JP2005112824A - Fluorine atom-containing polymerizable adamantane derivative, process for producing the same, and polymer compound - Google Patents
Fluorine atom-containing polymerizable adamantane derivative, process for producing the same, and polymer compound Download PDFInfo
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- JP2005112824A JP2005112824A JP2003352587A JP2003352587A JP2005112824A JP 2005112824 A JP2005112824 A JP 2005112824A JP 2003352587 A JP2003352587 A JP 2003352587A JP 2003352587 A JP2003352587 A JP 2003352587A JP 2005112824 A JP2005112824 A JP 2005112824A
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- fluorine atom
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- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- 150000001875 compounds Chemical class 0.000 title claims abstract description 54
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical class C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 34
- 125000001153 fluoro group Chemical group F* 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 13
- 125000001424 substituent group Chemical group 0.000 claims abstract description 13
- 239000012022 methylating agents Substances 0.000 claims abstract description 8
- 150000001266 acyl halides Chemical class 0.000 claims abstract description 7
- 125000004429 atom Chemical group 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 abstract description 35
- 239000000126 substance Substances 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 3
- -1 adamantanone compound Chemical class 0.000 description 47
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 18
- 125000006239 protecting group Chemical group 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 229920002120 photoresistant polymer Polymers 0.000 description 14
- 125000002252 acyl group Chemical group 0.000 description 13
- 238000005530 etching Methods 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- LKXYIIGMHKAPPU-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-(trifluoromethyl)prop-2-enoate Chemical compound C1C(C2)CC3CC1C(C)(OC(=O)C(=C)C(F)(F)F)C2C3 LKXYIIGMHKAPPU-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- IYKFYARMMIESOX-UHFFFAOYSA-N adamantanone Chemical compound C1C(C2)CC3CC1C(=O)C2C3 IYKFYARMMIESOX-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- WENNKWXPAWNIOO-UHFFFAOYSA-N undecan-5-one Chemical compound CCCCCCC(=O)CCCC WENNKWXPAWNIOO-UHFFFAOYSA-N 0.000 description 3
- DLDWUFCUUXXYTB-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 DLDWUFCUUXXYTB-UHFFFAOYSA-N 0.000 description 2
- JDKIDLYWKMUPJH-UHFFFAOYSA-N (4-hydroxycyclohexyl) 2-(trifluoromethyl)prop-2-enoate Chemical compound OC1CCC(OC(=O)C(=C)C(F)(F)F)CC1 JDKIDLYWKMUPJH-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 2
- HXSIAJREWWAACY-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoyl chloride Chemical compound FC(F)(F)C(=C)C(Cl)=O HXSIAJREWWAACY-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 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
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000002596 lactones Chemical group 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QAFVIYWGBDGLNM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-fluoroprop-2-enoate Chemical compound C1C(C2)CC3CC1C(C)(OC(=O)C(F)=C)C2C3 QAFVIYWGBDGLNM-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- FAQCWWQDIFCGEM-UHFFFAOYSA-N 1,5-dimethyladamantan-2-one Chemical compound C1C(C2)CC3CC1(C)CC2(C)C3=O FAQCWWQDIFCGEM-UHFFFAOYSA-N 0.000 description 1
- NGZBKHKFVNUESG-UHFFFAOYSA-N 1-ethenoxy-4-oxatricyclo[4.3.1.13,8]undecan-5-one Chemical compound O1C(=O)C(C2)CC3(OC=C)CC1CC2C3 NGZBKHKFVNUESG-UHFFFAOYSA-N 0.000 description 1
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 description 1
- 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 1
- CYBBXWXDGZIZCQ-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoyl bromide Chemical compound FC(F)(F)C(=C)C(Br)=O CYBBXWXDGZIZCQ-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- AZVZKZSLXJQRHK-UHFFFAOYSA-N 2-fluoroprop-2-enoyl bromide Chemical compound FC(=C)C(Br)=O AZVZKZSLXJQRHK-UHFFFAOYSA-N 0.000 description 1
- JBKRPXAZWRLPSW-UHFFFAOYSA-N 2-fluoroprop-2-enoyl chloride Chemical compound FC(=C)C(Cl)=O JBKRPXAZWRLPSW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FQQIPIVZYKEWGI-UHFFFAOYSA-N 3-hydroxy-5,5-dimethyloxolan-2-one Chemical compound CC1(C)CC(O)C(=O)O1 FQQIPIVZYKEWGI-UHFFFAOYSA-N 0.000 description 1
- KWIVRAVCZJXOQC-UHFFFAOYSA-N 3h-oxathiazole Chemical class N1SOC=C1 KWIVRAVCZJXOQC-UHFFFAOYSA-N 0.000 description 1
- MGUXBQYXBAIDLD-UHFFFAOYSA-N 5,7-dimethyladamantan-2-one Chemical compound C1C(C2=O)CC3(C)CC2CC1(C)C3 MGUXBQYXBAIDLD-UHFFFAOYSA-N 0.000 description 1
- FUBPSJUGYNKROM-UHFFFAOYSA-N C=COC1(CC2CC(C3)C1)CC3OC2O Chemical compound C=COC1(CC2CC(C3)C1)CC3OC2O FUBPSJUGYNKROM-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- FOWDOWQYRZXQDP-UHFFFAOYSA-N adamantan-2-ol Chemical class C1C(C2)CC3CC1C(O)C2C3 FOWDOWQYRZXQDP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005098 aryl alkoxy carbonyl group Chemical group 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 210000001217 buttock Anatomy 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 238000011161 development Methods 0.000 description 1
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001976 hemiacetal group Chemical group 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- OCUXHFVNHQTZKR-UHFFFAOYSA-M methanesulfonate;triphenylsulfanium Chemical compound CS([O-])(=O)=O.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 OCUXHFVNHQTZKR-UHFFFAOYSA-M 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000005246 nonafluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- ROLDQQDCCSZBNA-UHFFFAOYSA-N oxolane;hydrobromide Chemical compound Br.C1CCOC1 ROLDQQDCCSZBNA-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
【課題】 波長３００ｎｍ以下の光、特にＦ2エキシマレーザー（１５７ｎｍ）等の真空紫外光に対して透過性の高い高分子化合物を得る上で有用な新規なフッ素原子含有重合性不飽和単量体の製造法を提供する。
【解決手段】 下記式（１）
【化１】
（式中のアダマンタン環は置換基を有していてもよい）
で表される化合物に、下記式（２）
ＣＨ3−Ｍ （２）
［式中、Ｍは金属原子又は−ＭｇＸ1基（Ｘ1はハロゲン原子を示す）を示す］
で表されるメチル化剤を作用させ、得られた反応生成物に、下記式（３）
【化２】
（式中、Ｒ1はフッ素原子又はフルオロアルキル基を示し、Ｘ2はハロゲン原子を示す）
で表される不飽和アシルハライドを反応させて、下記式（４）
【化３】
（式中、Ｒ1は前記に同じ。式中のアダマンタン環は置換基を有していてもよい）
で表される化合物を得る。
【選択図】 なし
PROBLEM TO BE SOLVED: To provide a novel fluorine atom-containing polymerizable unsaturated monomer useful for obtaining a polymer compound having a high transmittance with respect to light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light such as F 2 excimer laser (157 nm). Provides a manufacturing method.
The following formula (1)
[Chemical 1]
(The adamantane ring in the formula may have a substituent)
In the compound represented by the following formula (2)
CH 3 -M (2)
[Wherein, M represents a metal atom or a —MgX 1 group (X 1 represents a halogen atom)]
A methylating agent represented by the following formula (3) is reacted with the resulting reaction product:
[Chemical 2]
(Wherein R 1 represents a fluorine atom or a fluoroalkyl group, and X 2 represents a halogen atom)
Is reacted with an unsaturated acyl halide represented by the following formula (4):
[Chemical 3]
(In the formula, R 1 is the same as above. The adamantane ring in the formula may have a substituent)
To obtain a compound represented by:
[Selection figure] None
Description
本発明は半導体の微細加工などを行う際に用いるフォトレジスト用樹脂の単量体成分等として有用な新規なフッ素原子含有重合性アダマンタン誘導体とその製造法、及びこの単量体に対応する繰り返し単位を含む高分子化合物に関する。 The present invention relates to a novel fluorine atom-containing polymerizable adamantane derivative useful as a monomer component or the like of a resin for a photoresist used when performing microfabrication of a semiconductor, a production method thereof, and a repeating unit corresponding to this monomer The present invention relates to a polymer compound containing
半導体の製造に用いられるリソグラフィの露光光源は、年々短波長になってきており、波長２４８ｎｍのＫｒＦエキシマレーザーから波長１９３ｎｍのＡｒＦエキシマレーザーへと移り、次世代の露光光源として波長１５７ｎｍのＦ2エキシマレーザーが有望視されている。従来のＫｒＦエキシマレーザー露光用やＡｒＦエキシマレーザー露光用のレジストに用いられる樹脂は、真空紫外光（１９０ｎｍ以下の波長の光）に対して充分な透過性を示さない。そこで、このような真空紫外光に対する透過性の高い樹脂として、分子内にフッ素原子を含有する高分子化合物がいくつか提案されている（特許文献１〜４参照）。しかしながら、これらの樹脂においても、真空紫外光に対する透過性（透明性）は必ずしも充分とは言えない。また、露光に用いる光に対する透明性に加え、光照射により照射部が酸によってアルカリ可溶性に変化する性質（酸脱離性）、ドライエッチング耐性（耐エッチング性）及び基板に対する密着性（基板密着性）などの特性をバランスよく備えた樹脂はほとんど無い。 Semiconductor lithography exposure light source used in the production of are becoming every year short wavelength shifts from a KrF excimer laser with a wavelength of 248nm to ArF excimer laser with a wavelength of 193 nm, F 2 excimer wavelength 157nm as a next generation exposure light source The laser is promising. Resins used for conventional resists for KrF excimer laser exposure and ArF excimer laser exposure do not exhibit sufficient transparency to vacuum ultraviolet light (light having a wavelength of 190 nm or less). Therefore, several polymer compounds containing fluorine atoms in the molecule have been proposed as such highly transparent resins for vacuum ultraviolet light (see Patent Documents 1 to 4). However, even in these resins, the transparency (transparency) to vacuum ultraviolet light is not always sufficient. In addition to the transparency to light used for exposure, the property that the irradiated part changes to alkali-soluble by acid (acid detachment), dry etching resistance (etching resistance), and adhesion to the substrate (substrate adhesion) ) And the like are hardly available.
一方、機能性高分子の原料として有用と期待されるα−フルオロアルキル−２−アダマンチルアクリレート類の製造方法として、α−フルオロアルキルアクリル酸誘導体を２−アダマンタノール類と反応させることによりα−フルオロアルキル−２−アダマンチルアクリレート類を得る方法が知られている（特許文献５参照）。しかし、この方法によりアダマンタン環の２位にアルキル基を有するα−フルオロアルキル−２−アダマンチルアクリレート類を得ようとする場合には、原料となる２−アルキル−２−アダマンタノール類の調製が煩雑であるという欠点がある。なお、前記特許文献１には、化学増幅型のレジスト用樹脂の重合単位を形成する単量体の１例として、２−（２−トリフルオロメチル−２−プロペノイルオキシ）−２−メチルアダマンタン［＝α−トリフルオロメチルアクリル酸２−メチル−２−アダマンチル］を示す化学構造式が記載されているが、この文献には、この化合物の物性値もこの化合物をいかにして製造するかについても何ら記載がないだけでなく、この単量体を用いたポリマーの合成例もない。 On the other hand, as a method for producing α-fluoroalkyl-2-adamantyl acrylates that are expected to be useful as raw materials for functional polymers, α-fluoroalkylacrylic acid derivatives are reacted with 2-adamantanols to react with α-fluoroalkyl. A method for obtaining alkyl-2-adamantyl acrylates is known (see Patent Document 5). However, when α-fluoroalkyl-2-adamantyl acrylates having an alkyl group at the 2-position of the adamantane ring are to be obtained by this method, preparation of 2-alkyl-2-adamantanols as raw materials is complicated. There is a drawback of being. Patent Document 1 discloses 2- (2-trifluoromethyl-2-propenoyloxy) -2-methyladamantane as an example of a monomer that forms a polymerization unit of a chemically amplified resist resin. The chemical structural formula showing [= α-trifluoromethyl acrylate 2-methyl-2-adamantyl] is described, but in this document, the physical properties of this compound are also related to how this compound is produced. In addition, there is no example of polymer synthesis using this monomer.
本発明の目的は、波長３００ｎｍ以下の光、特にＦ2エキシマレーザー（１５７ｎｍ）等の真空紫外光に対して透過性の高い高分子化合物の単量体等として有用な新規なフッ素原子含有重合性アダマンタン誘導体とその製造法を提供することにある。 The object of the present invention is to provide a novel fluorine atom-containing polymerizability that is useful as a monomer of a polymer compound that is highly transmissive to light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light such as F 2 excimer laser (157 nm). The object is to provide an adamantane derivative and a method for producing the same.
本発明の他の目的は、ポリマーに高い透明性と優れた酸脱離性及び耐エッチング性を付与できるとともに、フォトレジストとして要求される諸機能を付与するための他の単量体と容易に共重合できる新規なフッ素原子含有重合性アダマンタン誘導体とその製造法を提供することにある。 Another object of the present invention is to provide a polymer with high transparency, excellent acid detachability and etching resistance, and easily with other monomers for imparting various functions required as a photoresist. It is an object of the present invention to provide a novel fluorine atom-containing polymerizable adamantane derivative that can be copolymerized and a method for producing the same.
本発明のさらに他の目的は、波長３００ｎｍ以下の光、特に真空紫外光に対して高い透明性を有すると共に、酸脱離性及び耐エッチング性に優れた高分子化合物を提供することにある。 Still another object of the present invention is to provide a polymer compound having high transparency with respect to light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light, and excellent in acid detachment and etching resistance.
本発明の他の目的は、露光に用いる光に対して高い透明性を有するとともに、酸脱離性、耐エッチング性、基板密着性等の諸特性をバランスよく備えた高分子化合物を提供することにある。 Another object of the present invention is to provide a polymer compound having high transparency with respect to light used for exposure and having various properties such as acid detachment, etching resistance, and substrate adhesion in a balanced manner. It is in.
本発明者らは、上記目的を達成するため鋭意検討した結果、アダマンタノン化合物にメチル化剤を作用させ、得られた反応生成物に特定の不飽和アシルハライドを反応させると、フォトレジスト用高分子化合物の単量体として有用な新規なフッ素原子含有重合性アダマンタン誘導体が収率良く得られることを見出すとともに、この化合物がフォトレジストとして要求される諸機能を付与しうる他の単量体と容易に共重合できること、及びこの共重合により、波長３００ｎｍ以下の光、特に真空紫外光に対する透明性が高く、しかも酸脱離性、耐エッチング性及び基板密着性等の諸特性をバランスよく備えた高分子化合物が得られることを見出した。本発明はこれらの知見に基づいて完成されたものである。 As a result of diligent studies to achieve the above object, the present inventors have found that when a methylating agent is allowed to act on an adamantanone compound and a specific unsaturated acyl halide is reacted with the obtained reaction product, a high amount of photoresist is obtained. It is found that a novel fluorine atom-containing polymerizable adamantane derivative useful as a monomer of a molecular compound can be obtained with good yield, and this compound is capable of providing various functions required as a photoresist with other monomers. It can be easily copolymerized, and by this copolymerization, it is highly transparent to light with a wavelength of 300 nm or less, particularly vacuum ultraviolet light, and has various properties such as acid detachment, etching resistance, and substrate adhesion in a well-balanced manner. It has been found that a polymer compound can be obtained. The present invention has been completed based on these findings.
すなわち、本発明は、下記式（１）
で表される化合物に、下記式（２）
ＣＨ3−Ｍ （２）
［式中、Ｍは金属原子又は−ＭｇＸ1基（Ｘ1はハロゲン原子を示す）を示す］
で表されるメチル化剤を作用させ、得られた反応生成物に、下記式（３）
で表される不飽和アシルハライドを反応させて、下記式（４）
で表される化合物を得ることを特徴とするフッ素原子含有重合性アダマンタン誘導体の製造法を提供する。
That is, the present invention provides the following formula (1):
In the compound represented by the following formula (2)
CH 3 -M (2)
[Wherein, M represents a metal atom or a —MgX 1 group (X 1 represents a halogen atom)]
A methylating agent represented by the following formula (3) is reacted with the resulting reaction product:
Is reacted with an unsaturated acyl halide represented by the following formula (4):
A method for producing a fluorine atom-containing polymerizable adamantane derivative is provided.
本発明は、また、下記式（４）
で表されるフッ素原子含有重合性アダマンタン誘導体を提供する。
The present invention also provides the following formula (4):
The fluorine atom containing polymeric adamantane derivative represented by these is provided.
本発明は、さらに、上記のフッ素原子含有重合性アダマンタン誘導体に対応する繰り返し単位を含む高分子化合物を提供する。この高分子化合物は、さらに、基板密着性機能及び／又は親水性機能を有する繰り返し単位を含んでいてもよい。 The present invention further provides a polymer compound containing a repeating unit corresponding to the above-described fluorine atom-containing polymerizable adamantane derivative. The polymer compound may further contain a repeating unit having a substrate adhesion function and / or a hydrophilic function.
本発明によれば、波長３００ｎｍ以下の光、特にＦ2エキシマレーザー（１５７ｎｍ）等の真空紫外光に対して透過性の高い高分子化合物の単量体として有用な新規なフッ素原子含有重合性アダマンタン誘導体とその収率のよい製造法が提供される。また、ポリマーに高い透明性と優れた酸脱離性及び耐エッチング性を付与できるとともに、フォトレジストとして要求される諸機能を付与するための他の単量体と容易に共重合できる新規なフッ素原子含有重合性アダマンタン誘導体とその収率のよい製造法が提供される。 According to the present invention, a novel fluorine-atom-containing polymerizable adamantane that is useful as a monomer for a polymer compound having a high transmittance for light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light such as F 2 excimer laser (157 nm). Derivatives and production methods with good yields are provided. In addition, the polymer can provide high transparency, excellent acid detachment properties and etching resistance, and a novel fluorine that can be easily copolymerized with other monomers to provide various functions required as a photoresist. An atom-containing polymerizable adamantane derivative and a method for producing the same in good yield are provided.
本発明の高分子化合物は、波長３００ｎｍ以下の光、特に真空紫外光に対して高い透明性を有すると共に、酸脱離性に優れる。また、フォトレジストとして用いた場合に、酸脱離性、耐エッチング性、基板密着性、親水性等の諸特性をバランスよく発揮する。そのため、該高分子化合物を含むフォトレジスト用樹脂組成物を用いることにより、半導体の製造において微細なパターンを高い精度で形成することができる。 The polymer compound of the present invention has high transparency with respect to light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light, and is excellent in acid detachability. In addition, when used as a photoresist, it exhibits various properties such as acid detachment, etching resistance, substrate adhesion, and hydrophilicity in a well-balanced manner. Therefore, by using a photoresist resin composition containing the polymer compound, a fine pattern can be formed with high accuracy in the production of a semiconductor.
本発明の製造法では、式（１）で表される化合物に式（２）で表されるメチル化剤を作用させ、得られた反応生成物に、式（３）で表される不飽和アシルハライドを反応させる。式（１）中のアダマンタン環は置換基を有していてもよい。該置換基としては、例えば、ハロゲン原子、アルキル基、ハロアルキル基、アリール基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシ（ハロ）アルキル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいスルホ基、オキソ基、ニトロ基、シアノ基、保護基で保護されていてもよいアシル基などが挙げられる。 In the production method of the present invention, the methylation agent represented by the formula (2) is allowed to act on the compound represented by the formula (1), and the resulting reaction product is unsaturated by the formula (3). The acyl halide is reacted. The adamantane ring in formula (1) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, a hydroxy (halo) alkyl group which may be protected with a protecting group, and a protecting group. Protected with an amino group which may be protected with, a carboxyl group which may be protected with a protecting group, a sulfo group which may be protected with a protecting group, an oxo group, a nitro group, a cyano group, or a protecting group And a good acyl group.
前記ハロゲン原子としては、例えば、フッ素、塩素、臭素原子などが挙げられる。アルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ｔ−ブチル、ヘキシル基などのＣ1-10アルキル基（好ましくは、Ｃ1-5アルキル基）などが挙げられる。ハロアルキル基としては、例えば、クロロメチル基などのクロロアルキル基；トリフルオロメチル、２，２，２−トリフルオロエチル、ペンタフルオロエチル基などのフルオロアルキル基（例えばＣ1-10フルオロアルキル基、好ましくはＣ1-5フルオロアルキル基）などが挙げられる。アリール基としては、例えば、フェニル、ナフチル基などが挙げられる。アリール基の芳香環は、例えば、フッ素原子などのハロゲン原子、メチル基などのＣ1-4アルキル基、トリフルオロメチル基などＣ1-5ハロアルキル基、ヒドロキシル基、メトキシ基などのＣ1-4アルコキシ基、アミノ基、ジアルキルアミノ基、カルボキシル基、メトキシカルボニル基などのアルコキシカルボニル基、ニトロ基、シアノ基、アセチル基などのアシル基等の置換基を有していてもよい。ヒドロキシ（ハロ）アルキル基としては、例えば、ヒドロキシメチル、ヒドロキシエチル、ヒドロキシプロピル、１−ヒドロキシ−１−メチルエチル基、２，２，２−トリフルオロ−１−トリフルオロメチル−１−ヒドロキシエチル基など［好ましくは、ヒドロキシ−Ｃ1-4アルキル基、ヒドロキシ−Ｃ1-4ハロアルキル基等］が挙げられる。 Examples of the halogen atom include fluorine, chlorine, bromine atom and the like. Examples of the alkyl group include C 1-10 alkyl groups (preferably C 1-5 alkyl groups) such as methyl, ethyl, propyl, isopropyl, t-butyl, and hexyl groups. Examples of the haloalkyl group include chloroalkyl groups such as chloromethyl group; fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl groups (for example, C 1-10 fluoroalkyl groups, preferably Is a C 1-5 fluoroalkyl group). Examples of the aryl group include phenyl and naphthyl groups. The aromatic ring of the aryl group is, for example, a halogen atom such as a fluorine atom, a C 1-4 alkyl group such as a methyl group, a C 1-5 haloalkyl group such as a trifluoromethyl group, a C 1-4 such as a hydroxyl group or a methoxy group. It may have a substituent such as an alkoxy group such as an alkoxy group, an amino group, a dialkylamino group, a carboxyl group or a methoxycarbonyl group, an acyl group such as a nitro group, a cyano group or an acetyl group. Examples of the hydroxy (halo) alkyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl, 1-hydroxy-1-methylethyl group, 2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl group [Preferably, a hydroxy-C 1-4 alkyl group, a hydroxy-C 1-4 haloalkyl group, and the like].
前記ヒドロキシル基や、ヒドロキシ（ハロ）アルキル基におけるヒドロキシル基の保護基としては、有機合成の分野で慣用の保護基、例えば、アルキル基（例えば、メチル、ｔ−ブチル基などのＣ1-4アルキル基など）、アルケニル基（例えば、アリル基など）、シクロアルキル基（例えば、シクロヘキシル基など）、アリール基（例えば、２，４−ジニトロフェニル基など）、アラルキル基（例えば、ベンジル基など）；置換メチル基（例えば、メトキシメチル、メチルチオメチル、ベンジルオキシメチル、ｔ−ブトキシメチル、２−メトキシエトキシメチル基など）、置換エチル基（例えば、１−エトキシエチル基など）、テトラヒドロピラニル基、テトラヒドロフラニル基、１−ヒドロキシアルキル基（例えば、１−ヒドロキシエチル基など）等の、ヒドロキシル基とアセタール又はヘミアセタール基を形成可能な基；アシル基（例えば、ホルミル、アセチル、プロピオニル、ブチリル、イソブチリル、ピバロイル基などのＣ1-6脂肪族アシル基；アセトアセチル基；ベンゾイル基などの芳香族アシル基など）、アルコキシカルボニル基（例えば、メトキシカルボニル基などのＣ1-4アルコキシ−カルボニル基など）、アラルキルオキシカルボニル基、置換又は無置換カルバモイル基、置換シリル基（例えば、トリメチルシリル基など）など、及び、分子内にヒドロキシル基（ヒドロキシメチル基を含む）が２以上存在するときには、置換基を有していてもよい２価の炭化水素基（例えば、メチレン、エチリデン、イソプロピリデン、シクロペンチリデン、シクロヘキシリデン、ベンジリデン基など）などが例示できる。 Examples of the hydroxyl protecting group in the hydroxyl group or hydroxy (halo) alkyl group include protecting groups commonly used in the field of organic synthesis, for example, alkyl groups (for example, C 1-4 alkyl such as methyl and t-butyl groups). Group), alkenyl group (for example, allyl group), cycloalkyl group (for example, cyclohexyl group), aryl group (for example, 2,4-dinitrophenyl group), aralkyl group (for example, benzyl group); Substituted methyl group (eg, methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl group, etc.), tetrahydropyranyl group, tetrahydrofuran Nyl group, 1-hydroxyalkyl group (for example, 1-hydroxyethyl group) A group capable of forming an acetal or hemiacetal group with a hydroxyl group; an acyl group (for example, a C 1-6 aliphatic acyl group such as formyl, acetyl, propionyl, butyryl, isobutyryl, pivaloyl group); an acetoacetyl group An aromatic acyl group such as a benzoyl group), an alkoxycarbonyl group (eg, a C 1-4 alkoxy-carbonyl group such as a methoxycarbonyl group), an aralkyloxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted silyl group ( For example, when there are two or more hydroxyl groups (including hydroxymethyl groups) in the molecule, a divalent hydrocarbon group (for example, methylene, ethylidene) which may have a substituent. Isopropylidene, cyclopentylidene, cyclohexylidene, Njiriden group, etc.), and others.
前記アミノ基の保護基としては、例えば、前記ヒドロキシル基の保護基として例示したアルキル基、アラルキル基、アシル基、アルコキシカルボニル基などが挙げられる。また、カルボキシル基、スルホ基の保護基としては、例えば、アルコキシ基（例えば、メトキシ、エトキシ、ブトキシ基などのＣ1-6アルコキシ基など）、シクロアルキルオキシ基、アリールオキシ基、アラルキルオキシ基、トリアルキルシリルオキシ基、置換基を有していてもよいアミノ基、ヒドラジノ基、アルコキシカルボニルヒドラジノ基、アラルキルカルボニルヒドラジノ基などが挙げられる。 Examples of the protecting group for the amino group include an alkyl group, an aralkyl group, an acyl group, and an alkoxycarbonyl group exemplified as the protecting group for the hydroxyl group. Examples of the protecting group for carboxyl group and sulfo group include alkoxy groups (for example, C 1-6 alkoxy groups such as methoxy, ethoxy and butoxy groups), cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, Examples include a trialkylsilyloxy group, an amino group which may have a substituent, a hydrazino group, an alkoxycarbonylhydrazino group, an aralkylcarbonylhydrazino group, and the like.
前記アシル基としては、例えば、ホルミル、アセチル、プロピオニル、ブチリル、イソブチリル、ピバロイル基などのＣ1-6脂肪族アシル基；アセトアセチル基；ベンゾイル基などの芳香族アシル基などが挙げられる。アシル基の保護基としては有機合成分野で慣用の保護基を使用できる。アシル基の保護された形態としては、例えば、アセタール（ヘミアセタールを含む）などが挙げられる。 Examples of the acyl group include C 1-6 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, and pivaloyl groups; aromatic acyl groups such as acetoacetyl groups and benzoyl groups. As the protecting group for the acyl group, a protecting group conventionally used in the field of organic synthesis can be used. Examples of the protected form of the acyl group include acetal (including hemiacetal).
式（１）で表される化合物の代表例として、例えば、２−アダマンタノン、５，７−ジメチル−２−アダマンタノン、１，５−ジメチル−２−アダマンタノンなど挙げられる。 Typical examples of the compound represented by the formula (1) include 2-adamantanone, 5,7-dimethyl-2-adamantanone, 1,5-dimethyl-2-adamantanone and the like.
式（２）中、Ｍにおける金属原子としては、リチウムなどのアルカリ金属、セリウム、チタン、銅などの遷移金属原子などが挙げられる。該金属原子は配位子を有していてもよい。配位子としては、塩素原子などのハロゲン原子、イソプロポキシ基などのアルコキシ基、ジエチルアミノ基などのジアルキルアミノ基、シアノ基、アルキル基、リチウム原子などのアルカリ金属原子などが挙げられる。式（２）で表される化合物のうち、Ｍが−ＭｇＸ1基である化合物（有機マグネシウム化合物）は、一般にグリニヤール試薬と称される。グリニヤール試薬は通常の方法により調製できる。Ｘ1におけるハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 In formula (2), examples of the metal atom in M include alkali metals such as lithium, transition metal atoms such as cerium, titanium, and copper. The metal atom may have a ligand. Examples of the ligand include a halogen atom such as a chlorine atom, an alkoxy group such as an isopropoxy group, a dialkylamino group such as a diethylamino group, an alkali metal atom such as a cyano group, an alkyl group, and a lithium atom. Of the compounds represented by the formula (2), a compound (organomagnesium compound) in which M is a —MgX 1 group is generally referred to as a Grignard reagent. The Grignard reagent can be prepared by a usual method. Examples of the halogen atom for X 1 include a chlorine atom, a bromine atom, and an iodine atom.
式（２）で表されるメチル化剤の代表的な例として、メチルマグネシウムクロリド、メチルマグネシウムブロミド、メチルマグネシウムヨージド、メチルリチウムなどが挙げられる。有機マグネシウム化合物はハロゲン化銅と組み合わせて用いることもできる。 Typical examples of the methylating agent represented by the formula (2) include methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, methyllithium and the like. The organomagnesium compound can also be used in combination with a copper halide.
式（３）中、Ｒ1はフッ素原子又はフルオロアルキル基を示し、Ｘ2はハロゲン原子を示す。Ｒ1におけるフルオロアルキル基としては、例えば、炭素数１〜６程度（好ましくは１〜３程度）の直鎖状又は分岐鎖状のフルオロアルキル基などが挙げられる。このようなフルオロアルキル基の代表的な例として、トリフルオロメチル、ペンタフルオロエチル、２，２，２−トリフルオロエチル、２，２，２−トリフルオロ−１−（トリフルオロメチル）エチル、ヘプタフルオロプロピル、２，２，３，３，３−ペンタフルオロプロピル、２，２，３，３−テトラフルオロプロピル、ノナフルオロブチル、２，２，３，３，４，４，４−ヘプタフルオロブチル、２，２，３，３，４，４−ヘキサフルオロブチル、ウンデカフルオロペンチル、２，２，３，３，４，４，５，５，５−ノナフルオロペンチル、２，２，３，３，４，４，５，５−オクタフルオロペンチル、トリデカフルオロヘキシル、２，２，３，３，４，４，５，５，６，６，６−ウンデカフロオロヘキシル、２，２，３，３，４，４，５，５，６，６−デカフロオロヘキシル基などが挙げられる。Ｒ1としては、フッ素原子又は炭素数１〜３のフルオロアルキル基が好ましく、中でもトリフルオロメチル基が好ましい。Ｘ2におけるハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 In formula (3), R 1 represents a fluorine atom or a fluoroalkyl group, and X 2 represents a halogen atom. Examples of the fluoroalkyl group in R 1 include a linear or branched fluoroalkyl group having about 1 to 6 carbon atoms (preferably about 1 to 3 carbon atoms). Representative examples of such fluoroalkyl groups include trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl, hepta Fluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, nonafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl 2,2,3,3,4,4-hexafluorobutyl, undecafluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3, 3,4,4,5,5-octafluoropentyl, tridecafluorohexyl, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2 , 3, 3, 4, 4, , And the like 5,6,6- deca flow Oro hexyl group. R 1 is preferably a fluorine atom or a fluoroalkyl group having 1 to 3 carbon atoms, and more preferably a trifluoromethyl group. Examples of the halogen atom for X 2 include a chlorine atom, a bromine atom, and an iodine atom.
式（３）で表される不飽和アシルハライドの代表的な例として、例えば、２−フルオロアクリル酸クロリド、２−フルオロアクリル酸ブロミド等の２−フルオロアクリル酸ハライド；２−トリフルオロメチルアクリル酸クロリド、２−トリフルオロメチルアクリル酸ブロミド等の２−トリフルオロメチルアクリル酸ハライドなどが挙げられる。 Typical examples of the unsaturated acyl halide represented by the formula (3) include 2-fluoroacrylic acid halides such as 2-fluoroacrylic acid chloride and 2-fluoroacrylic acid bromide; 2-trifluoromethylacrylic acid Examples thereof include 2-trifluoromethylacrylic acid halides such as chloride and 2-trifluoromethylacrylic acid bromide.
式（１）で表される化合物と式（２）で表されるメチル化剤との反応（前段の反応）は、溶媒の存在下又は非存在下で行われる。溶媒としては、例えば、ジエチルエーテル、テトラヒドロフラン等のエーテル類、ヘキサン、トルエン等の炭化水素類、Ｎ，Ｎ−ジメチルホルムアミド等のアミド類、ジメチルスルホキシドなどが挙げられる。式（２）で表されるメチル化剤の使用量は、式（１）で表される化合物１モルに対して１〜１．５モル程度である。反応温度は、原料の種類によっても異なるが、通常−１００℃〜１５０℃程度の範囲から選択できる。式（２）の化合物として、Ｍが−ＭｇＸ1で表される基を示す化合物を用いる場合には、反応温度は、一般に０〜１５０℃、好ましくは２０〜１２０℃程度である。 The reaction (previous reaction) of the compound represented by the formula (1) and the methylating agent represented by the formula (2) is performed in the presence or absence of a solvent. Examples of the solvent include ethers such as diethyl ether and tetrahydrofuran, hydrocarbons such as hexane and toluene, amides such as N, N-dimethylformamide, and dimethyl sulfoxide. The usage-amount of the methylating agent represented by Formula (2) is about 1-1.5 mol with respect to 1 mol of compounds represented by Formula (1). Although reaction temperature changes also with the kind of raw material, it can be normally selected from the range of about -100 degreeC-150 degreeC. When a compound in which M represents a group represented by —MgX 1 is used as the compound of formula (2), the reaction temperature is generally 0 to 150 ° C., preferably about 20 to 120 ° C.
式（１）の化合物と式（２）のメチル化剤との反応で得られる反応混合物は、そのまま、式（３）で表される化合物との反応（後段の反応）に供することができるが、希釈や濃縮、溶媒交換等の処理を施した後に後段の反応に供してもよい。後段の反応において、式（３）で表される不飽和アシルハライドの使用量は、前段で使用した式（１）で表される化合物１モルに対して、通常１〜１．５モル程度である。後段の反応温度は、例えば０〜１５０℃程度、好ましくは２０〜１２０℃程度である。 The reaction mixture obtained by the reaction of the compound of the formula (1) and the methylating agent of the formula (2) can be used as it is for the reaction with the compound represented by the formula (3) (the latter reaction). Alternatively, after the treatment such as dilution, concentration, solvent exchange, etc., it may be subjected to the subsequent reaction. In the latter reaction, the amount of the unsaturated acyl halide represented by the formula (3) is usually about 1 to 1.5 mol with respect to 1 mol of the compound represented by the formula (1) used in the former stage. is there. The subsequent reaction temperature is, for example, about 0 to 150 ° C., preferably about 20 to 120 ° C.
上記反応により、対応する前記式（４）で表される新規なフッ素原子含有重合性アダマンタン誘導体が生成する。反応生成物は、抽出、水洗、濃縮、蒸留、晶析、再結晶、カラムクロマトグラフィーなどの手段により分離精製できる。 By the above reaction, a novel fluorine atom-containing polymerizable adamantane derivative represented by the corresponding formula (4) is generated. The reaction product can be separated and purified by means such as extraction, washing with water, concentration, distillation, crystallization, recrystallization, column chromatography and the like.
式（４）で表されるフッ素原子含有重合性アダマンタン誘導体の代表的な例として、例えば、２−（２−フルオロ−２−プロペノイルオキシ）−２−メチルアダマンタン、２−（２−フルオロ−２−プロペノイルオキシ）−２，５，７−トリメチルアダマンタン、２−（２−トリフルオロメチル−２−プロペノイルオキシ）−２−メチルアダマンタン、２−（２−トリフルオロメチル−２−プロペノイルオキシ）−２，５，７−トリメチルアダマンタンなどが挙げられる。 As typical examples of the fluorine atom-containing polymerizable adamantane derivative represented by the formula (4), for example, 2- (2-fluoro-2-propenoyloxy) -2-methyladamantane, 2- (2-fluoro- 2-propenoyloxy) -2,5,7-trimethyladamantane, 2- (2-trifluoromethyl-2-propenoyloxy) -2-methyladamantane, 2- (2-trifluoromethyl-2-propenoyl) And (oxy) -2,5,7-trimethyladamantane.
こうして得られるフッ素原子含有重合性アダマンタン誘導体は不飽和アシル基の不飽和部位において重合して高分子化合物を与える。この単量体は、不飽和アシル基の２位の位置（カルボニル基のα位）の炭素原子にフッ素原子又はフッ素原子含有基が結合しているため、波長３００ｎｍ以下の光、特に真空紫外光に対する高い透明性をポリマーに付与するとともに、分子内に脂環式炭素環であるアダマンタン環を有しているので、優れた耐エッチング性を付与できる。また、この単量体は、不飽和アシルオキシ基が結合している炭素原子の隣接位に少なくとも１つの水素原子が結合した炭素原子が存在するので、酸により脱離反応が進行して前記不飽和アシルオキシ基に相当するカルボン酸とオレフィン化合物とが生成しアルカリ可溶性となることから、酸脱離性付与機能を有している。さらに、この単量体は、フォトレジストとして要求される諸機能（例えば、基板密着性、親水性、透明性、耐エッチング性等）を付与するために用いられる各種単量体、例えば他のアクリル系単量体やビニルエーテル系単量体、環状不飽和単量体などと共重合しやすい。そのため、例えば真空紫外光等に対する透明性に優れ、しかも酸脱離性、基板密着性、親水性、耐エッチング性等の特性をバランスよく具備した高分子化合物を容易に調製することができる。 The fluorine atom-containing polymerizable adamantane derivative thus obtained polymerizes at the unsaturated site of the unsaturated acyl group to give a polymer compound. In this monomer, since a fluorine atom or a fluorine atom-containing group is bonded to the carbon atom at the 2-position of the unsaturated acyl group (α-position of the carbonyl group), light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light In addition to imparting high transparency to the polymer to the polymer and having an adamantane ring that is an alicyclic carbocyclic ring in the molecule, excellent etching resistance can be imparted. In addition, this monomer has a carbon atom to which at least one hydrogen atom is bonded adjacent to the carbon atom to which the unsaturated acyloxy group is bonded. Since a carboxylic acid corresponding to an acyloxy group and an olefin compound are produced and become alkali-soluble, it has an acid-eliminating function. Furthermore, this monomer is used for various functions required as a photoresist (for example, substrate adhesion, hydrophilicity, transparency, etching resistance, etc.), such as various monomers such as other acrylics. It is easy to copolymerize with monomers, vinyl ether monomers, cyclic unsaturated monomers and the like. Therefore, for example, it is possible to easily prepare a polymer compound that is excellent in transparency to, for example, vacuum ultraviolet light and has a good balance of properties such as acid detachability, substrate adhesion, hydrophilicity, and etching resistance.
本発明の高分子化合物は、上記本発明の式（４）で表されるフッ素原子含有重合性アダマンタン誘導体に対応する繰り返し単位（モノマー単位）を含んでいる。該繰り返し単位は１種であってもよく２種以上であってもよい。このような高分子化合物は、上記フッ素原子含有重合性アダマンタン誘導体を重合に付すことにより得ることができる。 The polymer compound of the present invention contains a repeating unit (monomer unit) corresponding to the fluorine atom-containing polymerizable adamantane derivative represented by the formula (4) of the present invention. The repeating unit may be one type or two or more types. Such a polymer compound can be obtained by subjecting the fluorine atom-containing polymerizable adamantane derivative to polymerization.
本発明の高分子化合物は、レジストとして要求される諸機能を充分にバランスよく具備するため、上記フッ素原子含有重合性アダマンタン誘導体に対応する繰り返し単位に加えて、他の繰り返し単位を有していてもよい。このような他の繰り返し単位は、該繰り返し単位に対応する重合性不飽和単量体（例えば、（メタ）アクリル酸エステル類、ビニルエーテル類等）を本発明の重合性アダマンタン誘導体と共重合させることにより形成できる。前記他の繰り返し単位としては、例えば、基板密着性及び／又は親水性機能を有する繰り返し単位、酸脱離性機能を高める繰り返し単位、耐エッチング性機能を高める繰り返し単位、透明性を高める繰り返し単位などが挙げられる。前記親水性機能には、レジスト溶媒やアルカリ現像液に対する溶解性を高める機能が含まれる。また、上記高分子化合物の調製に際しては、共重合を円滑に進行させたり、共重合体組成を均一にするために用いる単量体をコモノマーとして用いることもできる。 Since the polymer compound of the present invention has various functions required as a resist in a sufficiently balanced manner, it has other repeating units in addition to the repeating unit corresponding to the fluorine atom-containing polymerizable adamantane derivative. Also good. Such other repeating unit is obtained by copolymerizing a polymerizable unsaturated monomer (for example, (meth) acrylic acid ester, vinyl ether, etc.) corresponding to the repeating unit with the polymerizable adamantane derivative of the present invention. Can be formed. Examples of the other repeating unit include a repeating unit having a substrate adhesion and / or hydrophilic function, a repeating unit that increases an acid detachment function, a repeating unit that increases an etching resistance function, and a repeating unit that increases transparency. Is mentioned. The hydrophilic function includes a function of increasing the solubility in a resist solvent or an alkali developer. In the preparation of the polymer compound, a monomer used for smoothly progressing copolymerization or making the copolymer composition uniform can be used as a comonomer.
基板密着性及び／又は親水性機能を有する繰り返し単位は、極性基を有する重合性不飽和単量体をコモノマーとして用いることによりポリマーに導入できる。前記極性基として、例えば、保護基を有していてもよいヒドロキシル基、保護基を有していてもよいカルボキシル基、保護基を有していてもよいアミノ基、保護基を有していてもよいスルホ基、ラクトン環含有基などが挙げられる。前記保護基としては有機合成の分野で慣用のもの（例えば、前記例示の保護基）を使用できる。極性基を有する重合性不飽和単量体としてはレジストの分野で公知の化合物を使用できる。極性基を有する重合性不飽和単量体の代表的な例として、例えば、γ，γ−ジメチル−α−ビニルオキシ−γ−ブチロラクトン、１−ビニルオキシ−４−オキサトリシクロ［４．３．１．１3,8］ウンデカン−５−オンなどの分子内にラクトン環を含有する重合性単量体［（メタ）アクリル酸エステル類、ビニルエーテル類等］、２−トリフルオロアクリル酸 ４−ヒドロキシシクロヘキシルなどのヒドロキシル基が結合した脂環式炭素環を有する重合性単量体［（メタ）アクリル酸エステル類、ビニルエーテル類等］などが挙げられる。 The repeating unit having substrate adhesion and / or hydrophilic function can be introduced into the polymer by using a polymerizable unsaturated monomer having a polar group as a comonomer. Examples of the polar group include a hydroxyl group that may have a protective group, a carboxyl group that may have a protective group, an amino group that may have a protective group, and a protective group. Examples thereof include a sulfo group and a lactone ring-containing group. As the protecting group, those commonly used in the field of organic synthesis (for example, the protecting groups exemplified above) can be used. As the polymerizable unsaturated monomer having a polar group, a compound known in the resist field can be used. As typical examples of the polymerizable unsaturated monomer having a polar group, for example, γ, γ-dimethyl-α-vinyloxy-γ-butyrolactone, 1-vinyloxy-4-oxatricyclo [4.3.1. 1 3,8 ] polymerizable monomers containing a lactone ring in the molecule such as undecan-5-one [(meth) acrylic acid esters, vinyl ethers, etc.], 2-trifluoroacrylic acid 4-hydroxycyclohexyl, etc. And polymerizable monomers having an alicyclic carbocyclic ring to which a hydroxyl group is bonded [(meth) acrylic acid esters, vinyl ethers, etc.].
酸脱離性機能を高める繰り返し単位は、例えば、（１）エステルを構成する酸素原子の隣接位に、第３級炭素を有する炭化水素基や２−テトラヒドロフラニル基、２−テトラヒドロピラニル基などが結合した（メタ）アクリル酸エステル誘導体、（２）エステルを構成する酸素原子の隣接位に炭化水素基（脂環式炭化水素基、脂肪族炭化水素基、これらが結合した基など）を有しており、且つ該炭化水素基に−ＣＯＯＲe基（Ｒeは第３級炭化水素基、２−テトラヒドロフラニル基又は２−テトラヒドロピラニル基を示す）が直接又は連結基を介して結合している（メタ）アクリル酸エステル誘導体などをコモノマーとして用いることによりポリマーに導入できる。このような（メタ）アクリル酸エステル誘導体としてはレジストの分野で公知の化合物を使用できる。 Examples of the repeating unit that enhances the acid-eliminating function include (1) a hydrocarbon group having a tertiary carbon, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, etc., adjacent to the oxygen atom constituting the ester. (Meth) acrylic acid ester derivatives to which is bonded, and (2) hydrocarbon groups (alicyclic hydrocarbon groups, aliphatic hydrocarbon groups, groups to which these are bonded, etc.) adjacent to the oxygen atom constituting the ester. And a —COOR e group (R e represents a tertiary hydrocarbon group, a 2-tetrahydrofuranyl group or a 2-tetrahydropyranyl group) bonded to the hydrocarbon group directly or via a linking group. (Meth) acrylic acid ester derivatives and the like can be introduced into the polymer by using them as comonomers. As such a (meth) acrylic acid ester derivative, a known compound in the resist field can be used.
耐エッチング性機能を高める繰り返し単位は、例えば、分子内に脂環式構造を有する重合性単量体をコモノマーとして用いることによりポリマーに導入できる。また、真空紫外光等に対する透明性を高める繰り返し単位は、例えば、分子内にフッ素原子を有する重合性単量体をコモノマーとして用いることによりポリマーに導入することができる。 The repeating unit that enhances the etching resistance function can be introduced into the polymer, for example, by using a polymerizable monomer having an alicyclic structure in the molecule as a comonomer. Moreover, the repeating unit which improves the transparency with respect to vacuum ultraviolet light etc. can be introduce | transduced into a polymer, for example by using the polymerizable monomer which has a fluorine atom in a molecule | numerator as a comonomer.
本発明の高分子化合物において、式（４）で表されるフッ素原子含有重合性アダマンタン誘導体に対応する繰り返し単位の割合は特に限定されないが、ポリマーを構成する全モノマー単位に対して、一般には１〜８０モル％、好ましくは５〜７５モル％、さらに好ましくは１０〜７０モル％程度である。酸脱離性機能を有する繰り返し単位の総割合は、ポリマーを構成する全モノマー単位に対して、例えば５〜８０モル％、好ましくは１０〜６０モル％程度である。基板密着性機能及び／又は親水性機能を有する繰り返し単位の割合は、ポリマーを構成する全モノマー単位に対して、例えば２０〜９５モル％、好ましくは４０〜９０モル％程度である。 In the polymer compound of the present invention, the proportion of the repeating unit corresponding to the fluorine atom-containing polymerizable adamantane derivative represented by the formula (4) is not particularly limited, but is generally 1 for all monomer units constituting the polymer. It is about -80 mol%, preferably 5-75 mol%, more preferably about 10-70 mol%. The total proportion of repeating units having an acid eliminating function is, for example, about 5 to 80 mol%, preferably about 10 to 60 mol%, based on all monomer units constituting the polymer. The ratio of the repeating unit having a substrate adhesion function and / or a hydrophilic function is, for example, about 20 to 95 mol%, preferably about 40 to 90 mol%, based on all monomer units constituting the polymer.
上記フッ素原子含有重合性アダマンタン誘導体を（共）重合に付して高分子化合物を得るに際し、重合は、溶液重合、塊状重合、懸濁重合、塊状−懸濁重合、乳化重合など、アクリル系ポリマーを製造する際に用いる慣用の方法により行うことができるが、特に溶液重合が好適である。溶液重合の際、均質なポリマーを得るため滴下重合法を用いてもよい。 When a polymer compound is obtained by subjecting the above fluorine atom-containing polymerizable adamantane derivative to (co) polymerization, the polymerization may be an acrylic polymer such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization. The polymerization can be carried out by a conventional method used in the production of solution, and solution polymerization is particularly preferred. In solution polymerization, a drop polymerization method may be used to obtain a homogeneous polymer.
重合溶媒としては公知の溶媒を使用でき、例えば、エーテル（ジエチルエーテル、プロピレングリコールモノメチルエーテル等グリコールエーテル類などの鎖状エーテル、テトラヒドロフラン、ジオキサン等の環状エーテルなど）、エステル（酢酸メチル、酢酸エチル、酢酸ブチル、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等のグリコールエーテルエステル類など）、ケトン（アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなど）、アミド（Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミドなど）、スルホキシド（ジメチルスルホキシドなど）、アルコール（メタノール、エタノール、プロパノールなど）、炭化水素（ベンゼン、トルエン、キシレン等の芳香族炭化水素、ヘキサン等の脂肪族炭化水素、シクロヘキサン等の脂環式炭化水素など）、これらの混合溶媒などが挙げられる。また、重合開始剤として公知の重合開始剤を使用できる。重合温度は、例えば３０〜１５０℃程度の範囲で適宜選択できる。 As the polymerization solvent, a known solvent can be used. For example, ether (chain ether such as diethyl ether, propylene glycol monomethyl ether, etc., chain ether such as tetrahydrofuran, dioxane, etc.), ester (methyl acetate, ethyl acetate, Glycol ether esters such as butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amides (N, N-dimethylacetamide, N, N-dimethylformamide, etc.) ), Sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol, propanol, etc.), hydrocarbon (aromatic hydrocarbons such as benzene, toluene, xylene, etc.) Aliphatic hydrocarbons such as hexane, and alicyclic hydrocarbons such as cyclohexane), and mixtures of these solvents. Moreover, a well-known polymerization initiator can be used as a polymerization initiator. The polymerization temperature can be appropriately selected within a range of about 30 to 150 ° C., for example.
重合により得られたポリマーは、沈殿又は再沈殿により精製できる。沈殿又は再沈殿溶媒は有機溶媒及び水の何れであってもよく、また混合溶媒であってもよい。沈殿又は再沈殿溶媒として用いる有機溶媒として、例えば、炭化水素（ペンタン、ヘキサン、ヘプタン、オクタンなどの脂肪族炭化水素；シクロヘキサン、メチルシクロヘキサンなどの脂環式炭化水素；ベンゼン、トルエン、キシレンなどの芳香族炭化水素）、ハロゲン化炭化水素（塩化メチレン、クロロホルム、四塩化炭素などのハロゲン化脂肪族炭化水素；クロロベンゼン、ジクロロベンゼンなどのハロゲン化芳香族炭化水素など）、ニトロ化合物（ニトロメタン、ニトロエタンなど）、ニトリル（アセトニトリル、ベンゾニトリルなど）、エーテル（ジエチルエーテル、ジイソプロピルエーテル、ジメトキシエタンなどの鎖状エーテル；テトラヒドロフラン、ジオキサンなどの環状エーテル）、ケトン（アセトン、メチルエチルケトン、ジイソブチルケトンなど）、エステル（酢酸エチル、酢酸ブチルなど）、カーボネート（ジメチルカーボネート、ジエチルカーボネート、エチレンカーボネート、プロピレンカーボネートなど）、アルコール（メタノール、エタノール、プロパノール、イソプロピルアルコール、ブタノールなど）、カルボン酸（酢酸など）、これらの溶媒を含む混合溶媒等が挙げられる。 The polymer obtained by polymerization can be purified by precipitation or reprecipitation. The precipitation or reprecipitation solvent may be either an organic solvent or water, or a mixed solvent. Examples of the organic solvent used as the precipitation or reprecipitation solvent include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatics such as benzene, toluene, and xylene. Aromatic hydrocarbons), halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.) , Nitrile (acetonitrile, benzonitrile, etc.), ether (chain ether such as diethyl ether, diisopropyl ether, dimethoxyethane; cyclic ether such as tetrahydrofuran, dioxane), ketone (acetone, methyl ethyl ketone) Diisobutyl ketone, etc.), ester (ethyl acetate, butyl acetate, etc.), carbonate (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohol (methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acid (acetic acid, etc.) Etc.), and mixed solvents containing these solvents.
高分子化合物の重量平均分子量（Ｍｗ）は、例えば１０００〜５０００００程度、好ましくは３０００〜５００００程度であり、分子量分布（Ｍｗ／Ｍｎ）は、例えば１．５〜２．５程度である。なお、前記Ｍｎは数平均分子量を示し、Ｍｎ、Ｍｗともにポリスチレン換算の値である。 The weight average molecular weight (Mw) of the polymer compound is, for example, about 1000 to 500000, preferably about 3000 to 50000, and the molecular weight distribution (Mw / Mn) is, for example, about 1.5 to 2.5. In addition, said Mn shows a number average molecular weight, and both Mn and Mw are values of polystyrene conversion.
フォトレジスト用樹脂組成物は、上記の高分子化合物と光酸発生剤とを混合することにより調製できる。フォトレジスト用樹脂組成物は、レジスト性能を損なわない範囲で、前記高分子化合物以外のポリマーを含んでいてもよい。 The resin composition for photoresist can be prepared by mixing the above polymer compound and a photoacid generator. The resin composition for photoresists may contain a polymer other than the polymer compound as long as the resist performance is not impaired.
光酸発生剤としては、露光により効率よく酸を生成する慣用乃至公知の化合物、例えば、ジアゾニウム塩、ヨードニウム塩（例えば、ジフェニルヨードヘキサフルオロホスフェートなど）、スルホニウム塩（例えば、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムメタンスルホネートなど）、スルホン酸エステル［例えば、１−フェニル−１−（４−メチルフェニル）スルホニルオキシ−１−ベンゾイルメタン、１，２，３−トリスルホニルオキシメチルベンゼン、１，３−ジニトロ−２−（４−フェニルスルホニルオキシメチル）ベンゼン、１−フェニル−１−（４−メチルフェニルスルホニルオキシメチル）−１−ヒドロキシ−１−ベンゾイルメタンなど］、オキサチアゾール誘導体、ｓ−トリアジン誘導体、ジスルホン誘導体（ジフェニルジスルホンなど）、イミド化合物、オキシムスルホネート、ジアゾナフトキノン、ベンゾイントシレートなどを使用できる。これらの光酸発生剤は単独で又は２種以上組み合わせて使用できる。 Examples of the photoacid generator include conventional or known compounds that efficiently generate acid upon exposure, such as diazonium salts, iodonium salts (for example, diphenyliodohexafluorophosphate), sulfonium salts (for example, triphenylsulfonium hexafluoroantimony). Nates, triphenylsulfonium hexafluorophosphate, triphenylsulfonium methanesulfonate, etc.), sulfonate esters [eg 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane, 1,2,3-tri Sulfonyloxymethylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenylsulfonyloxymethyl) -1-hydroxy-1-benzo Rumetan etc.], oxathiazole derivatives, s- triazine derivatives, disulfone derivatives (diphenyl sulfone) imide compound, an oxime sulfonate, a diazonaphthoquinone, and benzoin tosylate. These photoacid generators can be used alone or in combination of two or more.
光酸発生剤の使用量は、光照射により生成する酸の強度やポリマーおける各繰り返し単位の比率などに応じて適宜選択でき、例えば、高分子化合物１００重量部に対して０．１〜３０重量部、好ましくは１〜２５重量部、さらに好ましくは２〜２０重量部程度の範囲から選択できる。 The amount of the photoacid generator used can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of each repeating unit in the polymer, and the like. Parts, preferably 1 to 25 parts by weight, more preferably about 2 to 20 parts by weight.
フォトレジスト用樹脂組成物は、必要に応じて、アルカリ可溶性樹脂（例えば、ノボラック樹脂、フェノール樹脂、イミド樹脂、カルボキシル基含有樹脂など）などのアルカリ可溶成分、着色剤（例えば、染料など）、有機溶媒（例えば、炭化水素類、ハロゲン化炭化水素類、アルコール類、エステル類、アミド類、ケトン類、エーテル類、セロソルブ類、カルビトール類、グリコールエーテルエステル類、これらの混合溶媒など）、塩基性化合物（ヒンダードアミン化合物など）、界面活性剤、溶解阻止剤、増感剤、安定剤などを含んでいてもよい。 The resin composition for a photoresist, if necessary, an alkali-soluble component such as an alkali-soluble resin (for example, a novolak resin, a phenol resin, an imide resin, a carboxyl group-containing resin), a colorant (for example, a dye), Organic solvents (for example, hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, mixed solvents thereof), bases May contain a functional compound (such as a hindered amine compound), a surfactant, a dissolution inhibitor, a sensitizer, and a stabilizer.
こうして得られるフォトレジスト用樹脂組成物を基材又は基板上に塗布し、乾燥した後、所定のマスクを介して、塗膜（レジスト膜）に光線を露光して（又は、さらに露光後ベークを行い）潜像パターンを形成し、次いで現像することにより、微細なパターンを高い精度で形成できる。 The photoresist resin composition thus obtained is applied onto a substrate or a substrate, dried, and then exposed to light on a coating film (resist film) through a predetermined mask (or further subjected to post-exposure baking. Perform) By forming a latent image pattern and then developing it, a fine pattern can be formed with high accuracy.
基材又は基板としては、シリコンウエハ、金属、プラスチック、ガラス、セラミックなどが挙げられる。フォトレジスト用樹脂組成物の塗布は、スピンコータ、ディップコータ、ローラコータなどの慣用の塗布手段を用いて行うことができる。塗膜の厚みは、例えば０．０１〜２０μｍ、好ましくは０．０５〜１μｍ程度である。 Examples of the base material or the substrate include a silicon wafer, metal, plastic, glass, and ceramic. The application of the photoresist resin composition can be performed using a conventional application means such as a spin coater, a dip coater, or a roller coater. The thickness of the coating film is, for example, about 0.01 to 20 μm, preferably about 0.05 to 1 μm.
露光には、種々の波長の光線、例えば、紫外線、Ｘ線などが利用でき、半導体レジスト用では、通常、ｇ線、ｉ線、エキシマレーザー（例えば、ＸｅＣｌ、ＫｒＦ、ＫｒＣｌ、ＡｒＦ、ＡｒＣｌ、Ｆ2、Ｋｒ2、ＫｒＡｒ、Ａｒ2等）などが使用される。露光エネルギーは、例えば０．１〜１０００ｍＪ／ｃｍ2程度である。 For exposure, light of various wavelengths, such as ultraviolet rays and X-rays, can be used. For semiconductor resists, g-line, i-line, and excimer lasers (for example, XeCl, KrF, KrCl, ArF, ArCl, F) are generally used. 2 , Kr 2 , KrAr, Ar 2 etc.). The exposure energy is, for example, about 0.1 to 1000 mJ / cm 2 .
光照射により光酸発生剤から酸が生成し、この酸により、例えば前記高分子化合物の酸脱離性基の脱離部位が速やかに脱離して、可溶化に寄与するカルボキシル基等が生成する。そのため、水又はアルカリ現像液による現像により、所定のパターンを精度よく形成できる。 By irradiation with light, an acid is generated from the photoacid generator. By this acid, for example, the elimination site of the acid-leaving group of the polymer compound is rapidly eliminated, and a carboxyl group that contributes to solubilization is generated. . Therefore, a predetermined pattern can be accurately formed by development with water or an alkali developer.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。なお、ポリマーの構造式中の括弧の右下の数字は該繰り返し単位（モノマー単位）に対応する単量体の仕込みモル％を示す。重量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）は、検出器として屈折率計（ＲＩ）を用い、溶離液としてテトラヒドロフラン（ＴＨＦ）を用いたＧＰＣ測定により、標準ポリスチレン換算で求めた。ＧＰＣは、昭和電工（株）製のカラムＫＦ−８０６Ｌ（商品名）を３本直列につないだものを使用し、カラム温度４０℃、ＲＩ温度４０℃、溶離液の流速０．８ｍｌ／分の条件で行った。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the number on the lower right of the parentheses in the structural formula of the polymer indicates the charged mol% of the monomer corresponding to the repeating unit (monomer unit). The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined in terms of standard polystyrene by GPC measurement using a refractometer (RI) as a detector and tetrahydrofuran (THF) as an eluent. GPC uses three columns KF-806L (trade name) manufactured by Showa Denko Co., Ltd. connected in series, column temperature 40 ° C., RI temperature 40 ° C., eluent flow rate 0.8 ml / min. Performed under conditions.
製造例１
温度計を備えた３つ口フラスコに、１，４−シクロヘキサンジオール１１．６ｇ（０．１ｍｏｌ）、トリエチルアミン１２．１ｇ（０．１２ｍｏｌ）、テトラヒドロフラン２００ｍｌを入れ、窒素気流下、氷冷しつつ撹拌した。この混合液中に、２−トリフルオロメチルアクリル酸クロリド１９．０ｇ（０．１２ｍｏｌ）を加え、室温で２時間撹拌した。反応終了後、反応混合液を減圧濃縮し、濃縮残渣に純水を３００ｍｌ加え、酢酸エチル３００ｍｌで２回抽出した。有機層を合わせ、５重量％炭酸水素ナトリウム水溶液３００ｍｌ、１０重量％食塩水３００ｍｌでそれぞれ洗浄し、硫酸マグネシウムで乾燥して減圧濃縮した。濃縮残渣をシリカゲルクロマトグラフィーで精製することにより、下記式（５）で表される２−トリフルオロメチルアクリル酸 ４−ヒドロキシシクロヘキシル［＝１−（２−トリフルオロメチル−２−プロペノイルオキシ）−４−ヒドロキシシクロヘキサン］１３．８ｇ（０．０５８ｍｏｌ）を得た。
Into a three-necked flask equipped with a thermometer, 11.6 g (0.1 mol) of 1,4-cyclohexanediol, 12.1 g (0.12 mol) of triethylamine and 200 ml of tetrahydrofuran were added and stirred while cooling with ice in a nitrogen stream. did. In this mixed liquid, 19.0 g (0.12 mol) of 2-trifluoromethylacrylic acid chloride was added and stirred at room temperature for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, 300 ml of pure water was added to the concentrated residue, and the mixture was extracted twice with 300 ml of ethyl acetate. The organic layers were combined, washed with 300 ml of 5 wt% aqueous sodium hydrogen carbonate solution and 300 ml of 10 wt% brine, dried over magnesium sulfate, and concentrated under reduced pressure. By purifying the concentrated residue by silica gel chromatography, 2-trifluoromethylacrylic acid 4-hydroxycyclohexyl represented by the following formula (5) [= 1- (2-trifluoromethyl-2-propenoyloxy)- 4-hydroxycyclohexane] 13.8 g (0.058 mol) was obtained.
なお、下記実施例において単量体として用いたγ，γ−ジメチル−α−ビニルオキシ−γ−ブチロラクトン［下記式（６）］は、α−ヒドロキシ−γ，γ−ジメチル−γ−ブチロラクトンと酢酸ビニルとから、特開２００３−７３３２１号公報記載の方法に準じて合成し、減圧蒸留にて精製したものを用いた。
また、１−ビニルオキシ−４−オキサトリシクロ［４．３．１．１3,8］ウンデカン−５−オン［下記式（７）］は、１−ヒドロキシ−４−オキサトリシクロ［４．３．１．１3,8］ウンデカン−５−オンと酢酸ビニルから、特開２００３−７３３２１号公報記載の方法に準じて合成し、アルミナカラムクロマトグラフィーにて精製したものを用いた。
実施例１
反応は全て窒素雰囲気下で行った。温度計を備えた３つ口フラスコに、１Ｍ−メチルマグネシウムブロミド−テトラヒドロフラン溶液１１０ｍｌを入れた。この溶液に、室温で撹拌しつつ、２−アダマンタノン１５ｇとテトラヒドロフラン２００ｍｌの混合液を１時間かけて滴下した。滴下終了後、反応液を加熱還流させつつ２時間撹拌した。反応液を室温まで放冷し、撹拌しつつ、２−トリフルオロメチルアクリル酸クロリド１８ｇを１時間かけて滴下した。滴下終了後、反応液を加熱還流させながら２時間撹拌した。反応液を室温まで放冷した後、１０重量％食塩水５００ｍｌを加え、酢酸エチル５００ｍｌで２回抽出を行った。有機層を合わせ、１０重量％炭酸水素ナトリウム水溶液５００ｍｌ、１０重量％食塩水５００ｍｌで洗浄後、硫酸マグネシウムで乾燥し、減圧濃縮した。濃縮残渣をシリカゲルカラムクロマトグラフィーで精製し、下記式（８）で表される２−（２−トリフルオロメチル−２−プロペノイルオキシ）−２−メチルアダマンタン［＝２−（２−（トリフルオロメチル）アクリロイルオキシ）−２−メチルアダマンタン］１６．７ｇを得た。
［２−（２−トリフルオロメチル−２−プロペノイルオキシ）−２−メチルアダマンタンのスペクトルデータ］
1Ｈ−ＮＭＲ（CDCl3） δ：1.58(m, 1H), 1.61(m, 1H), 1.69(s, 3H), 1.73(m, 2H), 1.76(m, 1H), 1.79(m, 1H), 1.83(m, 2H), 1.89(m, 1H), 1.91(m, 1H), 2.02(m, 1H), 2.04(m, 1H), 2.36(m, 2H), 6.34(m, 1H), 6.66(m , 1H)
All reactions were performed under a nitrogen atmosphere. A three-necked flask equipped with a thermometer was charged with 110 ml of 1M-methylmagnesium bromide-tetrahydrofuran solution. To this solution, a mixture of 15 g of 2-adamantanone and 200 ml of tetrahydrofuran was added dropwise over 1 hour while stirring at room temperature. After completion of the dropping, the reaction solution was stirred for 2 hours while being heated to reflux. The reaction solution was allowed to cool to room temperature, and 18 g of 2-trifluoromethylacrylic chloride was added dropwise over 1 hour while stirring. After completion of the dropwise addition, the reaction solution was stirred for 2 hours while being heated to reflux. The reaction solution was allowed to cool to room temperature, 500 ml of 10 wt% brine was added, and the mixture was extracted twice with 500 ml of ethyl acetate. The organic layers were combined, washed with 500 ml of 10 wt% aqueous sodium hydrogen carbonate solution and 500 ml of 10 wt% brine, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography, and 2- (2-trifluoromethyl-2-propenoyloxy) -2-methyladamantane represented by the following formula (8) [= 2- (2- (trifluoro 16.7 g of (methyl) acryloyloxy) -2-methyladamantane].
[Spectral data of 2- (2-trifluoromethyl-2-propenoyloxy) -2-methyladamantane]
1 H-NMR (CDCl 3 ) δ: 1.58 (m, 1H), 1.61 (m, 1H), 1.69 (s, 3H), 1.73 (m, 2H), 1.76 (m, 1H), 1.79 (m, 1H ), 1.83 (m, 2H), 1.89 (m, 1H), 1.91 (m, 1H), 2.02 (m, 1H), 2.04 (m, 1H), 2.36 (m, 2H), 6.34 (m, 1H) , 6.66 (m, 1H)
実施例２
下記構造の高分子化合物の合成
Synthesis of polymer compounds with the following structure
実施例３
下記構造の高分子化合物の合成
Synthesis of polymer compounds with the following structure
評価試験
（ポリマーの透過率）
上記実施例２及び３で得られた各ポリマーについて、該ポリマー１ｇをプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）１０ｇに溶解させ、０．２μｍのフィルターで濾過してポリマー溶液を調製した。これらのポリマー溶液をＭｇＦ2基板上にスピンコートにより塗布した後、ホットプレートを用いて１００℃で１２０秒間ベークし、膜厚１００ｎｍのポリマー膜を作製した。このポリマー膜の波長１５７ｎｍにおける光の透過率を真空紫外光度計［日本分光（株）製、ＶＵＶ−２００Ｓ］を使用して測定したところ、何れの場合も４５％以上であった。
Evaluation test (Polymer permeability)
For each polymer obtained in Examples 2 and 3, 1 g of the polymer was dissolved in 10 g of propylene glycol monomethyl ether acetate (PGMEA), and filtered through a 0.2 μm filter to prepare a polymer solution. These polymer solutions were applied onto an MgF 2 substrate by spin coating and then baked at 100 ° C. for 120 seconds using a hot plate to prepare a polymer film having a thickness of 100 nm. When the transmittance of light at a wavelength of 157 nm of this polymer film was measured using a vacuum ultraviolet photometer [manufactured by JASCO Corporation, VUV-200S], it was 45% or more in any case.
（レジストの調製及びパターンの形成）
上記実施例２及び３で得られた各ポリマーについて、該ポリマー１００重量部とトリフェニルスルホニウムヘキサフルオロアンチモネート１０重量部とを溶媒であるプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）と混合して、ポリマー濃度１７重量％のフォトレジスト用樹脂組成物を調製した。この組成物をシリコンウエハーにスピンコーティング法により塗布し、厚み３００ｎｍ（０．３μｍ）の感光層を形成した。ホットプレートにより温度１００℃で１５０秒間プリベークした後、波長２４７ｎｍのＫｒＦエキシマレーザーを用い、マスクを介して、照射量３０ｍＪ／ｃｍ2で露光した後、１００℃の温度で６０秒間ポストベークした。次いで、０．３Ｍのテトラメチルアンモニウムヒドロキシド水溶液により６０秒間現像し、純水でリンスしたところ、０．２０μｍのライン・アンド・スペースパターンが得られた。
(Preparation of resist and formation of pattern)
For each polymer obtained in Examples 2 and 3, 100 parts by weight of the polymer and 10 parts by weight of triphenylsulfonium hexafluoroantimonate were mixed with propylene glycol monomethyl ether acetate (PGMEA) as a solvent to obtain a polymer concentration. A resin composition for photoresist of 17% by weight was prepared. This composition was applied to a silicon wafer by a spin coating method to form a photosensitive layer having a thickness of 300 nm (0.3 μm). After pre-baking at a temperature of 100 ° C. for 150 seconds using a hot plate, exposure was performed through a mask at a dose of 30 mJ / cm 2 using a KrF excimer laser with a wavelength of 247 nm, and then post-baking was performed at a temperature of 100 ° C. for 60 seconds. Subsequently, the film was developed with a 0.3M tetramethylammonium hydroxide aqueous solution for 60 seconds and rinsed with pure water. As a result, a 0.20 μm line and space pattern was obtained.
Claims (4)
で表される化合物に、下記式（２）
ＣＨ3−Ｍ （２）
［式中、Ｍは金属原子又は−ＭｇＸ1基（Ｘ1はハロゲン原子を示す）を示す］
で表されるメチル化剤を作用させ、得られた反応生成物に、下記式（３）
で表される不飽和アシルハライドを反応させて、下記式（４）
で表される化合物を得ることを特徴とするフッ素原子含有重合性アダマンタン誘導体の製造法。 Following formula (1)
In the compound represented by the following formula (2)
CH 3 -M (2)
[Wherein, M represents a metal atom or a —MgX 1 group (X 1 represents a halogen atom)]
A methylating agent represented by the following formula (3) is reacted with the resulting reaction product:
Is reacted with an unsaturated acyl halide represented by the following formula (4):
A method for producing a fluorine atom-containing polymerizable adamantane derivative, characterized in that a compound represented by the formula:
で表されるフッ素原子含有重合性アダマンタン誘導体。 Following formula (4)
A fluorine atom-containing polymerizable adamantane derivative represented by:
The polymer compound according to claim 3, further comprising a repeating unit having a substrate adhesion function and / or a hydrophilic function.
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