイミドモノマーが好ましい。モノマー（Ｂ）は、１種類を単独で用いてもよく、２種類以上を併用してもよい。
<Monomer (B)>
The monomer (B) is not particularly limited as long as it can be copolymerized with the unsaturated basic acid monomer (A), but is not particularly limited, but is a (meth) acrylic acid ester monomer, an aromatic vinyl compound, and a maleimide monomer. Is preferable. As the monomer (B), one type may be used alone, or two or more types may be used in combination.
（メタ）アクリル酸エステルモノマーとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸−２−メトキシエチル、（メタ）アクリル酸−３−メトキシブチル、（メタ）アクリル酸−２−ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸グリセロール、（メタ）アクリル酸ヒドロキシフェニル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸のエチレンオキサイド付加物などが挙げられ、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸−２−ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸グリセロール、（メタ）アクリル酸ヒドロキシフェニル、（メタ）アクリル酸グリシジルが好ましい。耐薬品性の観点から、（メタ）アクリル酸シクロヘキシルが特に好ましい。 Examples of the (meth) acrylic acid ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth). Hexyl acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, -2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth) Dodecyl acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, -2-methoxyethyl (meth) acrylate, -3-methoxybutyl (meth) acrylate, -2-methoxybutyl (meth) acrylate Hydroxyethyl, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, hydroxyphenyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) ) Acrylic acid ethylene oxide adducts, etc. include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, butyl (meth) acrylic acid, cyclohexyl (meth) acrylic acid, (meth). ) -2-Ethylhexyl acrylate, benzyl (meth) acrylate, -2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, hydroxyphenyl (meth) acrylate, ( Meta) Glycidyl acrylate is preferred. From the viewpoint of chemical resistance, cyclohexyl (meth) acrylate is particularly preferable.
芳香族ビニル化合物としては、例えば、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｍ−メチルスチレン、ｏ−メチルスチレン、ｐ−エチルスチレン、ｍ−エチルスチレン、ｏ−エチルスチレン、ｔ−ブチルスチレン、クロルスチレン、ヒドロキシスチレン、ｔ−ブトキシスチレン、ビニルトルエン、ビニルナフタレン、イソプロペニルフェノールなどが挙げられ、スチレンが好ましい。 Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, and t-butylstyrene. , Chlorstyrene, hydroxystyrene, t-butoxystyrene, vinyltoluene, vinylnaphthalene, isopropenylphenol and the like, and styrene is preferable.
マレイミドモノマーとしては、例えば、Ｎ−フェニルマレイミド、Ｎ−（２−メチルフェニル）マレイミド、Ｎ−（２，６−ジエチルフェニル）マレイミド、Ｎ−ラウリルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−ベンジルマレイミドなどが挙げられ、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミドが好ましく、Ｎ−シクロヘキシルマレイミドがより好ましい。 Examples of the maleimide monomer include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N-laurylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide. N-phenylmaleimide and N-cyclohexylmaleimide are preferable, and N-cyclohexylmaleimide is more preferable.
本発明のレジスト用樹脂組成物におけるモノマー（Ｂ）の含有割合としては、全モノマー成分１００質量％に対して、好ましくは６０〜９９質量％であり、より好ましくは７０〜９５質量％であり、さらに好ましくは７５〜９０質量％である。これら範囲にすることで、モノマー（Ｂ）によりレジスト特性を調整することができ、良好な重合体を得ることができる。 The content ratio of the monomer (B) in the resist resin composition of the present invention is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, based on 100% by mass of all the monomer components. More preferably, it is 75 to 90% by mass. Within these ranges, the resist properties can be adjusted with the monomer (B), and a good polymer can be obtained.
（メタ）アクリル酸エステルモノマーの含有割合としては、全モノマー成分１００質量％に対して、１〜９５質量％が好ましく、５〜９０質量％がより好ましい。 The content ratio of the (meth) acrylic acid ester monomer is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, based on 100% by mass of all the monomer components.
芳香族ビニル化合物の含有割合としては、全モノマー成分１００質量％に対して、０〜７０質量％が好ましく、５〜６０質量％がより好ましい。本範囲とすることで、耐熱性等の膜物性を付与することができる。 The content ratio of the aromatic vinyl compound is preferably 0 to 70% by mass, more preferably 5 to 60% by mass, based on 100% by mass of all the monomer components. Within this range, film physical characteristics such as heat resistance can be imparted.
マレイミドモノマーの含有割合としては、全モノマー成分１００質量％に対して、０〜３０質量％が好ましく、３〜１５質量％がより好ましい。本範囲とすることで、耐熱性を向上させることができる。 The content ratio of the maleimide monomer is preferably 0 to 30% by mass, more preferably 3 to 15% by mass, based on 100% by mass of all the monomer components. Within this range, heat resistance can be improved.
＜重合開始剤（Ｃ）＞
本発明で用いる重合開始剤（Ｃ）は、下記一般式（１）で示される有機過酸化物を含む。
<Polymerization initiator (C)>
The polymerization initiator (C) used in the present invention contains an organic peroxide represented by the following general formula (1).
（式（１）中、Ｒ１〜Ｒ３は、同一または異なって、それぞれ水素原子または炭素数１〜１０のアルキル基を示す。） (In the formula (1), R 1 to R 3 represent the same or different alkyl groups having hydrogen atoms or 1 to 10 carbon atoms, respectively.)
式（１）中、Ｒ１は水素原子または炭素数１〜１０のアルキル基であり、炭素数１〜１０のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基、２−エチルヘキシル基、デシル基などが挙げられる。合成のしやすさと有機過酸化物の活性の観点から、Ｒ１は炭素数１〜８のアルキル基が好ましく、炭素数１〜６のアルキル基がより好ましい。 In the formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group and an n-butyl group. , Iso-butyl group, tert-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group and the like. From the viewpoint of ease of synthesis and activity of organic peroxide, R 1 is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
式（１）中、Ｒ２は水素原子または炭素数１〜１０のアルキル基であり、炭素数１〜１０のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基、２−エチルヘキシル基、デシル基などが挙げられる。合成のしやすさと有機過酸化物の活性の観点から、Ｒ２は炭素数１〜５のアルキル基が好ましく、炭素数１〜２のアルキル基がより好ましい。 In the formula (1), R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group and an n-butyl group. , Iso-butyl group, tert-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group and the like. From the viewpoint of ease of synthesis and activity of the organic peroxide, R 2 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms.
式（１）中、Ｒ３は水素原子または炭素数１〜１０のアルキル基であり、炭素数１〜１０のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基、２−エチルヘキシル基、デシル基などが挙げられる。合成のしやすさと有機過酸化物の活性の観点から、Ｒ３は水素原子またはメチル基が好ましく、メチル基がより好ましい。 In the formula (1), R 3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group and an n-butyl group. , Iso-butyl group, tert-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group and the like. From the standpoint of activity of ease and organic peroxide synthesis, R 3 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
一般式（１）で示される有機過酸化物としては、１−シクロへキシル−１−メチルエチルペルオキシイソブチレート（Ｒ１＝メチル基、Ｒ２＝メチル基、Ｒ３＝水素原子）、１−シクロへキシル−１−メチルエチルペルオキシピバレート（Ｒ１＝メチル基、Ｒ２＝メチル基、Ｒ３＝メチル基）、１−シクロへキシル−１−メチルエチルペルオキシネオヘキサノエート（Ｒ１＝エチル基、Ｒ２＝メチル基、Ｒ３＝メチル基）、１−シクロへキシル−１−メチルエチルペルオキシオクトエート（Ｒ１＝ブチル基、Ｒ２＝エチル基、Ｒ３＝水素原子）、１−シクロへキシル−１−メチルエチルへルオキシネオノナノエート（Ｒ１＝ペンチル基、Ｒ２＝メチル基、Ｒ３＝メチル基）、１−シクロへキシル−１−メチルエチルペルオキシネオデカノエート（Ｒ１＝ヘキシル基、Ｒ２＝メチル基、Ｒ３＝メチル基）等が挙げられ、１−シクロへキシル−１−メチルエチルペルオキシイソブチレート、１−シクロへキシル−１−メチルエチルペルオキシピバレート、１−シクロへキシル−１−メチルエチルペルオキシネオヘキサノエート、１−シクロへキシル−１−メチルエチルペルオキシネオデカノエートが好ましく、１−シクロへキシル−１−メチルエチルペルオキシネオデカノエートが特に好ましい。 Examples of the organic peroxide represented by the general formula (1) include 1-cyclohexyl-1-methylethylperoxyisobutyrate (R 1 = methyl group, R 2 = methyl group, R 3 = hydrogen atom), 1 -Cyclohexyl-1-methylethyl peroxypivalate (R 1 = methyl group, R 2 = methyl group, R 3 = methyl group), 1-cyclohexyl-1-methylethyl peroxyneohexanoate (R 1) = Ethyl group, R 2 = methyl group, R 3 = methyl group), 1-cyclohexyl-1-methylethyl peroxyoctate (R 1 = butyl group, R 2 = ethyl group, R 3 = hydrogen atom), 1-Cyclohexyl-1-methylethyl heloxyneonanoate (R 1 = pentyl group, R 2 = methyl group, R 3 = methyl group), 1-cyclohexyl-1-methylethyl peroxyneodecano Examples include ate (R 1 = hexyl group, R 2 = methyl group, R 3 = methyl group), 1-cyclohexyl-1-methylethyl peroxyisobutyrate, 1-cyclohexyl-1-methylethyl. Peroxypivalate, 1-cyclohexyl-1-methylethyl peroxyneohexanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate are preferable, and 1-cyclohexyl-1-methylethylperoxyneoate is preferable. Decanoate is particularly preferred.
本発明のレジスト用樹脂組成物における重合開始剤（Ｃ）の含有割合としては、全モノマー成分１００質量％に対して、０．０１質量％〜５０質量％とすることが好ましく、より好ましくは１質量％〜３０質量％であり、さらに好ましくは５質量％〜２０質量％である。 The content ratio of the polymerization initiator (C) in the resist resin composition of the present invention is preferably 0.01% by mass to 50% by mass, more preferably 1 with respect to 100% by mass of all the monomer components. It is from mass% to 30% by mass, more preferably 5% by mass to 20% by mass.
重合開始剤（Ｃ）は、一般式（１）で示される有機過酸化物以外の重合開始剤を含んでいてもよい。このような重合開始剤としては、公知のものを使用することができ、例えば、ジ（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート、１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエートなどの有機過酸化物、２，２’−アゾビスイソブチロニトリルなどのアゾ系重合開始剤などを挙げることができる。これらの重合開始剤は、１種類のみを用いてもよく、２種以上を併用してもよい。
一般式（１）で示される有機過酸化物と他の重合開始剤を併用する場合は、重合開始剤（Ｃ）の総量に対する一般式（１）で示される有機過酸化物の割合として、５０質量％以上が好ましく、より好ましくは７０質量％以上であり、さらに好ましくは８０質量％以上である。
The polymerization initiator (C) may contain a polymerization initiator other than the organic peroxide represented by the general formula (1). As such a polymerization initiator, known ones can be used, for example, di (4-t-butylcyclohexyl) peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxy-2. Examples thereof include organic peroxides such as -ethylhexanoate and azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile. Only one kind of these polymerization initiators may be used, or two or more kinds thereof may be used in combination.
When the organic peroxide represented by the general formula (1) is used in combination with another polymerization initiator, the ratio of the organic peroxide represented by the general formula (1) to the total amount of the polymerization initiator (C) is 50. It is preferably mass% or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.
本発明のレジスト用樹脂組成物は、上記成分および必要に応じて下記＜その他成分＞を混合して調製することができる。混合方法は特に限定されるものではなく、全成分を同時に混合しても良いし、各成分を順次溶解させても良い。溶解させる順序や作業条件は特に限定されず、公知の方法で調製することができる。 The resin composition for resist of the present invention can be prepared by mixing the above components and, if necessary, the following <other components>. The mixing method is not particularly limited, and all the components may be mixed at the same time, or each component may be dissolved in sequence. The order of dissolution and working conditions are not particularly limited, and preparations can be made by a known method.
＜感光性樹脂組成物＞
本発明の感光性樹脂組成物は、本発明のレジスト用樹脂組成物（不飽和塩基酸モノマー（Ａ）、該不飽和塩基酸モノマー（Ａ）と共重合可能なモノマー（Ｂ）、及び重合開始剤（Ｃ）を含むレジスト用樹脂組成物）から得られる樹脂（以下、「レジスト用重合体」と称する場合がある。）、光重合開始剤、及び重合性化合物を含有する。
<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises the resin composition for resist of the present invention (unsaturated basic acid monomer (A), monomer (B) copolymerizable with the unsaturated basic acid monomer (A), and polymerization initiation. It contains a resin (hereinafter, may be referred to as a "polymer for resist") obtained from a resin composition for a resist containing the agent (C), a photopolymerization initiator, and a polymerizable compound.
＜レジスト用重合体＞
本発明におけるレジスト用重合体の重量平均分子量および分散度は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いてポリスチレン換算で求めることができる。重量平均分子量は、好ましくは３，０００〜１００，０００であり、より好ましくは４，０００〜５０，０００であり、さらに好ましくは５，０００〜３０，０００である。レジスト用重合体の重量平均分子量が３，０００〜１００，０００であれば、良好な密着性や現像性が得られやすい。レジスト用重合体の分散度（重量平均分子量Ｍｗと数平均分子量Ｍｎとの比（Ｍｗ／Ｍｎ））は、好ましくは１．０〜５．０であり、より好ましくは１．０〜３．５であり、さらに好ましくは１．０〜３．０である。分散度が１．０〜５．０であれば、良好なレジストの現像性やパターン形状が得られやすい。
<Polymer for resist>
The weight average molecular weight and the degree of dispersion of the resist polymer in the present invention can be determined in terms of polystyrene using gel permeation chromatography (GPC). The weight average molecular weight is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and even more preferably 5,000 to 30,000. When the weight average molecular weight of the resist polymer is 3,000 to 100,000, good adhesion and developability can be easily obtained. The dispersity of the resist polymer (ratio of weight average molecular weight Mw to number average molecular weight Mn (Mw / Mn)) is preferably 1.0 to 5.0, more preferably 1.0 to 3.5. It is more preferably 1.0 to 3.0. When the dispersity is 1.0 to 5.0, good resist developability and pattern shape can be easily obtained.
本発明の感光性樹脂組成物におけるレジスト用重合体の含有割合としては、感光性樹脂組成物の全固形分１００質量％に対して、１０質量％〜９０質量％とすることが好ましく、より好ましくは１５質量％〜８０質量％であり、さらに好ましくは２０質量％〜６０質量％である。レジスト用重合体の含有割合が１０質量％〜９０質量％であれば、レジストの現像性、成膜性および塗工性が十分に得られやすい。 The content ratio of the polymer for resist in the photosensitive resin composition of the present invention is preferably 10% by mass to 90% by mass, more preferably 10% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. Is 15% by mass to 80% by mass, more preferably 20% by mass to 60% by mass. When the content ratio of the polymer for resist is 10% by mass to 90% by mass, it is easy to sufficiently obtain the developability, film forming property and coatability of the resist.
＜光重合開始剤＞
本発明において、光重合開始剤は、光照射により重合性化合物の重合反応の起点となる化合物であり、公知のいかなる光重合開始剤も使用することができる。波長については特に限定されるものではないが、波長に適した開始剤種を選択し使用することができる。本発明における光重合開始剤は、１種類を単独で又は２種以上を組み合わせて使用することができる。
<Photopolymerization initiator>
In the present invention, the photopolymerization initiator is a compound that becomes the starting point of the polymerization reaction of the polymerizable compound by light irradiation, and any known photopolymerization initiator can be used. The wavelength is not particularly limited, but an initiator type suitable for the wavelength can be selected and used. The photopolymerization initiator in the present invention may be used alone or in combination of two or more.
本発明における光重合開始剤としては、例えば、ベンゾフェノン、Ｎ，Ｎ’−テトラアルキル−４，４’−ジアミノベンゾフェノン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパノン−１、４，４’−ビス（ジメチルアミノ）ベンゾフェノン（ミヒラーケトン）、４，４’−ビス（ジエチルアミノ）ベンゾフェノン、４−メトキシ−４’−ジメチルアミノベンゾフェノン等の芳香族ケトン類、アルキルアントラキノン、フェナントレンキノン等のキノン類、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物、ベンゾインアルキルエーテル、ベンゾインフェニルエーテル等のベンゾインエーテル化合物、ベンジルジメチルケタール等のベンジル誘導体、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−クロロフェニル）−４，５−ジ（ｍ−メトキシフェニル）イミダゾール二量体、２−（ｏ−フルオロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２，４−ジ（ｐ−メトキシフェニル）−５−フェニルイミダゾール二量体、２−（２，４−ジメトキシフェニル）−４，５−ジフェニルイミダゾール二量体等の２，４，５−トリアリールイミダゾール二量体、Ｎ−フェニルグリシン、Ｎ−フェニルグリシン誘導体、９−フェニルアクリジン等のアクリジン誘導体、１，２−オクタンジオン，１−［４−（フェニルチオ）−，２−（Ｏ−ベンゾイルオキシム）］等のオキシムエステル類、７−ジエチルアミノ−４−メチルクマリン等のクマリン系化合物、２，４−ジエチルチオキサントン等のチオキサントン系化合物、２，４，６−トリメチルベンゾイル−ジフェニル−ホスフィンオキサイド等のアシルホスフィンオキサイド系化合物などを使用することができる。 Examples of the photopolymerization initiator in the present invention include benzophenone, N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-. 1,2-Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 4,4'-bis (dimethylamino) benzophenone (Michler ketone), 4,4'-bis (diethylamino) benzophenone , Aromatic ketones such as 4-methoxy-4'-dimethylaminobenzophenone, quinones such as alkylanthraquinone and phenanthrenquinone, benzoin compounds such as benzoin and alkylbenzoin, benzoin ether compounds such as benzoin alkyl ether and benzoin phenyl ether, Benzyl derivatives such as benzyldimethylketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) 4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl)- 2,4,5-Triarylimidazole dimer such as 5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, N-phenylglycine, N- Phenylglycine derivatives, aclysine derivatives such as 9-phenylaclydin, 1,2-octanedione, oxime esters such as 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], 7-diethylamino-4 A coumarin compound such as −methylcoumarin, a thioxanthone compound such as 2,4-diethylthioxanthone, and an acylphosphine oxide compound such as 2,4,6-trimethylbenzoyl-diphenyl-phosphenyl oxide can be used.
本発明の感光性樹脂組成物における光重合開始剤の含有割合としては、感光性樹脂組成物の全固形分１００質量％に対して、０．０１質量％〜５０質量％とすることが好ましく、より好ましくは０．１質量％〜４０質量％であり、さらに好ましくは０．１質量％〜３０質量％である。 The content ratio of the photopolymerization initiator in the photosensitive resin composition of the present invention is preferably 0.01% by mass to 50% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. It is more preferably 0.1% by mass to 40% by mass, and further preferably 0.1% by mass to 30% by mass.
＜重合性化合物＞
本発明において、重合性化合物は、少なくとも１個の重合性官能基を有する化合物である。
<Polymerizable compound>
In the present invention, the polymerizable compound is a compound having at least one polymerizable functional group.
本発明における重合性化合物としては、例えば、２−ヒドロキシエチル（メタ）アクリレート、カルビトール（メタ）アクリレート、イソボロニル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられ、２個以上の重合性官能基を有する化合物が好ましく、２種以上を併用してもよい。 Examples of the polymerizable compound in the present invention include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobolonyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and tetraethylene. Glycoldi (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) Acrylate, Trimethylol Propanetri (meth) Acrylate, Glycerindi (Meta) Acrylate, Pentaerythritol Triacrylate, Pentaerythritol Tetraacrylate, Dipentaerythritol Pentaacrylate, Dipentaerythritol Hexaacrylate, Pentaerythritol di (meth) Acrylate, Pentaerythritol Examples thereof include tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, and compounds having two or more polymerizable functional groups are preferable. Two or more types may be used in combination.
本発明の感光性樹脂組成物における重合性化合物の含有割合としては、感光性樹脂組成物の全固形分１００質量％に対して、３質量％〜２００質量％とすることが好ましく、より好ましくは５質量％〜１５０質量％であり、さらに好ましくは１０質量％〜１００質量％である。 The content ratio of the polymerizable compound in the photosensitive resin composition of the present invention is preferably 3% by mass to 200% by mass, more preferably 3% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. It is 5% by mass to 150% by mass, more preferably 10% by mass to 100% by mass.
本発明の感光性樹脂組成物は、上記成分および必要に応じて下記＜その他成分＞を混合して調製することができる。混合方法は特に限定されるものではなく、全成分を同時に混合しても良いし、各成分を順次溶解させても良い。溶解させる順序や作業条件は特に限定されず、公知の方法で調製することができる。 The photosensitive resin composition of the present invention can be prepared by mixing the above components and, if necessary, the following <other components>. The mixing method is not particularly limited, and all the components may be mixed at the same time, or each component may be dissolved in sequence. The order of dissolution and working conditions are not particularly limited, and preparations can be made by a known method.
＜その他成分＞
本発明のレジスト用樹脂組成物および感光性樹脂組成物には、本発明の効果を損なわない限り、溶剤等のその他成分を添加することができる。溶剤は２種以上を併用してもよい。
<Other ingredients>
Other components such as a solvent can be added to the resist resin composition and the photosensitive resin composition of the present invention as long as the effects of the present invention are not impaired. Two or more kinds of solvents may be used in combination.
溶剤としては、例えば、メチルアルコール、エチルアルコール、酢酸エチル、酢酸ブチル、アセトン、メチルエチルケトン、Ｎ，Ｎ−ジメチルホルムアミド、テトラヒドロフラン、ベンゼン、トルエン、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エチルメチルエーテル、プロピレングリコールモノメチルエーテル、酢酸エチレングリコールモノメチルエーテル、酢酸プロピレングリコールモノメチルエーテルなどを挙げることができる。 Examples of the solvent include methyl alcohol, ethyl alcohol, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, N, N-dimethylformamide, tetrahydrofuran, benzene, toluene, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, and propylene. Examples thereof include glycol monomethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate.
＜一般式（１）で示される有機過酸化物の合成＞
一般式（１）で示される有機過酸化物は、例えば次の方法で合成することができる。下記式（２）で示される脂肪酸ハライドと１−シクロヘキシル−１−メチルエチルヒドロペルオキシドとをアルカリの存在下に反応させることにより合成することができる。
<Synthesis of organic peroxide represented by the general formula (1)>
The organic peroxide represented by the general formula (1) can be synthesized by, for example, the following method. It can be synthesized by reacting a fatty acid halide represented by the following formula (2) with 1-cyclohexyl-1-methylethyl hydroperoxide in the presence of an alkali.
（式（２）中、Ｒ１〜Ｒ３は、同一または異なって、それぞれ水素原子または炭素数１〜１０のアルキル基であり、Ｘは塩素原子、臭素原子、またはヨウ素原子のいずれかである。） (In the formula (2), R 1 to R 3 are the same or different, respectively, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X is either a chlorine atom, a bromine atom, or an iodine atom. .)
上記反応に用いるアルカリは、水酸化カリウム、水酸化ナトリウム等の無機塩基或いはそれらの水溶液、又はピリジン等のアミン類である。また、合成に際してベンゼン、ｎ−ヘキサン、ジオキサン等の溶媒存在下で反応を行なうことにより、反応時間の短縮或いは収率の向上を図ることができる。 The alkali used in the above reaction is an inorganic base such as potassium hydroxide or sodium hydroxide, an aqueous solution thereof, or amines such as pyridine. Further, by carrying out the reaction in the presence of a solvent such as benzene, n-hexane or dioxane during the synthesis, the reaction time can be shortened or the yield can be improved.
また、一般式（１）で示される有機過酸化物は、ヨードメトリーによる活性酸素の測定によってペルオキシド基の含有量（活性酸素量）を求めることができる。 Further, in the organic peroxide represented by the general formula (1), the content of the peroxide group (the amount of active oxygen) can be determined by measuring the active oxygen by iodometry.
＜レジスト用重合体の合成＞
本発明のレジスト用樹脂組成物を重合させることにより、レジスト用重合体を得ることができる。重合は公知の方法で行うことができる。例えば、溶液重合、懸濁重合、乳化重合などが挙げられるが、レジスト用重合体の重量平均分子量を上記範囲内に調整しやすいという面で、溶液重合が好ましい。重合開始剤（Ｃ）ならびにモノマー（Ａ）および（Ｂ）を投入するに際しては、例えば、全量を一括仕込みしても良いし、一部を一括仕込みして残りを滴下しても良いし、あるいは全量を滴下しても良い。発熱の制御しやすさから、一部を一括仕込みして残りを滴下するか、または全量を滴下するのが好ましい。
<Synthesis of resist polymer>
A resist polymer can be obtained by polymerizing the resist resin composition of the present invention. The polymerization can be carried out by a known method. For example, solution polymerization, suspension polymerization, emulsion polymerization and the like can be mentioned, but solution polymerization is preferable in that the weight average molecular weight of the resist polymer can be easily adjusted within the above range. When the polymerization initiator (C) and the monomers (A) and (B) are added, for example, the entire amount may be charged in a batch, a part may be charged in a batch, and the rest may be added dropwise. The entire amount may be dropped. From the viewpoint of easy control of heat generation, it is preferable to prepare a part in a batch and drop the rest, or drop the whole amount.
重合温度は、モノマー（Ａ）および（Ｂ）の種類や重合溶媒の種類などに依存し、例えば、５０℃〜１２０℃である。重合時間は、重合開始剤（Ｃ）の半減期温度と重合温度に依存し、例えば、１−シクロへキシル−１−メチルエチルペルオキシオクトエートを含む重合開始剤（Ｃ）では、９０℃で７時間程度が適している。 The polymerization temperature depends on the types of the monomers (A) and (B), the type of the polymerization solvent, and the like, and is, for example, 50 ° C to 120 ° C. The polymerization time depends on the half-life temperature and the polymerization temperature of the polymerization initiator (C). For example, in the polymerization initiator (C) containing 1-cyclohexyl-1-methylethylperoxyoctate, the polymerization initiator (C) is 7 at 90 ° C. About time is suitable.
以上の重合反応を行なうことにより、レジスト用重合体が得られる。得られたレジスト用重合体は、そのまま用いてもよいし、重合反応後の反応液に、ろ取や精製を施して単離してもよい。 By carrying out the above polymerization reaction, a polymer for resist can be obtained. The obtained polymer for resist may be used as it is, or the reaction solution after the polymerization reaction may be isolated by filtration or purification.
以下、実施例及び比較例を挙げて本発明をさらに具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
（合成例１：１−シクロへキシル−１−メチルエチルペルオキシネオデカノエート（Ｒ１＝ヘキシル基、Ｒ２＝メチル基、Ｒ３＝メチル基）の合成）
攪拌器を備えた２００ｍＬ４つロフラスコに３５％水酸化カリウム水溶液２８３ｇを入れ、攪拌下液温を２０℃に保ちながら、９５％１−シクロへキシル−１−メチルエチルヒドロペルオキシド１７．９ｇとヘキサン１０ｇの混合物を添加した。更に攪拌下、液温を２０℃に保ちつつネオデカン酸クロライド１９．１ｇを１０分間で滴下した。液温を２０℃に保ちつつ３時間攪拌を続けた後、冷水２０ｇを加え更に５分間攪拌した。水相を分離し、有機相を５％水酸化ナトリウム水溶液２０ｇで洗浄した後、水で３回洗浄した。この溶液（有機相）を無水硫酸マグネシウム上で乾燥後、真空下ヘキサンを除去した結果、無色液体の目的物２４．１ｇを得た。その活性酸素量は４．８３％であり、計算により純度９４％であった。
(Synthesis Example 1: Synthesis of 1-cyclohexyl-1-methylethyl peroxyneodecanoate (R 1 = hexyl group, R 2 = methyl group, R 3 = methyl group))
283 g of a 35% potassium hydroxide aqueous solution was placed in a 200 mL 4-roflask equipped with a stirrer, and 17.9 g of 95% 1-cyclohexyl-1-methylethyl hydroperoxide and 10 g of hexane were maintained while keeping the temperature of the solution under stirring at 20 ° C. The mixture of was added. Further, under stirring, 19.1 g of neodecanoic acid chloride was added dropwise over 10 minutes while maintaining the liquid temperature at 20 ° C. After continuing stirring for 3 hours while keeping the liquid temperature at 20 ° C., 20 g of cold water was added and the mixture was further stirred for 5 minutes. The aqueous phase was separated, and the organic phase was washed with 20 g of a 5% aqueous sodium hydroxide solution and then washed with water three times. After drying this solution (organic phase) on anhydrous magnesium sulfate, hexane was removed under vacuum to obtain 24.1 g of a colorless liquid target product. The amount of active oxygen was 4.83%, and the purity was 94% by calculation.
更にベンゼンを溶媒として熱分解速度を測定した（濃度：０．１ｍｏｌ／Ｌ）。その結果、この有機過酸化物の１０時間半減期温度（Ｔ１０）は４１．４℃であった。 Further, the thermal decomposition rate was measured using benzene as a solvent (concentration: 0.1 mol / L). As a result, the 10-hour half-life temperature (T 10 ) of this organic peroxide was 41.4 ° C.
（合成例２：１−シクロへキシル−１−メチルエチルペルオキシピバレート（Ｒ１＝メチル基、Ｒ２＝メチル基、Ｒ３＝メチル基）の合成）
脂肪酸ハライドとしてピバリン酸クロライドを用いた以外は合成例１と同様にして合成を行ない、無色液体の目的物を得た。その活性酸素量は６．２１％であり、計算により純度９４％であった。
(Synthesis Example 2: Synthesis of 1-cyclohexyl-1-methylethylperoxypivalate (R 1 = methyl group, R 2 = methyl group, R 3 = methyl group))
Synthesis was carried out in the same manner as in Synthesis Example 1 except that chloride chloride was used as the fatty acid halide, and a colorless liquid target product was obtained. The amount of active oxygen was 6.21%, and the purity was 94% by calculation.
更に合成例１と同様の方法で、熱分解速度を測定した。その結果、１０時間半減期温度は４９．１℃であった。 Further, the thermal decomposition rate was measured by the same method as in Synthesis Example 1. As a result, the 10-hour half-life temperature was 49.1 ° C.
（合成例３：１−シクロヘキシル−１−メチルエチルペルオキシネオヘキサノエート（Ｒ１＝エチル基、Ｒ２＝メチル基、Ｒ３＝メチル基）の合成）
脂肪酸ハライドとしてネオヘキサン酸クロライドを用いた以外は合成例１と同様にして合成を行ない、無色液体の目的物を得た。その活性酸素量は５．８０％であり、計算により純度９３％であった。
(Synthesis Example 3: Synthesis of 1-cyclohexyl-1-methylethyl peroxyneohexanoate (R 1 = ethyl group, R 2 = methyl group, R 3 = methyl group))
The synthesis was carried out in the same manner as in Synthesis Example 1 except that neocaproic acid chloride was used as the fatty acid halide, and a colorless liquid target product was obtained. The amount of active oxygen was 5.80%, and the purity was 93% by calculation.
更に合成例１と同様の方法で、熱分解速度を測定した。その結果、１０時間半減期温度は４６．２℃であった。 Further, the thermal decomposition rate was measured by the same method as in Synthesis Example 1. As a result, the 10-hour half-life temperature was 46.2 ° C.
（重合例１）
３００ｍＬビーカーを用い、メタクリル酸（製品名：ＭＡＡ、株式会社クラレ製）２８．４ｇ、メタクリル酸メチル（製品名：ＭＭＡモノマー、株式会社クラレ製）６６．０ｇ、メタクリル酸シクロヘキシル（製品名：ブレンマーＣＨＭＡ、日油株式会社製）１６６．３ｇ、Ｎ−シクロヘキシルマレイミド（製品名：イミレックスＣ、日本触媒株式会社製）３９．３ｇ、酢酸プロピレングリコールモノメチルエーテル（製品名：ＭＭＰＧＡＣ、ダイセル株式会社製）５０ｇを混合した後氷冷し、１−シクロへキシル−１−メチルエチルペルオキシネオデカノエート（合成例1）２４．０ｇを加えて、「レジスト用樹脂組成物」を得た。
(Polymerization Example 1)
Using a 300 mL beaker, 28.4 g of methacrylic acid (product name: MAA, manufactured by Kuraray Co., Ltd.), 66.0 g of methyl methacrylate (product name: MMA monomer, manufactured by Kuraray Co., Ltd.), cyclohexyl methacrylate (product name: Blemmer CHMA) , Nichiyu Co., Ltd.) 166.3 g, N-cyclohexyl maleimide (product name: Imirex C, manufactured by Nippon Catalyst Co., Ltd.) 39.3 g, propylene glycol acetate monomethyl ether (product name: MMPGAC, manufactured by Daicel Co., Ltd.) 50 g. After mixing, the mixture was ice-cooled, and 24.0 g of 1-cyclohexyl-1-methylethylperoxyneodecanoate (Synthesis Example 1) was added to obtain a "resin composition for resist".
続いて撹拌機、温度計、冷却器、滴下ロート及び窒素導入管を取り付けた１Ｌセパラブルフラスコに、酢酸プロピレングリコールモノメチルエーテル５５０．０ｇを仕込み、フラスコ内を窒素置換して、窒素雰囲気下にした。反応容器内を６７℃まで昇温し、上記で得たレジスト用樹脂組成物を３時間かけて滴下し、その後６７℃で３時間反応させることでレジスト用重合体Ｐ１を得た。 Subsequently, 550.0 g of propylene glycol monomethyl ether acetate was charged into a 1 L separable flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel and a nitrogen introduction tube, and the inside of the flask was replaced with nitrogen to create a nitrogen atmosphere. .. The temperature inside the reaction vessel was raised to 67 ° C., the resin composition for resist obtained above was added dropwise over 3 hours, and then the reaction was carried out at 67 ° C. for 3 hours to obtain a polymer P1 for resist.
（重合例２）
重合開始剤として１−シクロへキシル−１−メチルエチルペルオキシピバレート（合成例２）１５．０ｇを用い、重合温度を８０℃としたこと以外は重合例１と同様の手法でレジスト用重合体Ｐ２を得た。
(Polymerization Example 2)
15.0 g of 1-cyclohexyl-1-methylethylperoxypivalate (Synthesis Example 2) was used as a polymerization initiator, and a polymer for resist was used in the same manner as in Polymerization Example 1 except that the polymerization temperature was set to 80 ° C. Obtained P2.
（重合例３）
重合開始剤として１−シクロへキシル−１−メチルエチルペルオキシネオヘキサノエート（合成例３）３０．０ｇを用い、重合温度を７５℃としたこと以外は重合例１と同様の手法でレジスト用重合体Ｐ３を得た。
(Polymerization Example 3)
For resist, 1-cyclohexyl-1-methylethylperoxyneohexanoate (Synthesis Example 3) (30.0 g) was used as a polymerization initiator, and the same method as in Polymerization Example 1 was used except that the polymerization temperature was set to 75 ° C. Polymer P3 was obtained.
（重合例４）
モノマー（Ａ）をメタクリル酸３８．７ｇ、モノマー（Ｂ）をメタクリル酸メチル１０５．１ｇおよびスチレン（製品名：ＮＳスチレン、ＮＳスチレンモノマー株式会社製）１５６．２ｇに変更したこと以外は重合例１と同様の手法でレジスト用重合体Ｐ４を得た。
(Polymerization Example 4)
Polymerization Example 1 except that the monomer (A) was changed to 38.7 g of methacrylic acid, the monomer (B) was changed to 105.1 g of methyl methacrylate and 156.2 g of styrene (product name: NS styrene, manufactured by NS Styrene Monomer Co., Ltd.). The resist polymer P4 was obtained in the same manner as in the above.
（重合例５）
モノマー（Ａ）をメタクリル酸３９．５ｇ、モノマー（Ｂ）をメタクリル酸メチル２６０．５ｇに、開始剤量を３６．０ｇに変更したこと以外は重合例１と同様の手法でレジスト用重合体Ｐ５を得た。
(Polymerization Example 5)
The resist polymer P5 is the same as in Polymerization Example 1 except that the monomer (A) is changed to 39.5 g of methacrylic acid, the monomer (B) is changed to 260.5 g of methyl methacrylate, and the amount of the initiator is changed to 36.0 g. Got
（重合例６）
重合開始剤として２，２’−アゾビス−２，４−ジメチルバレロニトリル（製品名：Ｖ-６５、富士フィルム和光純薬株式会社製）１８．０ｇを用い、重合温度を７５℃としたこと以外は重合例１と同様の手法でレジスト用重合体Ｐ６を得た。
(Polymerization Example 6)
Except that 18.0 g of 2,2'-azobis-2,4-dimethylvaleronitrile (product name: V-65, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the polymerization initiator and the polymerization temperature was set to 75 ° C. Obtained a resist polymer P6 by the same method as in Polymerization Example 1.
（重合例７）
重合開始剤としてｔｅｒｔ−ブチルペルオキシネオデカノエート（製品名：パーブチルＮＤ、日油株式会社製）を用い、重合温度を７５℃としたこと以外は重合例１と同様の手法でレジスト用重合体Ｐ７を得た。
(Polymerization Example 7)
A polymer for resist was used as a polymerization initiator using tert-butylperoxyneodecanoate (product name: Perbutyl ND, manufactured by NOF CORPORATION) in the same manner as in Polymerization Example 1 except that the polymerization temperature was set to 75 ° C. Obtained P7.
（重合例８）
重合開始剤としてビス−４−ｔｅｒｔ−ブチルシクロヘキシルペルオキシジカーボネート（製品名：パーロイルＴＣＰ、日油株式会社製）を用い、重合温度を６５℃としたこと以外は重合例１と同様の手法でレジスト用重合体Ｐ８を得た。
(Polymerization Example 8)
Bis-4-tert-butylcyclohexylperoxydicarbonate (product name: Parloyl TCP, manufactured by NOF CORPORATION) was used as the polymerization initiator, and the resist was resisted in the same manner as in Polymerization Example 1 except that the polymerization temperature was 65 ° C. Polymer P8 for use was obtained.
（実施例１〜５および比較例１〜３：感光性樹脂組成物の調製）
重合例１〜８で得られたレジスト用重合体１０ｇに、ジペンタエリスリトールヘキサアクリレート（共栄社化学株式会社製「ライトアクリレートＤＰＥ−６Ａ」）１．５ｇ、光重合開始剤（ビーエーエスエフ製「イルガキュア９０７」）０．５ｇ、プロピレングリコールモノメチルエーテルアセテート４０ｇを混合し、孔径０．５μｍのフィルターを通過させ、感光性樹脂組成物を調製した。
(Examples 1 to 5 and Comparative Examples 1 to 3: Preparation of photosensitive resin composition)
To 10 g of the polymer for resist obtained in Polymerization Examples 1 to 8, 1.5 g of dipentaerythritol hexaacrylate (“Light Acrylate DPE-6A” manufactured by Kyoeisha Chemical Co., Ltd.) and a photopolymerization initiator (“Irgacure 907” manufactured by BSF). ”) 0.5 g and 40 g of propylene glycol monomethyl ether acetate were mixed and passed through a filter having a pore size of 0.5 μm to prepare a photosensitive resin composition.
〔レジスト用重合体の重量平均分子量および分散度の測定〕
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて以下の条件により、レジスト用重合体Ｐ１〜Ｐ８の重量平均分子量（Ｍｗ）および分散度（Ｍｗ/Ｍｎ）を求めた。
装置：東ソー（株）社製、ＨＬＣ−８２２０
カラム：ｓｈｏｄｅｘ社製、ＬＦ−８０４
標準物質：ポリスチレン
溶離液：ＴＨＦ（テトラヒドロフラン）
流量：１．０ｍＬ／ｍｉｎ
カラム温度：４０℃
検出器：ＲＩ（示差屈折率検出器）
[Measurement of weight average molecular weight and dispersity of resist polymer]
Using gel permeation chromatography (GPC), the weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resist polymers P1 to P8 were determined under the following conditions.
Equipment: HLC-8220 manufactured by Tosoh Corporation
Column: LF-804 manufactured by Shodex
Standard substance: Polystyrene Eluent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI (Differential Refractometer)
〔現像性の評価〕
調製した感光性樹脂組成物１０ｇにプロピレングリコールモノメチルエーテル１０ｇを混合した希釈溶液をシリコンウエハにスピンコートし、１２０℃で乾燥させ、膜厚５μｍの樹脂膜を得た。このシリコンウエハを２．４％テトラメチルアンモニウムヒドロキシド水溶液に１分間浸漬した。浸漬後のシリコンウエハを目視にて観察し、樹脂膜の残存の有無を評価した。３０秒未満で樹脂膜が溶解する場合を○、溶解に３０秒以上かかる場合を×とした。
[Evaluation of developability]
A diluted solution prepared by mixing 10 g of the prepared photosensitive resin composition with 10 g of propylene glycol monomethyl ether was spin-coated on a silicon wafer and dried at 120 ° C. to obtain a resin film having a film thickness of 5 μm. This silicon wafer was immersed in a 2.4% aqueous solution of tetramethylammonium hydroxide for 1 minute. The silicon wafer after immersion was visually observed to evaluate the presence or absence of residual resin film. The case where the resin film was dissolved in less than 30 seconds was evaluated as ◯, and the case where the dissolution took 30 seconds or more was evaluated as x.
〔硬化膜の作製〕
調製した感光性樹脂組成物をガラス基板上にスピンコートにより塗布し、９０℃で２分乾燥して感光性樹脂組成物層を形成した。得られた塗膜に超高圧水銀ランプにてマスクを介して２００ｍＪ／ｃｍ２の強度で紫外線を照射した。照射後、０．４％テトラメチルアンモニウムヒドロキシド水溶液に１分間浸漬し、水洗後、２３０℃で１時間硬化して膜厚３μｍの硬化膜を作製した。
[Preparation of cured film]
The prepared photosensitive resin composition was applied onto a glass substrate by spin coating and dried at 90 ° C. for 2 minutes to form a photosensitive resin composition layer. The obtained coating film was irradiated with ultraviolet rays at an intensity of 200 mJ / cm 2 through a mask with an ultra-high pressure mercury lamp. After irradiation, it was immersed in a 0.4% tetramethylammonium hydroxide aqueous solution for 1 minute, washed with water, and cured at 230 ° C. for 1 hour to prepare a cured film having a film thickness of 3 μm.
〔耐熱性の評価〕
作製した硬化膜を２５０℃で１時間加熱し、加熱前後の膜厚を測定した。以下のように膜厚変化率を定義し、膜厚変化率が５％未満のものを◎、５％以上８％未満のものを〇、８％以上１０％未満のものを△、１０％以上のものを×とした。
膜厚変化率（％）＝１００−［｛加熱後の膜厚（μｍ）／加熱前の膜厚（μｍ）｝×１００］
[Evaluation of heat resistance]
The prepared cured film was heated at 250 ° C. for 1 hour, and the film thickness before and after heating was measured. The rate of change in film thickness is defined as follows, and the rate of change in film thickness is less than 5% ◎, 5% or more and less than 8% is 〇, 8% or more and less than 10% is Δ, 10% or more. The thing was set as x.
Film thickness change rate (%) = 100- [{Film thickness after heating (μm) / Film thickness before heating (μm)} x 100]
〔耐薬品性の評価〕
作製した硬化膜を６０℃で１５分間Ｎ−メチルピロリドン（ＮＭＰ）に浸漬させ、浸漬前後の膜厚を測定した。以下のように膜厚変化率を定義し、膜厚変化率が２％未満のものを◎、２％以上５％未満のものを〇、５％以上８％未満のものを△、８％以上のものを×とした。
膜厚変化率（％）＝１００−［｛浸漬後の膜厚（μｍ）／浸漬前の膜厚（μｍ）｝×１００］
[Evaluation of chemical resistance]
The prepared cured film was immersed in N-methylpyrrolidone (NMP) at 60 ° C. for 15 minutes, and the film thickness before and after the immersion was measured. The film thickness change rate is defined as follows, and the film thickness change rate is less than 2% ◎, 2% or more and less than 5% is 〇, 5% or more and less than 8% is △, 8% or more The thing was set as x.
Film thickness change rate (%) = 100- [{Film thickness after immersion (μm) / Film thickness before immersion (μm)} x 100]
なお、表１および２中、モノマー（Ａ）および（Ｂ）、ならびに重合開始剤（Ｃ）の配合量は、全モノマー成分１００質量％に対する質量％で示される。 In Tables 1 and 2, the blending amounts of the monomers (A) and (B) and the polymerization initiator (C) are shown in mass% with respect to 100% by mass of all the monomer components.
実施例１〜５では、耐熱性および耐薬品性に優れた硬化膜を得ることができた。
一方、比較例１〜３では、重合開始剤としてアゾ系の開始剤を、比較例２では、重合開始剤としてパーオキシエステル型の有機過酸化物を、および比較例３では、重合開始剤としてジカーボネート型の有機過酸化物を用いたため（本発明における一般式（１）で示される有機過酸化物を用いなかったため）、いずれも耐熱性および耐薬品性に劣る硬化膜しか得ることができなかった。
In Examples 1 to 5, a cured film having excellent heat resistance and chemical resistance could be obtained.
On the other hand, in Comparative Examples 1 to 3, an azo-based initiator was used as the polymerization initiator, in Comparative Example 2, a peroxyester-type organic peroxide was used as the polymerization initiator, and in Comparative Example 3, the polymerization initiator was used. Since a dicarbonate-type organic peroxide is used (because the organic peroxide represented by the general formula (1) in the present invention is not used), only a cured film having inferior heat resistance and chemical resistance can be obtained. There wasn't.
本発明によれば、耐薬品性および耐熱性に優れる樹脂膜を与えるレジスト用樹脂組成物および感光性樹脂組成物を得ることができる。
According to the present invention, it is possible to obtain a resist resin composition and a photosensitive resin composition that provide a resin film having excellent chemical resistance and heat resistance.
Claims (2)
（式（１）中、Ｒ１〜Ｒ３は、同一または異なって、それぞれ水素原子または炭素数１〜１０のアルキル基を示す。）。 A resin composition for a resist comprising an unsaturated basic acid monomer (A), a monomer (B) copolymerizable with the unsaturated basic acid monomer (A), and a polymerization initiator (C), wherein the polymerization initiator. A resin composition for a resist, wherein (C) contains an organic peroxide represented by the following general formula (1):
(In the formula (1), R 1 to R 3 represent the same or different alkyl groups having hydrogen atoms or 1 to 10 carbon atoms, respectively).
A photosensitive resin composition containing a resin obtained from the resin composition for resist according to claim 1, a photopolymerization initiator, and a polymerizable compound.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04164065A (en) * | 1990-10-25 | 1992-06-09 | Nippon Oil & Fats Co Ltd | New organic peroxide |
| JPH07216007A (en) * | 1994-02-02 | 1995-08-15 | Kuraray Co Ltd | Production of methacrylic resin |
| JP2001002717A (en) * | 1999-06-22 | 2001-01-09 | Mitsubishi Rayon Co Ltd | Production of copolymer for chemical magnification type resist |
| JP2001255699A (en) * | 2000-03-08 | 2001-09-21 | Canon Inc | Toner and method of manufacturing nonmagnetic toner particle |
| WO2004035641A1 (en) * | 2002-10-18 | 2004-04-29 | Daikin Industries, Ltd. | Process for production of fluoropolymers and photoresist composition |
| JP2010024229A (en) * | 2008-06-20 | 2010-02-04 | Showa Denko Kk | (meth)acryloyloxy group-containing cage-like silsesquioxane compound, and method for producing the same |
| JP2011064768A (en) * | 2009-09-15 | 2011-03-31 | Canon Inc | Toner |
-
2020
- 2020-03-11 JP JP2020042465A patent/JP7318570B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04164065A (en) * | 1990-10-25 | 1992-06-09 | Nippon Oil & Fats Co Ltd | New organic peroxide |
| JPH07216007A (en) * | 1994-02-02 | 1995-08-15 | Kuraray Co Ltd | Production of methacrylic resin |
| JP2001002717A (en) * | 1999-06-22 | 2001-01-09 | Mitsubishi Rayon Co Ltd | Production of copolymer for chemical magnification type resist |
| JP2001255699A (en) * | 2000-03-08 | 2001-09-21 | Canon Inc | Toner and method of manufacturing nonmagnetic toner particle |
| WO2004035641A1 (en) * | 2002-10-18 | 2004-04-29 | Daikin Industries, Ltd. | Process for production of fluoropolymers and photoresist composition |
| JP2010024229A (en) * | 2008-06-20 | 2010-02-04 | Showa Denko Kk | (meth)acryloyloxy group-containing cage-like silsesquioxane compound, and method for producing the same |
| JP2011064768A (en) * | 2009-09-15 | 2011-03-31 | Canon Inc | Toner |
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