WO2009119469A1 - エポキシ化合物およびその製造方法 - Google Patents
エポキシ化合物およびその製造方法 Download PDFInfo
- Publication number
- WO2009119469A1 WO2009119469A1 PCT/JP2009/055576 JP2009055576W WO2009119469A1 WO 2009119469 A1 WO2009119469 A1 WO 2009119469A1 JP 2009055576 W JP2009055576 W JP 2009055576W WO 2009119469 A1 WO2009119469 A1 WO 2009119469A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- carbon atoms
- epoxy compound
- formula
- hydrogen atom
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 267
- 239000004593 Epoxy Substances 0.000 title claims abstract description 202
- 238000000034 method Methods 0.000 title abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 92
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 110
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 58
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 54
- 229920005591 polysilicon Polymers 0.000 claims description 54
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 44
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 35
- -1 siloxane skeleton Chemical group 0.000 description 32
- 125000003700 epoxy group Chemical group 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 238000000113 differential scanning calorimetry Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 238000002329 infrared spectrum Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- IZXLUEMTVRPVBL-UHFFFAOYSA-N ac1nbpy7 Chemical compound O1[Si](O[Si](O[SiH](C)C)(O2)O[Si](O[SiH](C)C)(O3)O4)(O[SiH](C)C)O[Si]4(O[SiH](C)C)O[Si]4(O[SiH](C)C)O[Si]1(O[SiH](C)C)O[Si]2(O[SiH](C)C)O[Si]3(O[SiH](C)C)O4 IZXLUEMTVRPVBL-UHFFFAOYSA-N 0.000 description 11
- 239000010409 thin film Substances 0.000 description 11
- 125000002723 alicyclic group Chemical group 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 125000004430 oxygen atom Chemical group O* 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- CCEFMUBVSUDRLG-KXUCPTDWSA-N (4R)-limonene 1,2-epoxide Natural products C1[C@H](C(=C)C)CC[C@@]2(C)O[C@H]21 CCEFMUBVSUDRLG-KXUCPTDWSA-N 0.000 description 9
- WEEGYLXZBRQIMU-UHFFFAOYSA-N 1,8-cineole Natural products C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- CCEFMUBVSUDRLG-XNWIYYODSA-N Limonene-1,2-epoxide Chemical compound C1[C@H](C(=C)C)CCC2(C)OC21 CCEFMUBVSUDRLG-XNWIYYODSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 238000001020 plasma etching Methods 0.000 description 8
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 8
- 210000002966 serum Anatomy 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 7
- 238000001382 dynamic differential scanning calorimetry Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 6
- WRGWYAZIVRHPFP-UHFFFAOYSA-N prop-2-enyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1C(C(=O)OCC=C)CCC2OC21 WRGWYAZIVRHPFP-UHFFFAOYSA-N 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 230000001568 sexual effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- MWSPFHZPVVWJCO-UHFFFAOYSA-M hydron;methyl(trioctyl)azanium;sulfate Chemical compound OS([O-])(=O)=O.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC MWSPFHZPVVWJCO-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003999 initiator 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
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RTLRLWWCGQYMJP-UHFFFAOYSA-N silyloxy(silyloxysilyloxysilyloxysilyloxysilyloxysilyloxy)silane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH3] RTLRLWWCGQYMJP-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- WZWGGYFEOBVNLA-UHFFFAOYSA-N sodium;dihydrate Chemical compound O.O.[Na] WZWGGYFEOBVNLA-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
Definitions
- the present invention relates to a novel epoxy compound and a method for producing the same, and more particularly useful as a raw material for sealing materials and coating materials for electrical / electronic / optical components, or adhesives, paints, silane coupling agents, modified silicones and the like.
- the present invention relates to an epoxy compound useful as a resist for a semiconductor manufacturing process, a patterned media magnetic recording medium manufacturing process, and the like, and a manufacturing method thereof.
- Epoxy compounds are cured with various curing agents to give cured products with excellent mechanical properties, moisture resistance, electrical properties, etc., sealing materials, molding materials, and casting materials for electrical, electronic, and optical components. It is used in a wide range of fields such as laminated materials, composite materials, adhesives and powder coatings. In recent years, with the advancement of technology, high performances related to curability, processability, etc. have been required as epoxy compounds. In particular, etching selectivity is also required for resist materials for semiconductor manufacturing processes.
- a siloxane skeleton into an epoxy compound for the purpose of imparting etching selectivity such as high resistance to a specific gas in various etching gases, and as an organopolysiloxane having an epoxy group-containing organic group, the molecular chain terminal
- organopolysiloxanes and cyclic siloxanes having a 3-glycidoxypropyl group or 2- (3,4-epoxycyclohexyl) ethyl group in the side chain of the molecular chain have been proposed (see Patent Document 1).
- the two steps of the siloxane epoxidation step and the polymerization step are required, and further, the treatment of the basic catalyst is essential, so that the production is complicated. It is accompanied by.
- an epoxy compound having a glycidyl group requires a relatively long curing time as compared with other curable functional groups, and therefore, it is desirable that the epoxy compound has a property of curing in a shorter time.
- a siloxane compound having a curable functional group there is a so-called sol-gel method in which an alkoxysilane is synthesized by a hydrolysis reaction, but the resulting product is a mixture and it is difficult to control components.
- the epoxy compound is liquid at room temperature, that is, about 10 to 30 ° C. in order to be applied to such applications.
- the present application aims to solve the above problems and provide an epoxy compound having excellent curability and etching selectivity. Furthermore, it aims at providing a liquid epoxy compound at normal temperature in addition to the said characteristic from a viewpoint of workability.
- n Y (p is a natural number of n or less) represents a group represented by any of the following formulas (1a) to (5a), and (np) Y represents a hydrogen atom or —OSiR 1 2 H, and n represents an integer of 2 to 500.
- Each R 1 independently represents an alkyl group having 1 to 5 carbon atoms.);
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms, and R 5 to R 11 are each independently a hydrogen atom, 1 to 6 carbon atoms. Or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, or an aryl group.
- * Represents a bonding portion with Si shown in the formula (I), and -X- * represents-* in which X is a single bond, or a group represented by the following formula (x). );
- R 1 represents an alkyl group having 1 to 5 carbon atoms.
- R 2 to R 11 are each independently a hydrogen atom or a methyl group
- R 12 is a hydrogen atom, a methyl group or a phenyl group.
- q out of 8 Zs (q is a natural number of 8 or less) represents —OSiR 1 2 Y 1 , and (8-q) Zs represent a hydrogen atom or —OSiR 1 2 H.
- R 1 represents an alkyl group having 1 to 5 carbon atoms
- Y 1 represents a group represented by any one of the following formulas (1b) to (5b)):
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms, and R 5 to R 11 are each independently a hydrogen atom, 1 to 6 carbon atoms. Or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, or an aryl group. ).
- R 1 is a methyl group or an ethyl group.
- R 2 to R 11 are each independently a hydrogen atom or a methyl group
- R 12 is a hydrogen atom, a methyl group or a phenyl group.
- Y 1 represents a hydrogen atom or —OSiR 1 2 H
- R 1 represents an alkyl group having 1 to 5 carbon atoms
- n represents an integer of 2 to 500.
- Z 1 represents —OSiR 1 2 H, R 1 represents an alkyl group having 1 to 5 carbon atoms
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms, and R 5 to R 11 are each independently a hydrogen atom, 1 to 6 carbon atoms. Or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, or an aryl group.
- the polysilicon compound is a polysilicon compound represented by the formula (III), and the polysilicon compound is a polysilicon compound having a cage-like silsesquioxane structure or a ladder-like silsesquioxane structure.
- the manufacturing method of the epoxy compound of description is a polysilicon compound represented by the formula (III), and the polysilicon compound is a polysilicon compound having a cage-like silsesquioxane structure or a ladder-like silsesquioxane structure.
- R 2 to R 11 are each independently a hydrogen atom or a methyl group
- R 12 is a hydrogen atom, a methyl group or a phenyl group.
- Z 1 represents —OSiR 1 2 H, R 1 represents an alkyl group having 1 to 5 carbon atoms
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms, and R 5 to R 11 are each independently a hydrogen atom, 1 to 6 carbon atoms. Or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, or an aryl group.
- R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, or an aryl group.
- R 1 is a methyl group of the formula (IV) polysilicic containing compound represented by, according to the above [14], wherein the epoxy compound is the formula (6) or (9) Epoxy compound.
- the epoxy compound of the present invention is a so-called alicyclic epoxy compound having an alicyclic epoxy group, has higher storage stability than a glycidyl type epoxy compound, and is easy for industrial use. Moreover, the alicyclic epoxy group which the epoxy compound of this invention has has high cationic polymerizability with an epoxy group compared with a normal glycidyl group. Therefore, the epoxy compound is very suitable as an electronic material that is required to be cured at a lower temperature and in a shorter time.
- the epoxy compound of the present invention exhibits excellent etching resistance as a resist used in a dry etching process such as a semiconductor manufacturing process or a patterned media magnetic recording medium manufacturing process. That is, the epoxy compound is useful in a wide range of fields such as molding materials and sealing materials for electric / electronic / optical components, as well as casting materials, laminated materials, composite materials, adhesives, and powder paints.
- the method for producing an epoxy compound according to the present invention includes a step of reacting a specific polysilicon compound and a specific epoxy compound under predetermined conditions, and therefore, compared with a generally known method using a sol-gel method. An epoxy compound having high stability can be obtained.
- the method for producing an epoxy compound of the present invention uses a so-called alicyclic epoxy compound having a functional group such as limonene oxide or allyl 3,4-epoxycyclohexane-1-carboxylate as the specific epoxy compound.
- the resulting epoxy compound can be easily liquefied. Therefore, the epoxy compound is also suitable for uses such as UV nanoimprints that are required to be liquid.
- FIG. 1 is a 1 H-NMR spectrum of the product obtained in Example 3.
- 3 is a 13 C-NMR spectrum of the product obtained in Example 3.
- 3 is an IR spectrum of the product obtained in Example 3.
- 1 is a 1 H-NMR spectrum of the product obtained in Example 4.
- 3 is a 13 C-NMR spectrum of the product obtained in Example 4.
- 4 is an IR spectrum of the product obtained in Example 4.
- Example 5 1 is a 1 H-NMR spectrum of the product obtained in Example 5.
- 3 is a 13 C-NMR spectrum of the product obtained in Example 5.
- 4 is an IR spectrum of the product obtained in Example 5.
- 1 is a 1 H-NMR spectrum of the product obtained in Example 6.
- 3 is a 13 C-NMR spectrum of the product obtained in Example 6.
- 2 is an IR spectrum of the product obtained in Example 6.
- the epoxy compound of the present invention is represented by the formula (I).
- p of Y (p is a natural number of n or less) represents a group represented by any of the following formulas (1a) to (5a), and (np) Y is a hydrogen atom Or -OSiR 1 2 H, and n is an integer of 2 to 500, preferably an even number of 6 to 18, more preferably 8.
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 2 and R 3 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a hexyl group, a trimethylsilyl group, and a triethylsilyl group.
- R 2 and R 3 may be the same or different from each other, but are preferably the same.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 4 include a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, hexyl group, trimethylsilyl group, triethylsilyl group, and tertiary group.
- a butyl dimethyl silyl group is mentioned, it is not limited to these.
- a hydrogen atom, a methyl group, a trimethylsilyl group, and a tertiary butyldimethylsilyl group are preferable, and a hydrogen atom and a methyl group are more preferable.
- R 5 to R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms.
- R 5 and R 11 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a hexyl group, a trimethylsilyl group, and a triethylsilyl group.
- Group, and tertiary butyldimethylsilyl group but are not limited thereto.
- R 5 to R 11 may be the same or different from each other, but are preferably the same.
- R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, or an aryl group.
- R 12 include a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, hexyl group, trimethylsilyl group, triethylsilyl group, and tertiary group. Examples include, but are not limited to, a butyldimethylsilyl group and a phenyl group.
- a hydrogen atom, a methyl group, a trimethylsilyl group, a tertiary butyldimethylsilyl group, and a phenyl group are preferable, and a hydrogen atom, a methyl group, and a phenyl group are more preferable.
- R 1 represents an alkyl group having 1 to 5 carbon atoms, and is preferably an alkyl group having 1 or 2 carbon atoms.
- R 1 include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a pentyl group. Of these, a methyl group and an ethyl group are preferable.
- the epoxy compound represented by the formula (I) has n Y. At least one of them, that is, p (p is a natural number of n or less) Y is a group represented by any one of the above formulas (1a) to (5a) as described above. Among these, Y is preferably a group represented by any one of formulas (1a), (4a), and (5a), and more preferably a group represented by formula (4a).
- an epoxy compound in which R 1 is a methyl group or an ethyl group is preferable.
- an epoxy compound in which R 2 to R 11 are each independently a hydrogen atom or a methyl group, and R 12 is a hydrogen atom, a methyl group, or a phenyl group is preferable.
- an epoxy compound in which R 1 is a methyl group or an ethyl group, R 2 to R 11 are each independently a hydrogen atom or a methyl group, and R 12 is a hydrogen atom, a methyl group or a phenyl group Is more preferable.
- the epoxy compound of the present invention is a so-called alicyclic epoxy compound having an alicyclic epoxy group as represented by the formula (I). Furthermore, the epoxy compound of the present invention is desirably an epoxy compound having a cage-like silsesquioxane structure or a ladder-like silsesquioxane structure.
- n Y of the epoxy compound represented by the formula (I) is a group represented by any one of the above formulas (1a) to (5a), that is, p is a natural number smaller than n.
- the epoxy compound represented by the formula (I) has (np) Y other than the groups represented by the formulas (1a) to (5a).
- This (np) Y is a hydrogen atom or —OSiR 1 2 H.
- R 1 represents an alkyl group having 1 to 5 same number of carbon atoms as R 1 in the formula (x).
- the (np) Ys are derived from a polysilicon compound that is a raw material for producing the epoxy compound represented by the formula (I). Residue.
- Epoxy compound having caged silsesquioxane structure includes an epoxy compound represented by the following formula (II), that is, an epoxy compound in which n is 8 in the above formula (I).
- q out of 8 Zs (q is a natural number of 8 or less) represents —OSiR 1 2 Y 1 , R 1 represents an alkyl group having 1 to 5 carbon atoms, and the above formula It is synonymous with R 1 in (x), and Y 1 represents a group represented by any of the following formulas (1b) to (5b).
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms, It is synonymous with R 2 and R 3 in (1a) to (5a).
- R 4 is a hydrogen atom, a trialkylsilyl group of the alkyl group having 1 to 6 carbon atoms or from 1 carbon atoms, up to 4, the same meaning as R 4 in the formula (1a) ⁇ (5a).
- R 5 ⁇ R 11 are each independently a hydrogen atom, a trialkylsilyl group of the alkyl group having 1 to 6 carbon atoms or from 1 carbon atoms, up to 4, R 5 in the formula (1a) ⁇ (5a) it is synonymous with ⁇ R 11.
- R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, or an aryl group, and has the same meaning as R 12 in the above formulas (1a) to (5a). is there.
- Y 1 is a group represented by any one of the following formulas (1b) to (5b) as described above, and among them, a group represented by any one of the formulas (1b), (4b), and (5b) It is preferable that it is a group represented by the formula (4b).
- an epoxy compound in which R 1 is a methyl group or an ethyl group is preferable.
- an epoxy compound in which R 2 to R 11 are each independently a hydrogen atom or a methyl group, and R 12 is a hydrogen atom, a methyl group, or a phenyl group is preferable.
- an epoxy compound in which R 1 is a methyl group or an ethyl group, R 2 to R 11 are each independently a hydrogen atom or a methyl group, and R 12 is a hydrogen atom, a methyl group or a phenyl group Is more preferable.
- the epoxy compound represented by the above formula (II) has (8-q) Z other than the groups represented by the formulas (1b) to (5b).
- the (8-q) pieces of Z are —OSiR 1 2 H.
- R 1 represents an alkyl group having 1 to 5 same number of carbon atoms as R 1 in the formula (x).
- the (8-q) Z is derived from a polysilicon compound which is a raw material for producing the epoxy compound represented by the formula (II). Residue.
- Epoxy compound having ladder-like silsesquioxane structure >> Preferred examples of the epoxy compound having a ladder-like silsesquioxane structure include, but are not limited to, an epoxy compound represented by the following formula (II ′).
- m represents an integer of 2 to 125, preferably 2 to 50, more preferably 2 to 30.
- Z is synonymous with the above formula (II). That is, the epoxy compound represented by the above formula (II ′) is an epoxy compound in which n is 8 to 500 in the above formula (I).
- the formula (II ′) has 4 m of Z, but the epoxy represented by the above formula (II ′) except that all 4 m of Z are groups represented by any of the above formulas (1b) to (5b)
- the compound will have Z other than the groups represented by formulas (1b) to (5b). At this time, Z other than the groups represented by the formulas (1b) to (5b) is —OSiR 1 2 H.
- R 1 represents an alkyl group having 1 to 5 same number of carbon atoms as R 1 in the formula (x).
- Z other than the groups represented by the formulas (1b) to (5b) represents the production of the epoxy compound represented by the formula (II ′). It is a residue derived from a polysilicon compound that is a raw material for use.
- the epoxy compound of the present invention is a so-called alicyclic epoxy compound having an alicyclic epoxy group
- the storage stability is higher than that of a glycidyl type epoxy compound, and industrial use is easy.
- this alicyclic epoxy group has higher cationic polymerizability with a carboxyl group than a normal glycidyl group, it can be cured at a lower temperature and in a shorter time.
- the epoxy compound of the present invention is liquid at about room temperature, that is, 10 to 30 ° C. Therefore, it can be suitably used for applications such as UV nanoimprints that are required to be liquid.
- being liquid means that the viscosity (mPa ⁇ s) can be measured using a viscosity measuring instrument (VISCOMETER DV-II + Pro, manufactured by BROOKFIELD) after removing the solvent.
- the viscosity is usually 1000 to 30000 mPa ⁇ s, and preferably 5000 to 20000 mPa ⁇ s.
- the method for producing an epoxy compound of the present invention comprises a polysilicon compound represented by formula (III) or a polysilicon compound represented by formula (IV), and an epoxy compound represented by any of the following formulas (6) to (10): And a step of reacting at a temperature of 10 to 200 ° C. This reaction is a hydrosilylation reaction, and can be sufficiently performed even at room temperature.
- Y 1 represents a hydrogen atom or —OSiR 1 2 H, and R 1 is an alkyl group having 1 to 5 carbon atoms.
- n represents an integer of 2 to 500, preferably an even number of 6 to 18, more preferably 8.
- Z 1 represents —OSiR 1 2 H, and R 1 represents an alkyl group having 1 to 5 carbon atoms.
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a trialkylsilyl group having 1 to 4 carbon atoms, It is synonymous with R 2 and R 3 in (1a) to (5a).
- R 4 is a hydrogen atom, a trialkylsilyl group of the alkyl group having 1 to 6 carbon atoms or from 1 carbon atoms, up to 4, the same meaning as R 4 in the formula (1a) ⁇ (5a).
- R 5 ⁇ R 11 are each independently a hydrogen atom, a trialkylsilyl group of the alkyl group having 1 to 6 carbon atoms or from 1 carbon atoms, up to 4, R 5 in the formula (1a) ⁇ (5a) it is synonymous with ⁇ R 11.
- R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, or an aryl group, and has the same meaning as R 12 in the above formulas (1a) to (5a). is there.
- Polysilicon compound As the polysilicon compound represented by the above formula (III), a polysilicon compound having a cage-like silsesquioxane structure or a ladder-like silsesquioxane structure is desirable.
- Preferred examples of the polysilicon compound having a ladder-shaped silsesquioxane structure include, but are not limited to, a polysilicon compound represented by the following formula (III ′).
- m represents an integer of 2 to 125, preferably 2 to 50, more preferably 2 to 30. That is, it is a polysilicon compound in which n is 8 to 500 in the above formula (III).
- Examples of the polysilicon compound having a cage silsesquioxane structure other than the polysilicon compound having a cage silsesquioxane structure represented by the above formula (III) include a polysilicon compound represented by the following formula (IV): Preferably mentioned.
- Z 1 represents —OSiR 1 2 H
- R 1 represents an alkyl group having 1 to 5 carbon atoms, and preferably an alkyl group having 1 or 2 carbon atoms.
- Specific examples of R 1 include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a pentyl group. Of these, a methyl group and an ethyl group are preferable.
- Epoxy compound is a compound having a double bond represented by any one of the above formulas (6) to (10), among which is represented by any one of the formulas (6), (9), and (10). It is preferable that it is an epoxy compound, and it is more preferable that it is an epoxy compound represented by Formula (9).
- an epoxy compound in which R 2 to R 11 are each independently a hydrogen atom or a methyl group, and R 12 is a hydrogen atom, a methyl group, or a phenyl group is preferable.
- a combination with a polysilicon compound which is an atom or a methyl group and R 12 is a hydrogen atom, a methyl group or a phenyl group is preferred.
- the compounding ratio of the polysilicon compound represented by the above formula (III) or (IV) and the epoxy compound having a double bond represented by any of the above formulas (6) to (10) is arbitrary and is particularly limited.
- the —SiH group in the polysilicon compound is usually 0.3 to 1.5 times the equivalent, preferably 0.8, to 1 equivalent of the ethylenic double bond in the epoxy compound. It is blended in an equivalent of 5 to 1.1 times. If the blending amount is outside the above range, one compound remains unreacted, which may be economically disadvantageous.
- an addition reaction catalyst composed of transition metals such as platinum, rhodium, palladium, nickel, iridium, ruthenium or the compounds thereof. it can. Specifically, chloroplatinic acid, various platinum complexes, platinum and vinylsiloxane complexes excluding chlorine, Karsted catalyst, various solutions of platinum compounds (alcohols, ketones, ethers, esters, aromatic hydrocarbons, etc. Dispersed type), Speier catalyst, catalyst supported on various solids (silica gel, activated carbon, etc.), Rh catalyst such as Wilkinson complex, and various complex catalysts of palladium, and the type or form is not particularly limited.
- platinum atoms when using a platinum catalyst, its amount is not particularly limited, relative to the number of moles of the hydroalkoxysilane, platinum atoms are usually 1 ⁇ 10 -2 ⁇ 10 -8 moles, preferably 1 ⁇ 10 - The amount is 3 to 10 ⁇ 6 times mole. If the platinum atom is less than the lower limit, the reaction rate may extremely decrease, and if the upper limit is exceeded, the reaction rate may be improved, but epoxy ring-opening polymerization may occur, economically. May also be disadvantageous.
- a solvent may be used as a reaction solvent or as a catalyst solution medium as necessary.
- a solvent can be used.
- Such a solvent include saturated hydrocarbons such as pentane, hexane, isooctane, decane, and cyclohexane, aromatic hydrocarbons such as toluene, xylene, mesitylene, ethylbenzene, decalin, and tetralin, diethyl ether, Examples include ethers such as THF, various silicones such as esters and polydimethylsiloxanes, and the like can be arbitrarily selected from these, and the amount used may be arbitrarily determined. These solvents may be used alone or in combination of two or more.
- a reactor filled with an inert gas such as a dry nitrogen gas is first filled with the above formula (6) to An epoxy compound represented by any one of (10) and a catalyst are charged. At this time, a solvent may be charged as necessary. Next, after stirring, the temperature is raised to a predetermined temperature, and then the polysilicon compound represented by the formula (III) or (IV) is dropped into the mixture to cause an addition reaction, and after completion of the dropping, the reaction is completed. Aging is performed.
- a method may be used in which a polysilicon compound represented by formula (III) or (IV) is first charged into the reactor, and then an epoxy compound represented by any one of formulas (6) to (10) is added. Also, a method of adding a mixed liquid of a polysilicon compound represented by the formula (III) or (IV) and an epoxy compound represented by any one of the formulas (6) to (10) to the catalyst and / or solvent. A method of raising the temperature after all the raw materials are charged all at once may be used. In addition, the production method of the present invention can be applied to any of reaction modes of batch, continuous and semi-continuous.
- the reaction temperature is preferably in the range of 10 to 200 ° C, particularly 10 to 150 ° C. If the reaction temperature is less than the above lower limit, the reaction rate decreases and the reaction may not be completed within a practical process time. Further, when the reaction temperature exceeds the above upper limit, the reaction rate is improved, but the ring opening polymerization of the epoxy group of the epoxy compound represented by any one of the formulas (6) to (10) or the target epoxy compound is performed. May occur.
- the atmosphere in the reactor is preferably an inert gas atmosphere such as nitrogen gas. Incorporation of moisture (or air containing moisture) not only adversely affects the reaction, but also the yield of the target epoxy compound decreases due to hydrolysis of the polysilicon compound represented by formula (III). There is a risk.
- a known technique of introducing dry air or an inert gas containing oxygen into the reaction atmosphere may be applied.
- the reaction time may vary depending on the reaction temperature, pressure conditions, catalyst concentration, and concentration of the raw material in the reaction system, but is usually 0.1 to 100 hours, and the reaction time is arbitrarily selected within the above range. Can do.
- the epoxy compound of the present invention represented by the formula (I) or the formula (II) includes the polysilicon compound represented by the formula (III) or the polysilicon compound represented by the formula (IV), and the formula (6) to It can be obtained by subjecting the epoxy compound represented by any one of (10) to a hydrosilylation reaction at 10 to 200 ° C.
- the epoxy compound represented by the formula (I) obtained by this reaction has n Y, but all the n Y are groups derived from the compound represented by any one of the formulas (6) to (10). Including cases other than certain cases. That is, in the epoxy compound obtained by this reaction, p (p is a natural number of n or less, that is, a natural number of 1 to n) of n Y contained in the compound is represented by the above formulas (1a) to (5a). One or two or more of the compounds that are groups represented by any of the above, are often obtained as a mixture of the above epoxy compounds having different p.
- this epoxy compound has (np) It has Y other than the groups represented by formulas (1a) to (5a).
- the (np) Y atoms are hydrogen atoms of the polysilicon compound represented by the formula (III) which is a raw material of the reaction, and are unreacted hydrogen atoms.
- the epoxy compound represented by the formula (II) obtained by this reaction has 8 Z, but all 8 Zs are compounds represented by any one of the formulas (6) to (10). Including. That is, in the epoxy compound obtained by this reaction, q out of 8 Z contained in this compound (q is a natural number of 8 or less, that is, a natural number of 1 to 8) is represented by the above formulas (1a) to (5a). In many cases, a mixture of the above epoxy compounds having a different q is obtained, which is one or more of the compounds represented by any of the above.
- a general method can be used for purification of the product.
- an adsorption separation method can be mentioned, and specifically, a method using an adsorbent such as activated carbon, acid clay, activated clay or the like can be mentioned.
- an adsorbent such as activated carbon, acid clay, activated clay or the like
- there are adsorption and removal methods for impurities and colored substances column chromatography, and thin layer chromatography.
- Specific examples of the adsorption removal method include adsorption removal methods using silica gel, hydrous silica gel, alumina, activated carbon, titania, and zirconia.
- Examples of column chromatography include column chromatography using these silica gel, hydrous silica gel, and alumina as a filler.
- distillation such as vacuum distillation and molecular distillation.
- distillation a small amount of amines, sulfur-containing compounds and the like are added together with the reaction solution before the distillation, and the epoxy compound of the present invention during distillation and any one of the formulas (6) to (10) as raw materials are used.
- the reaction vessel in the present invention is not particularly limited, but preferably includes a stirring device, a thermometer, a reflux condenser, a dropping device, and the like.
- Etching rate (nm / sec) step difference (nm) ⁇ processing time (sec)
- the mixture was heated using an oil bath maintained at 90 ° C., 80 ml of 30% aqueous hydrogen peroxide was dropped over 180 minutes through a dropping funnel, and aged for 4 hours. After cooling in an ice bath, excess hydrogen peroxide was removed with 300 ml of a saturated aqueous sodium thiosulfate solution, and then extracted twice with 200 ml of ethyl acetate. The obtained ethyl acetate solution was dried over anhydrous sodium sulfate overnight, the solvent ethyl acetate was removed using a rotary evaporator, and then purified by column chromatography packed with 25% hydrous silica gel to obtain 3,4-epoxy. 79.6 g of allyl cyclohexane-1-carboxylate were obtained.
- Example 1 A 50 ml three-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a serum cap is a polysilicon compound in which R 1 of eight Z 1 in formula (IV) is a methyl group PSS-octakis (dimethylsilyloxy) substituted ( 1,3,5,7,9,11,13,15- octakis (di methylsiloxy) f ° Ntashikuro [9.5.1.1 3,9 .1 5,15 .1 7,13] oct-siloxane 1.04 g (0.98 mmol) from Aldrich), 1.432 g (7.84 mmol) of allyl 3,4-epoxycyclohexane-1-carboxylate obtained in Preparation Example 1, and 5.0 ml of toluene.
- R 1 of eight Z 1 in formula (IV) is a methyl group PSS-octakis (dimethylsily
- PSS-octakis (dimethylsilyloxy) substituted is contained for one equivalent of the ethylenic double bond of allyl 3,4-epoxycyclohexane-1-carboxylate stirred at room temperature (25 ° C.) under an argon stream -SiH group corresponds to 1 equivalent).
- 0.00093 g (0.02 mol%) of a 2% divinyltetramethyldisiloxane platinum complex xylene solution was slowly added dropwise using a syringe and stirred at room temperature (25 ° C.).
- epoxy compound (V) Assuming that all of A in the reaction had reacted, a theoretical molecular weight of 2474.4) was obtained.
- Example 1 ⁇ Measurement and Evaluation of Reactive Ion Etching Rate; ⁇ Example 1 and Comparative Example 1 >> The epoxy compound (V) obtained in Example 1 was dissolved in propylene glycol monomethyl ether acetate so as to have a nonvolatile component concentration of 10% by mass, and the photocationic polymerization initiator triphenylsulfonium hexafluoroantimonate was added to the solution in a nonvolatile manner. After adding 1 part by mass to 100 parts by mass of the sexual component and dissolving, it was filtered through a 0.2 ⁇ m filter, and 0.5 ml was dropped onto a glass substrate set in a spin coater.
- epoxy compound (VI) an epoxy compound represented by the following formula (hereinafter also referred to as “epoxy compound (VI)”) as a non-volatile component. It was.
- Example 1 and Comparative Example 2 DSC measurement was performed by adding 1 part by mass of the photocationic polymerization initiator triphenylsulfonium hexafluoroantimonate to 100 parts by mass of the epoxy compound (V) obtained in Example 1.
- the UV illuminance was 6.0 mw / cm 2 .
- the obtained DSC and DDSC chart are shown in FIG.
- FIG. 3 shows a comparative chart in which the charts of FIGS. 1 and 2 are overlapped.
- the end point of the exothermic peak is faster in the DSC curve of the epoxy compound (V) obtained in Example 1 than in the DSC curve of the epoxy compound (VI) obtained in Comparative Example 2. It can be seen that the polymerization reaction was completed earlier with the epoxy compound (V).
- the end point of the exothermic change is faster in the DDSC curve of the epoxy compound (V) obtained in Example 1 than in the DDSC curve of the epoxy compound (VI) obtained in Comparative Example 2. This also shows that the epoxy compound (V) completed the polymerization reaction earlier.
- the epoxy compound (V) having an alicyclic epoxy group of the present invention is faster to cure by UV than the epoxy compound (VI) having a glycidyl type epoxy group.
- Example 2 In a 100 ml three-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a serum cap, 1.0 g (0.98 mmol) of PSS-octakis (dimethylsilyloxy) substituted, 1.1966 g (7.84 mmol) of limonene oxide, toluene 5.0 ml was added, and the mixture was stirred at room temperature (25 ° C.) under an argon stream (one equivalent of PSi-octakis (dimethylsilyloxy) substituted is equivalent to one equivalent of the ethylenic double bond of limonene oxide) Equivalent).
- Example 2 ⁇ Measurement and Evaluation of Reactive Ion Etching Rate; ⁇ Example 2 >> The epoxy compound (VII) obtained in Example 2 was dissolved in propylene glycol monomethyl ether acetate so as to have a nonvolatile component concentration of 10% by mass, and the photocationic polymerization initiator triphenylsulfonium hexafluoroantimonate was added to the solution in a nonvolatile manner. After adding 1 part by mass to 100 parts by mass of the sexual component and dissolving, it was filtered through a 0.2 ⁇ m filter, and 0.5 ml was dropped onto a glass substrate set in a spin coater.
- an epoxy compound (VII) thin film was formed on the glass substrate.
- the glass substrate on which the epoxy compound (VII) thin film was formed was irradiated with ultraviolet rays in a nitrogen stream.
- the cured film of the resulting epoxy compound (VII) was measured reactive ion etching rate with a CF 4 gas and oxygen. The results are shown in Table 2.
- DSC measurement and evaluation was performed by adding 1 part by mass of the photocationic polymerization initiator triphenylsulfonium hexafluoroantimonate to 100 parts by mass of the epoxy compound (VII) obtained in Example 2.
- the UV illuminance was 7.8 mw / cm 2 .
- the obtained DSC chart is shown in FIG.
- the epoxy compounds of Examples 1 and 2 are liquid at about room temperature, which is suitable for use as a resist for UV nanoimprint.
- Example 3 1.429 g (7.84 mmol) of allyl 3,4-epoxycyclohexane-1-carboxylate, 2% divinyltetramethyldisiloxane in a 100 ml three-necked flask equipped with a reflux condenser, thermometer, stirrer, and serum cap 0.00093 g (0.02 mol%) of a platinum complex xylene solution was added, and the mixture was stirred at 60 ° C. under an argon stream.
- PSS-octakis (dimethylsilyloxy) substituted dissolved in 5.0 ml of toluene was slowly added using a dropping funnel (the ethylenic property of allyl 3,4-epoxycyclohexane-1-carboxylate).
- the -SiH group of PSS-octakis (dimethylsilyloxy) substituted is equivalent to 1 equivalent with respect to 1 equivalent of the double bond), and the mixture was stirred for 12 hours while maintaining the temperature.
- peaks with (a) to (d) are peaks corresponding to the portions indicated by (a) to (d) in the structural formula, respectively.
- the peak marked with (x) is a peak corresponding to H of an unreacted Si—H group
- the peak marked with (y) is a peak corresponding to H other than the above.
- the characteristic peaks of the non-volatile component obtained in FIG. 6 are the carbon peak of the carbonyl group near 175.8 ppm, the peak of methylene carbon adjacent to the oxygen atom near 67.2 ppm, and the epoxy group near 50 ppm.
- a carbon peak adjacent to oxygen, a methylene carbon peak adjacent to a silicon atom near 14.0 ppm, and a methyl group carbon peak adjacent to a silicon atom near 0 ppm were observed.
- the nonvolatile component obtained from these results is a mixture obtained by reacting 1 to 8 of 8 A of the epoxy compound represented by the following formula (V) (hereinafter also referred to as “epoxy compound (V)”). I understood it.
- Example 4 In a 100 ml three-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a serum cap, 0.897 g (5.88 mmol) of limonene oxide, 0.00093 g of a 2% divinyltetramethyldisiloxane platinum complex xylene solution (0. 02 mol%) was added, and the mixture was stirred at 110 ° C. under an argon stream.
- the 1 H-NMR spectrum, 13 C-NMR spectrum and IR spectrum of the obtained nonvolatile component are shown in FIGS. 8, 9 and 10, respectively.
- the peak attached with (x) is a peak corresponding to H of the unreacted Si—H group
- the peak attached with (y) is 2 bonded to Si of the unreacted Si—H group. It is a peak corresponding to one CH 3 H.
- the peak of the unreacted Si—H group is present at 4.74 ppm.
- the characteristic peak of the non-volatile component obtained in FIG. 9 is a carbon peak adjacent to the oxygen atom of the epoxy group at 60.9 ppm, a carbon having a methyl group adjacent to the oxygen atom of the epoxy group around 57 ppm. And a methyl carbon peak adjacent to the silicon atom was observed near 0 ppm.
- Example 5 In a 100 ml three-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a serum cap, 0.598 g (3.92 mmol) of limonene oxide, 0.00093 g of a 2% divinyltetramethyldisiloxane platinum complex xylene solution (0. 02 mol%) was added, and the mixture was stirred at 110 ° C. under an argon stream.
- FIGS. 11, 12 and 13 The 1 H-NMR spectrum, 13 C-NMR spectrum and IR spectrum of the obtained non-volatile component are shown in FIGS. 11, 12 and 13, respectively.
- the peak marked with (x) is a peak corresponding to H of the unreacted Si—H group
- the peak marked with (y) is 2 bonded to Si of the unreacted Si—H group. It is a peak corresponding to one CH 3 H.
- the peak of the unreacted Si—H group is present at 4.73 ppm.
- the characteristic peak of the non-volatile component obtained in FIG. 12 is a carbon peak adjacent to the oxygen atom of the epoxy group at 61.0 ppm, a carbon having a methyl group adjacent to the oxygen atom of the epoxy group around 57 ppm. And a methyl carbon peak adjacent to the silicon atom was observed near 0 ppm.
- Example 6 In a 100 ml three-necked flask equipped with a reflux condenser, a thermometer, a stirring device, and a serum cap, 1.196 g (7.84 mmol) of limonene oxide, 0.00093 g of a 2% divinyltetramethyldisiloxane platinum complex xylene solution (0. 02 mol%) was added, and the mixture was stirred at 110 ° C. under an argon stream.
- the characteristic peak of the non-volatile component obtained in FIG. 15 is a carbon peak adjacent to the oxygen atom of the epoxy group at 61.0 ppm, and a carbon having a methyl group adjacent to the oxygen atom of the epoxy group around 57 ppm. And a methyl carbon peak adjacent to the silicon atom was observed near 0 ppm.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Silicon Polymers (AREA)
- Epoxy Compounds (AREA)
Abstract
Description
[1] 式(I)で表されるエポキシ化合物;
R4は、水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示し、R5~R11は、それぞれ独立に水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示す。
*は式(I)に示されるSiとの結合部分を示し、-X-*は、Xが単結合である-*、ま
たは下記式(x)で表わされる基を示す。);
[2] 前記エポキシ化合物が、篭状シルセスキオキサン構造または梯子状シルセスキオキサン構造を有するエポキシ化合物であることを特徴とする上記[1]に記載のエポキシ化合物。
R4は、水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示し、R5~R11は、それぞれ独立に水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示す。
[6]前記式(II)中、R1が、メチル基またはエチル基であることを特徴とする上記[5]に記載のエポキシ化合物。
[9]式(III)または式(IV)で表わされるポリケイ素化合物;
下記式(6)~(10)のいずれかで表わされるエポキシ化合物;
R4は、水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示し、R5~R11は、それぞれ独立に水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示す。
10~200℃で反応させる工程を含むことを特徴とする上記[1]に記載のエポキシ化合物の製造方法。
[11]前記ポリケイ素化合物が前記式(IV)で表わされるポリケイ素化合物であり、前記式(IV)中、R1が、メチル基またはエチル基であることを特徴とする上記[9]に記載のエポキシ化合物の製造方法。
[12]前記式(6)~(10)中、R2~R11が、それぞれ独立に水素原子またはメチル基であり、かつR12が、水素原子、メチル基またはフェニル基であることを特徴とする上記[9]~[11]のいずれかに記載のエポキシ化合物の製造方法。
下記式(6)~(10)のいずれかで表わされるエポキシ化合物;
R4は、水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示し、R5~R11は、それぞれ独立に水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示す。
前記エポキシ化合物が有するエチレン性二重結合の1当量に対し、前記ポリケイ素化合物が有する-SiH基の当量が0.3~1.5となるように配合し、
10~200℃でヒドロシリル化反応させて得られることを特徴とするエポキシ化合物。
<エポキシ化合物>
本発明のエポキシ化合物は、式(I)で表されることを特徴としている。
篭状シルセスキオキサン構造を有するエポキシ化合物としては、たとえば下記式(II)で表わされるエポキシ化合物、すなわち上記式(I)において、nが8であるエポキシ化合物が好ましく挙げられる。
梯子状シルセスキオキサン構造を有するエポキシ化合物としては、たとえば下記式(II')で表わされるエポキシ化合物が好ましく挙げられるが、これらに限定されるものではない。
本発明のエポキシ化合物の製造方法は、式(III)で表わされるポリケイ素化合物または式(IV)で表わされるポリケイ素化合物と、下記式(6)~(10)のいずれかで表わされるエポキシ化合物とを、10~200℃で反応させる工程を含むことを特徴としている。この反応は、すなわちヒドロシリル化反応であり、室温程度でも充分に反応させることができる。
式(III)中、nは2~500の整数、好ましくは6~18の偶数、より好ましくは8を示す。
R5~R11は、それぞれ独立に水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示し、上記式(1a)~(5a)におけるR5~R11と同義である。
上記式(III)で表わされるポリケイ素化合物としては、篭状シルセスキオキサン構造または梯子状シルセスキオキサン構造を有するポリケイ素化合物が望ましい。
上記エポキシ化合物は、上記式(6)~(10)のいずれかで表わされる二重結合を有する化合物であり、なかでも、式(6)、(9)、(10)のいずれかで表わされるエポキシ化合物であるのが好ましく、式(9)で表わされるエポキシ化合物であるのがより好ましい。
上記ポリケイ素化合物とポリケイ素化合物との組み合わせとしては、上記式(IV)で表わされ、R1がメチル基またはエチル基であるポリケイ素化合物と、R2~R11が、それぞれ独立に水素原子またはメチル基であり、かつR12が、水素原子、メチル基またはフェニル基であるポリケイ素化合物との組み合わせが好ましい。
反応器内の雰囲気としては、窒素ガス等の不活性ガス雰囲気が好ましい。水分(もしくは水分を含んだ空気)の混入は反応への悪影響を及ぼすだけでなく、式(III)で表されるポリケイ素化合物が加水分解して、目的物であるエポキシ化合物の収率が低下するおそれがある。なお、付加反応の触媒活性を高める目的で、反応雰囲気中へ乾燥空気または酸素含有の不活性ガス等を導入するという公知技術を適用してもよい。
なお、実施例および比較例において、各測定条件および評価項目は、以下の条件および基準にしたがって行った。
機器:示差走査熱量計 EXSTAR6000 DSC (SII社製)
UV照射機:UV-1(SII社製)
UV照度:6.0mw/cm2、または7.8mw/cm2
UV照射時間:20分
《反応性イオンエッチング速度の測定方法》
硬化した薄膜上にガラス小片を貼り付け、以下の条件にしたがってエッチング処理を実施した。ガラス小片を取り外し、ガラス小片に保護された薄膜部分とエッチングされた薄膜部分との段差を測定した。反応性イオンエッチングの処理時間と段差とから、下記式にしたがって、エッチング速度を求めた。
反応性イオンエッチングの条件
(フッ素系ガス)
エッチングガス : 四フッ化炭素
圧力 : 0.5Pa
ガス流量 : 40sccm
プラズマ電圧 : 200W
バイアス電圧 : 20W
処理時間 : 30sec
(酸素)
エッチングガス : 酸素
圧力 : 0.5Pa
ガス流量 : 40sccm
プラズマ電圧 : 200W
バイアス電圧 : 20W
処理時間 : 600sec
《粘度測定》
測定機器:VISCOMETER DV-II+Pro(BROOKFIELD製)
測定温度:24.9℃
[調製例1]
還流冷却器、温度計、攪拌装置、滴下ロートおよび油浴を備えた500mL三つ口フラスコに、3-シクロヘキセン-1-カルボン酸アリル100.0g、硫酸水素メチルトリオクチルアンモニウム2.34g、タングステン酸ナトリウム二水和物3.96g、アミノメチルホスホン酸0.45gを仕込んだ。90℃に保った油浴を用いて加熱し、滴下ロートを通じて30%過酸化水素水80mlを180分間かけて滴下し、そのまま4時間熟成させた。氷浴で冷却し、飽和チオ硫酸ナトリウム水溶液300mlで余剰の過酸化水素を除去した後、酢酸エチル200mlで2回抽出した。得られた酢酸エチル溶液を無水硫酸ナトリウム上で一晩乾燥させ、ロータリーエバポレーターを用いて溶媒の酢酸エチルを除去した後、25%含水シリカゲルを充填したカラムクロマトグラフィーによって精製し、3,4-エポキシシクロヘキサン-1-カルボン酸アリル79.6gを得た。
還流冷却器、温度計、攪拌装置、およびセラムキャップを備えた50ml三ツ口フラスコに、式(IV)における8つのZ1のR1がメチル基であるポリケイ素化合物である
PSS-octakis(dimethylsilyloxy)substituted(1,3,5,7,9,11,13,15-オクタキス (シ゛メチルシロキシ) ヘ゜ンタシクロ[9.5.1.13,9.15,15.17,13]オクタシロキサン、アルドリッチ社製)を1.0g(0.98 mmol)、調製例1で得られた3,4-エポキシシクロヘキサン-1-カルボン酸アリル1.432g(7.84 mmol)、トルエン5.0mlを加え、アルゴン気流下、室温(25℃)で攪拌した(3,4-エポキシシクロヘキサン-1-カルボン酸アリルが有するエチレン性二重結合の1当量に対して、PSS-octakis(dimethylsilyloxy)substitutedが有する-SiH基は1当量に相当)。その混合溶液に2%ジビニルテトラメチルジシロキサン白金錯体キシレン溶液0.00093g(0.02 mol%)をシリンジを用いてゆっくり滴下し、室温(25℃)で攪拌した。該温度を保持したまま2時間攪拌した後、減圧下でトルエン溶媒を除去し、不揮発性成分として下記式(V)で示されるエポキシ化合物(以下、「エポキシ化合物(V)」ともいう、8個のAが全て反応していると仮定した場合の理論分子量=2474.4)を得た。
エポキシ化合物の代わりに、ビスフェノールA型液状エポキシ樹脂(ジャパンエポキシレジン製:エピコート828US、以下、「エポキシ樹脂X」ともいう)を用いた。
実施例1で得られたエポキシ化合物(V)をプロピレングリコールモノメチルエーテルアセテートに不揮発性成分濃度10質量%になるように溶解し、溶液に光カチオン重合開始剤トリフェニルスルホニウムヘキサフルオロアンチモネートを、不揮発性成分100質量部に対して1質量部添加し溶解させた後、0.2μmのフィルターでろ過し、0.5mlをスピンコーター内にセットしたガラス基板上に滴下した。ガラス基板を500rpmで5秒間回転、次いで3000rpmで2秒間、さらに5000rpmで20秒間回転させることにより、ガラス基板上にエポキシ化合物(V)の薄膜を形成した。このエポキシ化合物(V)の薄膜を形成したガラス基板を窒素気流下、紫外線を照射した。得られたエポキシ化合物(V)の硬化薄膜について、CF4ガスおよび酸素による反応性イオンエッチング速度を測定した。結果を表1に示す。
還流冷却器、温度計、攪拌装置、セラムキャップを備えた100ml三ツ口フラスコに、PSS-octakis(dimethylsilyloxy)substitutedを1.0g(0.98 mmol)、アリルグリシジルエーテル0.897g(7.84 mmol)、トルエン5.0mlを加え、アルゴン気流下、室温(25℃)で攪拌した。その混合溶液に2%ジビニルテトラメチルジシロキサン白金錯体キシレン溶液0.00093g(0.02 mol%)を、シリンジを用いてゆっくり滴下し、室温(25℃)で攪拌した。該温度を保持したまま2時間攪拌した後、減圧下でトルエン溶媒を除去し、不揮発性成分として下記式(VI)で示されるエポキシ化合物(以下、「エポキシ化合物(VI)」ともいう)を得た。
実施例1で得られたエポキシ化合物(V)100質量部に対して、光カチオン重合開始剤トリフェニルスルホニウムヘキサフルオロアンチモネート1質量部を加え、DSC測定を行った。なお、UV照度は6.0mw/cm2とした。得られたDSCおよびDDSCのチャートを図1に示す。
還流冷却器、温度計、攪拌装置、およびセラムキャップを備えた100ml三ツ口フラスコに、PSS-octakis(dimethylsilyloxy)substitutedを1.0g(0.98 mmol)、リモネンオキサイド1.1966g(7.84 mmol)、トルエン5.0mlを加え、アルゴン気流下、室温(25℃)で攪拌した(リモネンオキサイドが有するエチレン性二重結合の1当量に対して、PSS-octakis(dimethylsilyloxy)substitutedが有する-SiH基は1当量に相当)。その混合溶液に2%ジビニルテトラメチルジシロキサン白金錯体キシレン溶液0.00093g(0.02 mol%)を、シリンジを用いてゆっくり滴下し、室温(25℃)で攪拌した。該温度を保持したまま2時間攪拌した後、減圧下でトルエン溶媒を除去し、不揮発性成分として下記式(VII)で示されるエポキシ化合物(以下、「エポキシ化合物(VII)」ともいう、8個のJが全て反応していると仮定した場合の理論分子量=2234.4)を得た。
実施例2で得られたエポキシ化合物(VII)をプロピレングリコールモノメチルエーテルアセテートに不揮発性成分濃度10質量%になるように溶解し、溶液に光カチオン重合開始剤トリフェニルスルホニウムヘキサフルオロアンチモネートを、不揮発性成分100質量部に対し、1質量部添加し溶解させた後、0.2μmのフィルターでろ過し、0.5mlをスピンコーター内にセットしたガラス基板上に滴下した。ガラス基板を500rpmで5秒間回転、次いで3000rpmで2秒間、さらに5000rpmで20秒間回転させることにより、ガラス基板上にエポキシ化合物(VII)の薄膜を形成した。このエポキシ化合物(VII)の薄膜を形成したガラス基板を窒素気流下、紫外線を照射した。得られたエポキシ化合物(VII)の硬化薄膜について、CF4ガスおよび酸素による反応性イオンエッチング速度を測定した。結果を表2に示す。
実施例2で得られたエポキシ化合物(VII)100質量部に対して、光カチオン重合開始剤トリフェニルスルホニウムヘキサフルオロアンチモネート1質量部を加え、DSC測定を行った。なお、UV照度は7.8mw/cm2とした。得られたDSCチャートを図4に示す。
[比較例3]
還流冷却器、温度計、攪拌装置、およびセラムキャップを備えた100ml三ツ口フラスコに、PSS-octakis(dimethylsilyloxy)substitutedを1.0g(0.98 mmol)、4-ビニルシクロヘキセンオキサイド0.9759g(7.84 mmol)、トルエン5.0mlを加え、アルゴン気流下、室温(25℃)で攪拌した。その混合溶液に2%ジビニルテトラメチルジシロキサン白金錯体キシレン溶液0.00093g(0.02 mol%)をシリンジを用いてゆっくり滴下し、室温(25℃)で攪拌した。2時間室温で攪拌した後、減圧下でトルエン溶媒を除去し、下記式(VIII)で示されるエポキシ化合物(以下、「エポキシ化合物(VIII)」ともいう)を得た。
実施例1で得られたエポキシ化合物(V)、実施例2で得られたエポキシ化合物(VII)、および比較例3で得られたエポキシ化合物(VIII)を用い、それぞれエバポレーター、真空ポンプで完全に溶媒を除去し、粘度を測定した。結果を表3に示す。
[実施例3]
還流冷却器、温度計、攪拌装置、およびセラムキャップを備えた100ml三ツ口フラ
スコに、3,4-エポキシシクロヘキサン-1-カルボン酸アリル1.429g(7.84 mmol)、2%ジビニルテトラメチルジシロキサン白金錯体キシレン溶液0.00093g(0.02 mol%)を加え、アルゴン気流下、60℃で攪拌した。その後、トルエン5.0mlに溶解させたPSS-octakis(dimethylsilyloxy)substituted1.0g(0.98 mmol)を滴下ロートを用いてゆっくり加え(3,4-エポキシシクロヘキサン-1-カルボン酸アリルが有するエチレン性二重結合の1当量に対して、PSS-octakis(dimethylsilyloxy)substitutedが有する-SiH基は1当量に相当)、該温度を保持したまま12時間攪拌した後、ガスクロマトグラフィーにより、PSS-octakis(dimethylsilyloxy)substitutedがすべて消費されていることを確認した後、反応を終了させ、減圧下でトルエン溶媒を除去した。その後、薄膜蒸留装置により、未反応の3,4-エポキシシクロヘキサン-1-カルボン酸アリルを除去し、不揮発性成分を得た。
これらの結果から得られた不揮発性成分は下記式(V)で示されるエポキシ化合物(以下、「エポキシ化合物(V)」ともいう)の8個のAの内1~8個反応した混合物であることがわかった。
還流冷却器、温度計、攪拌装置、およびセラムキャップを備えた100ml三ツ口フラスコに、リモネンオキサイド0.897g(5.88 mmol)、2%ジビニルテトラメチルジシロキサン白金錯体キシレン溶液0.00093g(0.02 mol%)を加え、アルゴン気流下、110℃で攪拌した。その後、トルエン5.0mlに溶解させたPSS-octakis(dimethylsilyloxy)substituted1.0g(0.98 mmol)を滴下ロートを用いてゆっくり加え、該温度を保持したまま12時間攪拌した後、ガスクロマトグラフィーにより、リモネンオキサイドがすべて消費されていることを確認した後、反応を終了させ、減圧下でトルエン溶媒を除去し、不揮発性成分として下記式(VII)で示されるエポキシ化合物(以下、「エポキシ化合物(VII)」)を得た。
これらの結果から得られた不揮発性成分は下記式(VII)で示されるエポキシ化合物(以下、「エポキシ化合物(VII)」ともいう)の8個のJの内6個反応したものであることがわかった。
還流冷却器、温度計、攪拌装置、およびセラムキャップを備えた100ml三ツ口フラスコに、リモネンオキサイド0.598g(3.92 mmol)、2%ジビニルテトラメチルジシロキサン白金錯体キシレン溶液0.00093g(0.02 mol%)を加え、アルゴン気流下、110℃で攪拌した。その後、トルエン5.0mlに溶解させたPSS-octakis(dimethylsilyloxy)substituted1.0g(0.98 mmol)を滴下ロートを用いてゆっくり加え、該温度を保持したまま12時間攪拌した後、ガスクロマトグラフィーにより、リモネンオキサイドがすべて消費されていることを確認した後、反応を終了させ、減圧下でトルエン溶媒を除去し、不揮発性成分として下記式(VII)で示されるエポキシ化合物(以下、「エポキシ化合物(VII)」)を得た。
図11より未反応のSi-H基のピークが4.73ppmに存在し、このピークと約3ppmに存在するエポキシ基の酸素原子の隣接炭素上の1Hのピークとを比較すると、反応部8個中、(未反応部(Si-H)の個数): (既反応部の個数)=4:4であり、この結果は、反応の仕込み比と一致した。
これらの結果から得られた不揮発性成分は下記式(VII)で示されるエポキシ化合物(以下、「エポキシ化合物(VII)」ともいう)の8個のJの内4個反応したものであることがわかった。
還流冷却器、温度計、攪拌装置、およびセラムキャップを備えた100ml三ツ口フラスコに、リモネンオキサイド1.196g(7.84 mmol)、2%ジビニルテトラメチルジシロキサン白金錯体キシレン溶液0.00093g(0.02 mol%)を加え、アルゴン気流下、110℃で攪拌した。その後、トルエン5.0mlに溶解させたPSS-octakis(dimethylsilyloxy)substituted1.0g(0.98 mmol)を滴下ロートを用いてゆっくり加え(リモネンオキサイドが有するエチレン性二重結合の1当量に対して、PSS-octakis(dimethylsilyloxy)substitutedが有する-SiH基は1当量に相当)、該温度を保持したまま12時間攪拌した後、ガスクロマトグラフィーにより、リモネンオキサイドがすべて消費されていることを確認した後、反応を終了させ、減圧下でトルエン溶媒を除去し、不揮発性成分として下記式(VII)で示されるエポキシ化合物(以下、「エポキシ化合物(VII)」)を得た。
図14において未反応のSi-H基に対応する4.7ppm付近にピークが認められなかった。
Claims (15)
- 式(I)で表されるエポキシ化合物;
R4は、水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示し、R5~R11は、それぞれ独立に水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示す。
R12は、水素原子、炭素数1から6までのアルキル基、炭素数1から4までのトリアルキルシリル基、またはアリール基を示す。
*は式(I)に示されるSiとの結合部分を示し、-X-*は、Xが単結合である-*、または下記式(x)で表わされる基を示す。);
- 前記エポキシ化合物が、篭状シルセスキオキサン構造または梯子状シルセスキオキサン構造を有するエポキシ化合物であることを特徴とする請求項1に記載のエポキシ化合物。
- 前記式(1a)~(5a)中、-X-*が、前記式(x)で表わされる基であり、前記式(x)中、R1が、メチル基またはエチル基であることを特徴とする請求項1または2に記載のエポキシ化合物。
- 前記式(1a)~(5a)中、R2~R11が、それぞれ独立に水素原子またはメチル基であり、かつR12が、水素原子、メチル基またはフェニル基であることを特徴とする請求項1~3のいずれかに記載のエポキシ化合物。
- 下記式(II)で表わされることを特徴とするエポキシ化合物;
R4は、水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示し、R5~R11は、それぞれ独立に水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示す。
R12は、水素原子、炭素数1から6までのアルキル基、炭素数1から4までのトリアルキルシリル基、またはアリール基を示す。)。 - 前記式(II)中、R1が、メチル基またはエチル基であることを特徴とする請求項5に記載のエポキシ化合物。
- 前記式(1b)~(5b)中、R2~R11が、それぞれ独立に水素原子またはメチル基であり、かつR12が、水素原子、メチル基またはフェニル基であることを特徴とする請求項5または6に記載のエポキシ化合物。
- 10~30℃において液状であることを特徴とする請求項1~7のいずれかに記載のエポキシ化合物。
- 式(III)または式(IV)で表わされるポリケイ素化合物;
下記式(6)~(10)のいずれかで表わされるエポキシ化合物;
R4は、水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示し、R5~R11は、それぞれ独立に水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示す。
R12は、水素原子、炭素数1から6までのアルキル基、炭素数1から4までのトリアルキルシリル基、またはアリール基を示す。)とを、
10~200℃で反応させる工程を含むことを特徴とする請求項1に記載のエポキシ化合物の製造方法。 - 前記ポリケイ素化合物が前記式(III)で表わされるポリケイ素化合物であり、該ポリケイ素化合物が、篭状シルセスキオキサン構造または梯子状シルセスキオキサン構造を有するポリケイ素化合物であることを特徴とする請求項9に記載のエポキシ化合物の製造方法。
- 前記ポリケイ素化合物が前記式(IV)で表わされるポリケイ素化合物であり、前記式(IV)中、R1が、メチル基またはエチル基であることを特徴とする請求項9に記載のエポキシ化合物の製造方法。
- 前記式(6)~(10)中、R2~R11が、それぞれ独立に水素原子またはメチル基であり、かつR12が、水素原子、メチル基またはフェニル基であることを特徴とする請求項9~11のいずれかに記載のエポキシ化合物の製造方法。
- 前記エポキシ化合物が有するエチレン性二重結合の1当量に対し、前記ポリケイ素化合物が有する-SiH基の当量が0.3~1.5となるように配合することを特徴とする請求項9~12のいずれかに記載のエポキシ化合物の製造方法。
- 式(IV)で表わされるポリケイ素化合物;
下記式(6)~(10)のいずれかで表わされるエポキシ化合物;
R4は、水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示し、R5~R11は、それぞれ独立に水素原子、炭素数1から6までのアルキル基、または炭素数1から4までのトリアルキルシリル基を示す。
R12は、水素原子、炭素数1から6までのアルキル基、炭素数1から4までのトリアルキルシリル基、またはアリール基を示す。)とを、
前記エポキシ化合物が有するエチレン性二重結合の1当量に対し、前記ポリケイ素化合物が有する-SiH基の当量が0.3~1.5となるように配合し、
10~200℃でヒドロシリル化反応させて得られることを特徴とするエポキシ化合物。 - 前記式(IV)で表わされるポリケイ素化合物のR1がメチル基であり、前記エポキシ化合物が前記式(6)または(9)であることを特徴とする請求項14に記載のエポキシ化合物。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200980110402.4A CN101977919B (zh) | 2008-03-24 | 2009-03-23 | 环氧化合物及其制造方法 |
US12/933,828 US8426614B2 (en) | 2008-03-24 | 2009-03-23 | Epoxy compound and process for producing the epoxy compound |
EP09724479.2A EP2270020B1 (en) | 2008-03-24 | 2009-03-23 | Epoxy compound and process for producing the epoxy compound |
JP2010505608A JP5325206B2 (ja) | 2008-03-24 | 2009-03-23 | エポキシ化合物およびその製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008075344 | 2008-03-24 | ||
JP2008-075344 | 2008-03-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009119469A1 true WO2009119469A1 (ja) | 2009-10-01 |
Family
ID=41113662
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/055576 WO2009119469A1 (ja) | 2008-03-24 | 2009-03-23 | エポキシ化合物およびその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8426614B2 (ja) |
EP (1) | EP2270020B1 (ja) |
JP (1) | JP5325206B2 (ja) |
KR (1) | KR101215736B1 (ja) |
CN (1) | CN101977919B (ja) |
WO (1) | WO2009119469A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010013513A (ja) * | 2008-07-02 | 2010-01-21 | Fujifilm Corp | ナノインプリント用硬化性組成物、これを用いた硬化物、並びに、液晶表示装置用部材 |
JP2010024229A (ja) * | 2008-06-20 | 2010-02-04 | Showa Denko Kk | (メタ)アクリロイルオキシ基含有篭状シルセスキオキサン化合物およびその製造方法 |
JP2010053204A (ja) * | 2008-08-27 | 2010-03-11 | Nof Corp | 熱硬化性樹脂組成物 |
JP2010083955A (ja) * | 2008-09-30 | 2010-04-15 | Nof Corp | 熱硬化性樹脂組成物 |
WO2012020730A1 (ja) * | 2010-08-11 | 2012-02-16 | 昭和電工株式会社 | エポキシシリコーン縮合物、該縮合物を含む硬化性組成物およびその硬化物 |
WO2012144480A1 (ja) * | 2011-04-20 | 2012-10-26 | セントラル硝子株式会社 | シロキサン化合物およびその硬化物 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20160006403A (ko) * | 2014-07-09 | 2016-01-19 | 동우 화인켐 주식회사 | 접착제 조성물 및 이를 포함하는 편광판 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03255130A (ja) | 1990-03-05 | 1991-11-14 | Shin Etsu Chem Co Ltd | エポキシ基含有オルガノポリシロキサンの製造方法 |
US5484867A (en) * | 1993-08-12 | 1996-01-16 | The University Of Dayton | Process for preparation of polyhedral oligomeric silsesquioxanes and systhesis of polymers containing polyhedral oligomeric silsesqioxane group segments |
JP2006104325A (ja) * | 2004-10-05 | 2006-04-20 | Shin Etsu Chem Co Ltd | かご状オリゴシロキサン構造を有する一官能性モノマー及びその製造方法 |
JP2008013544A (ja) * | 2006-06-07 | 2008-01-24 | Showa Denko Kk | 新規エポキシ化合物とその製造方法 |
WO2008020637A1 (fr) * | 2006-08-15 | 2008-02-21 | Showa Denko K.K. | Nouveau composé époxy et son procédé de fabrication |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5206328A (en) | 1990-02-08 | 1993-04-27 | Shin-Etsu Chemical Co., Ltd. | Process for the production of an organopolysiloxane |
US5484950A (en) * | 1992-12-21 | 1996-01-16 | Polyset Company, Inc. | Process for selective monoaddition to silanes containing two silicon-hydrogen bonds and products thereof |
US5468826A (en) * | 1994-05-10 | 1995-11-21 | Dow Corning Corporation | Adhesion promoting additives and curable organosiloxane compositions containing same |
US5516823A (en) * | 1994-05-10 | 1996-05-14 | Dow Corning Corporation | Adhesion promoting compositions and curable organosiloxane compositions containing same |
SG48462A1 (en) | 1995-10-26 | 1998-04-17 | Ibm | Lead protective coating composition process and structure thereof |
US6790473B2 (en) | 1995-10-26 | 2004-09-14 | International Business Machines Corporation | Lead protective coating composition, process and structure thereof |
US5863970A (en) * | 1995-12-06 | 1999-01-26 | Polyset Company, Inc. | Epoxy resin composition with cycloaliphatic epoxy-functional siloxane |
JP3505889B2 (ja) | 1995-12-18 | 2004-03-15 | 東洋インキ製造株式会社 | 紫外線硬化型樹脂組成物およびこれを含む被覆剤 |
US6210790B1 (en) * | 1998-07-15 | 2001-04-03 | Rensselaer Polytechnic Institute | Glass-like composites comprising a surface-modified colloidal silica and method of making thereof |
US6265459B1 (en) | 1998-12-31 | 2001-07-24 | 3M Innovative Properties Company | Accelerators useful for energy polymerizable compositions |
US6482868B1 (en) | 1998-12-31 | 2002-11-19 | 3M Innovative Properties Company | Accelerators useful for energy polymerizable compositions |
FR2818989B1 (fr) | 2000-12-29 | 2004-03-19 | Rhodia Chimie Sa | Utilisation d'un polyorganosiloxane fonctionnalise epoxy et/ou carboxy, a titre de matiere active dans une composition silicone liquide d'hydrofugation de materiaux de construction |
US7049044B2 (en) * | 2002-12-19 | 2006-05-23 | The University Of North Carolina At Charlotte | Nanocomposite negative resists for next generation lithographies |
JP2004029126A (ja) * | 2002-06-21 | 2004-01-29 | Toyo Metallizing Co Ltd | 帯電防止性反射防止フィルム |
AU2003275534A1 (en) | 2002-09-26 | 2004-04-19 | Toagosei Co., Ltd. | Hardening accelerator for cationic polymerization type composition |
US7034089B2 (en) * | 2002-12-20 | 2006-04-25 | National Starch And Chemical Investment Holding Corporation | Epoxy-functional hybrid copolymers |
US6962948B2 (en) * | 2003-08-07 | 2005-11-08 | Polyset Company, Inc. | Solventless, non-polluting radiation and thermal curable coatings |
JP4491283B2 (ja) * | 2004-06-10 | 2010-06-30 | 信越化学工業株式会社 | 反射防止膜形成用組成物を用いたパターン形成方法 |
US7732552B2 (en) * | 2006-01-27 | 2010-06-08 | Momentive Performance Materials Inc. | Low VOC epoxy silane oligomer and compositions containing same |
WO2007142248A1 (en) | 2006-06-07 | 2007-12-13 | Showa Denko K.K. | Novel epoxy compounds and process for their production |
US8653294B2 (en) * | 2011-02-17 | 2014-02-18 | Gelest Technologies, Inc. | Silicones derived from 2-propenyl functional cyclic terpenes and methods of preparation |
-
2009
- 2009-03-23 WO PCT/JP2009/055576 patent/WO2009119469A1/ja active Application Filing
- 2009-03-23 EP EP09724479.2A patent/EP2270020B1/en not_active Not-in-force
- 2009-03-23 JP JP2010505608A patent/JP5325206B2/ja not_active Expired - Fee Related
- 2009-03-23 CN CN200980110402.4A patent/CN101977919B/zh not_active Expired - Fee Related
- 2009-03-23 US US12/933,828 patent/US8426614B2/en not_active Expired - Fee Related
- 2009-03-23 KR KR1020107023613A patent/KR101215736B1/ko not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03255130A (ja) | 1990-03-05 | 1991-11-14 | Shin Etsu Chem Co Ltd | エポキシ基含有オルガノポリシロキサンの製造方法 |
US5484867A (en) * | 1993-08-12 | 1996-01-16 | The University Of Dayton | Process for preparation of polyhedral oligomeric silsesquioxanes and systhesis of polymers containing polyhedral oligomeric silsesqioxane group segments |
JP2006104325A (ja) * | 2004-10-05 | 2006-04-20 | Shin Etsu Chem Co Ltd | かご状オリゴシロキサン構造を有する一官能性モノマー及びその製造方法 |
JP2008013544A (ja) * | 2006-06-07 | 2008-01-24 | Showa Denko Kk | 新規エポキシ化合物とその製造方法 |
WO2008020637A1 (fr) * | 2006-08-15 | 2008-02-21 | Showa Denko K.K. | Nouveau composé époxy et son procédé de fabrication |
Non-Patent Citations (2)
Title |
---|
CHOI J. ET AL.: "Organic/Inorganic Hybrid Composites from Cubic Silsesquioxanes. Epoxy Resins of Octa (dimethylsiloxyethylcyclohexylepoxide) Silsesquioxane", MACROMOLECULES, vol. 36, no. 15, 2003, pages 5666 - 5682, XP008140836 * |
See also references of EP2270020A4 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010024229A (ja) * | 2008-06-20 | 2010-02-04 | Showa Denko Kk | (メタ)アクリロイルオキシ基含有篭状シルセスキオキサン化合物およびその製造方法 |
JP2010013513A (ja) * | 2008-07-02 | 2010-01-21 | Fujifilm Corp | ナノインプリント用硬化性組成物、これを用いた硬化物、並びに、液晶表示装置用部材 |
JP2010053204A (ja) * | 2008-08-27 | 2010-03-11 | Nof Corp | 熱硬化性樹脂組成物 |
JP2010083955A (ja) * | 2008-09-30 | 2010-04-15 | Nof Corp | 熱硬化性樹脂組成物 |
WO2012020730A1 (ja) * | 2010-08-11 | 2012-02-16 | 昭和電工株式会社 | エポキシシリコーン縮合物、該縮合物を含む硬化性組成物およびその硬化物 |
KR101408006B1 (ko) | 2010-08-11 | 2014-06-17 | 쇼와 덴코 가부시키가이샤 | 에폭시 실리콘 축합물, 그 축합물을 포함하는 경화성 조성물 및 그 경화물 |
US8957136B2 (en) | 2010-08-11 | 2015-02-17 | Showa Denko K.K. | Epoxysilicone condensate, curable composition comprising condensate, and cured product thereof |
JP5855001B2 (ja) * | 2010-08-11 | 2016-02-09 | 昭和電工株式会社 | エポキシシリコーン縮合物、該縮合物を含む硬化性組成物およびその硬化物 |
WO2012144480A1 (ja) * | 2011-04-20 | 2012-10-26 | セントラル硝子株式会社 | シロキサン化合物およびその硬化物 |
JP2012233174A (ja) * | 2011-04-20 | 2012-11-29 | Central Glass Co Ltd | シロキサン化合物およびその硬化物 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2009119469A1 (ja) | 2011-07-21 |
EP2270020A1 (en) | 2011-01-05 |
EP2270020B1 (en) | 2014-03-19 |
US20110021788A1 (en) | 2011-01-27 |
US8426614B2 (en) | 2013-04-23 |
JP5325206B2 (ja) | 2013-10-23 |
KR20100125438A (ko) | 2010-11-30 |
CN101977919A (zh) | 2011-02-16 |
CN101977919B (zh) | 2014-04-23 |
KR101215736B1 (ko) | 2012-12-26 |
EP2270020A4 (en) | 2012-04-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5325206B2 (ja) | エポキシ化合物およびその製造方法 | |
CN106866722B (zh) | 一种含苯并环丁烯官能化的有机硅化合物及其制备方法 | |
JP5821761B2 (ja) | シロキサン化合物およびその硬化物 | |
JP4948813B2 (ja) | ケチミン構造含有アルコキシシランの製造方法 | |
JP5153635B2 (ja) | 新規エポキシ化合物およびその製造方法 | |
JP5611544B2 (ja) | (メタ)アクリロイルオキシ基含有篭状シルセスキオキサン化合物およびその製造方法 | |
CN107987278A (zh) | 一种苯并环丁烯官能化有机硅树脂及其制备方法 | |
JP2014201534A (ja) | ケイ素化合物 | |
JP5861618B2 (ja) | オルガノポリシロキサン及びその製造方法 | |
JP5438447B2 (ja) | ヒドロシリル化合物の製造方法 | |
US7402648B2 (en) | Method for producing cyclic organic silicon compound and organic silicon resin having alcoholic hydroxyl group | |
JP5503963B2 (ja) | 有機ケイ素化合物、その製造方法、及びその有機ケイ素化合物を接着性付与剤として含む硬化性シリコーン組成物 | |
JP6048380B2 (ja) | オキセタン環を有する有機珪素化合物及びその製造方法 | |
WO2007007598A1 (ja) | アルコ-ル性水酸基を有する有機ケイ素樹脂及びその製造方法 | |
KR101064063B1 (ko) | 알코올성 수산기를 갖는 규소계 수지 및 그의 제조 방법 | |
JP5052209B2 (ja) | 新規エポキシ化合物とその製造方法 | |
JP2016204287A (ja) | 加水分解性シリル基含有環状オルガノハイドロジェンシロキサン | |
JP2015059108A (ja) | チオール化合物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980110402.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09724479 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010505608 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009724479 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12933828 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20107023613 Country of ref document: KR Kind code of ref document: A |