WO2014112584A1 - Silicon compound containing hexafluoroisopropanol groups, method for producing same, and polymer compound obtained by polymerizing same - Google Patents
Silicon compound containing hexafluoroisopropanol groups, method for producing same, and polymer compound obtained by polymerizing same Download PDFInfo
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- WO2014112584A1 WO2014112584A1 PCT/JP2014/050787 JP2014050787W WO2014112584A1 WO 2014112584 A1 WO2014112584 A1 WO 2014112584A1 JP 2014050787 W JP2014050787 W JP 2014050787W WO 2014112584 A1 WO2014112584 A1 WO 2014112584A1
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- Prior art keywords
- carbon atoms
- group
- alkyl group
- hfip
- integer
- Prior art date
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- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 124
- 150000001875 compounds Chemical class 0.000 title claims abstract description 96
- 229920000642 polymer Polymers 0.000 title claims abstract description 92
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 230000000379 polymerizing effect Effects 0.000 title abstract description 5
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical group FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 title description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 219
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 105
- 125000003118 aryl group Chemical group 0.000 claims abstract description 74
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 69
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 64
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 35
- 125000006165 cyclic alkyl group Chemical group 0.000 claims abstract description 29
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- 150000001491 aromatic compounds Chemical class 0.000 claims description 42
- 229910052731 fluorine Inorganic materials 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- -1 polysiloxane Polymers 0.000 abstract description 104
- 229920001296 polysiloxane Polymers 0.000 abstract description 85
- 239000003513 alkali Substances 0.000 abstract description 18
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 43
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 5
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000005370 alkoxysilyl group Chemical group 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 4
- 0 *CC*C1CCCCC1 Chemical compound *CC*C1CCCCC1 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZIBLHOBPBGAKNV-SUESZSCISA-N acetonitrile;(1z,5z)-cycloocta-1,5-diene;rhodium;tetrafluoroborate Chemical compound [Rh].CC#N.CC#N.F[B-](F)(F)F.C\1C\C=C/CC\C=C/1 ZIBLHOBPBGAKNV-SUESZSCISA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 2
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 2
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- MXQOYLRVSVOCQT-UHFFFAOYSA-N palladium;tritert-butylphosphane Chemical compound [Pd].CC(C)(C)P(C(C)(C)C)C(C)(C)C.CC(C)(C)P(C(C)(C)C)C(C)(C)C MXQOYLRVSVOCQT-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- PDJQCHVMABBNQW-MIXQCLKLSA-L (1z,5z)-cycloocta-1,5-diene;rhodium;dichloride Chemical compound [Cl-].[Cl-].[Rh].[Rh].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 PDJQCHVMABBNQW-MIXQCLKLSA-L 0.000 description 1
- LYXHWHHENVLYCN-QMDOQEJBSA-N (1z,5z)-cycloocta-1,5-diene;rhodium;tetrafluoroborate Chemical compound [Rh].F[B-](F)(F)F.C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 LYXHWHHENVLYCN-QMDOQEJBSA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- GQCZPFJGIXHZMB-UHFFFAOYSA-N 1-tert-Butoxy-2-propanol Chemical compound CC(O)COC(C)(C)C GQCZPFJGIXHZMB-UHFFFAOYSA-N 0.000 description 1
- NTKBNCABAMQDIG-UHFFFAOYSA-N 3-butoxypropan-1-ol Chemical compound CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OCKPCBLVNKHBMX-UHFFFAOYSA-N CCCCc1ccccc1 Chemical compound CCCCc1ccccc1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 238000000023 Kugelrohr distillation Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- FERQZYSWBVOPNX-UHFFFAOYSA-N carbonyl dichloride;rhodium;triphenylphosphane Chemical compound [Rh].ClC(Cl)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FERQZYSWBVOPNX-UHFFFAOYSA-N 0.000 description 1
- LNAMMBFJMYMQTO-FNEBRGMMSA-N chloroform;(1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].ClC(Cl)Cl.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 LNAMMBFJMYMQTO-FNEBRGMMSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- HZLIIKNXMLEWPA-UHFFFAOYSA-N diethoxy(dipropyl)silane Chemical compound CCC[Si](CCC)(OCC)OCC HZLIIKNXMLEWPA-UHFFFAOYSA-N 0.000 description 1
- SUUYDMDGZWFQNU-UHFFFAOYSA-N diethoxy(phenyl)silane Chemical compound CCO[SiH](OCC)C1=CC=CC=C1 SUUYDMDGZWFQNU-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- UFWOWQYGXPYINE-UHFFFAOYSA-N diethyl(diphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](CC)(CC)OC1=CC=CC=C1 UFWOWQYGXPYINE-UHFFFAOYSA-N 0.000 description 1
- BZCJJERBERAQKQ-UHFFFAOYSA-N diethyl(dipropoxy)silane Chemical compound CCCO[Si](CC)(CC)OCCC BZCJJERBERAQKQ-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- JVUVKQDVTIIMOD-UHFFFAOYSA-N dimethoxy(dipropyl)silane Chemical compound CCC[Si](OC)(OC)CCC JVUVKQDVTIIMOD-UHFFFAOYSA-N 0.000 description 1
- MHDIVRGCDHHRIZ-UHFFFAOYSA-N dimethoxy(phenyl)silicon Chemical compound CO[Si](OC)C1=CC=CC=C1 MHDIVRGCDHHRIZ-UHFFFAOYSA-N 0.000 description 1
- PHXBVCXQKBHRQP-UHFFFAOYSA-N dimethoxy-bis(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](OC)(CCC(F)(F)F)OC PHXBVCXQKBHRQP-UHFFFAOYSA-N 0.000 description 1
- SWLVAJXQIOKFSJ-UHFFFAOYSA-N dimethyl(diphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](C)(C)OC1=CC=CC=C1 SWLVAJXQIOKFSJ-UHFFFAOYSA-N 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- YLDKQPMORVEBRU-UHFFFAOYSA-N diphenoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)OC1=CC=CC=C1 YLDKQPMORVEBRU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- PESLMYOAEOTLFJ-UHFFFAOYSA-N ethoxymethylsilane Chemical compound CCOC[SiH3] PESLMYOAEOTLFJ-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- KUCGHDUQOVVQED-UHFFFAOYSA-N ethyl(tripropoxy)silane Chemical compound CCCO[Si](CC)(OCCC)OCCC KUCGHDUQOVVQED-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- VJOOEHFQQLYDJI-UHFFFAOYSA-N methoxy(dimethyl)silane Chemical compound CO[SiH](C)C VJOOEHFQQLYDJI-UHFFFAOYSA-N 0.000 description 1
- WQEWAQFTKKOSJK-UHFFFAOYSA-N methoxymethylsilane Chemical compound COC[SiH3] WQEWAQFTKKOSJK-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FABOKLHQXVRECE-UHFFFAOYSA-N phenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=CC=C1 FABOKLHQXVRECE-UHFFFAOYSA-N 0.000 description 1
- VPLNCHFJAOKWBT-UHFFFAOYSA-N phenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C1=CC=CC=C1 VPLNCHFJAOKWBT-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- NDBYXKQCPYUOMI-UHFFFAOYSA-N platinum(4+) Chemical compound [Pt+4] NDBYXKQCPYUOMI-UHFFFAOYSA-N 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- SZEGZMUSBCXNLO-UHFFFAOYSA-N propan-2-yl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C(C)C SZEGZMUSBCXNLO-UHFFFAOYSA-N 0.000 description 1
- YHNFWGSEMSWPBF-UHFFFAOYSA-N propan-2-yl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C(C)C YHNFWGSEMSWPBF-UHFFFAOYSA-N 0.000 description 1
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- VRKHAMWCGMJAMI-UHFFFAOYSA-M tetrahexylazanium;iodide Chemical compound [I-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC VRKHAMWCGMJAMI-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- MQVCTPXBBSKLFS-UHFFFAOYSA-N tri(propan-2-yloxy)-propylsilane Chemical compound CCC[Si](OC(C)C)(OC(C)C)OC(C)C MQVCTPXBBSKLFS-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- RTMJRVHEBLESPE-UHFFFAOYSA-N trimethoxy(1,1,2,2,2-pentafluoroethyl)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)F RTMJRVHEBLESPE-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- ORVBHOQTQDOUIW-UHFFFAOYSA-N trimethoxy(trifluoromethyl)silane Chemical compound CO[Si](OC)(OC)C(F)(F)F ORVBHOQTQDOUIW-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Definitions
- the present invention relates to a silicon compound containing a hexafluoroisopropanol group, a method for producing the same, and a polymer compound obtained by polymerization thereof.
- the polymer compound of the present invention can be used in coating materials or sealants that require high heat resistance, particularly resist materials that require alkali solubility in the semiconductor field.
- a polymer compound containing a siloxane bond (hereinafter sometimes referred to as a polysiloxane polymer compound) is used in the semiconductor field as a coating material and a sealing material, taking advantage of its high heat resistance and transparency.
- an alkali developer an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass is usually used in photolithography.
- Patent Document 1 discloses an alkali-soluble polysiloxane resin characterized by containing an alkali-soluble group-containing siloxane unit and an alkali-insoluble group-containing siloxane unit having no acid-dissociable group.
- This polysiloxane resin is useful for a process using a light source of a shorter wavelength than KrF excimer laser (248 nm), for example, F 2 excimer laser (157 nm) or EUV (vacuum ultraviolet ray 13 nm), and has a high resolution and a sectional shape. It is a positive resist composition capable of forming a good resist pattern.
- an acidic group can be introduced into the polysiloxane polymer compound.
- examples of such an acidic group include a phenol group, a carboxyl group, and a fluorocarbinol group.
- a polysiloxane polymer compound containing a phenol group or a carboxyl group is inferior in heat resistance such as deterioration of transparency and coloring when used at a high temperature.
- an acidic group such as a fluorocarbinol group, for example, a hexafluoroisopropanol group ⁇ 2-hydroxy-1,1,1,3,3,3-fluoroisopropyl group [—C (CF 3 ) 2 OH], hereinafter referred to as HFIP group ⁇ , is disclosed in Patent Document 2 and Patent Document 3.
- a fluorocarbinol group for example, a hexafluoroisopropanol group ⁇ 2-hydroxy-1,1,1,3,3,3-fluoroisopropyl group [—C (CF 3 ) 2 OH], hereinafter referred to as HFIP group ⁇
- Patent Document 3 a fluorocarbinol group is bonded to a main chain composed only of siloxane via a linear, branched, cyclic or bridged divalent hydrocarbon group having 1 to 20 carbon atoms.
- Polymeric compounds are disclosed.
- the organosilicon compound described in Patent Document 2 includes an ethylene bond (—CH 2 —CH 2 —) between the HFIP group and the silicon atom Si, and the polymer compound described in Patent Document 3 includes an HFIP group and a siloxane main group. Since an aliphatic hydrocarbon group is interposed between the silicon atoms of the chain, there is a problem that heat resistance is impaired.
- Non-Patent Document 1 describes a method of directly reacting an aromatic halogen compound and metal silicon and a method using a Grignard reaction as means for obtaining an aromatic silicon compound by directly bonding a silyl group to an aromatic ring. .
- a Grignard reaction as means for obtaining an aromatic silicon compound by directly bonding a silyl group to an aromatic ring.
- Non-Patent Documents 1 and 2 and Patent Document 4 a compound containing an aromatic halogen compound and a hydrosilyl (Si—H) group (hereinafter sometimes referred to as a hydrosilyl compound) is used as a raw material compound, and a transition metal catalyst is used to produce an aromatic compound.
- a method for synthesizing a group III silicon compound is disclosed.
- Non-Patent Document 2 discloses the synthesis of an aromatic silicon compound containing a hydroxy (OH) group.
- Patent Document 4 discloses a method of performing this production method using an inexpensive aromatic chlorine compound as a raw material.
- Patent Document 5 methods for synthesizing HFIP group-containing aromatic halogen compounds are disclosed in Patent Document 5 and Non-Patent Documents 3 and 4.
- An object of the present invention is to provide a polysiloxane polymer compound that is soluble in an alkali developer and has excellent heat resistance, and a silicon compound as a precursor thereof.
- the present inventors have reacted a HFIP group-containing aromatic compound having a halogen group with a silicon compound having a hydrosilyl group and an alkoxysilyl group in the presence of a transition metal catalyst, whereby an HFIP group and an alkoxysilyl group are reacted. It was found that an HFIP group-containing silicon compound directly bonded to an aromatic ring can be synthesized.
- the HFIP group-containing polysiloxane polymer compound obtained by polymerizing this HFIP group-containing silicon compound was found to exhibit high heat resistance and alkali solubility, and the present invention was achieved.
- the present invention includes the following inventions 1 to 8.
- R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a straight chain having 2 to 10 carbon atoms.
- the silicon compound of the invention 1 represented by these.
- the HFIP group-containing polysiloxane polymer compound of the present invention is soluble in an alkali developer and has excellent heat resistance, and the precursor compound HFIP group-containing silicon compound is the HFIP group-containing polysiloxane polymer compound. It is useful for the production of
- the HFIP group-containing silicon compound of the present invention and the production method thereof, and then the HFIP group-containing polysiloxane polymer compound obtained by the polymerization reaction of the HFIP group-containing silicon compound of the present invention will be described in order.
- HFIP group-containing silicon compound [HFIP group-containing silicon compound represented by the general formula (1)]
- the HFIP group-containing silicon compound (1) represented by the general formula (1) of the present invention will be described.
- n is preferably 3. It is preferable that a is 1 or 2, and aa is 1.
- the number of HFIP group-containing aryl groups contained in the HFIP group-containing silicon compound (1) is preferably one, specifically, the HFIP group represented by the general formula (2) It is preferable that it is a containing silicon compound (2).
- R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a straight chain having 2 to 10 carbon atoms.
- [HFIP group-containing silicon compound represented by general formula (3)] Of the HFIP group-containing silicon compound (1), the HFIP group-containing silicon compound (3) represented by the following general formula (3) is more preferable.
- R 2 is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and a is an integer of 1 to 5)
- the HFIP group-containing silicon compound of the present invention the HFIP group-containing compound (3-1) represented by the following formula (3-1) and the HFIP group-containing compound represented by the formula (3-2):
- the compound (3-2) and the HFIP group-containing compound (3-3) represented by the formula (3-3) can be shown.
- Et is an ethyl group (—CH 2 CH 3 ), and the same applies hereinafter.
- the present invention relates to a method for producing a HFIP group-containing silicon compound.
- X is a chlorine atom, bromine atom, iodine atom, —OSO 2 (p—C 6 H 4 CH 3 ) group or —OSO 2 CF 3 group, and a is an integer of 1 to 5)
- HFIP group-containing aromatic compound (4) represented by the general formula (5) wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are May be substituted with a fluor
- the HFIP group-containing silicon compound (1) is represented by the HFIP group-containing aromatic compound (4) represented by the general formula (4) and the general formula (5).
- the resulting hydrosilyl group-containing silicon compound (5) is obtained by heating and reacting in an organic solvent under a transition metal catalyst.
- R 1 is a hydrogen atom, having 1 to 10 carbon atoms
- R 2 are each Independently, it is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, aa is 1 to 3, m is 0 to 2, and n is 1 to 3.
- HFIP group-containing aromatic compound (4) and a hydrosilyl group-containing silicon compound (5), a transition metal catalyst, an organic solvent, a base, and an additive are collected in a reaction vessel, mixed, heated, and reacted.
- HFIP group-containing silicon compound (1) can be obtained by distillation purification of the reaction product.
- reaction and raw material compound The reaction and raw material compound, reaction product, catalyst, organic solvent, reaction conditions, etc. will be described below.
- HFIP group-containing aromatic compound Specific examples of the HFIP group-containing aromatic compound (4) include an HFIP group-containing aromatic compound (4-1) represented by the following general formula (4-1) and a general formula (4-2). Examples thereof include HFIP group-containing aromatic compound (4-2) and HFIP group-containing aromatic compound (4-3) represented by formula (4-3).
- Patent Document 5 describes a method for synthesizing an HFIP group-containing aromatic compound (4-1).
- Non-Patent Document 3 describes an HFIP group-containing aromatic compound (4-2),
- Non-Patent Document 4 Describes a method for synthesizing an HFIP group-containing aromatic compound (4-3).
- X in the HFIP group-containing aromatic compound (4) is preferably a bromine atom.
- the HFIP group-containing silicon compound (1) is obtained from the HFIP group-containing aromatic compound (4) and the hydrosilyl group-containing silicon compound (5).
- the combination of the HFIP group-containing aromatic compound (4) and the hydrosilyl group-containing silicon compound (5) is not particularly limited. Below, the case where triethoxysilane is used as a hydrosilyl group containing silicon compound (5) is illustrated.
- the HFIP group-containing aromatic compounds (4-1) to (4-3) are used as the HFIP group-containing aromatic compound (4), they are represented by the following formulas (3-1) to (3-3). HFIP group-containing silicon compounds (3-1) to (3-3) can be obtained.
- hydrosilyl group-containing silicon compound (5) can be selected from monoalkoxysilane, dialkoxysilane, or trialkoxysilane.
- Examples of the monoalkoxysilane include methoxysilane, ethoxysilane, isopropoxysilane, ethoxydimethylsilane, methoxydimethylsilane, ethoxymethylsilane, and methoxymethylsilane.
- Examples of dialkoxysilane include diethoxysilane, dimethoxysilane, diethoxymethylsilane, dimethoxymethylsilane, diethoxyphenylsilane, and dimethoxyphenylsilane.
- Examples of trialkoxysilanes include triethoxysilane, trimethoxysilane, and triisopropoxysilane.
- triethoxysilane, trimethoxysilane, diethoxymethylsilane or dimethoxymethylsilane is preferable.
- HFIP group-containing polysiloxane polymer compounds having relatively high molecular weight can be obtained by polymerization reaction in HFIP group-containing silicon compounds using these compounds as raw materials. .
- transition metal catalyst used in this reaction is a group 8-10 element, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum, and an organometallic complex, metal salt or metal thereof.
- An oxide can be illustrated.
- the HFIP group-containing silicon compound (1) of the present invention can be obtained in a high yield, specifically, chloro (1,5-cyclooctadiene) rhodium (I) dimer, bis (acetonitrile) (1,5 -Cyclooctadiene) rhodium (I) tetrafluoroborate, bis (1,5-cyclooctadiene) rhodium (I) tetrafluoroborate, bis (triphenylphosphine) rhodium (I) carbonyl chloride, palladium (II) Dichloride, tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct, bis (tri-tert-butylphosphine) palladium (0), palladium (II) acetate or oxidation Platinum (IV) is a preferred example
- Organic solvent used for this reaction should just be a solvent in which a raw material compound melt
- N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, 1,4-dioxane, diethyl ether or diisopropyl ether can be exemplified.
- a base for capturing the by-product acid coexists in the reaction system.
- Specific examples include triethylamine, diethylamine, diisopropylethylamine, pyridine, potassium carbonate, potassium acetate, potassium phosphate, potassium hydroxide, sodium hydroxide, or lithium hydroxide.
- the amount of the base is not particularly limited as long as the by-product acid can be supplemented. It is preferable that they are 0.1 mol or more and 10 mol or less with respect to 1 mol of HFIP group containing aromatic compounds (4).
- the additive may be exemplified by tetrabutylammonium iodide, tetrapropylammonium iodide, tetraethylammonium iodide, tetramethylammonium iodide, tetrahexylammonium iodide, potassium iodide or sodium iodide. it can.
- reaction temperature The reaction temperature in this reaction is preferably in the range of room temperature (about 20 ° C. in the present invention) to 120 ° C.
- HFIP group-containing polysiloxane polymer compound [HFIP group-containing polysiloxane polymer compound containing a repeating unit represented by formula (6)]
- the HFIP group-containing polysiloxane polymer compound (6) of the present invention containing the repeating unit represented by the general formula (6) will be described.
- R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms,
- a branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group may be substituted with a fluorine atom, and each R 2 independently represents 1 to 4 is a linear or branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, aa is 1 to 3, m is 0 to 2, and n is an integer of 1 to 3, aa + m
- the HFIP group-containing polysiloxane polymer compound of the present invention includes any one of the following formulas (6-1) to (6-3).
- Formula (6-1) represents a case where n is 1 in Formula (6), Formula (6-2) is n, and Formula (6-3) is n.
- formula (6-1), formula (6-2) and formula (6-3) may be mixed with each other in the polysiloxane chain, that is, may coexist.
- R 1a is a monovalent organic group represented by the following formula (6-4)
- R 1b and R 1c are represented by the following formula ( A monovalent organic group represented by 6-4) or an organic group represented by R 1 .
- a line segment intersecting with the wavy line represents a coupling position.
- the molecular weight of the HFIP group-containing polysiloxane polymer compound of the present invention is preferably 1,000 or more and 200,000 or less, expressed as a weight average molecular weight in terms of polystyrene.
- the content of the HFIP group of the HFIP group-containing polysiloxane polymer compound (6) of the present invention is not particularly limited as long as alkali solubility can be imparted.
- the content of HFIP groups is one silicon atom.
- HFIP Group-Containing Polysiloxane Polymer Containing Repeating Unit Represented by General Formula (7) In the HFIP group-containing polysiloxane polymer compound (6), it is preferable that the number of HFIP group-containing aryl groups contained is one from the viewpoint of ease of production, and the HFIP group includes a repeating unit represented by the general formula (7). It is preferable that it is a containing silicon compound (7).
- HFIP Group-Containing Polysiloxane Polymer Containing Repeating Unit Represented by General Formula (7-1), General Formula (7-2), or General Formula (7-3) Specifically, an HFIP group-containing polysiloxane polymer compound (7-1) containing a repeating unit represented by the following general formula (7-1), and a repeating represented by the following general formula (7-2) HFIP group-containing polysiloxane polymer compound (7-2) containing a unit or HFIP group-containing polysiloxane polymer compound (7-3) containing a repeating unit represented by the following general formula (7-3) can do.
- Method for Producing HFIP Group-Containing Polysiloxane Polymer Compound HFIP group-containing polysiloxane polymer compound (6), (7), (7-1), (7-2) or (7-3) of the present invention is
- the HFIP group-containing silicon compounds (1) to (3) are obtained by hydrolysis and polycondensation reaction. This hydrolysis and polycondensation reaction can be performed by a general method in the hydrolysis and condensation reaction of alkoxysilane.
- the reaction vessel When the reaction is carried out with heating, in order to prevent unreacted raw materials, water, acid catalyst or reaction solvent in the reaction system from distilling out of the reaction system, the reaction vessel is closed or a condenser is used.
- the reaction system is preferably refluxed.
- the time required for the condensation reaction is usually from 3 hours to 24 hours depending on the type of acid catalyst, and the reaction temperature is from room temperature to 180 ° C.
- the removal of the water, alcohol, and acid catalyst may be performed by an extraction operation, or a solvent that does not adversely influence the reaction, such as toluene, may be added to the reaction system and removed azeotropically with a Dean-Stark tube.
- a solvent that does not adversely influence the reaction such as toluene
- the water used is expressed in a molar ratio with respect to the total number of moles of alkoxy groups of the raw material HFIP group-containing aromatic silicon compound. 0.5 mol or more and 5.0 mol or less. If the amount is less than 0.5 mol, hydrolysis does not proceed efficiently, and if it exceeds 5.0 mol, gelation tends to be difficult.
- acid catalyst used in the polycondensation reaction include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid.
- organic acids include acetic acid, Examples include fluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, formic acid, oxalic acid, maleic acid, camphorsulfonic acid, benzenesulfonic acid or tosylic acid.
- the reaction solvent used in the polycondensation reaction is preferably an alcohol solvent.
- the organic solvent used as an extraction solvent for the HFIP group-containing polysiloxane polymer compound (6) which is a condensate in the system after the polycondensation reaction, can dissolve and extract the HFIP group-containing polysiloxane polymer compound (6). If it is a thing, it will not specifically limit. Specifically, diethyl ether, diisopropyl ether, dibutyl ether, chloroform, dichloromethane, ethyl acetate, toluene and the like can be exemplified.
- Solid desiccant After the reaction system is extracted and washed with an organic solvent, a trace amount of water dissolved in the extract may be removed using a solid desiccant, if necessary.
- the solid desiccant used is not particularly limited. Specifically, magnesium sulfate, sodium sulfate, calcium sulfate, or synthetic zeolite can be exemplified.
- an HFIP group represented by the general formula (1) which is an alkoxysilane for the purpose of adjusting physical properties such as solubility in an alkali developer and heat resistance.
- other dialkoxysilanes, trialkoxysilanes or tetraalkoxysilanes may be copolymerized.
- dialkoxysilane examples include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiphenoxysilane, Dipropyldimethoxysilane, dipropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, bis (3,3,3-trifluoropropyl) dimethoxysilane or methyl (3,3,3-trifluoro) A propyl) dimethoxysilane can be illustrated.
- trialkoxysilane examples include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and propyltriethoxy.
- Silane isopropyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, propyltripropoxysilane, isopropyltripropoxysilane, phenyltripropoxysilane, methyltriisopropoxysilane, ethyltriisopropoxysilane, propyl Triisopropoxysilane, isopropyltriisopropoxysilane, phenyltriisopropoxysilane, trifluoromethyl Trimethoxysilane, pentafluoroethyl trimethoxysilane may be exemplified 3,3,3-trifluoropropyl trimethoxy silane or 3,3,3-trifluoropropyl triethoxysilane.
- tetraalkoxysilane examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane.
- dialkoxysilane, trialkoxysilane or tetraalkoxysilane may be used alone or in combination of two or more.
- At least one compound selected from the dialkoxysilane, trialkoxysilane, and tetraalkoxysilane is referred to as “other alkoxysilane”.
- the total amount is not particularly limited, but is preferably 0.1 to 10 moles per mole of the HFIP group-containing aromatic compound, 0.2 to More preferably, it is 5 moles. If it exceeds 10 mol, alkali solubility may not be imparted.
- Film containing HFIP group-containing polysiloxane polymer compound The HFIP group-containing polysiloxane polymer compound of the present invention can be dissolved in an organic solvent and applied as a coating solution to form a film. At that time, additives such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator, and a sensitizer can be added as necessary.
- the HFIP group-containing polysiloxane polymer compound of the present invention is dissolved in an organic solvent to form a coating solution, which is then applied to a substrate such as a glass substrate, a silicon substrate or a metal substrate, and then dried to form a film.
- organic solvent examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone. be able to.
- the concentration of the HFIP group-containing polysiloxane polymer compound when the HFIP group-containing polysiloxane of the present invention is dissolved in the organic solvent is not particularly limited.
- the range is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less.
- the method for applying the coating solution is not particularly limited, and a known method such as spin coating, bar coater or dip coating can be used.
- a coating film can be obtained by the above method without using an organic solvent.
- HFIP group-containing polysiloxane polymer compound of the present invention and the film obtained therefrom are soluble in an alkaline developer is an effect due to having HFIP groups in the chemical structure. Furthermore, since the silicon atom and the aromatic ring are directly bonded in the chemical structure, the HFIP group-containing polysiloxane polymer compound of the present invention and the film obtained therefrom are excellent in heat resistance.
- the coated film can be made into a cured film having better mechanical strength and solvent resistance by heating, addition of an acid or base, or condensation using a photopolymerization initiator.
- the curing conditions are not particularly limited.
- the temperature is preferably 100 ° C. or higher and 350 ° C. or lower, and the curing time is preferably 1 hour or longer and 24 hours or shorter.
- the HFIP group-containing polysiloxane polymer compound of the present invention is solid or liquid at room temperature, and in the case of liquid, a bulk cured product can be obtained by performing potting molding and the above-described curing method.
- the HFIP group-containing polysiloxane polymer compound of the present invention and a film obtained therefrom are soluble in an alkaline developer and excellent in heat resistance, and thus are used for a protective film for a semiconductor, a protective film for a display, and a resist material. be able to.
- the bulk cured product can be used for optical transparent encapsulants including those for LEDs, heat-resistant encapsulants for semiconductors, and the like.
- Nuclear Magnetic Resonance Measurement Using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model AL400) with a resonance frequency of 400 MHz, 1 H-NMR, 19 F-NMR, 13 C-NMR Alternatively, HFIP group-containing silicon compounds and HFIP group-containing polysiloxane polymer compounds were identified by measuring 29 Si-NMR.
- GPC Gel Permeation Chromatography
- thermogravimetric measurement (TGA, manufactured by Rigaku Corporation, type TG8120) was carried out to thermally decompose the temperature at which the weight loss was 5% of the initial weight. The temperature (T d5 ) was used.
- Example 1 Synthesis of HFIP group-containing silicon compound (3-1)
- the following reaction for synthesizing the HFIP group-containing silicon compound (3-1) was performed.
- Et is an ethyl group (—CH 2 CH 3 ), and the same applies hereinafter.
- reaction product was distilled and purified using a Kugelrohr distillation apparatus under the conditions of a temperature of 130 ° C. to 140 ° C. and a pressure of 180 Pa to obtain 1.82 g of HFIP group-containing silicon compound (3-1) as a colorless liquid. Obtained at 32%.
- HFIP group-containing aromatic compound (4-2), 6.46 g (20.0 mmol), tetrabutylammonium iodide, 7.38 g (40.0 mmol) and bis (acetonitrile) (1,5-cyclooctadiene) rhodium (I) tetrafluoroborate, 0.2280 g (0.60 mmol) were collected at room temperature.
- the resulting precipitate was contacted with celite and filtered, and the filtrate was washed 3 times with 100 mL of water, dried by adding Na 2 SO 4 , further filtered, and then the solvent was distilled off.
- the residue as a reaction product was purified by distillation using a Kugelrohr apparatus under conditions of a temperature of 140 ° C. to 190 ° C. and a pressure of 200 Pa to obtain 4.56 g of a HFIP group-containing silicon compound (3-2) as a colorless liquid. Obtained at 56%.
- Example 3 Synthesis of HFIP group-containing silicon compound (3-3)
- the following reaction for synthesizing the HFIP group-containing silicon compound (3-3) was performed.
- the reaction was carried out in the same manner as in Example 2 except that the HFIP group-containing aromatic compound (4-3) was used instead of the HFIP group-containing aromatic compound (4-2). After completion of the reaction, the reaction mixture was post-treated in the same manner as in Example 2 and purified by distillation using a Kugelrohr apparatus to obtain 2.84 g of a HFIP group-containing silicon compound (3-3) as a colorless liquid in a yield of 35%. It was.
- Example 4 [Synthesis of HFIP group-containing polysiloxane polymer compound using HFIP group-containing silicon compound (3-1) as a raw material compound] HFIP group-containing silicon compound (3-1), 11.45 g (20.0 mmol) was dissolved in methanol to a total amount of 57 g, and then 1.08 mL (60.0 mmol) of water and 0.25 mL of 4 mol / L hydrochloric acid were added. The mixture was further stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (8) containing a repeating unit represented by the following formula (8) as a colorless transparent highly viscous liquid.
- Example 5 [Synthesis of HFIP group-containing polysiloxane polymer compound (9) using HFIP group-containing silicon compound (3-2) as a raw material] HFIP group-containing silicon compound (3-2), 8.13 g (20.0 mmol) was dissolved in methanol to a total amount of 41 g, and then 1.08 mL (60.0 mmol) of water and 0.25 mL of 4 mol / L hydrochloric acid were added. The mixture was further stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (9) containing a repeating unit represented by the following formula (9) as a colorless transparent highly viscous liquid.
- Example 6 [Synthesis of HFIP group-containing polysiloxane polymer compound (10) using HFIP group-containing silicon compound (3-3) as a raw material] HFIP group-containing silicon compound (3-3), 1.63 g (4.0 mmol), dissolved in methanol to a total amount of 8.2 g, 0.216 mL (12.0 mmol) of water, 0.1 mol of 4 mol / L hydrochloric acid, 05 mL was added and stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (10) containing a repeating unit represented by the following formula (10) as a colorless transparent highly viscous liquid.
- Example 7 [Synthesis of HFIP group-containing polysiloxane polymer compound (11) containing HFIP group-containing silicon compound (3-1)] To a 50 mL flask, HFIP group-containing silicon compound (3-1), 4.58 g (8 mmol), phenyltrimethoxysilane, 6.35 g (32 mmol), water, 2.16 g (120 mmol), acetic acid, 0.12 g ( 2 mmol) was added and the mixture was stirred at 100 ° C. for 12 hours. After completion of the reaction, toluene is added and refluxed (bath temperature 150 ° C.) to distill off water, generated ethanol, methanol and acetic acid. Finally, toluene is distilled off to obtain the following formula (11). An HFIP group-containing polysiloxane polymer compound (11) containing the represented repeating unit was obtained as a white solid.
- Example 8 [Synthesis of HFIP group-containing polysiloxane polymer compound (12) containing HFIP group-containing silicon compound (3-2)]
- HFIP group-containing silicon compound (3-2) 5.59 g (13.75 mmol), phenyltrimethoxysilane, 2.23 g (11.25 mmol), water, 1.35 g (75 mmol), acetic acid, 0.075 g (1.25 mmol) was added, and the mixture was stirred at 100 ° C. for 12 hours.
- Table 1 shows the mass ratio of the raw material compounds in Examples 4 to 8.
- Comparative Example 1 Comparative polysiloxane polymer compound 1 was synthesized as a polysiloxane polymer compound not within the scope of the present invention. Dissolve 4.80 g (20.0 mmol) of phenyltriethoxysilane in methanol to make a total amount of 27 g, mix 1.08 mL of water and 0.25 mL of 4 mol / L hydrochloric acid, and perform the same procedure as in Example 4 for comparison. Polysiloxane polymer compound 1 was obtained. Mw obtained from GPC measurement of the obtained comparative polysiloxane polymer compound 1 was 2000, and the solubility in an alkali developer was confirmed to be “insoluble”.
- Comparative Example 3 HFIP group-containing silicon compound (13) represented by the following formula (13), 4.34 g (10.0 mmol) was dissolved in methanol to make the total amount 21.74 g. This, 0.54 g of water, and 0.125 mL of 4 mol / L hydrochloric acid were mixed, and a comparative polysiloxane polymer compound 3 was obtained in the same procedure as in Example 4.
- the HFIP group-containing silicon compound (13) and the comparative polysiloxane polymer compound 3 obtained therefrom have an ethylene bond (—CH 2 —CH 2 —) between the silicon atom and the aromatic ring. Therefore, it differs from the HFIP group-containing silicon compound and HFIP group-containing polysiloxane polymer compound of the present invention in which a silicon atom and an aromatic ring are directly bonded.
- Mw of the obtained comparative polysiloxane polymer compound 3 was 3400.
- the solubility in an alkaline developer was confirmed, it was “dissolved”.
- the 5% mass reduction temperature (T d5 ) was 320 ° C. This result was lower than the 5% mass reduction temperature (T d5 ) of the HFIP group-containing polysiloxane polymer compounds (8) to (12) of the present invention obtained in Examples 4 to 8.
- Table 1 shows the raw material compounds in Comparative Examples 1 to 3 above.
- Table 2 shows Mw obtained from GPC measurement in the above comparative polysiloxane polymer compounds 1 to 3, solubility in alkali developer, and 5% mass reduction temperature (T d5 ).
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Abstract
[Problem] To provide a polysiloxane polymer compound containing HFIP groups, wherein the polysiloxane polymer compound has solubility in an alkali developer and excellent heat resistance, and to provide an HFIP group-containing silicon compound as a precursor thereof. [Solution] A silicon compound represented by general formula (1) (in the formula, R1 is a hydrogen atom, a linear alkyl group having 1-10 carbon atoms, a branched alkyl group having 3-10 carbon atoms, a cyclic alkyl group having 3-10 carbon atoms, a linear alkenyl group having 2-10 carbon atoms, a branched alkenyl group having 3-10 carbon atoms, a cyclic alkenyl group having 3-10 carbon atoms, or an aryl group having 6-10 carbon atoms, and some or all of the hydrogen atoms in the alkyl groups, alkenyl groups, or aryl groups may be substituted by fluorine atoms; R2 are each independently a linear alkyl group having 1-4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms; a is an integer of 1-5, aa is an integer of 1-3, m is an integer of 0-2, n is an integer of 1-3, and aa + m + n = 4) and a polymer compound obtained by polymerizing the same.
Description
本発明は、ヘキサフルオロイソプロパノール基を含む珪素化合物およびその製造方法、並びにそれが重合してなる高分子化合物に関する。本発明の高分子化合物は、半導体分野において、高い耐熱性が要求されるコーティング材料または封止剤、特にアルカリ可溶性が要求されるレジスト材料等に使用できる。
The present invention relates to a silicon compound containing a hexafluoroisopropanol group, a method for producing the same, and a polymer compound obtained by polymerization thereof. The polymer compound of the present invention can be used in coating materials or sealants that require high heat resistance, particularly resist materials that require alkali solubility in the semiconductor field.
シロキサン結合を含む高分子化合物（以下、ポリシロキサン高分子化合物と呼ぶことがある）は、その高い耐熱性および透明性等を活かし、コーティング材料および封止材として、半導体分野で使用されている。
A polymer compound containing a siloxane bond (hereinafter sometimes referred to as a polysiloxane polymer compound) is used in the semiconductor field as a coating material and a sealing material, taking advantage of its high heat resistance and transparency.
近年、レジスト材料への耐熱性の要求が高まり、アルカリ現像液に可溶なポリシロキサン高分子化合物が開発されてきた。尚、アルカリ現像液には、通常、フォトリソグラフィーにおいて、濃度２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液が用いられる。
In recent years, the demand for heat resistance of resist materials has increased, and polysiloxane polymer compounds that are soluble in an alkaline developer have been developed. As the alkali developer, an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass is usually used in photolithography.
例えば、特許文献１には、アルカリ可溶性基含有シロキサン単位、および酸解離性基を有しないアルカリ不溶性基含有シロキサン単位を含むことを特徴とするアルカリ可溶なポリシロキサン樹脂が開示されている。本ポリシロキサン樹脂は、ＫｒＦエキシマレーザー（２４８ｎｍ）より短波長、例えば、Ｆ2エキシマレーザー（１５７ｎｍ）やＥＵＶ（真空紫外線１３ｎｍ）を光源とするプロセスに有用であり、高解像性で断面形状の良好なレジストパターンを形成可能なポジ型レジスト組成物とされている。
For example, Patent Document 1 discloses an alkali-soluble polysiloxane resin characterized by containing an alkali-soluble group-containing siloxane unit and an alkali-insoluble group-containing siloxane unit having no acid-dissociable group. This polysiloxane resin is useful for a process using a light source of a shorter wavelength than KrF excimer laser (248 nm), for example, F 2 excimer laser (157 nm) or EUV (vacuum ultraviolet ray 13 nm), and has a high resolution and a sectional shape. It is a positive resist composition capable of forming a good resist pattern.
アルカリ現像液に可溶とする手段としては、ポリシロキサン高分子化合物に酸性基を導入することが挙げられる。このような酸性基としては、フェノール基、カルボキシル基、フルオロカルビノール基等が挙げられる。しかし、フェノール基またはカルボキシル基を含むポリシロキサン高分子化合物は、高温下で使用すると透明性劣化および着色等、耐熱性に劣ることが知られている。
As a means for making it soluble in an alkali developer, an acidic group can be introduced into the polysiloxane polymer compound. Examples of such an acidic group include a phenol group, a carboxyl group, and a fluorocarbinol group. However, it is known that a polysiloxane polymer compound containing a phenol group or a carboxyl group is inferior in heat resistance such as deterioration of transparency and coloring when used at a high temperature.
ポリシロキサン高分子化合物に、酸性基であるフルオロカルビノール基、例えば、ヘキサフルオロイソプロパノール基｛２－ヒドロキシ－１，１，１，３，３，３－フルオロイソプロピル基［－Ｃ（ＣＦ3）2ＯＨ］、以下、ＨＦＩＰ基と呼ぶことがある｝を導入したポリシロキサン高分子化合物が特許文献２と特許文献３に開示されている。
To the polysiloxane polymer compound, an acidic group such as a fluorocarbinol group, for example, a hexafluoroisopropanol group {2-hydroxy-1,1,1,3,3,3-fluoroisopropyl group [—C (CF 3 ) 2 OH], hereinafter referred to as HFIP group}, is disclosed in Patent Document 2 and Patent Document 3.
特許文献２にはＨＦＩＰ基を有する有機珪素化合物（Ｒ3Ｓｉ－ＣＨ2－ＣＨ2－ＣＨ2－Ｃ（ＣＦ3）2ＯＨ）の製造方法が開示されている。当該有機珪素化合物はＣＨ2＝ＣＨ－ＣＨ2－Ｃ（ＣＦ3）2ＯＨで表わされるＨＦＩＰ基を有する化合物と、炭素数１～３のアルコキシ基を含むトリアルコキシシランをヒドロシリル化することによって得られる。
Patent Document 2 discloses a method for producing an organosilicon compound having an HFIP group (R 3 Si—CH 2 —CH 2 —CH 2 —C (CF 3 ) 2 OH). Obtained the organic silicon compound by a hydrosilylation trialkoxysilane containing CH 2 = CH-CH 2 -C (CF 3) 2 with a compound having an HFIP group represented by OH, alkoxy group having 1 to 3 carbon atoms It is done.
特許文献３には、シロキサンのみからなる主鎖に、炭素数１～２０の直鎖状、分岐状、環状もしくは有橋環状の２価の炭化水素基を介して、フルオロカルビノール基が結合した高分子化合物が開示されている。
In Patent Document 3, a fluorocarbinol group is bonded to a main chain composed only of siloxane via a linear, branched, cyclic or bridged divalent hydrocarbon group having 1 to 20 carbon atoms. Polymeric compounds are disclosed.
特許文献２に記載の有機珪素化合物は、ＨＦＩＰ基と珪素原子Ｓｉの間にエチレン結合（－ＣＨ2－ＣＨ2－）を含み、特許文献３に記載の高分子化合物は、ＨＦＩＰ基とシロキサン主鎖の珪素原子間に脂肪族炭化水素基を介していることから耐熱性が損なわれるという問題がある。
The organosilicon compound described in Patent Document 2 includes an ethylene bond (—CH 2 —CH 2 —) between the HFIP group and the silicon atom Si, and the polymer compound described in Patent Document 3 includes an HFIP group and a siloxane main group. Since an aliphatic hydrocarbon group is interposed between the silicon atoms of the chain, there is a problem that heat resistance is impaired.
上記耐熱性の問題を解決するためには、熱的安定性に優れたＨＦＩＰ基を有する芳香環を直接シロキサン主鎖中の珪素原子に導入することが有効であると考えられる。
In order to solve the above heat resistance problem, it is considered effective to introduce an aromatic ring having an HFIP group excellent in thermal stability directly into a silicon atom in the siloxane main chain.
非特許文献１には、シリル基を直接芳香環に結合させて芳香族珪素化合物を得る手段として、芳香族ハロゲン化合物と金属ケイ素を直接反応させる方法、およびグリニャール反応を用いる方法が記載されている。しかしこれらの方法では、ＨＦＩＰ基のような反応中に副反応を起こし易い置換基を含有した芳香族珪素化合物を得ることは困難であり、特定の化学構造の芳香族珪素化合物のみしか得ることができない。
Non-Patent Document 1 describes a method of directly reacting an aromatic halogen compound and metal silicon and a method using a Grignard reaction as means for obtaining an aromatic silicon compound by directly bonding a silyl group to an aromatic ring. . However, in these methods, it is difficult to obtain an aromatic silicon compound containing a substituent that easily undergoes a side reaction during a reaction such as an HFIP group, and only an aromatic silicon compound having a specific chemical structure can be obtained. Can not.
非特許文献１～２および特許文献４において、芳香族ハロゲン化合物とヒドロシリル（Ｓｉ－Ｈ）基を含む化合物（以下、ヒドロシリル化合物と呼ぶことがある）を原料化合物とし、遷移金属触媒を用いて芳香族珪素化合物を合成する方法が開示されている。
In Non-Patent Documents 1 and 2 and Patent Document 4, a compound containing an aromatic halogen compound and a hydrosilyl (Si—H) group (hereinafter sometimes referred to as a hydrosilyl compound) is used as a raw material compound, and a transition metal catalyst is used to produce an aromatic compound. A method for synthesizing a group III silicon compound is disclosed.
また、非特許文献２ではヒドロキシ（ＯＨ）基を含有した芳香族珪素化合物の合成について開示されている。また特許文献４では、本製造法を、安価な芳香族塩素化合物を原料として行う手法が開示されている。
Further, Non-Patent Document 2 discloses the synthesis of an aromatic silicon compound containing a hydroxy (OH) group. Patent Document 4 discloses a method of performing this production method using an inexpensive aromatic chlorine compound as a raw material.
また、ＨＦＩＰ基含有芳香族ハロゲン化合物の合成法が、特許文献５、および非特許文献３及び４に開示されている。
Further, methods for synthesizing HFIP group-containing aromatic halogen compounds are disclosed in Patent Document 5 and Non-Patent Documents 3 and 4.
本発明は、アルカリ現像液に可溶、且つ優れた耐熱性を有するポリシロキサン高分子化合物、およびその前駆体としての珪素化合物を提供することを目的とする。
An object of the present invention is to provide a polysiloxane polymer compound that is soluble in an alkali developer and has excellent heat resistance, and a silicon compound as a precursor thereof.
本発明者らは、鋭意検討した結果、ハロゲン基を有するＨＦＩＰ基含有芳香族化合物を、遷移金属触媒下、ヒドロシリル基およびアルコキシシリル基を有する珪素化合物と反応させることで、ＨＦＩＰ基およびアルコキシシリル基が芳香環に直接結合したＨＦＩＰ基含有珪素化合物の合成ができることを見出した。このＨＦＩＰ基含有珪素化合物を重合させて得られるＨＦＩＰ基含有ポリシロキサン高分子化合物は、高い耐熱性とアルカリ可溶性を示すことが判明し、本発明に至った。
As a result of intensive studies, the present inventors have reacted a HFIP group-containing aromatic compound having a halogen group with a silicon compound having a hydrosilyl group and an alkoxysilyl group in the presence of a transition metal catalyst, whereby an HFIP group and an alkoxysilyl group are reacted. It was found that an HFIP group-containing silicon compound directly bonded to an aromatic ring can be synthesized. The HFIP group-containing polysiloxane polymer compound obtained by polymerizing this HFIP group-containing silicon compound was found to exhibit high heat resistance and alkali solubility, and the present invention was achieved.
本発明は、以下の発明１～８を含む。
The present invention includes the following inventions 1 to 8.
［発明１］
一般式（１）
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３もしくは４の分岐状のアルキル基であり、ａは１～５、ａａは１～３、ｍは０～２およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
で表される珪素化合物。 [Invention 1]
General formula (1)
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are May be substituted with a fluorine atom, and each R 2 is independently a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, and aa is 1 to 3, m is 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4)
The silicon compound represented by these.
一般式（１）
で表される珪素化合物。 [Invention 1]
General formula (1)
The silicon compound represented by these.
［発明２］
一般式（２）
（式中、Ｒ1は、水素原子、または炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３もしくは４の分岐状のアルキル基であり、ａは１～５、ｍは０～２およびｎは１～３の整数であり、ｍ＋ｎ＝３である。）
で表される、発明１の珪素化合物。 [Invention 2]
General formula (2)
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a straight chain having 2 to 10 carbon atoms. A branched or alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or one of hydrogen atoms in the alkyl group, alkenyl group or aryl group. Part may be substituted with a fluorine atom, and each R 2 is independently a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and a is 1 to 5, m is an integer of 0 to 2 and n is an integer of 1 to 3, and m + n = 3.)
The silicon compound of the invention 1 represented by these.
一般式（２）
で表される、発明１の珪素化合物。 [Invention 2]
General formula (2)
The silicon compound of the invention 1 represented by these.
［発明３］
一般式（３）
（式中、Ｒ2は、炭素数１～４の直鎖状または炭素数３もしくは４の分岐状のアルキル基であり、ａは１～５の整数である。）
で表される発明１または発明２の珪素化合物。 [Invention 3]
General formula (3)
(Wherein R 2 is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and a is an integer of 1 to 5)
The silicon compound of the invention 1 or the invention 2 represented by these.
一般式（３）
で表される発明１または発明２の珪素化合物。 [Invention 3]
General formula (3)
The silicon compound of the invention 1 or the invention 2 represented by these.
［発明４］
一般式（４）
（式中、Ｘは塩素原子、臭素原子、ヨウ素原子、－ＯＳＯ2（ｐ－Ｃ6Ｈ4ＣＨ3）基または－ＯＳＯ2ＣＦ3基であり、ａは１～５の範囲の整数である。）
で表される芳香族化合物、および
一般式（５）
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３もしくは４の分岐状のアルキル基であり、ａは１～５、ａａは１～３、ｍは０～２およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
で表される珪素化合物を、遷移金属触媒の存在下で反応させて、
一般式（１）
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３もしくは４の分岐状のアルキル基であり、ａは１～５、ａａは１～３、ｍは０～２およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
で表される珪素化合物を得る、珪素化合物の製造方法。 [Invention 4]
General formula (4)
Wherein X is a chlorine atom, bromine atom, iodine atom, —OSO 2 (pC 6 H 4 CH 3 ) group or —OSO 2 CF 3 group, and a is an integer in the range of 1 to 5. .)
And an aromatic compound represented by the general formula (5)
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are May be substituted with a fluorine atom, and each R 2 is independently a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, and aa is 1 to 3, m is 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4)
Is reacted in the presence of a transition metal catalyst,
General formula (1)
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are May be substituted with a fluorine atom, and each R 2 is independently a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, and aa is 1 to 3, m is 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4)
The manufacturing method of the silicon compound which obtains the silicon compound represented by these.
一般式（４）
で表される芳香族化合物、および
一般式（５）
で表される珪素化合物を、遷移金属触媒の存在下で反応させて、
一般式（１）
で表される珪素化合物を得る、珪素化合物の製造方法。 [Invention 4]
General formula (4)
And an aromatic compound represented by the general formula (5)
Is reacted in the presence of a transition metal catalyst,
General formula (1)
The manufacturing method of the silicon compound which obtains the silicon compound represented by these.
［発明５］
一般式（６）
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、ａは１～５、ａａは１～３、ｍは０～２、およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
で表される繰り返し単位を含む、高分子化合物。 [Invention 5]
General formula (6)
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group may be substituted with a fluorine atom, a is 1 to 5, aa is 1 to 3, m is an integer of 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4.)
The high molecular compound containing the repeating unit represented by these.
一般式（６）
で表される繰り返し単位を含む、高分子化合物。 [Invention 5]
General formula (6)
The high molecular compound containing the repeating unit represented by these.
［発明６］
一般式（７）：
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、ａは１～５、ｍは０～２、およびｎは１～３の整数であり、ｍ＋ｎ＝３である。）
で表される繰り返し単位を含む、発明５の高分子化合物。 [Invention 6]
General formula (7):
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, a is 1 to 5, m is 0 to 2, and n is an integer of 1 to 3, and m + n = 3.
The high molecular compound of the invention 5 containing the repeating unit represented by these.
一般式（７）：
で表される繰り返し単位を含む、発明５の高分子化合物。 [Invention 6]
General formula (7):
The high molecular compound of the invention 5 containing the repeating unit represented by these.
［発明７］
一般式（１）
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３もしくは４の分岐状のアルキル基であり、ａは１～５、ａａは１～３、ｍは０～２およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
で表される珪素化合物を、加水分解重縮合することで
一般式（６）
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、ａは１～５、ａａは１～３、ｍは０～２、およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
で表される繰り返し単位を含む高分子化合物を得る、高分子化合物の製造方法。 [Invention 7]
General formula (1)
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are May be substituted with a fluorine atom, and each R 2 is independently a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, and aa is 1 to 3, m is 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4)
The silicon compound represented by general formula (6) is obtained by hydrolytic polycondensation.
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group may be substituted with a fluorine atom, a is 1 to 5, aa is 1 to 3, m is an integer of 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4.)
The manufacturing method of a high molecular compound which obtains the high molecular compound containing the repeating unit represented by these.
一般式（１）
で表される珪素化合物を、加水分解重縮合することで
一般式（６）
で表される繰り返し単位を含む高分子化合物を得る、高分子化合物の製造方法。 [Invention 7]
General formula (1)
The silicon compound represented by general formula (6) is obtained by hydrolytic polycondensation.
The manufacturing method of a high molecular compound which obtains the high molecular compound containing the repeating unit represented by these.
［発明８］
発明５または発明６の高分子化合物を含む、膜。 [Invention 8]
A membrane comprising the polymer compound of Invention 5 or Invention 6.
発明５または発明６の高分子化合物を含む、膜。 [Invention 8]
A membrane comprising the polymer compound of Invention 5 or Invention 6.
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物は、アルカリ現像液に可溶、且つ優れた耐熱性を有し、その前駆体化合物のＨＦＩＰ基含有珪素化合物は、該ＨＦＩＰ基含有ポリシロキサン高分子化合物の製造に有用である。
The HFIP group-containing polysiloxane polymer compound of the present invention is soluble in an alkali developer and has excellent heat resistance, and the precursor compound HFIP group-containing silicon compound is the HFIP group-containing polysiloxane polymer compound. It is useful for the production of
本発明のＨＦＩＰ基含有珪素化合物およびその製造方法、次いで本発明のＨＦＩＰ基含有珪素化合物の重合反応によって得られるＨＦＩＰ基含有ポリシロキサン高分子化合物について順を追って説明する。
The HFIP group-containing silicon compound of the present invention and the production method thereof, and then the HFIP group-containing polysiloxane polymer compound obtained by the polymerization reaction of the HFIP group-containing silicon compound of the present invention will be described in order.
The HFIP group-containing silicon compound of the present invention and the production method thereof, and then the HFIP group-containing polysiloxane polymer compound obtained by the polymerization reaction of the HFIP group-containing silicon compound of the present invention will be described in order.
１．ＨＦＩＰ基含有珪素化合物
［一般式（１）で表されるＨＦＩＰ基含有珪素化合物］
本発明の一般式（１）で表されるＨＦＩＰ基含有珪素化合物（１）について説明する。
1. HFIP group-containing silicon compound [HFIP group-containing silicon compound represented by the general formula (1)]
The HFIP group-containing silicon compound (1) represented by the general formula (1) of the present invention will be described.
［一般式（１）で表されるＨＦＩＰ基含有珪素化合物］
本発明の一般式（１）で表されるＨＦＩＰ基含有珪素化合物（１）について説明する。
The HFIP group-containing silicon compound (1) represented by the general formula (1) of the present invention will be described.
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３もしくは４の分岐状のアルキル基であり、ａは１～５、ａａは１～３、ｍは０～２およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
ＨＦＩＰ基およびアルコキシシリル基が芳香環に直接結合したＨＦＩＰ基含有珪素化合物（１）を重合させてなる、以下の一般式（６）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（６）は、高い耐熱性とアルカリ可溶性を示す。
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are May be substituted with a fluorine atom, and each R 2 is independently a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, and aa is 1 to 3, m is 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4)
HFIP group-containing polysiloxane polymer containing a repeating unit represented by the following general formula (6), which is obtained by polymerizing HFIP group-containing silicon compound (1) in which an HFIP group and an alkoxysilyl group are directly bonded to an aromatic ring (6) shows high heat resistance and alkali solubility.
ＨＦＩＰ基およびアルコキシシリル基が芳香環に直接結合したＨＦＩＰ基含有珪素化合物（１）を重合させてなる、以下の一般式（６）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（６）は、高い耐熱性とアルカリ可溶性を示す。
HFIP group-containing polysiloxane polymer containing a repeating unit represented by the following general formula (6), which is obtained by polymerizing HFIP group-containing silicon compound (1) in which an HFIP group and an alkoxysilyl group are directly bonded to an aromatic ring (6) shows high heat resistance and alkali solubility.
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、ａは１～５、ａａは１～３、ｍは０～２、およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
尚、ＨＦＩＰ基含有珪素化合物（１）およびＨＦＩＰ基含有ポリシロキサン高分子化合物（６）において、Ｒ1としては、具体的には、メチル基、エチル基、フェニル基を例示することができる。ｍは好ましくは０である。Ｒ2としては、具体的には、メチル基、エチル基、イソプロピル基等を例示することができ、好ましくはメチル基もしくはエチル基（－Ｃ2Ｈ5、以下、Ｅｔと表わすことがある）である。ｎは好ましくは３である。ａは１または２、ａａは１であることが好ましい。 (Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group may be substituted with a fluorine atom, a is 1 to 5, aa is 1 to 3, m is an integer of 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4.)
In the HFIP group-containing silicon compound (1) and HFIP group-containing polysiloxane polymer compound (6), specific examples of R 1 include a methyl group, an ethyl group, and a phenyl group. m is preferably 0. Specific examples of R 2 include a methyl group, an ethyl group, an isopropyl group, and the like, and preferably a methyl group or an ethyl group (—C 2 H 5 , hereinafter sometimes referred to as Et). is there. n is preferably 3. It is preferable that a is 1 or 2, and aa is 1.
尚、ＨＦＩＰ基含有珪素化合物（１）およびＨＦＩＰ基含有ポリシロキサン高分子化合物（６）において、Ｒ1としては、具体的には、メチル基、エチル基、フェニル基を例示することができる。ｍは好ましくは０である。Ｒ2としては、具体的には、メチル基、エチル基、イソプロピル基等を例示することができ、好ましくはメチル基もしくはエチル基（－Ｃ2Ｈ5、以下、Ｅｔと表わすことがある）である。ｎは好ましくは３である。ａは１または２、ａａは１であることが好ましい。 (Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group may be substituted with a fluorine atom, a is 1 to 5, aa is 1 to 3, m is an integer of 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4.)
In the HFIP group-containing silicon compound (1) and HFIP group-containing polysiloxane polymer compound (6), specific examples of R 1 include a methyl group, an ethyl group, and a phenyl group. m is preferably 0. Specific examples of R 2 include a methyl group, an ethyl group, an isopropyl group, and the like, and preferably a methyl group or an ethyl group (—C 2 H 5 , hereinafter sometimes referred to as Et). is there. n is preferably 3. It is preferable that a is 1 or 2, and aa is 1.
［一般式（２）で表されるＨＦＩＰ基含有珪素化合物］
製造容易性の観点から、ＨＦＩＰ基含有珪素化合物（１）に含まれるＨＦＩＰ基含有アリール基の数は１個であることが好ましく、具体的には、一般式（２）で表されるＨＦＩＰ基含有珪素化合物（２）であることが好ましい。
[HFIP group-containing silicon compound represented by general formula (2)]
From the viewpoint of ease of production, the number of HFIP group-containing aryl groups contained in the HFIP group-containing silicon compound (1) is preferably one, specifically, the HFIP group represented by the general formula (2) It is preferable that it is a containing silicon compound (2).
製造容易性の観点から、ＨＦＩＰ基含有珪素化合物（１）に含まれるＨＦＩＰ基含有アリール基の数は１個であることが好ましく、具体的には、一般式（２）で表されるＨＦＩＰ基含有珪素化合物（２）であることが好ましい。
From the viewpoint of ease of production, the number of HFIP group-containing aryl groups contained in the HFIP group-containing silicon compound (1) is preferably one, specifically, the HFIP group represented by the general formula (2) It is preferable that it is a containing silicon compound (2).
（式中、Ｒ1は、水素原子、または炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３もしくは４の分岐状のアルキル基であり、ａは１～５、ｍは０～２およびｎは１～３の整数であり、ｍ＋ｎ＝３である。）
ＨＦＩＰ基およびアルコキシシリル基が芳香環に直接結合したＨＦＩＰ基含有珪素化合物（２）を重合させてなる、以下の一般式（７）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（７）は、高い耐熱性とアルカリ可溶性を示す。
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, or a straight chain having 2 to 10 carbon atoms. A branched or alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or one of hydrogen atoms in the alkyl group, alkenyl group or aryl group. Part may be substituted with a fluorine atom, and each R 2 is independently a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and a is 1 to 5, m is an integer of 0 to 2 and n is an integer of 1 to 3, and m + n = 3.)
An HFIP group-containing polysiloxane polymer compound containing a repeating unit represented by the following general formula (7), which is obtained by polymerizing an HFIP group-containing silicon compound (2) in which an HFIP group and an alkoxysilyl group are directly bonded to an aromatic ring (7) shows high heat resistance and alkali solubility.
ＨＦＩＰ基およびアルコキシシリル基が芳香環に直接結合したＨＦＩＰ基含有珪素化合物（２）を重合させてなる、以下の一般式（７）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（７）は、高い耐熱性とアルカリ可溶性を示す。
An HFIP group-containing polysiloxane polymer compound containing a repeating unit represented by the following general formula (7), which is obtained by polymerizing an HFIP group-containing silicon compound (2) in which an HFIP group and an alkoxysilyl group are directly bonded to an aromatic ring (7) shows high heat resistance and alkali solubility.
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、ａは１～５、ｍは０～２、およびｎは１～３の整数であり、ｍ＋ｎ＝３である。）
［一般式（３）で表されるＨＦＩＰ基含有珪素化合物］
ＨＦＩＰ基含有珪素化合物（１）の中でも、さらに好ましくは、以下の一般式（３）で表される、ＨＦＩＰ基含有珪素化合物（３）である。
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, a is 1 to 5, m is 0 to 2, and n is an integer of 1 to 3, and m + n = 3.
[HFIP group-containing silicon compound represented by general formula (3)]
Of the HFIP group-containing silicon compound (1), the HFIP group-containing silicon compound (3) represented by the following general formula (3) is more preferable.
［一般式（３）で表されるＨＦＩＰ基含有珪素化合物］
ＨＦＩＰ基含有珪素化合物（１）の中でも、さらに好ましくは、以下の一般式（３）で表される、ＨＦＩＰ基含有珪素化合物（３）である。
[HFIP group-containing silicon compound represented by general formula (3)]
Of the HFIP group-containing silicon compound (1), the HFIP group-containing silicon compound (3) represented by the following general formula (3) is more preferable.
（式中、Ｒ2は、炭素数１～４の直鎖状または炭素数３、４の分岐状のアルキル基であり、ａは１～５の整数である。）
具体的には、本発明のＨＦＩＰ基含有珪素化合物として、以下の式（３－１）で表されるＨＦＩＰ基含有化合物（３－１）、式（３－２）で表されるＨＦＩＰ基含有化合物（３－２）、および式（３－３）で表されるＨＦＩＰ基含有化合物（３－３）を示すことができる。
(Wherein R 2 is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and a is an integer of 1 to 5)
Specifically, as the HFIP group-containing silicon compound of the present invention, the HFIP group-containing compound (3-1) represented by the following formula (3-1) and the HFIP group-containing compound represented by the formula (3-2): The compound (3-2) and the HFIP group-containing compound (3-3) represented by the formula (3-3) can be shown.
具体的には、本発明のＨＦＩＰ基含有珪素化合物として、以下の式（３－１）で表されるＨＦＩＰ基含有化合物（３－１）、式（３－２）で表されるＨＦＩＰ基含有化合物（３－２）、および式（３－３）で表されるＨＦＩＰ基含有化合物（３－３）を示すことができる。
Specifically, as the HFIP group-containing silicon compound of the present invention, the HFIP group-containing compound (3-1) represented by the following formula (3-1) and the HFIP group-containing compound represented by the formula (3-2): The compound (3-2) and the HFIP group-containing compound (3-3) represented by the formula (3-3) can be shown.
尚、Ｅｔはエチル基（－ＣＨ2ＣＨ3）であり、以下、同様である。
Et is an ethyl group (—CH 2 CH 3 ), and the same applies hereinafter.
Et is an ethyl group (—CH 2 CH 3 ), and the same applies hereinafter.
２．ＨＦＩＰ基含有珪素化合物の製造方法
本発明は、一般式（４）
（式中、Ｘは塩素原子、臭素原子、ヨウ素原子、－ＯＳＯ2（ｐ－Ｃ6Ｈ4ＣＨ3）基または－ＯＳＯ2ＣＦ3基であり、ａは１～５の整数である。）
で表されるＨＦＩＰ基含有芳香族化合物（４）、および
一般式（５）
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３、４の分岐状のアルキル基であり、ａａは１～３、ｍは０～２およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
で表されるヒドロシリル基含有珪素化合物（５）を、遷移金属触媒の存在下で反応させて、
一般式（１）
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３、４の分岐状のアルキル基であり、ａは１～５、ａａは１～３、ｍは０～２およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
で表されるＨＦＩＰ基含有珪素化合物（１）を得る製造方法である。 2. TECHNICAL FIELD The present invention relates to a method for producing a HFIP group-containing silicon compound.
(Wherein X is a chlorine atom, bromine atom, iodine atom, —OSO 2 (p—C 6 H 4 CH 3 ) group or —OSO 2 CF 3 group, and a is an integer of 1 to 5)
HFIP group-containing aromatic compound (4) represented by the general formula (5)
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are May be substituted with a fluorine atom, and each R 2 is independently a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, aa is 1 to 3, m is 0 to 2 and n are integers of 1 to 3, aa + m + n = 4)
A hydrosilyl group-containing silicon compound represented by the formula (5) is reacted in the presence of a transition metal catalyst,
General formula (1)
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are May be substituted with a fluorine atom, and each R 2 is independently a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, and aa is 1 to 3, m is 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4)
In which the HFIP group-containing silicon compound (1) is obtained.
本発明は、一般式（４）
で表されるＨＦＩＰ基含有芳香族化合物（４）、および
一般式（５）
で表されるヒドロシリル基含有珪素化合物（５）を、遷移金属触媒の存在下で反応させて、
一般式（１）
で表されるＨＦＩＰ基含有珪素化合物（１）を得る製造方法である。 2. TECHNICAL FIELD The present invention relates to a method for producing a HFIP group-containing silicon compound.
HFIP group-containing aromatic compound (4) represented by the general formula (5)
A hydrosilyl group-containing silicon compound represented by the formula (5) is reacted in the presence of a transition metal catalyst,
General formula (1)
In which the HFIP group-containing silicon compound (1) is obtained.
本方法において、以下の反応式に示すように、ＨＦＩＰ基含有珪素化合物（１）は、一般式（４）で表されるＨＦＩＰ基含有芳香族化合物（４）と、一般式（５）で表されるヒドロシリル基含有珪素化合物（５）を、有機溶剤中で遷移金属触媒下に加熱し、反応させることで得られる。
In this method, as shown in the following reaction formula, the HFIP group-containing silicon compound (1) is represented by the HFIP group-containing aromatic compound (4) represented by the general formula (4) and the general formula (5). The resulting hydrosilyl group-containing silicon compound (5) is obtained by heating and reacting in an organic solvent under a transition metal catalyst.
（式中、Ｘは塩素原子、臭素原子、ヨウ素原子、－ＯＳＯ2（ｐ－Ｃ6Ｈ4ＣＨ3）基または－ＯＳＯ2ＣＦ3基であり、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３、４の分岐状のアルキル基であり、ａは１～５、ａａは１～３、ｍは０～２およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
具体的には、反応容器内にＨＦＩＰ基含有芳香族化合物（４）およびヒドロシリル基含有珪素化合物（５）と、遷移金属触媒、有機溶剤、塩基、添加剤を採取、混合し、加熱して反応を行い、反応物を蒸留精製することでＨＦＩＰ基含有珪素化合物（１）を得ることができる。 (Wherein X is a chlorine atom, bromine atom, iodine atom, —OSO 2 (p—C 6 H 4 CH 3 ) group or —OSO 2 CF 3 group, R 1 is a hydrogen atom, having 1 to 10 carbon atoms) A linear alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a 3 to 10 carbon atom. an aryl group having a cyclic alkenyl group or a C 6-10, alkyl group, all or part of the hydrogen atoms in the alkenyl group or aryl group may be substituted with a fluorine atom, R 2 are each Independently, it is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, aa is 1 to 3, m is 0 to 2, and n is 1 to 3. (Aa + m + n = 4)
Specifically, an HFIP group-containing aromatic compound (4) and a hydrosilyl group-containing silicon compound (5), a transition metal catalyst, an organic solvent, a base, and an additive are collected in a reaction vessel, mixed, heated, and reacted. And HFIP group-containing silicon compound (1) can be obtained by distillation purification of the reaction product.
具体的には、反応容器内にＨＦＩＰ基含有芳香族化合物（４）およびヒドロシリル基含有珪素化合物（５）と、遷移金属触媒、有機溶剤、塩基、添加剤を採取、混合し、加熱して反応を行い、反応物を蒸留精製することでＨＦＩＰ基含有珪素化合物（１）を得ることができる。 (Wherein X is a chlorine atom, bromine atom, iodine atom, —OSO 2 (p—C 6 H 4 CH 3 ) group or —OSO 2 CF 3 group, R 1 is a hydrogen atom, having 1 to 10 carbon atoms) A linear alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a 3 to 10 carbon atom. an aryl group having a cyclic alkenyl group or a C 6-10, alkyl group, all or part of the hydrogen atoms in the alkenyl group or aryl group may be substituted with a fluorine atom, R 2 are each Independently, it is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, aa is 1 to 3, m is 0 to 2, and n is 1 to 3. (Aa + m + n = 4)
Specifically, an HFIP group-containing aromatic compound (4) and a hydrosilyl group-containing silicon compound (5), a transition metal catalyst, an organic solvent, a base, and an additive are collected in a reaction vessel, mixed, heated, and reacted. And HFIP group-containing silicon compound (1) can be obtained by distillation purification of the reaction product.
反応および原料化合物、反応生成物、触媒、有機溶剤および反応条件等について、以下に説明する。
The reaction and raw material compound, reaction product, catalyst, organic solvent, reaction conditions, etc. will be described below.
［ＨＦＩＰ基含有芳香族化合物］
ＨＦＩＰ基含有芳香族化合物（４）の具体例としては、下記の一般式（４－１）で表されるＨＦＩＰ基含有芳香族化合物（４－１）、一般式（４－２）で表されるＨＦＩＰ基含有芳香族化合物（４－２）、一般式（４－３）で表されるＨＦＩＰ基含有芳香族化合物（４－３）を例示することができる。
[HFIP group-containing aromatic compound]
Specific examples of the HFIP group-containing aromatic compound (4) include an HFIP group-containing aromatic compound (4-1) represented by the following general formula (4-1) and a general formula (4-2). Examples thereof include HFIP group-containing aromatic compound (4-2) and HFIP group-containing aromatic compound (4-3) represented by formula (4-3).
ＨＦＩＰ基含有芳香族化合物（４）の具体例としては、下記の一般式（４－１）で表されるＨＦＩＰ基含有芳香族化合物（４－１）、一般式（４－２）で表されるＨＦＩＰ基含有芳香族化合物（４－２）、一般式（４－３）で表されるＨＦＩＰ基含有芳香族化合物（４－３）を例示することができる。
Specific examples of the HFIP group-containing aromatic compound (4) include an HFIP group-containing aromatic compound (4-1) represented by the following general formula (4-1) and a general formula (4-2). Examples thereof include HFIP group-containing aromatic compound (4-2) and HFIP group-containing aromatic compound (4-3) represented by formula (4-3).
（式中、Ｘは塩素原子、臭素原子、ヨウ素原子、－ＯＳＯ2（ｐ－Ｃ6Ｈ4ＣＨ3）基または－ＯＳＯ2ＣＦ3基である。）
ＨＦＩＰ基含有芳香族化合物（４－１）～（４－３）の各式中のＸが臭素原子（Ｂｒ）である場合については、以下の先行文献に合成方法がそれぞれ記載されている。具体的には、特許文献５にＨＦＩＰ基含有芳香族化合物（４－１）の合成方法が記載されており、非特許文献３にＨＦＩＰ基含有芳香族化合物（４－２）、非特許文献４にＨＦＩＰ基含有芳香族化合物（４－３）の合成方法が記載されている。 (Wherein X is a chlorine atom, bromine atom, iodine atom, —OSO 2 (p—C 6 H 4 CH 3 ) group or —OSO 2 CF 3 group)
In the case where X in each formula of the HFIP group-containing aromatic compounds (4-1) to (4-3) is a bromine atom (Br), the synthesis methods are described in the following prior documents. Specifically, Patent Document 5 describes a method for synthesizing an HFIP group-containing aromatic compound (4-1). Non-Patent Document 3 describes an HFIP group-containing aromatic compound (4-2), Non-Patent Document 4 Describes a method for synthesizing an HFIP group-containing aromatic compound (4-3).
ＨＦＩＰ基含有芳香族化合物（４－１）～（４－３）の各式中のＸが臭素原子（Ｂｒ）である場合については、以下の先行文献に合成方法がそれぞれ記載されている。具体的には、特許文献５にＨＦＩＰ基含有芳香族化合物（４－１）の合成方法が記載されており、非特許文献３にＨＦＩＰ基含有芳香族化合物（４－２）、非特許文献４にＨＦＩＰ基含有芳香族化合物（４－３）の合成方法が記載されている。 (Wherein X is a chlorine atom, bromine atom, iodine atom, —OSO 2 (p—C 6 H 4 CH 3 ) group or —OSO 2 CF 3 group)
In the case where X in each formula of the HFIP group-containing aromatic compounds (4-1) to (4-3) is a bromine atom (Br), the synthesis methods are described in the following prior documents. Specifically, Patent Document 5 describes a method for synthesizing an HFIP group-containing aromatic compound (4-1). Non-Patent Document 3 describes an HFIP group-containing aromatic compound (4-2), Non-Patent Document 4 Describes a method for synthesizing an HFIP group-containing aromatic compound (4-3).
合成のし易さから、ＨＦＩＰ基含有芳香族化合物（４）中のＸは臭素原子であることが好ましい。
From the viewpoint of ease of synthesis, X in the HFIP group-containing aromatic compound (4) is preferably a bromine atom.
前記反応式に示すように、ＨＦＩＰ基含有珪素化合物（１）は、ＨＦＩＰ基含有芳香族化合物（４）とヒドロシリル基含有珪素化合物（５）から得られる。ＨＦＩＰ基含有芳香族化合物（４）とヒドロシリル基含有珪素化合物（５）の組み合わせは特に限定されない。以下に、ヒドロシリル基含有珪素化合物（５）としてトリエトキシシランを用いる場合を例示する。このとき、ＨＦＩＰ基含有芳香族化合物（４）としてＨＦＩＰ基含有芳香族化合物（４－１）～（４－３）を用いると、下記式（３－１）～（３－３）で表されるＨＦＩＰ基含有珪素化合物（３－１）～（３－３）をそれぞれ得ることができる。
As shown in the reaction formula, the HFIP group-containing silicon compound (1) is obtained from the HFIP group-containing aromatic compound (4) and the hydrosilyl group-containing silicon compound (5). The combination of the HFIP group-containing aromatic compound (4) and the hydrosilyl group-containing silicon compound (5) is not particularly limited. Below, the case where triethoxysilane is used as a hydrosilyl group containing silicon compound (5) is illustrated. At this time, when the HFIP group-containing aromatic compounds (4-1) to (4-3) are used as the HFIP group-containing aromatic compound (4), they are represented by the following formulas (3-1) to (3-3). HFIP group-containing silicon compounds (3-1) to (3-3) can be obtained.
［ヒドロシリル基含有珪素化合物］
ヒドロシリル基含有珪素化合物（５）は、モノアルコキシシラン、ジアルコキシシランまたはトリアルコキシシランから選ぶことができる。 [Hydrosilyl group-containing silicon compound]
The hydrosilyl group-containing silicon compound (5) can be selected from monoalkoxysilane, dialkoxysilane, or trialkoxysilane.
ヒドロシリル基含有珪素化合物（５）は、モノアルコキシシラン、ジアルコキシシランまたはトリアルコキシシランから選ぶことができる。 [Hydrosilyl group-containing silicon compound]
The hydrosilyl group-containing silicon compound (5) can be selected from monoalkoxysilane, dialkoxysilane, or trialkoxysilane.
モノアルコキシシランとしては、例えば、メトキシシラン、エトキシシラン、イソプロポキシシラン、エトキシジメチルシラン、メトキシジメチルシラン、エトキシメチルシランまたはメトキシメチルシランを例示することができる。ジアルコキシシランとしては、例えば、ジエトキシシラン、ジメトキシシラン、ジエトキシメチルシラン、ジメトキシメチルシラン、ジエトキシフェニルシランまたはジメトキシフェニルシランを例示することができる。トリアルコキシシランとしては、例えば、トリエトキシシラン、トリメトキシシラン、トリイソプロポキシシランを例示することができる。
Examples of the monoalkoxysilane include methoxysilane, ethoxysilane, isopropoxysilane, ethoxydimethylsilane, methoxydimethylsilane, ethoxymethylsilane, and methoxymethylsilane. Examples of dialkoxysilane include diethoxysilane, dimethoxysilane, diethoxymethylsilane, dimethoxymethylsilane, diethoxyphenylsilane, and dimethoxyphenylsilane. Examples of trialkoxysilanes include triethoxysilane, trimethoxysilane, and triisopropoxysilane.
中でも、トリエトキシシラン、トリメトキシシラン、ジエトキシメチルシランまたはジメトキシメチルシランが好ましい。これらの化合物は入手が容易であり、また、これらの化合物を原料とするＨＦＩＰ基含有珪素化合物においては、重合反応によって、比較的高分子量体のＨＦＩＰ基含有ポリシロキサン高分子化合物を得ることができる。
Of these, triethoxysilane, trimethoxysilane, diethoxymethylsilane or dimethoxymethylsilane is preferable. These compounds are easily available, and HFIP group-containing polysiloxane polymer compounds having relatively high molecular weight can be obtained by polymerization reaction in HFIP group-containing silicon compounds using these compounds as raw materials. .
［遷移金属触媒］
本反応に用いる遷移金属触媒は、第８族～第１０族元素の単体、例えば、鉄、コバルト、ニッケル、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウムまたは白金、およびその有機金属錯体、金属塩または金属酸化物を例示することができる。 [Transition metal catalyst]
The transition metal catalyst used in this reaction is a group 8-10 element, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum, and an organometallic complex, metal salt or metal thereof. An oxide can be illustrated.
本反応に用いる遷移金属触媒は、第８族～第１０族元素の単体、例えば、鉄、コバルト、ニッケル、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウムまたは白金、およびその有機金属錯体、金属塩または金属酸化物を例示することができる。 [Transition metal catalyst]
The transition metal catalyst used in this reaction is a group 8-10 element, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum, and an organometallic complex, metal salt or metal thereof. An oxide can be illustrated.
本発明のＨＦＩＰ基含有珪素化合物（１）が高収率で得られることから、具体的には、クロロ（１，５－シクロオクタジエン）ロジウム（Ｉ）ダイマー、ビス（アセトニトリル）（１，５－シクロオクタジエン）ロジウム（Ｉ）テトラフルオロボラート、ビス（１，５－シクロオクタジエン）ロジウム（Ｉ）テトラフルオロボラート、ビス（トリフェニルホスフィン）ロジウム（Ｉ）カルボニルクロリド、パラジウム（ＩＩ）ジクロリド、テトラキス（トリフェニルホスフィン）パラジウム（０）、トリス（ジベンジリデンアセトン）ジパラジウム（０）－クロロホルム付加体、ビス（トリ－ｔｅｒｔ－ブチルホスフィン）パラジウム（０）、酢酸パラジウム（ＩＩ）または酸化白金（ＩＶ）が好ましい例として挙げられる。遷移金属触媒の使用量は、特に限定されるものではない。ＨＦＩＰ基含有芳香族化合物（４）１モルに対して、０．００１モル以上、０．１モル以下が好ましい。
Since the HFIP group-containing silicon compound (1) of the present invention can be obtained in a high yield, specifically, chloro (1,5-cyclooctadiene) rhodium (I) dimer, bis (acetonitrile) (1,5 -Cyclooctadiene) rhodium (I) tetrafluoroborate, bis (1,5-cyclooctadiene) rhodium (I) tetrafluoroborate, bis (triphenylphosphine) rhodium (I) carbonyl chloride, palladium (II) Dichloride, tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct, bis (tri-tert-butylphosphine) palladium (0), palladium (II) acetate or oxidation Platinum (IV) is a preferred example. The amount of the transition metal catalyst used is not particularly limited. 0.001 mol or more and 0.1 mol or less are preferable with respect to 1 mol of HFIP group containing aromatic compounds (4).
［有機溶剤］
本反応に用いる有機溶剤は、原料化合物が溶解する溶媒であればよい。具体的には、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド、アセトニトリル、テトラヒドロフラン、１，４－ジオキサン、ジエチルエーテルまたはジイソプロピルエーテルを例示することができる。 [Organic solvent]
The organic solvent used for this reaction should just be a solvent in which a raw material compound melt | dissolves. Specifically, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, 1,4-dioxane, diethyl ether or diisopropyl ether can be exemplified.
本反応に用いる有機溶剤は、原料化合物が溶解する溶媒であればよい。具体的には、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド、アセトニトリル、テトラヒドロフラン、１，４－ジオキサン、ジエチルエーテルまたはジイソプロピルエーテルを例示することができる。 [Organic solvent]
The organic solvent used for this reaction should just be a solvent in which a raw material compound melt | dissolves. Specifically, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, 1,4-dioxane, diethyl ether or diisopropyl ether can be exemplified.
［塩基］
反応を円滑に進行させるには、副生する酸を捕捉するための塩基を反応系に共存させることが好ましい。具体的には、トリエチルアミン、ジエチルアミン、ジイソプロピルエチルアミン、ピリジン、炭酸カリウム、酢酸カリウム、リン酸カリウム、水酸化カリウム、水酸化ナトリウムまたは水酸化リチウムを例示することができる。塩基の量は、副生する酸を補足できれば特に限定されるものではない。ＨＦＩＰ基含有芳香族化合物（４）１モルに対して、０．１モル以上、１０モル以下であることが好ましい。 [base]
In order to make the reaction proceed smoothly, it is preferable that a base for capturing the by-product acid coexists in the reaction system. Specific examples include triethylamine, diethylamine, diisopropylethylamine, pyridine, potassium carbonate, potassium acetate, potassium phosphate, potassium hydroxide, sodium hydroxide, or lithium hydroxide. The amount of the base is not particularly limited as long as the by-product acid can be supplemented. It is preferable that they are 0.1 mol or more and 10 mol or less with respect to 1 mol of HFIP group containing aromatic compounds (4).
反応を円滑に進行させるには、副生する酸を捕捉するための塩基を反応系に共存させることが好ましい。具体的には、トリエチルアミン、ジエチルアミン、ジイソプロピルエチルアミン、ピリジン、炭酸カリウム、酢酸カリウム、リン酸カリウム、水酸化カリウム、水酸化ナトリウムまたは水酸化リチウムを例示することができる。塩基の量は、副生する酸を補足できれば特に限定されるものではない。ＨＦＩＰ基含有芳香族化合物（４）１モルに対して、０．１モル以上、１０モル以下であることが好ましい。 [base]
In order to make the reaction proceed smoothly, it is preferable that a base for capturing the by-product acid coexists in the reaction system. Specific examples include triethylamine, diethylamine, diisopropylethylamine, pyridine, potassium carbonate, potassium acetate, potassium phosphate, potassium hydroxide, sodium hydroxide, or lithium hydroxide. The amount of the base is not particularly limited as long as the by-product acid can be supplemented. It is preferable that they are 0.1 mol or more and 10 mol or less with respect to 1 mol of HFIP group containing aromatic compounds (4).
［添加剤］
式中のＸがヨウ素原子以外であるＨＦＩＰ基含有芳香族化合物（４）を本反応に用いる場合、具体的には、Ｘが臭素原子、塩素原子、－ＯＳＯ2（ｐ－Ｃ6Ｈ4ＣＨ3）基または－ＯＳＯ2ＣＦ3基である場合、反応系の中へヨウ素イオンを含む添加剤を加えることにより反応速度を高めることができる。添加剤は、具体的には、テトラブチルアンモニウムヨージド、テトラプロピルアンモニウムヨージド、テトラエチルアンモニウムヨージド、テトラメチルアンモニウムヨージド、テトラヘキシルアンモニウムヨージド、ヨウ化カリウムまたはヨウ化ナトリウムを例示することができる。 [Additive]
When an HFIP group-containing aromatic compound (4) in which X in the formula is other than an iodine atom is used in this reaction, specifically, X is a bromine atom, a chlorine atom, —OSO 2 (p—C 6 H 4 CH 3 ) In the case of a group or —OSO 2 CF 3 group, the reaction rate can be increased by adding an additive containing iodine ions into the reaction system. Specifically, the additive may be exemplified by tetrabutylammonium iodide, tetrapropylammonium iodide, tetraethylammonium iodide, tetramethylammonium iodide, tetrahexylammonium iodide, potassium iodide or sodium iodide. it can.
式中のＸがヨウ素原子以外であるＨＦＩＰ基含有芳香族化合物（４）を本反応に用いる場合、具体的には、Ｘが臭素原子、塩素原子、－ＯＳＯ2（ｐ－Ｃ6Ｈ4ＣＨ3）基または－ＯＳＯ2ＣＦ3基である場合、反応系の中へヨウ素イオンを含む添加剤を加えることにより反応速度を高めることができる。添加剤は、具体的には、テトラブチルアンモニウムヨージド、テトラプロピルアンモニウムヨージド、テトラエチルアンモニウムヨージド、テトラメチルアンモニウムヨージド、テトラヘキシルアンモニウムヨージド、ヨウ化カリウムまたはヨウ化ナトリウムを例示することができる。 [Additive]
When an HFIP group-containing aromatic compound (4) in which X in the formula is other than an iodine atom is used in this reaction, specifically, X is a bromine atom, a chlorine atom, —OSO 2 (p—C 6 H 4 CH 3 ) In the case of a group or —OSO 2 CF 3 group, the reaction rate can be increased by adding an additive containing iodine ions into the reaction system. Specifically, the additive may be exemplified by tetrabutylammonium iodide, tetrapropylammonium iodide, tetraethylammonium iodide, tetramethylammonium iodide, tetrahexylammonium iodide, potassium iodide or sodium iodide. it can.
［反応温度］
本反応における反応温度は、室温（本発明において約２０℃とする）から１２０℃の範囲が好ましい。
[Reaction temperature]
The reaction temperature in this reaction is preferably in the range of room temperature (about 20 ° C. in the present invention) to 120 ° C.
本反応における反応温度は、室温（本発明において約２０℃とする）から１２０℃の範囲が好ましい。
[Reaction temperature]
The reaction temperature in this reaction is preferably in the range of room temperature (about 20 ° C. in the present invention) to 120 ° C.
３．ＨＦＩＰ基含有ポリシロキサン高分子化合物
［一般式（６）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物］
一般式（６）で表される繰り返し単位を含む、本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物（６）について説明する。
3. HFIP group-containing polysiloxane polymer compound [HFIP group-containing polysiloxane polymer compound containing a repeating unit represented by formula (6)]
The HFIP group-containing polysiloxane polymer compound (6) of the present invention containing the repeating unit represented by the general formula (6) will be described.
［一般式（６）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物］
一般式（６）で表される繰り返し単位を含む、本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物（６）について説明する。
The HFIP group-containing polysiloxane polymer compound (6) of the present invention containing the repeating unit represented by the general formula (6) will be described.
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、Ｒ2は、それぞれ独立に、炭素数１～４の直鎖状または炭素数３、４の分岐状のアルキル基であり、ａは１～５、ａａは１～３、ｍは０～２、およびｎは１～３の整数であり、ａａ＋ｍ＋ｎ＝４である。）
式（６）中のＯn/2は、ポリシロキサン高分子化合物の表記として一般的に使用されるものである。本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物は、以下の式（６－１）～式（６－３）のいずれかの構造を含む。式（６－１）は式（６）中のｎが１、式（６－２）はｎが２、式（６－３）はｎが３の場合を表したものである。ｎ＝１の場合は式（６－１）であり、ポリシロキサン高分子化合物においてポリシロキサン鎖の末端に位置する。 (Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group may be substituted with a fluorine atom, and each R 2 independently represents 1 to 4 is a linear or branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, aa is 1 to 3, m is 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4)
On / 2 in formula (6) is generally used as a notation of a polysiloxane polymer compound. The HFIP group-containing polysiloxane polymer compound of the present invention includes any one of the following formulas (6-1) to (6-3). Formula (6-1) represents a case where n is 1 in Formula (6), Formula (6-2) is n, and Formula (6-3) is n. When n = 1, the formula is (6-1), which is located at the end of the polysiloxane chain in the polysiloxane polymer compound.
式（６）中のＯn/2は、ポリシロキサン高分子化合物の表記として一般的に使用されるものである。本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物は、以下の式（６－１）～式（６－３）のいずれかの構造を含む。式（６－１）は式（６）中のｎが１、式（６－２）はｎが２、式（６－３）はｎが３の場合を表したものである。ｎ＝１の場合は式（６－１）であり、ポリシロキサン高分子化合物においてポリシロキサン鎖の末端に位置する。 (Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group may be substituted with a fluorine atom, and each R 2 independently represents 1 to 4 is a linear or branched alkyl group having 3 or 4 carbon atoms, a is 1 to 5, aa is 1 to 3, m is 0 to 2, and n is an integer of 1 to 3, aa + m + n = 4)
On / 2 in formula (6) is generally used as a notation of a polysiloxane polymer compound. The HFIP group-containing polysiloxane polymer compound of the present invention includes any one of the following formulas (6-1) to (6-3). Formula (6-1) represents a case where n is 1 in Formula (6), Formula (6-2) is n, and Formula (6-3) is n. When n = 1, the formula is (6-1), which is located at the end of the polysiloxane chain in the polysiloxane polymer compound.
式（６－１）、式（６－２）および式（６－３）の構造は、ポリシロキサン鎖で相互に混合していても、即ち、共存していてもよい。
The structures of formula (6-1), formula (6-2) and formula (6-3) may be mixed with each other in the polysiloxane chain, that is, may coexist.
上記式（６－１）～（６－３）中、Ｒ1aは、以下の式（６－４）で表される１価の有機基であり、Ｒ1bおよびＲ1cは、以下の式（６－４）で表される１価の有機基または前記Ｒ1で表わされる有機基である。また波線と交差する線分は結合位置を表す。
In the above formulas (6-1) to (6-3), R 1a is a monovalent organic group represented by the following formula (6-4), and R 1b and R 1c are represented by the following formula ( A monovalent organic group represented by 6-4) or an organic group represented by R 1 . A line segment intersecting with the wavy line represents a coupling position.
（式中、ａは１～５の整数である。）
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物の分子量は、ポリスチレン換算による重量平均分子量で表して、１０００以上、２０００００以下であることが好ましい。 (Wherein, a is an integer of 1 to 5)
The molecular weight of the HFIP group-containing polysiloxane polymer compound of the present invention is preferably 1,000 or more and 200,000 or less, expressed as a weight average molecular weight in terms of polystyrene.
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物の分子量は、ポリスチレン換算による重量平均分子量で表して、１０００以上、２０００００以下であることが好ましい。 (Wherein, a is an integer of 1 to 5)
The molecular weight of the HFIP group-containing polysiloxane polymer compound of the present invention is preferably 1,000 or more and 200,000 or less, expressed as a weight average molecular weight in terms of polystyrene.
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物（６）のＨＦＩＰ基の含有率は、アルカリ溶解性を付与できれば特に限定されるものではないが、アルカリ溶解性という観点では、珪素素原子１個に対して０．１～５個を含むことが好ましい。
The content of the HFIP group of the HFIP group-containing polysiloxane polymer compound (6) of the present invention is not particularly limited as long as alkali solubility can be imparted. However, from the viewpoint of alkali solubility, the content of HFIP groups is one silicon atom. On the other hand, it is preferable to contain 0.1-5.
［一般式（７）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物］
ＨＦＩＰ基含有ポリシロキサン高分子化合物（６）において、製造のしやすさより、含まれるＨＦＩＰ基含有アリール基は１個であることが好ましく、一般式（７）で表される繰り返し単位を含むＨＦＩＰ基含有珪素化合物（７）であることが好ましい。
[HFIP Group-Containing Polysiloxane Polymer Containing Repeating Unit Represented by General Formula (7)]
In the HFIP group-containing polysiloxane polymer compound (6), it is preferable that the number of HFIP group-containing aryl groups contained is one from the viewpoint of ease of production, and the HFIP group includes a repeating unit represented by the general formula (7). It is preferable that it is a containing silicon compound (7).
ＨＦＩＰ基含有ポリシロキサン高分子化合物（６）において、製造のしやすさより、含まれるＨＦＩＰ基含有アリール基は１個であることが好ましく、一般式（７）で表される繰り返し単位を含むＨＦＩＰ基含有珪素化合物（７）であることが好ましい。
In the HFIP group-containing polysiloxane polymer compound (6), it is preferable that the number of HFIP group-containing aryl groups contained is one from the viewpoint of ease of production, and the HFIP group includes a repeating unit represented by the general formula (7). It is preferable that it is a containing silicon compound (7).
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、ａは１～５、ｍは０～２およびｎは１～３の整数であり、ｍ＋ｎ＝３である。）
［一般式（７－１）、一般式（７－２）または一般式（７－３）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物］
具体的には、以下の一般式（７－１）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（７－１）、以下の一般式（７－２）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（７－２）、または以下の一般式（７－３）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（７－３）を例示することができる。
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, a is an integer of 1 to 5, m is an integer of 0 to 2, and n is an integer of 1 to 3, and m + n = 3.
[HFIP Group-Containing Polysiloxane Polymer Containing Repeating Unit Represented by General Formula (7-1), General Formula (7-2), or General Formula (7-3)]
Specifically, an HFIP group-containing polysiloxane polymer compound (7-1) containing a repeating unit represented by the following general formula (7-1), and a repeating represented by the following general formula (7-2) HFIP group-containing polysiloxane polymer compound (7-2) containing a unit or HFIP group-containing polysiloxane polymer compound (7-3) containing a repeating unit represented by the following general formula (7-3) can do.
［一般式（７－１）、一般式（７－２）または一般式（７－３）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物］
具体的には、以下の一般式（７－１）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（７－１）、以下の一般式（７－２）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（７－２）、または以下の一般式（７－３）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（７－３）を例示することができる。
[HFIP Group-Containing Polysiloxane Polymer Containing Repeating Unit Represented by General Formula (7-1), General Formula (7-2), or General Formula (7-3)]
Specifically, an HFIP group-containing polysiloxane polymer compound (7-1) containing a repeating unit represented by the following general formula (7-1), and a repeating represented by the following general formula (7-2) HFIP group-containing polysiloxane polymer compound (7-2) containing a unit or HFIP group-containing polysiloxane polymer compound (7-3) containing a repeating unit represented by the following general formula (7-3) can do.
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、ｍは０～２の整数、ｎは１～３の整数であり、ｍ＋ｎ＝３である。）
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n = 3.)
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、ｍは０～２の整数、ｎは１～３の整数であり、ｍ＋ｎ＝３である。）
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n = 3.)
（式中、Ｒ1は水素原子、炭素数１～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルキル基、炭素数２～１０の直鎖状、炭素数３～１０の分岐状もしくは炭素数３～１０の環状のアルケニル基、または炭素数６～１０のアリール基であり、アルキル基、アルケニル基またはアリール基中の水素原子の全てまたは一部がフッ素原子と置換されていてもよく、ｍは０～２の整数、ｎは１～３の整数であり、ｍ＋ｎ＝３である。）
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n = 3.)
(Wherein R 1 is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms, A branched or alkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and all or part of the hydrogen atoms in the alkyl group, alkenyl group or aryl group are It may be substituted with a fluorine atom, m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n = 3.)
４．ＨＦＩＰ基含有ポリシロキサン高分子化合物の製造方法
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物（６）、（７）、（７－１）、（７－２）または（７－３）は、前記ＨＦＩＰ基含有珪素化合物（１）～（３）が加水分解し、重縮合反応することによって得られる。本加水分解および重縮合反応は、アルコキシシランの加水分解および縮合反応における一般的な方法で行うことができる。具体的には、ＨＦＩＰ基含有珪素化合物（１）～（３）を反応容器内に採取した後、本ＨＦＩＰ基含有珪素化合物（１）～（３）を加水分解するための水、重縮合反応を進行させるための酸触媒および反応溶媒を反応器内に加え、次いで反応溶液を室温で、または加熱しつつ撹拌し、加水分解および重縮合反応を進行させることで、本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物が得られる。 4). Method for Producing HFIP Group-Containing Polysiloxane Polymer Compound HFIP group-containing polysiloxane polymer compound (6), (7), (7-1), (7-2) or (7-3) of the present invention is The HFIP group-containing silicon compounds (1) to (3) are obtained by hydrolysis and polycondensation reaction. This hydrolysis and polycondensation reaction can be performed by a general method in the hydrolysis and condensation reaction of alkoxysilane. Specifically, after collecting the HFIP group-containing silicon compounds (1) to (3) in a reaction vessel, water and polycondensation reaction for hydrolyzing the HFIP group-containing silicon compounds (1) to (3) An acid catalyst and a reaction solvent for proceeding the reaction are added to the reactor, and then the reaction solution is stirred at room temperature or while heating to advance the hydrolysis and polycondensation reaction. A siloxane polymer compound is obtained.
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物（６）、（７）、（７－１）、（７－２）または（７－３）は、前記ＨＦＩＰ基含有珪素化合物（１）～（３）が加水分解し、重縮合反応することによって得られる。本加水分解および重縮合反応は、アルコキシシランの加水分解および縮合反応における一般的な方法で行うことができる。具体的には、ＨＦＩＰ基含有珪素化合物（１）～（３）を反応容器内に採取した後、本ＨＦＩＰ基含有珪素化合物（１）～（３）を加水分解するための水、重縮合反応を進行させるための酸触媒および反応溶媒を反応器内に加え、次いで反応溶液を室温で、または加熱しつつ撹拌し、加水分解および重縮合反応を進行させることで、本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物が得られる。 4). Method for Producing HFIP Group-Containing Polysiloxane Polymer Compound HFIP group-containing polysiloxane polymer compound (6), (7), (7-1), (7-2) or (7-3) of the present invention is The HFIP group-containing silicon compounds (1) to (3) are obtained by hydrolysis and polycondensation reaction. This hydrolysis and polycondensation reaction can be performed by a general method in the hydrolysis and condensation reaction of alkoxysilane. Specifically, after collecting the HFIP group-containing silicon compounds (1) to (3) in a reaction vessel, water and polycondensation reaction for hydrolyzing the HFIP group-containing silicon compounds (1) to (3) An acid catalyst and a reaction solvent for proceeding the reaction are added to the reactor, and then the reaction solution is stirred at room temperature or while heating to advance the hydrolysis and polycondensation reaction. A siloxane polymer compound is obtained.
反応を加熱しながら行う場合には、反応系中の未反応原料、水、酸触媒または反応溶媒が反応系外へと留去されることを防ぐために、反応容器を閉鎖系にするか、コンデンサーを取り付け、反応系を還流させることが好ましい。縮合反応に必要な時間は、酸触媒の種類にもよるが通常３時間～２４時間、反応温度は室温～１８０℃である。反応後は、ＨＦＩＰ基含有ポリシロキサン高分子化合物のハンドリングの観点から、反応系内に残存する水、生成するアルコール、および、酸触媒を、ＨＦＩＰ基含有ポリシロキサン高分子化合物から除去するのが好ましい。前記水、アルコール、酸触媒の除去は、抽出作業で行ってもよいし、トルエンなどの反応に悪影響を与えない溶媒を反応系内に加え、ディーン・スターク管で共沸除去してもよい。
When the reaction is carried out with heating, in order to prevent unreacted raw materials, water, acid catalyst or reaction solvent in the reaction system from distilling out of the reaction system, the reaction vessel is closed or a condenser is used. The reaction system is preferably refluxed. The time required for the condensation reaction is usually from 3 hours to 24 hours depending on the type of acid catalyst, and the reaction temperature is from room temperature to 180 ° C. After the reaction, from the viewpoint of handling the HFIP group-containing polysiloxane polymer compound, it is preferable to remove water remaining in the reaction system, the alcohol to be generated, and the acid catalyst from the HFIP group-containing polysiloxane polymer compound. . The removal of the water, alcohol, and acid catalyst may be performed by an extraction operation, or a solvent that does not adversely influence the reaction, such as toluene, may be added to the reaction system and removed azeotropically with a Dean-Stark tube.
［水］
本発明の ＨＦＩＰ基含有ポリシロキサン高分子化合物を得るための加水分解および重縮合反応において、使用する水は、原料のＨＦＩＰ基含有芳香族珪素化合物が有するアルコキシ基全モル数に対するモル比で表して、０．５モル以上、５．０モル以下である。０．５モルを下回ると加水分解が効率よく進行せず、５．０モルを上回るとゲル化する等、ハンドリングが困難となりやすい。 [water]
In the hydrolysis and polycondensation reaction for obtaining the HFIP group-containing polysiloxane polymer compound of the present invention, the water used is expressed in a molar ratio with respect to the total number of moles of alkoxy groups of the raw material HFIP group-containing aromatic silicon compound. 0.5 mol or more and 5.0 mol or less. If the amount is less than 0.5 mol, hydrolysis does not proceed efficiently, and if it exceeds 5.0 mol, gelation tends to be difficult.
本発明の ＨＦＩＰ基含有ポリシロキサン高分子化合物を得るための加水分解および重縮合反応において、使用する水は、原料のＨＦＩＰ基含有芳香族珪素化合物が有するアルコキシ基全モル数に対するモル比で表して、０．５モル以上、５．０モル以下である。０．５モルを下回ると加水分解が効率よく進行せず、５．０モルを上回るとゲル化する等、ハンドリングが困難となりやすい。 [water]
In the hydrolysis and polycondensation reaction for obtaining the HFIP group-containing polysiloxane polymer compound of the present invention, the water used is expressed in a molar ratio with respect to the total number of moles of alkoxy groups of the raw material HFIP group-containing aromatic silicon compound. 0.5 mol or more and 5.0 mol or less. If the amount is less than 0.5 mol, hydrolysis does not proceed efficiently, and if it exceeds 5.0 mol, gelation tends to be difficult.
［酸触媒］
重縮合反応において用いる酸触媒は、無機酸としては、具体的には、塩酸、硫酸、硝酸、リン酸またはホウ酸が例示することができ、有機酸としては、具体的には、酢酸、トリフルオロ酢酸、メタンスルホン酸、トリフルオロメタンスルホン酸、ギ酸、シュウ酸、マレイン酸、カンファースルホン酸、ベンゼンスルホン酸またはトシル酸を例示することができる。 [Acid catalyst]
Specific examples of the acid catalyst used in the polycondensation reaction include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid. Specific examples of organic acids include acetic acid, Examples include fluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, formic acid, oxalic acid, maleic acid, camphorsulfonic acid, benzenesulfonic acid or tosylic acid.
重縮合反応において用いる酸触媒は、無機酸としては、具体的には、塩酸、硫酸、硝酸、リン酸またはホウ酸が例示することができ、有機酸としては、具体的には、酢酸、トリフルオロ酢酸、メタンスルホン酸、トリフルオロメタンスルホン酸、ギ酸、シュウ酸、マレイン酸、カンファースルホン酸、ベンゼンスルホン酸またはトシル酸を例示することができる。 [Acid catalyst]
Specific examples of the acid catalyst used in the polycondensation reaction include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid. Specific examples of organic acids include acetic acid, Examples include fluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, formic acid, oxalic acid, maleic acid, camphorsulfonic acid, benzenesulfonic acid or tosylic acid.
［反応溶媒］
重縮合反応において用いる反応溶媒はアルコール系溶剤が好適である。具体的には、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、ｔ－ブチルアルコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－プロピルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコールモノ－ｔ－ブチルエーテル、３－メトキシ－１－ブタノールまたは３－メチル－３－メトキシ－１－ブタノールを例示することができる。 [Reaction solvent]
The reaction solvent used in the polycondensation reaction is preferably an alcohol solvent. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, Examples include propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, 3-methoxy-1-butanol or 3-methyl-3-methoxy-1-butanol.
重縮合反応において用いる反応溶媒はアルコール系溶剤が好適である。具体的には、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、ｔ－ブチルアルコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－プロピルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコールモノ－ｔ－ブチルエーテル、３－メトキシ－１－ブタノールまたは３－メチル－３－メトキシ－１－ブタノールを例示することができる。 [Reaction solvent]
The reaction solvent used in the polycondensation reaction is preferably an alcohol solvent. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, Examples include propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, 3-methoxy-1-butanol or 3-methyl-3-methoxy-1-butanol.
［抽出溶媒］
重縮合反応後に系中の縮合物であるＨＦＩＰ基含有ポリシロキサン高分子化合物（６）の抽出溶媒として用いられる有機溶剤は、ＨＦＩＰ基含有ポリシロキサン高分子化合物（６）を溶解し、抽出作業できるものであれば特に限定されるものではない。具体的には、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、クロロホルム、ジクロロメタン、酢酸エチル、トルエンなどを例示することができる。 [Extraction solvent]
The organic solvent used as an extraction solvent for the HFIP group-containing polysiloxane polymer compound (6), which is a condensate in the system after the polycondensation reaction, can dissolve and extract the HFIP group-containing polysiloxane polymer compound (6). If it is a thing, it will not specifically limit. Specifically, diethyl ether, diisopropyl ether, dibutyl ether, chloroform, dichloromethane, ethyl acetate, toluene and the like can be exemplified.
重縮合反応後に系中の縮合物であるＨＦＩＰ基含有ポリシロキサン高分子化合物（６）の抽出溶媒として用いられる有機溶剤は、ＨＦＩＰ基含有ポリシロキサン高分子化合物（６）を溶解し、抽出作業できるものであれば特に限定されるものではない。具体的には、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、クロロホルム、ジクロロメタン、酢酸エチル、トルエンなどを例示することができる。 [Extraction solvent]
The organic solvent used as an extraction solvent for the HFIP group-containing polysiloxane polymer compound (6), which is a condensate in the system after the polycondensation reaction, can dissolve and extract the HFIP group-containing polysiloxane polymer compound (6). If it is a thing, it will not specifically limit. Specifically, diethyl ether, diisopropyl ether, dibutyl ether, chloroform, dichloromethane, ethyl acetate, toluene and the like can be exemplified.
［固体乾燥剤］
反応系を有機溶剤で抽出洗浄後、必要に応じて、抽出液に溶解している微量の水を固体乾燥剤を用いて除去してもよい。用いる固体乾燥剤は、特に限定されるものではない。具体的には、硫酸マグネシウム、硫酸ナトリウム、硫酸カルシウムまたは合成ゼオライトを例示することができる。 [Solid desiccant]
After the reaction system is extracted and washed with an organic solvent, a trace amount of water dissolved in the extract may be removed using a solid desiccant, if necessary. The solid desiccant used is not particularly limited. Specifically, magnesium sulfate, sodium sulfate, calcium sulfate, or synthetic zeolite can be exemplified.
反応系を有機溶剤で抽出洗浄後、必要に応じて、抽出液に溶解している微量の水を固体乾燥剤を用いて除去してもよい。用いる固体乾燥剤は、特に限定されるものではない。具体的には、硫酸マグネシウム、硫酸ナトリウム、硫酸カルシウムまたは合成ゼオライトを例示することができる。 [Solid desiccant]
After the reaction system is extracted and washed with an organic solvent, a trace amount of water dissolved in the extract may be removed using a solid desiccant, if necessary. The solid desiccant used is not particularly limited. Specifically, magnesium sulfate, sodium sulfate, calcium sulfate, or synthetic zeolite can be exemplified.
［他のアルコキシシラン］
また、ＨＦＩＰ基含有ポリシロキサン高分子化合物（６）の製造において、アルカリ現像液に対する溶解性、耐熱性などの物性を調整する目的で、アルコキシシランである一般式（１）で表されるＨＦＩＰ基含有芳香族珪素化合物に加えて、他のジアルコキシシラン、トリアルコキシシランまたはテトラアルコキシシランと共重合してもよい。 [Other alkoxysilanes]
Further, in the production of the HFIP group-containing polysiloxane polymer compound (6), an HFIP group represented by the general formula (1) which is an alkoxysilane for the purpose of adjusting physical properties such as solubility in an alkali developer and heat resistance. In addition to the contained aromatic silicon compound, other dialkoxysilanes, trialkoxysilanes or tetraalkoxysilanes may be copolymerized.
また、ＨＦＩＰ基含有ポリシロキサン高分子化合物（６）の製造において、アルカリ現像液に対する溶解性、耐熱性などの物性を調整する目的で、アルコキシシランである一般式（１）で表されるＨＦＩＰ基含有芳香族珪素化合物に加えて、他のジアルコキシシラン、トリアルコキシシランまたはテトラアルコキシシランと共重合してもよい。 [Other alkoxysilanes]
Further, in the production of the HFIP group-containing polysiloxane polymer compound (6), an HFIP group represented by the general formula (1) which is an alkoxysilane for the purpose of adjusting physical properties such as solubility in an alkali developer and heat resistance. In addition to the contained aromatic silicon compound, other dialkoxysilanes, trialkoxysilanes or tetraalkoxysilanes may be copolymerized.
前記ジアルコキシシランとしては、具体的には、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジプロポキシシラン、ジメチルジフェノキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチルジプロポキシシラン、ジエチルジフェノキシシラン、ジプロピルジメトキシシラン、ジプロピルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、ジフェニルジフェノキシシラン、ビス（３，３，３－トリフルオロプロピル）ジメトキシシランまたはメチル（３，３，３－トリフルオロプロピル）ジメトキシシランを例示することができる。
Specific examples of the dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiphenoxysilane, Dipropyldimethoxysilane, dipropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, bis (3,3,3-trifluoropropyl) dimethoxysilane or methyl (3,3,3-trifluoro) A propyl) dimethoxysilane can be illustrated.
前記トリアルコキシシランとしては、具体的には、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、イソプロピルトリメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、プロピルトリエトキシシラン、イソプロピルトリエトキシシラン、フェニルトリエトキシシラン、メチルトリプロポキシシラン、エチルトリプロポキシシラン、プロピルトリプロポキシシラン、イソプロピルトリプロポキシシラン、フェニルトリプロポキシシラン、メチルトリイソプロポキシシラン、エチルトリイソプロポキシシラン、プロピルトリイソプロポキシシラン、イソプロピルトリイソプロポキシシラン、フェニルトリイソプロポキシシラン、トリフルオロメチルトリメトキシシラン、ペンタフルオロエチルトリメトキシシラン、３，３，３－トリフルオロプロピルトリメトキシシランまたは３，３，３－トリフルオロプロピルトリエトキシシランを例示することができる。
Specific examples of the trialkoxysilane include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and propyltriethoxy. Silane, isopropyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, propyltripropoxysilane, isopropyltripropoxysilane, phenyltripropoxysilane, methyltriisopropoxysilane, ethyltriisopropoxysilane, propyl Triisopropoxysilane, isopropyltriisopropoxysilane, phenyltriisopropoxysilane, trifluoromethyl Trimethoxysilane, pentafluoroethyl trimethoxysilane may be exemplified 3,3,3-trifluoropropyl trimethoxy silane or 3,3,3-trifluoropropyl triethoxysilane.
前記テトラアルコキシシランとしては、具体的には、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシランまたはテトライソプロポキシシランを例示することができる。
Specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane.
前記ジアルコキシシラン、トリアルコキシシランまたはテトラアルコキシシランは単独で用いてもよいし、２種以上を混合して用いてもよい。
The dialkoxysilane, trialkoxysilane or tetraalkoxysilane may be used alone or in combination of two or more.
ここで、前記ジアルコキシシラン、トリアルコキシシランおよびテトラアルコキシシランから選ばれる少なくとも１種の化合物を「他のアルコキシシラン」と表す。本発明に当該「他のアルコキシシラン」を用いる場合、その総量は特に限定されないが、ＨＦＩＰ基含有芳香族化合物１モルに対して、０．１～１０モルであることが好ましく、０．２～５モルであることがさらに好ましい。１０モル超であると、アルカリ溶解性を付与できない場合がある。
Here, at least one compound selected from the dialkoxysilane, trialkoxysilane, and tetraalkoxysilane is referred to as “other alkoxysilane”. When the “other alkoxysilane” is used in the present invention, the total amount is not particularly limited, but is preferably 0.1 to 10 moles per mole of the HFIP group-containing aromatic compound, 0.2 to More preferably, it is 5 moles. If it exceeds 10 mol, alkali solubility may not be imparted.
Here, at least one compound selected from the dialkoxysilane, trialkoxysilane, and tetraalkoxysilane is referred to as “other alkoxysilane”. When the “other alkoxysilane” is used in the present invention, the total amount is not particularly limited, but is preferably 0.1 to 10 moles per mole of the HFIP group-containing aromatic compound, 0.2 to More preferably, it is 5 moles. If it exceeds 10 mol, alkali solubility may not be imparted.
５．ＨＦＩＰ基含有ポリシロキサン高分子化合物を含む膜
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物は有機溶剤に溶解し、塗布液として塗布し膜とすることが可能である。その際、必要に応じて酸化安定剤、フィラー、シランカップリング剤、感光剤、光重合開始剤および増感剤等の添加物を加えることが可能である。本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物を有機溶剤に溶解させ塗布液とした後、ガラス基板、シリコン基板または金属基板等の基体に塗布した後、乾燥させることで膜とする。 5. Film containing HFIP group-containing polysiloxane polymer compound The HFIP group-containing polysiloxane polymer compound of the present invention can be dissolved in an organic solvent and applied as a coating solution to form a film. At that time, additives such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator, and a sensitizer can be added as necessary. The HFIP group-containing polysiloxane polymer compound of the present invention is dissolved in an organic solvent to form a coating solution, which is then applied to a substrate such as a glass substrate, a silicon substrate or a metal substrate, and then dried to form a film.
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物は有機溶剤に溶解し、塗布液として塗布し膜とすることが可能である。その際、必要に応じて酸化安定剤、フィラー、シランカップリング剤、感光剤、光重合開始剤および増感剤等の添加物を加えることが可能である。本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物を有機溶剤に溶解させ塗布液とした後、ガラス基板、シリコン基板または金属基板等の基体に塗布した後、乾燥させることで膜とする。 5. Film containing HFIP group-containing polysiloxane polymer compound The HFIP group-containing polysiloxane polymer compound of the present invention can be dissolved in an organic solvent and applied as a coating solution to form a film. At that time, additives such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator, and a sensitizer can be added as necessary. The HFIP group-containing polysiloxane polymer compound of the present invention is dissolved in an organic solvent to form a coating solution, which is then applied to a substrate such as a glass substrate, a silicon substrate or a metal substrate, and then dried to form a film.
この際、有機溶剤としては、具体的にプロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、シクロヘキサノン、乳酸エチル、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、またはＮ－メチルピロリドン等を例示することができる。
In this case, specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone. be able to.
前記有機溶剤に本発明のＨＦＩＰ基含有ポリシロキサンを溶解させる際の、ＨＦＩＰ基含有ポリシロキサン高分子化合物の濃度は、特に限定されるものではない。５質量％以上、５０質量％以下の範囲であることが好ましく、さらに好ましくは１０質量％以上、４０質量％以下である。
The concentration of the HFIP group-containing polysiloxane polymer compound when the HFIP group-containing polysiloxane of the present invention is dissolved in the organic solvent is not particularly limited. The range is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less.
前記塗布液を塗布する手法としては、特に制限されることなく、スピンコート、バーコーターまたはディップコーティング等の公知の方法を使用することができる。本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物が室温で液体の場合は、有機溶剤を使用せずに前記方法により、塗布膜を得ることができる。
The method for applying the coating solution is not particularly limited, and a known method such as spin coating, bar coater or dip coating can be used. When the HFIP group-containing polysiloxane polymer compound of the present invention is liquid at room temperature, a coating film can be obtained by the above method without using an organic solvent.
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物およびそれより得られる膜が、アルカリ現像液に可溶であることは、その化学構造においてＨＦＩＰ基を有することによる効果である。さらに、当該化学構造において珪素原子と芳香環が直接結合していることで、本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物およびそれより得られる膜は耐熱性に優れる。
The fact that the HFIP group-containing polysiloxane polymer compound of the present invention and the film obtained therefrom are soluble in an alkaline developer is an effect due to having HFIP groups in the chemical structure. Furthermore, since the silicon atom and the aromatic ring are directly bonded in the chemical structure, the HFIP group-containing polysiloxane polymer compound of the present invention and the film obtained therefrom are excellent in heat resistance.
前記塗布膜は、加熱、酸もしくは塩基の添加、または光重合開始剤による縮合等を行うことで、より機械強度および耐溶剤性に優れた硬化膜とすることができる。このうち加熱による硬化において、硬化条件は特に限定されるものではない。温度は１００℃以上、３５０℃以下であることが好ましく、硬化時間は１時間以上、２４時間以下であることが好ましい。前記方法により、本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物がさらに重縮合反応し、網目状の架橋構造を形成することで、硬化膜が得られる。
The coated film can be made into a cured film having better mechanical strength and solvent resistance by heating, addition of an acid or base, or condensation using a photopolymerization initiator. Among these, in the curing by heating, the curing conditions are not particularly limited. The temperature is preferably 100 ° C. or higher and 350 ° C. or lower, and the curing time is preferably 1 hour or longer and 24 hours or shorter. By the above method, the HFIP group-containing polysiloxane polymer compound of the present invention further undergoes a polycondensation reaction to form a network-like crosslinked structure, whereby a cured film is obtained.
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物は、室温で固体または液体であり、液体の場合はポッティング成型、および前記の硬化方法を行うことにより、バルク状の硬化物を得ることができる。
The HFIP group-containing polysiloxane polymer compound of the present invention is solid or liquid at room temperature, and in the case of liquid, a bulk cured product can be obtained by performing potting molding and the above-described curing method.
本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物およびそれより得られる膜は、アルカリ現像液に可溶であり、且つ耐熱性に優れることから、半導体用保護膜やディスプレイ用保護膜、レジスト材料に用いることができる。また、そのバルク状の硬化物は、ＬＥＤ用を含む光学系透明封止材、半導体用耐熱封止剤等に用いることができる。
The HFIP group-containing polysiloxane polymer compound of the present invention and a film obtained therefrom are soluble in an alkaline developer and excellent in heat resistance, and thus are used for a protective film for a semiconductor, a protective film for a display, and a resist material. be able to. In addition, the bulk cured product can be used for optical transparent encapsulants including those for LEDs, heat-resistant encapsulants for semiconductors, and the like.
The HFIP group-containing polysiloxane polymer compound of the present invention and a film obtained therefrom are soluble in an alkaline developer and excellent in heat resistance, and thus are used for a protective film for a semiconductor, a protective film for a display, and a resist material. be able to. In addition, the bulk cured product can be used for optical transparent encapsulants including those for LEDs, heat-resistant encapsulants for semiconductors, and the like.
本発明における実施例を具体的に示すが、本発明は以下の実施例に限定されるものではない。
Examples of the present invention are specifically shown, but the present invention is not limited to the following examples.
［分析および評価方法］
合成したＨＦＩＰ基含有珪素化合物およびＨＦＩＰ基含有ポリシロキサン高分子化合物の分析および評価方法を以下の（１）～（４）に示す。 [Analysis and Evaluation Method]
Analyzes and evaluation methods of the synthesized HFIP group-containing silicon compound and HFIP group-containing polysiloxane polymer compound are shown in the following (1) to (4).
合成したＨＦＩＰ基含有珪素化合物およびＨＦＩＰ基含有ポリシロキサン高分子化合物の分析および評価方法を以下の（１）～（４）に示す。 [Analysis and Evaluation Method]
Analyzes and evaluation methods of the synthesized HFIP group-containing silicon compound and HFIP group-containing polysiloxane polymer compound are shown in the following (1) to (4).
（１）核磁気共鳴（ＮＭＲ：Ｎｕｃｌｅａｒ Ｍａｇｎｅｔｉｃ Ｒｅｓｏｎａｎｃｅ）測定
共鳴周波数４００ＭＨｚの核磁気共鳴装置（日本電子株式会社製、形式ＡＬ４００）を使用し、1Ｈ－ＮＭＲ、19Ｆ－ＮＭＲ、13Ｃ－ＮＭＲまたは29Ｓｉ－ＮＭＲの測定を行うことで、ＨＦＩＰ基含有珪素化合物、ＨＦＩＰ基含有ポリシロキサン高分子化合物の同定を行った。 (1) Nuclear Magnetic Resonance (NMR) Measurement Using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model AL400) with a resonance frequency of 400 MHz, 1 H-NMR, 19 F-NMR, 13 C-NMR Alternatively, HFIP group-containing silicon compounds and HFIP group-containing polysiloxane polymer compounds were identified by measuring 29 Si-NMR.
共鳴周波数４００ＭＨｚの核磁気共鳴装置（日本電子株式会社製、形式ＡＬ４００）を使用し、1Ｈ－ＮＭＲ、19Ｆ－ＮＭＲ、13Ｃ－ＮＭＲまたは29Ｓｉ－ＮＭＲの測定を行うことで、ＨＦＩＰ基含有珪素化合物、ＨＦＩＰ基含有ポリシロキサン高分子化合物の同定を行った。 (1) Nuclear Magnetic Resonance (NMR) Measurement Using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model AL400) with a resonance frequency of 400 MHz, 1 H-NMR, 19 F-NMR, 13 C-NMR Alternatively, HFIP group-containing silicon compounds and HFIP group-containing polysiloxane polymer compounds were identified by measuring 29 Si-NMR.
（２）ゲル浸透クロマトグラフ（ＧＰＣ：Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）測定
ゲル浸透クロマトグラフ（東ソー株式会社製、ＨＬＣ－８３２０ＧＰＣ）を使用してＧＰＣを測定し、ポリスチレン換算により、ＨＦＩＰ基含有ポリシロキサン高分子化合物の重量平均分子量（Ｍｗ：ｗｅｉｇｈｔ－ａｖｅｒａｇｅ ｍｏｌｅｃｕｌａｒ ｗｅｉｇｈｔ）を算出した。 (2) Gel Permeation Chromatography (GPC) Measurement GPC was measured using a gel permeation chromatograph (HLC-8320GPC, manufactured by Tosoh Corporation), and converted to polystyrene, and an HFIP group-containing polysiloxane polymer compound. The weight average molecular weight (Mw: weight-average molecular weight) was calculated.
ゲル浸透クロマトグラフ（東ソー株式会社製、ＨＬＣ－８３２０ＧＰＣ）を使用してＧＰＣを測定し、ポリスチレン換算により、ＨＦＩＰ基含有ポリシロキサン高分子化合物の重量平均分子量（Ｍｗ：ｗｅｉｇｈｔ－ａｖｅｒａｇｅ ｍｏｌｅｃｕｌａｒ ｗｅｉｇｈｔ）を算出した。 (2) Gel Permeation Chromatography (GPC) Measurement GPC was measured using a gel permeation chromatograph (HLC-8320GPC, manufactured by Tosoh Corporation), and converted to polystyrene, and an HFIP group-containing polysiloxane polymer compound. The weight average molecular weight (Mw: weight-average molecular weight) was calculated.
（３）アルカリ現像液に対する溶解性試験
ＨＦＩＰ基含有ポリシロキサン高分子化合物の濃度３３質量％のプロピレングリコールモノメチルエーテルアセテート溶液を調製し、ガラス基板またはシリコン基板上に垂らし、スピンコーターを用い４００ｒｐｍで１０秒間保持して塗布し、ホットプレート上で９０℃で１分間加熱させた。このようにして得られた塗布膜を、フォトリソグラフィーのアルカリ現像液として用いられる、濃度２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液に浸漬し、目視によって、薄膜の干渉色が認められなかった場合を「溶解」、認められた場合を「不溶」とした。 (3) Solubility test in alkali developer A propylene glycol monomethyl ether acetate solution having a concentration of 33% by mass of a HFIP group-containing polysiloxane polymer compound is prepared and hung on a glass substrate or a silicon substrate, and 10 times at 400 rpm using a spin coater. The coating was held for 2 seconds and heated on a hot plate at 90 ° C. for 1 minute. The coating film thus obtained was immersed in an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass used as an alkaline developer for photolithography, and no interference color of the thin film was visually observed. The case was “dissolved”, and the case was recognized as “insoluble”.
ＨＦＩＰ基含有ポリシロキサン高分子化合物の濃度３３質量％のプロピレングリコールモノメチルエーテルアセテート溶液を調製し、ガラス基板またはシリコン基板上に垂らし、スピンコーターを用い４００ｒｐｍで１０秒間保持して塗布し、ホットプレート上で９０℃で１分間加熱させた。このようにして得られた塗布膜を、フォトリソグラフィーのアルカリ現像液として用いられる、濃度２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液に浸漬し、目視によって、薄膜の干渉色が認められなかった場合を「溶解」、認められた場合を「不溶」とした。 (3) Solubility test in alkali developer A propylene glycol monomethyl ether acetate solution having a concentration of 33% by mass of a HFIP group-containing polysiloxane polymer compound is prepared and hung on a glass substrate or a silicon substrate, and 10 times at 400 rpm using a spin coater. The coating was held for 2 seconds and heated on a hot plate at 90 ° C. for 1 minute. The coating film thus obtained was immersed in an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass used as an alkaline developer for photolithography, and no interference color of the thin film was visually observed. The case was “dissolved”, and the case was recognized as “insoluble”.
（４）熱分解温度の測定
後述の実施例４～８で得られたＨＦＩＰ基含有ポリシロキサン高分子化合物８～１２と、比較例１～３で得られた比較用ポリシロキサン高分子化合物１～３をそれぞれ１５０℃のオーブンで１時間乾燥した後、熱重量測定（ＴＧＡ、株式会社リガク製、形式ＴＧ８１２０）を実施し、初期の重量に対して５％の重量損失があった温度を熱分解温度（Ｔd5）とした。
(4) Measurement of thermal decomposition temperature HFIP group-containing polysiloxane polymer compounds 8 to 12 obtained in Examples 4 to 8 described later, and comparative polysiloxane polymer compounds 1 to 3 obtained in Comparative Examples 1 to 3 3 was dried in an oven at 150 ° C. for 1 hour, and then thermogravimetric measurement (TGA, manufactured by Rigaku Corporation, type TG8120) was carried out to thermally decompose the temperature at which the weight loss was 5% of the initial weight. The temperature (T d5 ) was used.
後述の実施例４～８で得られたＨＦＩＰ基含有ポリシロキサン高分子化合物８～１２と、比較例１～３で得られた比較用ポリシロキサン高分子化合物１～３をそれぞれ１５０℃のオーブンで１時間乾燥した後、熱重量測定（ＴＧＡ、株式会社リガク製、形式ＴＧ８１２０）を実施し、初期の重量に対して５％の重量損失があった温度を熱分解温度（Ｔd5）とした。
(4) Measurement of thermal decomposition temperature HFIP group-containing polysiloxane polymer compounds 8 to 12 obtained in Examples 4 to 8 described later, and comparative polysiloxane polymer compounds 1 to 3 obtained in Comparative Examples 1 to 3 3 was dried in an oven at 150 ° C. for 1 hour, and then thermogravimetric measurement (TGA, manufactured by Rigaku Corporation, type TG8120) was carried out to thermally decompose the temperature at which the weight loss was 5% of the initial weight. The temperature (T d5 ) was used.
実施例１
［ＨＦＩＰ基含有珪素化合物（３－１）の合成］
ＨＦＩＰ基含有珪素化合物（３－１）を合成するための以下の反応を行った。
Example 1
[Synthesis of HFIP group-containing silicon compound (3-1)]
The following reaction for synthesizing the HFIP group-containing silicon compound (3-1) was performed.
［ＨＦＩＰ基含有珪素化合物（３－１）の合成］
ＨＦＩＰ基含有珪素化合物（３－１）を合成するための以下の反応を行った。
[Synthesis of HFIP group-containing silicon compound (3-1)]
The following reaction for synthesizing the HFIP group-containing silicon compound (3-1) was performed.
Ｅｔはエチル基（－ＣＨ2ＣＨ3）であり、以下、同様である。
Et is an ethyl group (—CH 2 CH 3 ), and the same applies hereinafter.
還流管を取り付けた３００ｍＬ三口フラスコ内に、予め乾燥させておいた、テトラブチルアンモニウムヨージド、３．６９ｇ（１０．０ｍｍｏｌ）、およびビス（アセトニトリル）（１，５－シクロオクタジエン）ロジウム（Ｉ）テトラフルオロボラート、０．１１４０ｇ（０．３０ｍｍｏｌ）を室温で採取した。次いで、アルゴン雰囲気下で、脱水処理したＮ，Ｎ－ジメチルホルムアミド、１４３ｍＬ、ＨＦＩＰ基含有芳香族化合物（４－１）、４．８９ｇ（１０．０ｍｍｏｌ）、脱水処理したトリエチルアミン、６．９４ｍＬ（５０．０ｍｍｏｌ）、およびトリエトキシシラン３．６９ｍＬ（２０．０ｍｍｏｌ）を加え、温度８０℃に昇温し３時間攪拌した。反応系を室温まで自然冷却した後、溶媒であるＮ，Ｎ－ジメチルホルムアミドを留去し、次いでジイソプロピルエーテル約５０ｍＬを加えた。生じた沈殿に、セライト、次いで活性炭を接触させた後、ジイソプロピルエーテルを留去し反応物を得た。次いで、反応物を、クーゲルロール蒸留装置を用い、温度１３０℃～１４０℃、圧力１８０Ｐａの条件にて蒸留精製し、無色液体としてＨＦＩＰ基含有珪素化合物（３－１）、１．８２ｇを収率３２％で得た。
In a 300 mL three-necked flask equipped with a reflux tube, tetrabutylammonium iodide, 3.69 g (10.0 mmol), and bis (acetonitrile) (1,5-cyclooctadiene) rhodium (I ) Tetrafluoroborate, 0.1140 g (0.30 mmol) was collected at room temperature. Next, under argon atmosphere, dehydrated N, N-dimethylformamide, 143 mL, HFIP group-containing aromatic compound (4-1), 4.89 g (10.0 mmol), dehydrated triethylamine, 6.94 mL (50 0.0 mmol) and 3.69 mL (20.0 mmol) of triethoxysilane were added, the temperature was raised to 80 ° C., and the mixture was stirred for 3 hours. After the reaction system was naturally cooled to room temperature, N, N-dimethylformamide as a solvent was distilled off, and then about 50 mL of diisopropyl ether was added. The resulting precipitate was contacted with Celite and then activated carbon, and then diisopropyl ether was distilled off to obtain a reaction product. Next, the reaction product was distilled and purified using a Kugelrohr distillation apparatus under the conditions of a temperature of 130 ° C. to 140 ° C. and a pressure of 180 Pa to obtain 1.82 g of HFIP group-containing silicon compound (3-1) as a colorless liquid. Obtained at 32%.
得られたＨＦＩＰ基含有珪素化合物（３－１）の、1Ｈ－ＮＭＲ、19Ｆ－ＮＭＲ、13Ｃ－ＮＭＲおよび29Ｓｉ－ＮＭＲ測定結果を以下に示す。
The results of 1 H-NMR, 19 F-NMR, 13 C-NMR and 29 Si-NMR measurements of the resulting HFIP group-containing silicon compound (3-1) are shown below.
1Ｈ－ＮＭＲ（溶媒ＣＤＣｌ3（重水素化クロロホルム）、ＴＭＳ（テトラメチルシラン））：δ８．１８（１Ｈ，ｓ），８．１１（２Ｈ，ｓ），３．８８（６Ｈ，ｑ，Ｊ＝７．０Ｈｚ），３．８０（２Ｈ，ｓ），１．２４（９Ｈ，ｔ，Ｊ＝７．０Ｈｚ）
19Ｆ－ＮＭＲ（溶媒ＣＤＣｌ3，ＣＣｌ3Ｆ）：δ－７６．０１（ｓ）
13Ｃ－ＮＭＲ（溶媒ＣＤＣｌ3，ＴＭＳ）：δ１３４．６６（ｓ），１３３．１２（ｓ），１３０．０６（ｓ），１２７．２６（ｓ），１２２．７１（ｑ，Ｊ＝２８５．７Ｈｚ），７７．２９（ｓｅｐ，Ｊ＝２９．９Ｈｚ），５９．２５（ｓ），１８．１２（ｓ）
29Ｓｉ－ＮＭＲ（溶媒ＣＤＣｌ3，ＴＭＳ，緩和剤クロム（ＩＩＩ）アセチルアセトナート）：δ－６０．３８（ｓ）
1 H-NMR (solvent CDCl 3 (deuterated chloroform), TMS (tetramethylsilane)): δ8.18 (1H, s), 8.11 (2H, s), 3.88 (6H, q, J = 7.0 Hz), 3.80 (2H, s), 1.24 (9 H, t, J = 7.0 Hz)
19 F-NMR (solvent CDCl 3 , CCl 3 F): δ-76.01 (s)
13 C-NMR (solvent CDCl 3 , TMS): δ 134.66 (s), 133.12 (s), 130.06 (s), 127.26 (s), 122.71 (q, J = 285. 7 Hz), 77.29 (sep, J = 29.9 Hz), 59.25 (s), 18.12 (s)
29 Si-NMR (solvent CDCl 3 , TMS, relaxation agent chromium (III) acetylacetonate): δ-60.38 (s)
19Ｆ－ＮＭＲ（溶媒ＣＤＣｌ3，ＣＣｌ3Ｆ）：δ－７６．０１（ｓ）
13Ｃ－ＮＭＲ（溶媒ＣＤＣｌ3，ＴＭＳ）：δ１３４．６６（ｓ），１３３．１２（ｓ），１３０．０６（ｓ），１２７．２６（ｓ），１２２．７１（ｑ，Ｊ＝２８５．７Ｈｚ），７７．２９（ｓｅｐ，Ｊ＝２９．９Ｈｚ），５９．２５（ｓ），１８．１２（ｓ）
29Ｓｉ－ＮＭＲ（溶媒ＣＤＣｌ3，ＴＭＳ，緩和剤クロム（ＩＩＩ）アセチルアセトナート）：δ－６０．３８（ｓ）
1 H-NMR (solvent CDCl 3 (deuterated chloroform), TMS (tetramethylsilane)): δ8.18 (1H, s), 8.11 (2H, s), 3.88 (6H, q, J = 7.0 Hz), 3.80 (2H, s), 1.24 (9 H, t, J = 7.0 Hz)
19 F-NMR (solvent CDCl 3 , CCl 3 F): δ-76.01 (s)
13 C-NMR (solvent CDCl 3 , TMS): δ 134.66 (s), 133.12 (s), 130.06 (s), 127.26 (s), 122.71 (q, J = 285. 7 Hz), 77.29 (sep, J = 29.9 Hz), 59.25 (s), 18.12 (s)
29 Si-NMR (solvent CDCl 3 , TMS, relaxation agent chromium (III) acetylacetonate): δ-60.38 (s)
実施例２
［ＨＦＩＰ基含有珪素化合物（３－２）の合成］
ＨＦＩＰ基含有珪素化合物（３－２）を合成するための以下の反応を行った。
Example 2
[Synthesis of HFIP group-containing silicon compound (3-2)]
The following reaction for synthesizing the HFIP group-containing silicon compound (3-2) was performed.
［ＨＦＩＰ基含有珪素化合物（３－２）の合成］
ＨＦＩＰ基含有珪素化合物（３－２）を合成するための以下の反応を行った。
[Synthesis of HFIP group-containing silicon compound (3-2)]
The following reaction for synthesizing the HFIP group-containing silicon compound (3-2) was performed.
具体的には、還流管を取り付けた３００ｍＬ三口フラスコ内に、予め乾燥させておいた、ＨＦＩＰ基含有芳香族化合物（４－２）、６．４６ｇ（２０．０ｍｍｏｌ）、テトラブチルアンモニウムヨージド、７．３８ｇ（４０．０ｍｍｏｌ）、およびビス（アセトニトリル）（１，５－シクロオクタジエン）ロジウム（Ｉ）テトラフルオロボラート、０．２２８０ｇ（０．６０ｍｍｏｌ）を室温で採取した。次いで、アルゴン雰囲気下で、脱水処理したＮ，Ｎ－ジメチルホルムアミド１２０ｍＬ、脱水処理したトリエチルアミン１１．１ｍＬ（８０．０ｍｍｏｌ）、およびトリエトキシシラン７．４０ｍＬ（４０．０ｍｍｏｌ）を加え、温度８０℃に昇温し４時間攪拌した。反応系を室温まで自然冷却した後、溶媒であるＮ，Ｎ－ジメチルホルムアミドを留去し、次いでジイソプロピルエーテル約２００ｍＬを加えた。生じた沈殿に、セライトを接触させて濾過した後、濾液を１００ｍＬの水で３回洗浄し、Ｎａ2ＳＯ4を加えて脱水し乾燥させ、さらに濾過した後、溶媒を留去した。反応物である残渣を、クーゲルロール装置を用い、温度１４０℃～１９０℃、圧力２００Ｐａの条件にて蒸留精製し、無色液体としてＨＦＩＰ基含有珪素化合物（３－２）、４．５６ｇを収率５６％で得た。
Specifically, in a 300 mL three-necked flask equipped with a reflux tube, HFIP group-containing aromatic compound (4-2), 6.46 g (20.0 mmol), tetrabutylammonium iodide, 7.38 g (40.0 mmol) and bis (acetonitrile) (1,5-cyclooctadiene) rhodium (I) tetrafluoroborate, 0.2280 g (0.60 mmol) were collected at room temperature. Next, under an argon atmosphere, 120 mL of dehydrated N, N-dimethylformamide, 11.1 mL (80.0 mmol) of dehydrated triethylamine, and 7.40 mL (40.0 mmol) of triethoxysilane were added, and the temperature was raised to 80 ° C. The temperature was raised and the mixture was stirred for 4 hours. After the reaction system was naturally cooled to room temperature, N, N-dimethylformamide as a solvent was distilled off, and then about 200 mL of diisopropyl ether was added. The resulting precipitate was contacted with celite and filtered, and the filtrate was washed 3 times with 100 mL of water, dried by adding Na 2 SO 4 , further filtered, and then the solvent was distilled off. The residue as a reaction product was purified by distillation using a Kugelrohr apparatus under conditions of a temperature of 140 ° C. to 190 ° C. and a pressure of 200 Pa to obtain 4.56 g of a HFIP group-containing silicon compound (3-2) as a colorless liquid. Obtained at 56%.
得られたＨＦＩＰ基含有珪素化合物（３－２）の、1Ｈ－ＮＭＲ、19Ｆ－ＮＭＲの測定結果を以下に示す。
The measurement results of 1 H-NMR and 19 F-NMR of the obtained HFIP group-containing silicon compound (3-2) are shown below.
1Ｈ－ＮＭＲ（溶媒ＣＤＣｌ3，ＴＭＳ）：δ７．７４（４Ｈ，ｄｄ，Ｊ＝１８．６，８．３Ｈｚ），３．８９（６Ｈ，ｑ，Ｊ＝７．０Ｈｚ），３．５７（１Ｈ，ｓ），１．２６（９Ｈ，ｔ，Ｊ＝７．０Ｈｚ）
19Ｆ－ＮＭＲ（溶媒ＣＤＣｌ3，ＣＣｌ3Ｆ）：δ－７５．９４（ｓ）
13Ｃ－ＮＭＲ（溶媒ＣＤＣｌ3）：δ１３４．８７（ｓ），１３３．３２（ｓ），１３２．０２（ｓ），１２５．９７（ｓ），１２２．７４（ｑ，Ｊ＝２８７．６Ｈｚ），７７．１５（ｓｅｐ，Ｊ＝２９．７Ｈｚ），５８．９５（ｓ），１７．９８（ｓ）
29Ｓｉ－ＮＭＲ（溶媒ＣＤＣｌ3，緩和剤クロム（ＩＩＩ）アセチルアセトナート）：δ－５８．５２（ｓ）
1 H-NMR (solvent CDCl 3 , TMS): δ 7.74 (4H, dd, J = 18.6, 8.3 Hz), 3.89 (6H, q, J = 7.0 Hz), 3.57 ( 1H, s), 1.26 (9H, t, J = 7.0 Hz)
19 F-NMR (solvent CDCl 3 , CCl 3 F): δ-75.94 (s)
13 C-NMR (solvent CDCl 3 ): δ 134.87 (s), 133.32 (s), 132.02 (s), 125.97 (s), 122.74 (q, J = 287.6 Hz) , 77.15 (sep, J = 29.7 Hz), 58.95 (s), 17.98 (s)
29 Si-NMR (solvent CDCl 3 , relaxation agent chromium (III) acetylacetonate): δ-58.52 (s)
19Ｆ－ＮＭＲ（溶媒ＣＤＣｌ3，ＣＣｌ3Ｆ）：δ－７５．９４（ｓ）
13Ｃ－ＮＭＲ（溶媒ＣＤＣｌ3）：δ１３４．８７（ｓ），１３３．３２（ｓ），１３２．０２（ｓ），１２５．９７（ｓ），１２２．７４（ｑ，Ｊ＝２８７．６Ｈｚ），７７．１５（ｓｅｐ，Ｊ＝２９．７Ｈｚ），５８．９５（ｓ），１７．９８（ｓ）
29Ｓｉ－ＮＭＲ（溶媒ＣＤＣｌ3，緩和剤クロム（ＩＩＩ）アセチルアセトナート）：δ－５８．５２（ｓ）
1 H-NMR (solvent CDCl 3 , TMS): δ 7.74 (4H, dd, J = 18.6, 8.3 Hz), 3.89 (6H, q, J = 7.0 Hz), 3.57 ( 1H, s), 1.26 (9H, t, J = 7.0 Hz)
19 F-NMR (solvent CDCl 3 , CCl 3 F): δ-75.94 (s)
13 C-NMR (solvent CDCl 3 ): δ 134.87 (s), 133.32 (s), 132.02 (s), 125.97 (s), 122.74 (q, J = 287.6 Hz) , 77.15 (sep, J = 29.7 Hz), 58.95 (s), 17.98 (s)
29 Si-NMR (solvent CDCl 3 , relaxation agent chromium (III) acetylacetonate): δ-58.52 (s)
実施例３
［ＨＦＩＰ基含有珪素化合物（３－３）の合成］
ＨＦＩＰ基含有珪素化合物（３－３）を合成するための以下の反応を行った。
Example 3
[Synthesis of HFIP group-containing silicon compound (3-3)]
The following reaction for synthesizing the HFIP group-containing silicon compound (3-3) was performed.
［ＨＦＩＰ基含有珪素化合物（３－３）の合成］
ＨＦＩＰ基含有珪素化合物（３－３）を合成するための以下の反応を行った。
[Synthesis of HFIP group-containing silicon compound (3-3)]
The following reaction for synthesizing the HFIP group-containing silicon compound (3-3) was performed.
反応は、ＨＦＩＰ基含有芳香族化合物（４－２）の代わりに、ＨＦＩＰ基含有芳香族化合物（４－３）を用いた以外は、実施例２と同様に実施した。反応終了後、実施例２と同様に後処理し、クーゲルロール装置を用いて蒸留精製することにより、無色液体としてＨＦＩＰ基含有珪素化合物（３－３）、２．８４ｇを収率３５％で得た。
The reaction was carried out in the same manner as in Example 2 except that the HFIP group-containing aromatic compound (4-3) was used instead of the HFIP group-containing aromatic compound (4-2). After completion of the reaction, the reaction mixture was post-treated in the same manner as in Example 2 and purified by distillation using a Kugelrohr apparatus to obtain 2.84 g of a HFIP group-containing silicon compound (3-3) as a colorless liquid in a yield of 35%. It was.
The reaction was carried out in the same manner as in Example 2 except that the HFIP group-containing aromatic compound (4-3) was used instead of the HFIP group-containing aromatic compound (4-2). After completion of the reaction, the reaction mixture was post-treated in the same manner as in Example 2 and purified by distillation using a Kugelrohr apparatus to obtain 2.84 g of a HFIP group-containing silicon compound (3-3) as a colorless liquid in a yield of 35%. It was.
実施例４
［ＨＦＩＰ基含有珪素化合物（３－１）を原料化合物とする、ＨＦＩＰ基含有ポリシロキサン高分子化合物の合成］
ＨＦＩＰ基含有珪素化合物（３－１）、１１．４５ｇ（２０．０ｍｍｏｌ）をメタノールに溶かして全量を５７ｇとした後、水１．０８ｍＬ（６０．０ｍｍｏｌ）、４ｍｏｌ／Ｌの塩酸０．２５ｍＬを加え、室温で４時間攪拌した。反応液から溶媒を留去し、以下の式（８）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（８）を無色透明高粘性液体として得た。
Example 4
[Synthesis of HFIP group-containing polysiloxane polymer compound using HFIP group-containing silicon compound (3-1) as a raw material compound]
HFIP group-containing silicon compound (3-1), 11.45 g (20.0 mmol) was dissolved in methanol to a total amount of 57 g, and then 1.08 mL (60.0 mmol) of water and 0.25 mL of 4 mol / L hydrochloric acid were added. The mixture was further stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (8) containing a repeating unit represented by the following formula (8) as a colorless transparent highly viscous liquid.
［ＨＦＩＰ基含有珪素化合物（３－１）を原料化合物とする、ＨＦＩＰ基含有ポリシロキサン高分子化合物の合成］
ＨＦＩＰ基含有珪素化合物（３－１）、１１．４５ｇ（２０．０ｍｍｏｌ）をメタノールに溶かして全量を５７ｇとした後、水１．０８ｍＬ（６０．０ｍｍｏｌ）、４ｍｏｌ／Ｌの塩酸０．２５ｍＬを加え、室温で４時間攪拌した。反応液から溶媒を留去し、以下の式（８）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（８）を無色透明高粘性液体として得た。
[Synthesis of HFIP group-containing polysiloxane polymer compound using HFIP group-containing silicon compound (3-1) as a raw material compound]
HFIP group-containing silicon compound (3-1), 11.45 g (20.0 mmol) was dissolved in methanol to a total amount of 57 g, and then 1.08 mL (60.0 mmol) of water and 0.25 mL of 4 mol / L hydrochloric acid were added. The mixture was further stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (8) containing a repeating unit represented by the following formula (8) as a colorless transparent highly viscous liquid.
（式中、ｘは任意の整数を表す。）
(In the formula, x represents an arbitrary integer.)
(In the formula, x represents an arbitrary integer.)
実施例５
［ＨＦＩＰ基含有珪素化合物（３－２）を原料とするＨＦＩＰ基含有ポリシロキサン高分子化合物（９）の合成］
ＨＦＩＰ基含有珪素化合物（３－２）、８．１３ｇ（２０．０ｍｍｏｌ）をメタノールに溶かして全量を４１ｇとした後、水１．０８ｍＬ（６０．０ｍｍｏｌ）、４ｍｏｌ／Ｌの塩酸０．２５ｍＬを加え、室温で４時間攪拌した。反応液から溶媒を留去し、以下の式（９）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（９）を無色透明高粘性液体として得た。
Example 5
[Synthesis of HFIP group-containing polysiloxane polymer compound (9) using HFIP group-containing silicon compound (3-2) as a raw material]
HFIP group-containing silicon compound (3-2), 8.13 g (20.0 mmol) was dissolved in methanol to a total amount of 41 g, and then 1.08 mL (60.0 mmol) of water and 0.25 mL of 4 mol / L hydrochloric acid were added. The mixture was further stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (9) containing a repeating unit represented by the following formula (9) as a colorless transparent highly viscous liquid.
［ＨＦＩＰ基含有珪素化合物（３－２）を原料とするＨＦＩＰ基含有ポリシロキサン高分子化合物（９）の合成］
ＨＦＩＰ基含有珪素化合物（３－２）、８．１３ｇ（２０．０ｍｍｏｌ）をメタノールに溶かして全量を４１ｇとした後、水１．０８ｍＬ（６０．０ｍｍｏｌ）、４ｍｏｌ／Ｌの塩酸０．２５ｍＬを加え、室温で４時間攪拌した。反応液から溶媒を留去し、以下の式（９）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（９）を無色透明高粘性液体として得た。
[Synthesis of HFIP group-containing polysiloxane polymer compound (9) using HFIP group-containing silicon compound (3-2) as a raw material]
HFIP group-containing silicon compound (3-2), 8.13 g (20.0 mmol) was dissolved in methanol to a total amount of 41 g, and then 1.08 mL (60.0 mmol) of water and 0.25 mL of 4 mol / L hydrochloric acid were added. The mixture was further stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (9) containing a repeating unit represented by the following formula (9) as a colorless transparent highly viscous liquid.
（式中、ｘは任意の整数を表す。）
(In the formula, x represents an arbitrary integer.)
(In the formula, x represents an arbitrary integer.)
実施例６
［ＨＦＩＰ基含有珪素化合物（３－３）を原料とするＨＦＩＰ基含有ポリシロキサン高分子化合物（１０）の合成］
ＨＦＩＰ基含有珪素化合物（３－３）、１．６３ｇ（４．０ｍｍｏｌ）をメタノールに溶かして全量を８．２ｇとした後、水０．２１６ｍＬ（１２．０ｍｍｏｌ）、４ｍｏｌ／Ｌの塩酸０．０５ｍＬを加え、室温で４時間攪拌した。反応液から溶媒を留去し、以下の式（１０）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（１０）を無色透明高粘性液体として得た。
Example 6
[Synthesis of HFIP group-containing polysiloxane polymer compound (10) using HFIP group-containing silicon compound (3-3) as a raw material]
HFIP group-containing silicon compound (3-3), 1.63 g (4.0 mmol), dissolved in methanol to a total amount of 8.2 g, 0.216 mL (12.0 mmol) of water, 0.1 mol of 4 mol / L hydrochloric acid, 05 mL was added and stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (10) containing a repeating unit represented by the following formula (10) as a colorless transparent highly viscous liquid.
［ＨＦＩＰ基含有珪素化合物（３－３）を原料とするＨＦＩＰ基含有ポリシロキサン高分子化合物（１０）の合成］
ＨＦＩＰ基含有珪素化合物（３－３）、１．６３ｇ（４．０ｍｍｏｌ）をメタノールに溶かして全量を８．２ｇとした後、水０．２１６ｍＬ（１２．０ｍｍｏｌ）、４ｍｏｌ／Ｌの塩酸０．０５ｍＬを加え、室温で４時間攪拌した。反応液から溶媒を留去し、以下の式（１０）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（１０）を無色透明高粘性液体として得た。
[Synthesis of HFIP group-containing polysiloxane polymer compound (10) using HFIP group-containing silicon compound (3-3) as a raw material]
HFIP group-containing silicon compound (3-3), 1.63 g (4.0 mmol), dissolved in methanol to a total amount of 8.2 g, 0.216 mL (12.0 mmol) of water, 0.1 mol of 4 mol / L hydrochloric acid, 05 mL was added and stirred at room temperature for 4 hours. The solvent was distilled off from the reaction solution to obtain an HFIP group-containing polysiloxane polymer compound (10) containing a repeating unit represented by the following formula (10) as a colorless transparent highly viscous liquid.
（式中、ｘは任意の整数を表す。）
(In the formula, x represents an arbitrary integer.)
(In the formula, x represents an arbitrary integer.)
実施例７
［ＨＦＩＰ基含有珪素化合物（３－１）を含有するＨＦＩＰ基含有ポリシロキサン高分子化合物（１１）の合成］
５０ｍＬのフラスコに、ＨＦＩＰ基含有珪素化合物（３－１）、４．５８ｇ（８ｍｍｏｌ）、フェニルトリメトキシシラン、６．３５ｇ（３２ｍｍｏｌ）、水、２．１６ｇ（１２０ｍｍｏｌ）、酢酸、０．１２ｇ（２ｍｍｏｌ）を加え、１００℃で１２時間攪拌した。反応終了後、トルエンを加え、還流（バス温度１５０℃）させることにより、水、生成するエタノール、メタノール、酢酸を留去し、最後にトルエンを留去することによって、以下の式（１１）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（１１）を白色固体として得た。
Example 7
[Synthesis of HFIP group-containing polysiloxane polymer compound (11) containing HFIP group-containing silicon compound (3-1)]
To a 50 mL flask, HFIP group-containing silicon compound (3-1), 4.58 g (8 mmol), phenyltrimethoxysilane, 6.35 g (32 mmol), water, 2.16 g (120 mmol), acetic acid, 0.12 g ( 2 mmol) was added and the mixture was stirred at 100 ° C. for 12 hours. After completion of the reaction, toluene is added and refluxed (bath temperature 150 ° C.) to distill off water, generated ethanol, methanol and acetic acid. Finally, toluene is distilled off to obtain the following formula (11). An HFIP group-containing polysiloxane polymer compound (11) containing the represented repeating unit was obtained as a white solid.
［ＨＦＩＰ基含有珪素化合物（３－１）を含有するＨＦＩＰ基含有ポリシロキサン高分子化合物（１１）の合成］
５０ｍＬのフラスコに、ＨＦＩＰ基含有珪素化合物（３－１）、４．５８ｇ（８ｍｍｏｌ）、フェニルトリメトキシシラン、６．３５ｇ（３２ｍｍｏｌ）、水、２．１６ｇ（１２０ｍｍｏｌ）、酢酸、０．１２ｇ（２ｍｍｏｌ）を加え、１００℃で１２時間攪拌した。反応終了後、トルエンを加え、還流（バス温度１５０℃）させることにより、水、生成するエタノール、メタノール、酢酸を留去し、最後にトルエンを留去することによって、以下の式（１１）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（１１）を白色固体として得た。
[Synthesis of HFIP group-containing polysiloxane polymer compound (11) containing HFIP group-containing silicon compound (3-1)]
To a 50 mL flask, HFIP group-containing silicon compound (3-1), 4.58 g (8 mmol), phenyltrimethoxysilane, 6.35 g (32 mmol), water, 2.16 g (120 mmol), acetic acid, 0.12 g ( 2 mmol) was added and the mixture was stirred at 100 ° C. for 12 hours. After completion of the reaction, toluene is added and refluxed (bath temperature 150 ° C.) to distill off water, generated ethanol, methanol and acetic acid. Finally, toluene is distilled off to obtain the following formula (11). An HFIP group-containing polysiloxane polymer compound (11) containing the represented repeating unit was obtained as a white solid.
（式中、ｙおよびｚはモル比を表わし、ｙ／ｚ＝２０／８０である。）
(In the formula, y and z represent a molar ratio, and y / z = 20/80.)
(In the formula, y and z represent a molar ratio, and y / z = 20/80.)
実施例８
［ＨＦＩＰ基含有珪素化合物（３－２）を含有するＨＦＩＰ基含有ポリシロキサン高分子化合物（１２）の合成］
５０ｍＬのフラスコに、ＨＦＩＰ基含有珪素化合物（３－２）、５．５９ｇ（１３．７５ｍｍｏｌ）、フェニルトリメトキシシラン、２．２３ｇ（１１．２５ｍｍｏｌ）、水、１．３５ｇ（７５ｍｍｏｌ）、酢酸、０．０７５ｇ（１．２５ｍｍｏｌ）を加え、１００℃で１２時間攪拌した。反応終了後、トルエンを加え、還流（バス温度１５０℃）させることにより、水、生成するエタノール、酢酸を留去し、最後にトルエンを留去することによって、以下の式（１２）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（１２）を白色固体として得た。
Example 8
[Synthesis of HFIP group-containing polysiloxane polymer compound (12) containing HFIP group-containing silicon compound (3-2)]
In a 50 mL flask, HFIP group-containing silicon compound (3-2), 5.59 g (13.75 mmol), phenyltrimethoxysilane, 2.23 g (11.25 mmol), water, 1.35 g (75 mmol), acetic acid, 0.075 g (1.25 mmol) was added, and the mixture was stirred at 100 ° C. for 12 hours. After completion of the reaction, toluene is added and refluxed (bath temperature 150 ° C.), thereby distilling off water, generated ethanol and acetic acid, and finally distilling off toluene, which is expressed by the following formula (12). HFIP group-containing polysiloxane polymer compound (12) containing a repeating unit was obtained as a white solid.
［ＨＦＩＰ基含有珪素化合物（３－２）を含有するＨＦＩＰ基含有ポリシロキサン高分子化合物（１２）の合成］
５０ｍＬのフラスコに、ＨＦＩＰ基含有珪素化合物（３－２）、５．５９ｇ（１３．７５ｍｍｏｌ）、フェニルトリメトキシシラン、２．２３ｇ（１１．２５ｍｍｏｌ）、水、１．３５ｇ（７５ｍｍｏｌ）、酢酸、０．０７５ｇ（１．２５ｍｍｏｌ）を加え、１００℃で１２時間攪拌した。反応終了後、トルエンを加え、還流（バス温度１５０℃）させることにより、水、生成するエタノール、酢酸を留去し、最後にトルエンを留去することによって、以下の式（１２）で表される繰り返し単位を含むＨＦＩＰ基含有ポリシロキサン高分子化合物（１２）を白色固体として得た。
[Synthesis of HFIP group-containing polysiloxane polymer compound (12) containing HFIP group-containing silicon compound (3-2)]
In a 50 mL flask, HFIP group-containing silicon compound (3-2), 5.59 g (13.75 mmol), phenyltrimethoxysilane, 2.23 g (11.25 mmol), water, 1.35 g (75 mmol), acetic acid, 0.075 g (1.25 mmol) was added, and the mixture was stirred at 100 ° C. for 12 hours. After completion of the reaction, toluene is added and refluxed (bath temperature 150 ° C.), thereby distilling off water, generated ethanol and acetic acid, and finally distilling off toluene, which is expressed by the following formula (12). HFIP group-containing polysiloxane polymer compound (12) containing a repeating unit was obtained as a white solid.
（式中、ｙおよびｚはモル比を表わし、ｙ／ｚ＝５５／４５である。）
表１に、実施例４～実施例８における原料化合物の質量比を示す。
(In the formula, y and z represent a molar ratio, and y / z = 55/45.)
Table 1 shows the mass ratio of the raw material compounds in Examples 4 to 8.
表１に、実施例４～実施例８における原料化合物の質量比を示す。
(In the formula, y and z represent a molar ratio, and y / z = 55/45.)
Table 1 shows the mass ratio of the raw material compounds in Examples 4 to 8.
［ＨＦＩＰ基含有ポリシロキサン高分子化合物のアルカリ現像液に対する溶解性評価］
合成したＨＦＩＰ基含有ポリシロキサン高分子化合物（８）～（１２）の重量平均分子量Ｍｗを測定した。次いで、前述の方法で、アルカリ現像液（濃度２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液）に対する溶解性の評価を行った。結果を以下の表２に示す。ＨＦＩＰ基含有ポリシロキサン高分子化合物（８）～（１２）は、いずれもアルカリ現像液に「溶解」した。 [Evaluation of solubility of HFIP group-containing polysiloxane polymer in alkaline developer]
The weight average molecular weights Mw of the synthesized HFIP group-containing polysiloxane polymer compounds (8) to (12) were measured. Next, the solubility in an alkali developer (tetramethylammonium hydroxide aqueous solution having a concentration of 2.38% by mass) was evaluated by the above-described method. The results are shown in Table 2 below. The HFIP group-containing polysiloxane polymer compounds (8) to (12) were all “dissolved” in the alkaline developer.
合成したＨＦＩＰ基含有ポリシロキサン高分子化合物（８）～（１２）の重量平均分子量Ｍｗを測定した。次いで、前述の方法で、アルカリ現像液（濃度２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液）に対する溶解性の評価を行った。結果を以下の表２に示す。ＨＦＩＰ基含有ポリシロキサン高分子化合物（８）～（１２）は、いずれもアルカリ現像液に「溶解」した。 [Evaluation of solubility of HFIP group-containing polysiloxane polymer in alkaline developer]
The weight average molecular weights Mw of the synthesized HFIP group-containing polysiloxane polymer compounds (8) to (12) were measured. Next, the solubility in an alkali developer (tetramethylammonium hydroxide aqueous solution having a concentration of 2.38% by mass) was evaluated by the above-described method. The results are shown in Table 2 below. The HFIP group-containing polysiloxane polymer compounds (8) to (12) were all “dissolved” in the alkaline developer.
［ＨＦＩＰ基含有ポリシロキサン高分子化合物の耐熱性評価］
上記手法に従って、熱分解温度（Ｔd5）を測定し、ＨＦＩＰ基含有ポリシロキサン高分子化合物（８）～（１２）の熱安定性を評価した。結果を表２に示す。この結果、ＨＦＩＰ基含有ポリシロキサン高分子化合物（８）～（１２）のＴd5は、いずれも３９０℃以上であり、高い耐熱性を有することが分かった。
[Heat resistance evaluation of HFIP group-containing polysiloxane polymer compound]
According to the above method, the thermal decomposition temperature (T d5 ) was measured, and the thermal stability of the HFIP group-containing polysiloxane polymer compounds (8) to (12) was evaluated. The results are shown in Table 2. As a result, it was found that T d5 of the HFIP group-containing polysiloxane polymer compounds (8) to (12) is 390 ° C. or higher and has high heat resistance.
上記手法に従って、熱分解温度（Ｔd5）を測定し、ＨＦＩＰ基含有ポリシロキサン高分子化合物（８）～（１２）の熱安定性を評価した。結果を表２に示す。この結果、ＨＦＩＰ基含有ポリシロキサン高分子化合物（８）～（１２）のＴd5は、いずれも３９０℃以上であり、高い耐熱性を有することが分かった。
[Heat resistance evaluation of HFIP group-containing polysiloxane polymer compound]
According to the above method, the thermal decomposition temperature (T d5 ) was measured, and the thermal stability of the HFIP group-containing polysiloxane polymer compounds (8) to (12) was evaluated. The results are shown in Table 2. As a result, it was found that T d5 of the HFIP group-containing polysiloxane polymer compounds (8) to (12) is 390 ° C. or higher and has high heat resistance.
比較例１
本発明の範疇にないポリシロキサン高分子化合物として、比較用ポリシロキサン高分子化合物１を合成した。フェニルトリエトキシシラン４．８０ｇ（２０．０ｍｍｏｌ）をメタノールに溶かして全量を２７ｇとし、水１．０８ｍＬ、４ｍｏｌ／Ｌの塩酸０．２５ｍＬを混合し、実施例４と同様の手順で、比較用ポリシロキサン高分子化合物１を得た。得られた比較用ポリシロキサン高分子化合物１のＧＰＣ測定から求めたＭｗは２０００であり、アルカリ現像液に対する溶解性を確認したところ、「不溶」であった。
Comparative Example 1
Comparative polysiloxane polymer compound 1 was synthesized as a polysiloxane polymer compound not within the scope of the present invention. Dissolve 4.80 g (20.0 mmol) of phenyltriethoxysilane in methanol to make a total amount of 27 g, mix 1.08 mL of water and 0.25 mL of 4 mol / L hydrochloric acid, and perform the same procedure as in Example 4 for comparison. Polysiloxane polymer compound 1 was obtained. Mw obtained from GPC measurement of the obtained comparative polysiloxane polymer compound 1 was 2000, and the solubility in an alkali developer was confirmed to be “insoluble”.
本発明の範疇にないポリシロキサン高分子化合物として、比較用ポリシロキサン高分子化合物１を合成した。フェニルトリエトキシシラン４．８０ｇ（２０．０ｍｍｏｌ）をメタノールに溶かして全量を２７ｇとし、水１．０８ｍＬ、４ｍｏｌ／Ｌの塩酸０．２５ｍＬを混合し、実施例４と同様の手順で、比較用ポリシロキサン高分子化合物１を得た。得られた比較用ポリシロキサン高分子化合物１のＧＰＣ測定から求めたＭｗは２０００であり、アルカリ現像液に対する溶解性を確認したところ、「不溶」であった。
Comparative Example 1
Comparative polysiloxane polymer compound 1 was synthesized as a polysiloxane polymer compound not within the scope of the present invention. Dissolve 4.80 g (20.0 mmol) of phenyltriethoxysilane in methanol to make a total amount of 27 g, mix 1.08 mL of water and 0.25 mL of 4 mol / L hydrochloric acid, and perform the same procedure as in Example 4 for comparison. Polysiloxane polymer compound 1 was obtained. Mw obtained from GPC measurement of the obtained comparative polysiloxane polymer compound 1 was 2000, and the solubility in an alkali developer was confirmed to be “insoluble”.
比較例２
フェニルトリメトキシシラン、１９．８３ｇ（１００ｍｍｏｌ）、水、５．４０ｇ（３００ｍｍｏｌ）、酢酸、０．３ｇ（５ｍｍｏｌ）を加え、１００℃で１２時間攪拌した。反応終了後、トルエンを加え、還流（バス温度１５０℃）させることにより、水、生成するエタノール、酢酸を留去し、最後にトルエンを留去することによって、比較用ポリシロキサン高分子化合物２を得た。得られた比較用ポリシロキサン高分子化合物２のＧＰＣ測定から求めたＭｗは３５００であり、アルカリ現像液に対する溶解性を確認したところ、「不溶」であった。
Comparative Example 2
Phenyltrimethoxysilane, 19.83 g (100 mmol), water, 5.40 g (300 mmol), acetic acid and 0.3 g (5 mmol) were added, and the mixture was stirred at 100 ° C. for 12 hours. After completion of the reaction, toluene is added and refluxed (bath temperature 150 ° C.), thereby distilling off water, generated ethanol and acetic acid, and finally distilling off toluene to obtain comparative polysiloxane polymer compound 2. Obtained. Mw obtained from GPC measurement of the obtained comparative polysiloxane polymer compound 2 was 3500, and the solubility in an alkali developer was confirmed to be “insoluble”.
フェニルトリメトキシシラン、１９．８３ｇ（１００ｍｍｏｌ）、水、５．４０ｇ（３００ｍｍｏｌ）、酢酸、０．３ｇ（５ｍｍｏｌ）を加え、１００℃で１２時間攪拌した。反応終了後、トルエンを加え、還流（バス温度１５０℃）させることにより、水、生成するエタノール、酢酸を留去し、最後にトルエンを留去することによって、比較用ポリシロキサン高分子化合物２を得た。得られた比較用ポリシロキサン高分子化合物２のＧＰＣ測定から求めたＭｗは３５００であり、アルカリ現像液に対する溶解性を確認したところ、「不溶」であった。
Comparative Example 2
Phenyltrimethoxysilane, 19.83 g (100 mmol), water, 5.40 g (300 mmol), acetic acid and 0.3 g (5 mmol) were added, and the mixture was stirred at 100 ° C. for 12 hours. After completion of the reaction, toluene is added and refluxed (bath temperature 150 ° C.), thereby distilling off water, generated ethanol and acetic acid, and finally distilling off toluene to obtain comparative polysiloxane polymer compound 2. Obtained. Mw obtained from GPC measurement of the obtained comparative polysiloxane polymer compound 2 was 3500, and the solubility in an alkali developer was confirmed to be “insoluble”.
比較例３
下記式（１３）で表されるＨＦＩＰ基含有珪素化合物（１３）、４．３４ｇ（１０．０ｍｍｏｌ）をメタノールに溶かして全量を２１．７４ｇとした。これと、水０．５４ｇと、４ｍｏｌ／Ｌの塩酸０．１２５ｍＬとを混合し、実施例４と同様の手順で、比較用ポリシロキサン高分子化合物３を得た。 Comparative Example 3
HFIP group-containing silicon compound (13) represented by the following formula (13), 4.34 g (10.0 mmol) was dissolved in methanol to make the total amount 21.74 g. This, 0.54 g of water, and 0.125 mL of 4 mol / L hydrochloric acid were mixed, and a comparative polysiloxane polymer compound 3 was obtained in the same procedure as in Example 4.
下記式（１３）で表されるＨＦＩＰ基含有珪素化合物（１３）、４．３４ｇ（１０．０ｍｍｏｌ）をメタノールに溶かして全量を２１．７４ｇとした。これと、水０．５４ｇと、４ｍｏｌ／Ｌの塩酸０．１２５ｍＬとを混合し、実施例４と同様の手順で、比較用ポリシロキサン高分子化合物３を得た。 Comparative Example 3
HFIP group-containing silicon compound (13) represented by the following formula (13), 4.34 g (10.0 mmol) was dissolved in methanol to make the total amount 21.74 g. This, 0.54 g of water, and 0.125 mL of 4 mol / L hydrochloric acid were mixed, and a comparative polysiloxane polymer compound 3 was obtained in the same procedure as in Example 4.
ＨＦＩＰ基含有珪素化合物（１３）およびそれから得られる比較用ポリシロキサン高分子化合物３は、珪素原子と芳香環の間にエチレン結合（－ＣＨ2－ＣＨ2－）を有する。したがって、珪素原子と芳香環が直接結合する本発明のＨＦＩＰ基含有珪素化合物およびＨＦＩＰ基含有ポリシロキサン高分子化合物とは異なる。
The HFIP group-containing silicon compound (13) and the comparative polysiloxane polymer compound 3 obtained therefrom have an ethylene bond (—CH 2 —CH 2 —) between the silicon atom and the aromatic ring. Therefore, it differs from the HFIP group-containing silicon compound and HFIP group-containing polysiloxane polymer compound of the present invention in which a silicon atom and an aromatic ring are directly bonded.
得られた比較用ポリシロキサン高分子化合物３のＭｗは３４００であった。アルカリ現像液に対する溶解性を確認したところ、「溶解」であった。また、熱分解温度の測定を行った結果、５％質量減少温度（Ｔd5）は３２０℃であった。この結果は、実施例４～８で得られた本発明のＨＦＩＰ基含有ポリシロキサン高分子化合物（８）～（１２）の５％質量減少温度（Ｔd5）よりも低かった。
Mw of the obtained comparative polysiloxane polymer compound 3 was 3400. When the solubility in an alkaline developer was confirmed, it was “dissolved”. As a result of measuring the thermal decomposition temperature, the 5% mass reduction temperature (T d5 ) was 320 ° C. This result was lower than the 5% mass reduction temperature (T d5 ) of the HFIP group-containing polysiloxane polymer compounds (8) to (12) of the present invention obtained in Examples 4 to 8.
表１に、上記比較例１～比較例３における原料化合物を示す
Table 1 shows the raw material compounds in Comparative Examples 1 to 3 above.
表２に、上記比較用ポリシロキサン高分子化合物１～３におけるＧＰＣ測定から求めたＭｗ、アルカリ現像液に対する溶解性、５％質量減少温度（Ｔd5）を示す。
Table 2 shows Mw obtained from GPC measurement in the above comparative polysiloxane polymer compounds 1 to 3, solubility in alkali developer, and 5% mass reduction temperature (T d5 ).
Claims (8)
- 一般式（１）
で表される珪素化合物。 General formula (1)
The silicon compound represented by these. - 一般式（２）
で表される、請求項１に記載の珪素化合物。 General formula (2)
The silicon compound of Claim 1 represented by these. - 一般式（３）
で表される請求項１または請求項２に記載の珪素化合物。 General formula (3)
The silicon compound of Claim 1 or Claim 2 represented by these. - 一般式（４）
で表される芳香族化合物、および
一般式（５）
で表される珪素化合物を、遷移金属触媒の存在下で反応させて、
一般式（１）
で表される珪素化合物を得る、珪素化合物の製造方法。 General formula (4)
And an aromatic compound represented by the general formula (5)
Is reacted in the presence of a transition metal catalyst,
General formula (1)
The manufacturing method of the silicon compound which obtains the silicon compound represented by these. - 一般式（６）
で表される繰り返し単位を含む、高分子化合物。 General formula (6)
The high molecular compound containing the repeating unit represented by these. - 一般式（７）：
で表される繰り返し単位を含む、請求項５に記載の高分子化合物。 General formula (7):
The high molecular compound of Claim 5 containing the repeating unit represented by these. - 一般式（１）
で表される珪素化合物を、加水分解重縮合することで
一般式（６）
で表される繰り返し単位を含む高分子化合物を得る、高分子化合物の製造方法。 General formula (1)
The silicon compound represented by general formula (6) is obtained by hydrolytic polycondensation.
The manufacturing method of a high molecular compound which obtains the high molecular compound containing the repeating unit represented by these. - 請求項５または請求項６に記載の高分子化合物を含む、膜。 A film comprising the polymer compound according to claim 5.
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| JP2021070758A (en) * | 2019-10-31 | 2021-05-06 | 東レ株式会社 | Resin composition and cured film thereof |
| JPWO2021187324A1 (en) * | 2020-03-16 | 2021-09-23 | ||
| KR20230142534A (en) | 2021-02-05 | 2023-10-11 | 샌트랄 글래스 컴퍼니 리미티드 | Silicon compound containing hexafluoroisopropanol group, method for producing silicon compound, polysiloxane and method for producing polysiloxane |
| WO2023171487A1 (en) * | 2022-03-07 | 2023-09-14 | 東レ株式会社 | Photosensitive resin composition, cured article, display device, and method for producing display device |
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- 2014-01-17 WO PCT/JP2014/050787 patent/WO2014112584A1/en active Application Filing
- 2014-01-21 TW TW103102154A patent/TW201439109A/en unknown
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160266491A1 (en) * | 2013-11-01 | 2016-09-15 | Central Glass Company, Limited | Positive Photosensitive Resin Composition, Method for Producing Film Using Same, and Electronic Component |
| US9778569B2 (en) * | 2013-11-01 | 2017-10-03 | Central Glass Company, Limited | Positive photosensitive resin composition, method for producing film using same, and electronic component |
| CN111819183A (en) * | 2018-02-28 | 2020-10-23 | 中央硝子株式会社 | Silicon compound containing hexafluoroisopropanol group and method for producing same |
| WO2020045214A1 (en) * | 2018-08-31 | 2020-03-05 | 東レ株式会社 | Resin composition and cured film obtained therefrom |
| CN116034127A (en) * | 2020-09-16 | 2023-04-28 | 中央硝子株式会社 | Silicon-containing monomer mixture, polysiloxane, resin composition, photosensitive resin composition, cured film, method for producing cured film, pattern cured film, and method for producing pattern cured film |
| CN116034127B (en) * | 2020-09-16 | 2024-03-01 | 中央硝子株式会社 | Silicon-containing monomer mixture, polysiloxane, resin composition, photosensitive resin composition, cured film, method for producing cured film, pattern cured film, and method for producing pattern cured film |
| WO2022113724A1 (en) * | 2020-11-24 | 2022-06-02 | セントラル硝子株式会社 | Silicon-containing monomer, mixture, polysiloxane, and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201439109A (en) | 2014-10-16 |
| JP6281288B2 (en) | 2018-02-21 |
| JP2014156461A (en) | 2014-08-28 |
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