JP5996412B2 - Bis (meth) acryloyl-terminated benzyl ether compound and process for producing the same - Google Patents
Bis (meth) acryloyl-terminated benzyl ether compound and process for producing the same Download PDFInfo
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- JP5996412B2 JP5996412B2 JP2012274474A JP2012274474A JP5996412B2 JP 5996412 B2 JP5996412 B2 JP 5996412B2 JP 2012274474 A JP2012274474 A JP 2012274474A JP 2012274474 A JP2012274474 A JP 2012274474A JP 5996412 B2 JP5996412 B2 JP 5996412B2
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- Japan
- Prior art keywords
- bis
- meth
- compound
- acryloyl
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 benzyl ether compound Chemical class 0.000 title claims description 46
- 238000000034 method Methods 0.000 title description 19
- 150000001875 compounds Chemical class 0.000 claims description 46
- 125000003118 aryl group Chemical group 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 39
- 238000005227 gel permeation chromatography Methods 0.000 description 30
- 238000005259 measurement Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000011342 resin composition Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000002329 infrared spectrum Methods 0.000 description 18
- 239000007795 chemical reaction product Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000000523 sample Substances 0.000 description 15
- 239000002966 varnish Substances 0.000 description 15
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000003848 UV Light-Curing Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 6
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 6
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000003384 imaging method Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 4
- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000004455 differential thermal analysis Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000004970 halomethyl group Chemical group 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- 150000001253 acrylic acids Chemical class 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 2
- OXHOPZLBSSTTBU-UHFFFAOYSA-N 1,3-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC(CBr)=C1 OXHOPZLBSSTTBU-UHFFFAOYSA-N 0.000 description 2
- GRJWOKACBGZOKT-UHFFFAOYSA-N 1,3-bis(chloromethyl)benzene Chemical compound ClCC1=CC=CC(CCl)=C1 GRJWOKACBGZOKT-UHFFFAOYSA-N 0.000 description 2
- RBZMSGOBSOCYHR-UHFFFAOYSA-N 1,4-bis(bromomethyl)benzene Chemical compound BrCC1=CC=C(CBr)C=C1 RBZMSGOBSOCYHR-UHFFFAOYSA-N 0.000 description 2
- HFEMYLZYZUPETN-UHFFFAOYSA-N 1,6-bis(bromomethyl)naphthalene Chemical compound BrCC1=CC=CC2=CC(CBr)=CC=C21 HFEMYLZYZUPETN-UHFFFAOYSA-N 0.000 description 2
- ZDDXYBCNZLAXJO-UHFFFAOYSA-N 1,6-bis(chloromethyl)naphthalene Chemical compound ClCC1=CC=CC2=CC(CCl)=CC=C21 ZDDXYBCNZLAXJO-UHFFFAOYSA-N 0.000 description 2
- VDXGURZGBXUKES-UHFFFAOYSA-N 1-(bromomethyl)-2-[2-(bromomethyl)phenyl]benzene Chemical group BrCC1=CC=CC=C1C1=CC=CC=C1CBr VDXGURZGBXUKES-UHFFFAOYSA-N 0.000 description 2
- RAFYFUWHDWAUKS-UHFFFAOYSA-N 1-(bromomethyl)-3-[3-(bromomethyl)phenyl]benzene Chemical group BrCC1=CC=CC(C=2C=C(CBr)C=CC=2)=C1 RAFYFUWHDWAUKS-UHFFFAOYSA-N 0.000 description 2
- HMUGRILXVBKBID-UHFFFAOYSA-N 1-(bromomethyl)-4-[4-(bromomethyl)phenyl]benzene Chemical group C1=CC(CBr)=CC=C1C1=CC=C(CBr)C=C1 HMUGRILXVBKBID-UHFFFAOYSA-N 0.000 description 2
- FVRWZGLTJFGUJF-UHFFFAOYSA-N 1-(chloromethyl)-2-[2-(chloromethyl)phenyl]benzene Chemical group ClCC1=CC=CC=C1C1=CC=CC=C1CCl FVRWZGLTJFGUJF-UHFFFAOYSA-N 0.000 description 2
- YHKXFIHFUOMWFG-UHFFFAOYSA-N 1-(chloromethyl)-3-[3-(chloromethyl)phenyl]benzene Chemical group ClCC1=CC=CC(C=2C=C(CCl)C=CC=2)=C1 YHKXFIHFUOMWFG-UHFFFAOYSA-N 0.000 description 2
- DURKIAQJGSFQIL-UHFFFAOYSA-N 1-(chloromethyl)-3-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=CC(CCl)=C1 DURKIAQJGSFQIL-UHFFFAOYSA-N 0.000 description 2
- RHOOUTWPJJQGSK-UHFFFAOYSA-N 2-phenylsulfanylethyl prop-2-enoate Chemical compound C=CC(=O)OCCSC1=CC=CC=C1 RHOOUTWPJJQGSK-UHFFFAOYSA-N 0.000 description 2
- KBKLXLYSUOMJQE-UHFFFAOYSA-N 4-[9-(4-hydroxy-2-methylphenyl)fluoren-9-yl]-3-methylphenol Chemical compound CC1=CC(O)=CC=C1C1(C=2C(=CC(O)=CC=2)C)C2=CC=CC=C2C2=CC=CC=C21 KBKLXLYSUOMJQE-UHFFFAOYSA-N 0.000 description 2
- SNPPMOSOWNHABX-UHFFFAOYSA-N 4-[9-(4-hydroxy-3,5-dimethylphenyl)fluoren-9-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=C(C)C=2)=C1 SNPPMOSOWNHABX-UHFFFAOYSA-N 0.000 description 2
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000005825 oxyethoxy group Chemical group [H]C([H])(O[*:1])C([H])([H])O[*:2] 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- QVLAWKAXOMEXPM-DICFDUPASA-N 1,1,1,2-tetrachloro-2,2-dideuterioethane Chemical compound [2H]C([2H])(Cl)C(Cl)(Cl)Cl QVLAWKAXOMEXPM-DICFDUPASA-N 0.000 description 1
- CXQMWXOULXGMEY-UHFFFAOYSA-N 1,3-bis(bromomethyl)naphthalene Chemical compound C1=CC=CC2=CC(CBr)=CC(CBr)=C21 CXQMWXOULXGMEY-UHFFFAOYSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UZHZQZOMHXNQBJ-UHFFFAOYSA-N 1,4-bis(bromomethyl)naphthalene Chemical compound C1=CC=C2C(CBr)=CC=C(CBr)C2=C1 UZHZQZOMHXNQBJ-UHFFFAOYSA-N 0.000 description 1
- PMIHHEJEQAQZET-UHFFFAOYSA-N 1,4-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=C(CCl)C2=C1 PMIHHEJEQAQZET-UHFFFAOYSA-N 0.000 description 1
- ZNHUYTIFYQXOCM-UHFFFAOYSA-N 1,5-bis(bromomethyl)naphthalene Chemical compound C1=CC=C2C(CBr)=CC=CC2=C1CBr ZNHUYTIFYQXOCM-UHFFFAOYSA-N 0.000 description 1
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- GDZNZLKIUYVMPK-UHFFFAOYSA-N 1-(bromomethyl)-3-[4-(bromomethyl)phenyl]benzene Chemical group C1=CC(CBr)=CC=C1C1=CC=CC(CBr)=C1 GDZNZLKIUYVMPK-UHFFFAOYSA-N 0.000 description 1
- OSCCKWHVVNOREE-UHFFFAOYSA-N 1-(dibromomethyl)-3-phenylbenzene Chemical group BrC(Br)C1=CC=CC(C=2C=CC=CC=2)=C1 OSCCKWHVVNOREE-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HSFRODBENVJLHS-UHFFFAOYSA-N 2,3-bis(bromomethyl)naphthalene Chemical compound C1=CC=C2C=C(CBr)C(CBr)=CC2=C1 HSFRODBENVJLHS-UHFFFAOYSA-N 0.000 description 1
- LFJANESFAGYVTE-UHFFFAOYSA-N 2,3-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C=C(CCl)C(CCl)=CC2=C1 LFJANESFAGYVTE-UHFFFAOYSA-N 0.000 description 1
- JRPBSTGRRSTANR-UHFFFAOYSA-N 2,6-bis(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC=CC(CC(C)C)=C1O JRPBSTGRRSTANR-UHFFFAOYSA-N 0.000 description 1
- JRHSGFPVPTWMND-UHFFFAOYSA-N 2,6-bis(bromomethyl)naphthalene Chemical compound C1=C(CBr)C=CC2=CC(CBr)=CC=C21 JRHSGFPVPTWMND-UHFFFAOYSA-N 0.000 description 1
- RGAMXQRIMZYOPM-UHFFFAOYSA-N 2,6-bis(chloromethyl)naphthalene Chemical compound C1=C(CCl)C=CC2=CC(CCl)=CC=C21 RGAMXQRIMZYOPM-UHFFFAOYSA-N 0.000 description 1
- SRENQLLNRJNIHR-UHFFFAOYSA-N 2,6-ditert-butyl-4-[9-(3,5-ditert-butyl-4-hydroxyphenyl)fluoren-9-yl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 SRENQLLNRJNIHR-UHFFFAOYSA-N 0.000 description 1
- NPDSNSVKPZSSCL-UHFFFAOYSA-N 2,7-bis(bromomethyl)-9,9-bis(2-methylpropyl)fluorene Chemical compound BrCC1=CC=2C(C3=CC(=CC=C3C2C=C1)CBr)(CC(C)C)CC(C)C NPDSNSVKPZSSCL-UHFFFAOYSA-N 0.000 description 1
- VOHAJPWDXMTHMY-UHFFFAOYSA-N 2,7-bis(bromomethyl)-9,9-di(propan-2-yl)fluorene Chemical compound BrCC1=CC=2C(C3=CC(=CC=C3C2C=C1)CBr)(C(C)C)C(C)C VOHAJPWDXMTHMY-UHFFFAOYSA-N 0.000 description 1
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- IUEWVQYLPFZWOM-UHFFFAOYSA-N 2,7-bis(bromomethyl)-9,9-diethylfluorene Chemical compound C1=C(CBr)C=C2C(CC)(CC)C3=CC(CBr)=CC=C3C2=C1 IUEWVQYLPFZWOM-UHFFFAOYSA-N 0.000 description 1
- AAYBOWRNDXNQRC-UHFFFAOYSA-N 2,7-bis(bromomethyl)-9,9-dipropylfluorene Chemical compound C1=C(CBr)C=C2C(CCC)(CCC)C3=CC(CBr)=CC=C3C2=C1 AAYBOWRNDXNQRC-UHFFFAOYSA-N 0.000 description 1
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- HSRZSMMIVQXCLY-UHFFFAOYSA-N 2,7-bis(chloromethyl)-9h-fluorene Chemical compound ClCC1=CC=C2C3=CC=C(CCl)C=C3CC2=C1 HSRZSMMIVQXCLY-UHFFFAOYSA-N 0.000 description 1
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- QVWWBNLHPPGOJD-UHFFFAOYSA-N 2,7-bis(iodomethyl)-9,9-dimethylfluorene Chemical compound ICC1=CC=2C(C3=CC(=CC=C3C2C=C1)CI)(C)C QVWWBNLHPPGOJD-UHFFFAOYSA-N 0.000 description 1
- SKIIKRJAQOSWFT-UHFFFAOYSA-N 2-[3-[1-(2,2-difluoroethyl)piperidin-4-yl]oxy-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCC(CC1)OC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SKIIKRJAQOSWFT-UHFFFAOYSA-N 0.000 description 1
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- HDDBAPDCLCLKSH-UHFFFAOYSA-N 9,9-bis[3-(chloromethyl)phenyl]fluorene Chemical compound ClCC1=CC=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(CCl)C=CC=2)=C1 HDDBAPDCLCLKSH-UHFFFAOYSA-N 0.000 description 1
- YISRGFBOPKBOPM-UHFFFAOYSA-N 9,9-di(butan-2-yl)-2,7-bis(chloromethyl)fluorene Chemical compound ClCC1=CC=2C(C3=CC(=CC=C3C2C=C1)CCl)(C(C)CC)C(C)CC YISRGFBOPKBOPM-UHFFFAOYSA-N 0.000 description 1
- PWZPEWIINKOYFE-UHFFFAOYSA-N 9,9-di(butan-2-yl)-2,7-bis(iodomethyl)fluorene Chemical compound ICC1=CC=2C(C3=CC(=CC=C3C2C=C1)CI)(C(C)CC)C(C)CC PWZPEWIINKOYFE-UHFFFAOYSA-N 0.000 description 1
- FVADBWAFOZXKPY-UHFFFAOYSA-N 9,9-dibutyl-2,7-bis(chloromethyl)fluorene Chemical compound ClCC1=CC=2C(C3=CC(=CC=C3C2C=C1)CCl)(CCCC)CCCC FVADBWAFOZXKPY-UHFFFAOYSA-N 0.000 description 1
- PMMIUEJLJXMCGX-UHFFFAOYSA-N 9,9-diethyl-2,7-bis(iodomethyl)fluorene Chemical compound ICC1=CC=2C(C3=CC(=CC=C3C2C=C1)CI)(CC)CC PMMIUEJLJXMCGX-UHFFFAOYSA-N 0.000 description 1
- DHNZQGXKIYOTSC-UHFFFAOYSA-N BrC(C1=CC=C2C=3C=CC=CC3C(C2=C1)(C)C)Br Chemical compound BrC(C1=CC=C2C=3C=CC=CC3C(C2=C1)(C)C)Br DHNZQGXKIYOTSC-UHFFFAOYSA-N 0.000 description 1
- AFLXZLIYIKIUAJ-UHFFFAOYSA-N BrCC1=CC=2C(C3=CC(=CC=C3C2C=C1)CBr)(C(C)CC)C(C)CC Chemical compound BrCC1=CC=2C(C3=CC(=CC=C3C2C=C1)CBr)(C(C)CC)C(C)CC AFLXZLIYIKIUAJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(CI[Al]COC(C(*)=*)=*)OC(C)=CC=C(C1(c2ccccc2-c2c1cccc2)C(CC1)=CC=C1OC[Al]=ICC(C)(C)OC(C(*)=C)=O)C=C Chemical compound CC(C)(CI[Al]COC(C(*)=*)=*)OC(C)=CC=C(C1(c2ccccc2-c2c1cccc2)C(CC1)=CC=C1OC[Al]=ICC(C)(C)OC(C(*)=C)=O)C=C 0.000 description 1
- DYNNIZQNFJULAF-UHFFFAOYSA-N CC1=CC=C(C(C2=C3C(O)=CC(C)=C2)(C2=CC=CC=C2)C2=CC=CC=C2)C3=C1 Chemical compound CC1=CC=C(C(C2=C3C(O)=CC(C)=C2)(C2=CC=CC=C2)C2=CC=CC=C2)C3=C1 DYNNIZQNFJULAF-UHFFFAOYSA-N 0.000 description 1
- NHGQVWAZWQVQCI-UHFFFAOYSA-N ClCC1(C2=CC=CC=C2C=2C=CC=CC12)CCl.BrCC1=CC2=CC(=CC=C2C=C1)CBr Chemical compound ClCC1(C2=CC=CC=C2C=2C=CC=CC12)CCl.BrCC1=CC2=CC(=CC=C2C=C1)CBr NHGQVWAZWQVQCI-UHFFFAOYSA-N 0.000 description 1
- XIARYNBEVSBVRW-UHFFFAOYSA-N ClCC1=CC(=CC2=CC=CC=C12)CCl Chemical compound ClCC1=CC(=CC2=CC=CC=C12)CCl XIARYNBEVSBVRW-UHFFFAOYSA-N 0.000 description 1
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- BIJZAYLJTCAWID-UHFFFAOYSA-N ClCC1=CC=2C(C3=CC(=CC=C3C2C=C1)CCl)(CC(C)C)CC(C)C Chemical compound ClCC1=CC=2C(C3=CC(=CC=C3C2C=C1)CCl)(CC(C)C)CC(C)C BIJZAYLJTCAWID-UHFFFAOYSA-N 0.000 description 1
- ZXURYLDHRIOUMJ-UHFFFAOYSA-N ClCC1=CC=2C(C3=CC(=CC=C3C2C=C1)CCl)(CC)CC Chemical compound ClCC1=CC=2C(C3=CC(=CC=C3C2C=C1)CCl)(CC)CC ZXURYLDHRIOUMJ-UHFFFAOYSA-N 0.000 description 1
- FCVYNCTXUGGPOP-UHFFFAOYSA-N ClCC1=CC=2C(C3=CC(=CC=C3C=2C=C1)CCl)(C(C)C)C(C)C Chemical compound ClCC1=CC=2C(C3=CC(=CC=C3C=2C=C1)CCl)(C(C)C)C(C)C FCVYNCTXUGGPOP-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- MCIYLIYPQIMHSI-UHFFFAOYSA-N ICC1=CC=2C(C3=CC(=CC=C3C2C=C1)CI)(C(C)(C)C)C(C)(C)C Chemical compound ICC1=CC=2C(C3=CC(=CC=C3C2C=C1)CI)(C(C)(C)C)C(C)(C)C MCIYLIYPQIMHSI-UHFFFAOYSA-N 0.000 description 1
- BSBSUAQSYPQWLH-UHFFFAOYSA-N ICC1=CC=2C(C3=CC(=CC=C3C2C=C1)CI)(C(C)C)C(C)C Chemical compound ICC1=CC=2C(C3=CC(=CC=C3C2C=C1)CI)(C(C)C)C(C)C BSBSUAQSYPQWLH-UHFFFAOYSA-N 0.000 description 1
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- YQEILPMUFXGUAG-UHFFFAOYSA-N ICC1=CC=2C(C3=CC(=CC=C3C2C=C1)CI)(CCC)CCC Chemical compound ICC1=CC=2C(C3=CC(=CC=C3C2C=C1)CI)(CCC)CCC YQEILPMUFXGUAG-UHFFFAOYSA-N 0.000 description 1
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- UYTYRWIJXTXYDS-UHFFFAOYSA-N ICC1=CC=2CC3=CC(=CC=C3C2C=C1)CI Chemical compound ICC1=CC=2CC3=CC(=CC=C3C2C=C1)CI UYTYRWIJXTXYDS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 244000144980 herd Species 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
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- 238000001226 reprecipitation Methods 0.000 description 1
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Images
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Description
本発明は新規なビス（メタ）アクリロイル末端ベンジルエーテル化合物、及びその製造方法とその中間体としての芳香族ビスハロメチル化合物に関する。 The present invention relates to a novel bis (meth) acryloyl-terminated benzyl ether compound, a production method thereof and an aromatic bishalomethyl compound as an intermediate thereof.
近年、電子機器の小型化が進むにつれ、電子素子の高集積化を行うためにプリント配線の多層化が進み、絶縁層と導体層を交互に形成、積層する所謂ビルドアップ工法が多く採用されるようになった。そして、ここで使用される樹脂絶縁材料には、情報の高速処理化、信号の高周波化による熱損失の低減のため、低誘電率であることが要求されるようになってきている。 In recent years, as electronic devices have become more compact, printed wiring has become more multilayered in order to achieve higher integration of electronic elements, and so-called build-up methods in which insulating layers and conductor layers are alternately formed and stacked are often employed. It became so. The resin insulating material used here is required to have a low dielectric constant in order to reduce the heat loss due to high-speed information processing and high-frequency signals.
光又は熱硬化性樹脂組成物としては、特開平６−１９３８号公報等で知られているが、これらは誘電率が満足できる程度には低くならない。一方、低誘電率を達成する手法として、特開２０００−２０８８８９号公報や特開２００１−１２６５３４号公報のように、フィラーを充填する方法や、空孔を持たせるといった技術が知られているが、いずれもパッケージの層間絶縁膜といった用途には、信頼性に劣るといった欠点がある。さらに、特開２００４−３００３２６号公報には、特定の不飽和化合物（Ａ）に対して、光重合性の（メタ）アクリレート類（Ｂ）、エポキシ基を有する化合物（Ｃ）、及び光重合開始剤又は増感剤（Ｄ）を含有する光又は熱硬化性樹脂組成物において、硬化後において樹脂として存在することとなる樹脂分１００ｇ当たり、メタクリロイル基を５０ｍｍｏｌ以上含む光又は熱硬化性樹脂組成物が開示されており、低誘電性と高信頼性を両立できるとしている。しかし、最近、求められるようになって来ている低誘電特性には到達することはできなかった。 Light or thermosetting resin compositions are known from JP-A-6-1938 and the like, but these do not decrease to such an extent that the dielectric constant is satisfactory. On the other hand, as a technique for achieving a low dielectric constant, there are known techniques such as a method of filling a filler and a technique of providing voids as disclosed in Japanese Patent Application Laid-Open Nos. 2000-208889 and 2001-126534. Both of them have the drawback of being inferior in reliability in applications such as an interlayer insulating film of a package. Furthermore, JP-A-2004-300366 discloses a photopolymerizable (meth) acrylate (B), a compound having an epoxy group (C), and photopolymerization start for a specific unsaturated compound (A). Light or thermosetting resin composition containing 50 mmol or more of methacryloyl group per 100 g of resin component that will be present as a resin after curing in a light or thermosetting resin composition containing an agent or sensitizer (D) It is disclosed that both low dielectric properties and high reliability can be achieved. However, it has not been possible to reach the low dielectric properties that have recently been required.
一方、携帯電話などに用いられる撮像ユニットは、一般に、ＣＣＤ（Charge Coupled Device）イメージセンサやＣＭＯＳ（Complementary Metal-Oxide Semiconductor）イメージセンサなどの固体撮像素子と、固体撮像素子の受光面に結像するレンズユニットとで構成される。レンズユニットに含まれるレンズは、近年、安価で成形性に優れる熱又は光硬化性の樹脂で形成されたレンズも用いられている。そして、撮像用のレンズを中心に硬化性樹脂組成物を使用した光学物品及び光学レンズに於いては、種々の光学特性の向上が求められている。光学特性向上で要求されている特性の例を挙げると、例えば、低比重、高透明性、低黄色度、高屈折率、高アッベ数、強靭性などの特性の向上が要求されている。特に、近年、携帯電話などに用いられる撮像ユニットでは、筐体の薄型化及びバッテリーの大容量化からの要求で、薄型化が強く求められている。レンズユニットを構成するレンズの薄肉化を可能にするためには、光学レンズ材料の高屈折率化が必要であった。 On the other hand, an imaging unit used for a cellular phone or the like generally forms an image on a solid-state imaging device such as a charge coupled device (CCD) image sensor or a complementary metal-oxide semiconductor (CMOS) image sensor and a light receiving surface of the solid-state imaging device. It consists of a lens unit. In recent years, lenses made of heat or photo-curing resins that are inexpensive and have excellent moldability are also used as lenses included in the lens unit. In optical articles and optical lenses using a curable resin composition centering on imaging lenses, various optical characteristics are required to be improved. For example, characteristics required for improving optical characteristics are required to improve characteristics such as low specific gravity, high transparency, low yellowness, high refractive index, high Abbe number, and toughness. In particular, in recent years, an imaging unit used in a mobile phone or the like has been strongly demanded to be thin in response to demands from a thin casing and a large battery capacity. In order to make the lens constituting the lens unit thin, it is necessary to increase the refractive index of the optical lens material.
特開２００８−９４９８７号公報には、ビスフェノールフルオレン骨格を有する二官能（メタ）アクリレート化合物およびビフェニル骨格を有する単官能（メタ）アクリレート化合物を有する光学材料用高屈折率樹脂組成物およびその硬化物が開示されている。しかし、これから得られる光学レンズは、近年、レンズユニットの薄型化で求められる高屈折率を満たすものではなく、また、寸法安定性についても不足したものであった。 JP 2008-94987 A discloses a high refractive index resin composition for optical materials having a bifunctional (meth) acrylate compound having a bisphenolfluorene skeleton and a monofunctional (meth) acrylate compound having a biphenyl skeleton, and a cured product thereof. It is disclosed. However, the optical lens obtained from this does not satisfy the high refractive index required in recent years for reducing the thickness of the lens unit, and the dimensional stability is insufficient.
本発明は、高度の誘電特性（低誘電率・低誘電正接）を有し、かつ高いガラス転移温度と難燃性を有する硬化物を与えるビス（メタ）アクリロイル末端ベンジルエーテル化合物を提供することにある。また、本発明はビス（メタ）アクリロイル末端ベンジルエーテル化合物の中間体として有用な芳香族ビスハロメチル化合物を提供することにある。 The present invention provides a bis (meth) acryloyl-terminated benzyl ether compound having a high dielectric property (low dielectric constant / low dielectric loss tangent) and giving a cured product having a high glass transition temperature and flame retardancy. is there. Another object of the present invention is to provide an aromatic bishalomethyl compound useful as an intermediate of a bis (meth) acryloyl-terminated benzyl ether compound.
本発明者らは、大きな平面構造と屈曲部位を持つビスフェノールフルオレン骨格を有するビス（メタ）アクリロイル末端ベンジルエーテル化合物が上記課題を解決するために有効であることを見出し、本発明を完成した。 The present inventors have found that a bis (meth) acryloyl-terminated benzyl ether compound having a bisphenolfluorene skeleton having a large planar structure and a bent part is effective for solving the above problems, and completed the present invention.
下記式（１）で表される芳香族ビスハロメチル化合物は、ビス（メタ）アクリロイル末端ベンジルエーテル化合物の中間体として有用である。
（式中、Ａｒ1は炭素数６〜５０の芳香族炭化水素基を表し、Ｘはハロゲン元素を表し、ｎは１〜１０の数を表し、Ｒ1及びＲ2は独立に炭素数１〜５０の炭化水素基を表し、ｐ及びｑは独立に０〜２の整数を表す。）
Aromatic Bisuharomechiru compound represented by the following formula (1) is useful as an intermediate bis (meth) acryloyl-terminated benzyl ether compound.
(In the formula, Ar 1 represents an aromatic hydrocarbon group having 6 to 50 carbon atoms, X represents a halogen element, n represents a number of 1 to 10, and R 1 and R 2 are independently 1 to 1 carbon atoms. 50 represents a hydrocarbon group, and p and q independently represent an integer of 0 to 2.)
本発明は、下記式（２）で表されるビス（メタ）アクリロイル末端ベンジルエーテル化合物である。
（式（２）中、Ａｒ1は炭素数６〜５０の芳香族炭化水素基を表し、Ｙは水素またはメチル基を表し、ｎは１〜１０の数を表し、Ｒ1及びＲ2は独立に炭素数１〜５０の炭化水素基を表し、ｐ及びｑは独立に０〜２の整数を表す。）
The present invention is a bis (meth) acryloyl-terminated benzyl ether compound represented by the following formula (2).
(In the formula (2), Ar 1 represents an aromatic hydrocarbon group having 6 to 50 carbon atoms, Y represents hydrogen or a methyl group, n represents a number of 1 to 10, and R 1 and R 2 are independent. Represents a hydrocarbon group having 1 to 50 carbon atoms, and p and q independently represent an integer of 0 to 2.)
更に、本発明は、上記の芳香族ビスハロメチル化合物と、下記式（４）で表される（メタ）アクリル系化合物とを反応させることを特徴とする上記のビス（メタ）アクリロイル末端ベンジルエーテル化合物の製造方法である。
（式中、Ｙは水素またはメチル基を表し、Ｚは水素、アルカリ金属、または（メタ）アクリロイル基を表す。）
Furthermore, the present invention relates to the above bis (meth) acryloyl-terminated benzyl ether compound characterized by reacting the above aromatic bishalomethyl compound with a (meth) acrylic compound represented by the following formula (4): It is a manufacturing method.
(In the formula, Y represents hydrogen or a methyl group, and Z represents hydrogen, an alkali metal, or a (meth) acryloyl group.)
本発明の大きな平面構造と屈曲部位を持つビスフェノールフルオレン骨格を有するビス（メタ）アクリロイル末端ベンジルエーテル化合物は、これを硬化性化合物として使用することにより、分子内に分子サイズの大きな自由体積を有し、極性基が少ないことに起因して、高度の低誘電率特性の硬化物が得られる。そして、高度の難燃性・耐熱性で誘電率及び誘電正接の小さな材料を実現できるばかりではなく、高屈折率性をはじめとする光学特性に優れ、高い耐熱性と寸法安定性を有している光学材料も得ることができる。 The bis (meth) acryloyl-terminated benzyl ether compound having a bisphenolfluorene skeleton having a large planar structure and a bent portion according to the present invention has a large free volume with a molecular size in the molecule by using it as a curable compound. Due to the small number of polar groups, a cured product having a high low dielectric constant characteristic can be obtained. In addition to being able to realize materials with high flame retardancy and heat resistance and low dielectric constant and dielectric loss tangent, it has excellent optical properties such as high refractive index, high heat resistance and dimensional stability. Optical materials that are present can also be obtained.
以下、本発明を更に説明する。
本発明の式（１）で表される芳香族ビスハロメチル化合物は、その製法は特に限定されるものではないが、芳香族架橋剤とビスフェノールフルオレン系化合物とを反応させて合成することが望ましい。芳香族架橋剤としては、-CH2-Ar1-CH2-で表わされる架橋基を与える化合物が使用でき、ビスハロメチル化合物、ビスヒドロキシメチル化合物等があるが、ビスハロメチル化合物が好ましい。以下、芳香族架橋剤をビスハロメチル化合物で代表して説明するが、式（１）の芳香族ビスハロメチル化合物と区別する必要があるときは、これをビスハロメチル類又は芳香族ビスハロメチル類という。
なお、本明細書中で、同一の記号は特に断りがない限り、同一の意味を有する。
The present invention will be further described below.
The production method of the aromatic bishalomethyl compound represented by the formula (1) of the present invention is not particularly limited, but it is preferable to synthesize the aromatic bishalomethyl compound by reacting an aromatic crosslinking agent with a bisphenolfluorene compound. As the aromatic cross-linking agent, a compound giving a cross-linking group represented by —
In the present specification, the same symbols have the same meanings unless otherwise specified.
式（１）中のＡｒ１は炭素数６〜５０の芳香族炭化水素基であり、芳香族架橋剤から誘導される構造単位である。芳香族架橋剤が芳香族ビスハロメチル類である場合、好適なものとしては、例えば下記式（３）で表される芳香族ビスハロメチル類を挙げることができるが、これらに限定される訳ではない。 Ar 1 in the formula (1) is an aromatic hydrocarbon group having 6 to 50 carbon atoms, and is a structural unit derived from an aromatic crosslinking agent. In the case where the aromatic crosslinking agent is an aromatic bishalomethyl compound, suitable examples include aromatic bishalomethyl compounds represented by the following formula (3), but are not limited thereto.
（式中、Ａｒ１及びＸは、式（１）と同意である。）
(In the formula, Ar 1 and X are the same as the formula (1).)
Ａｒ１の具体例としては、−Ph−、−Ph−Ph−、−Ｎｐ−、−Ｎｐ−ＣＨ２−Ｎｐ−、−Ph−ＣＨ２−Ph−、−Ph−Ｃ（ＣＨ３）２−Ph−、−Ph−ＣＨ（ＣＨ３）−Ph−、−Ph−ＣＨ（Ｃ６Ｈ５）−Ph−、−Ph−Flu−Ph−、及び−Flu（ＣＨ３）２−からなる群れから選ばれる炭素数６〜５０の芳香族炭化水素基であることが好ましく、より好ましくは、炭素数が６〜２０である芳香族炭化水素基である。ここで、Phはフェニレン基（-Ｃ６Ｈ４-）を表し、Ｎｐはナフチレン基（-Ｃ１０Ｈ６−）を表し、Fluはフルオレニル基を表す。ここで、Ｐｈ、ＮｐおよびＦｌｕは、置換基を有しても良く、例えば、アルキル基、アルコキシ基、フェニル基である。好ましくは炭素数が１〜６のアルキル基である。特に好ましくは、無置換、メチル置換及びジメチル置換の−Ph−Ph−及び−Ph−である。Ｘはハロゲン元素を表すが、塩素、臭素、及びヨウ素から選ばれるハロゲン元素が工業的実施に於ける入手の容易さより、好んで使用され、より好ましくは塩素である。 Specific examples of Ar 1 include —Ph—, —Ph—Ph—, —Np—, —Np—CH 2 —Np—, —Ph—CH 2 —Ph—, —Ph—C (CH 3 ) 2 —. Ph -, - Ph-CH ( CH 3) -Ph -, - Ph-CH (C 6 H 5) -Ph -, - Ph-Flu-Ph-, and -Flu (CH 3) 2 - from herd consisting of It is preferably an aromatic hydrocarbon group having 6 to 50 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms. Here, Ph represents a phenylene group (—C 6 H 4 —), Np represents a naphthylene group (—C 10 H 6 —), and Flu represents a fluorenyl group. Here, Ph, Np and Flu may have a substituent, for example, an alkyl group, an alkoxy group, or a phenyl group. Preferably it is a C1-C6 alkyl group. Particularly preferred are unsubstituted, methyl-substituted and dimethyl-substituted -Ph-Ph- and -Ph-. X represents a halogen element, but a halogen element selected from chlorine, bromine and iodine is preferably used because of its availability in industrial practice, and more preferably chlorine.
式（１）中、ｎは１〜１０の数を表すが、分子量分布を有するときは、平均値（数平均）である。 In formula (1), n represents a number of 1 to 10, but when it has a molecular weight distribution, it is an average value (number average).
上記式（３）で表される芳香族ビスハロメチル類をさらに具体的に例示すると、ｐ−ビスクロロメチルベンゼン、ｍ−ビスクロロメチルベンゼン、ｐ−ビスブロモメチルベンゼン、ｍ−ビスブロモメチルベンゼン、４，４’−ビスクロロメチルビフェニル、４，３’−ビスクロロメチルビフェニル、３，３’−ビスクロロメチルビフェニル、２，２’−ビスクロロメチルビフェニル、４，４’−ビスブロモメチルビフェニル、４，３’−ビスブロモメチルビフェニル、３，３’−ビスブロモメチルビフェニル、２，２’−ビスブロモメチルビフェニル、１，４−ビスクロロメチルナフタレン、１，５−ビスクロロメチルナフタレン、１，６−ビスクロロメチルナフタレン、２，３−ビスクロロメチルナフタレン、２，４−ビスクロロメチルナフタレン、２，５−ビスクロロメチルナフタレン、２，６−ビスクロロメチルナフタレン、２，７−ビスクロロメチルナフタレン、１，４−ビスブロモメチルナフタレン、１，５−ビスブロモメチルナフタレン、１，６−ビスブロモメチルナフタレン、２，３−ビスブロモメチルナフタレン、２，４−ビスブロモメチルナフタレン、２，５−ビスブロモメチルナフタレン、２，６−ビスブロモメチルナフタレン、２，７−ビスブロモメチルナフタレン、９，９−ビスクロロメチルフルオレン、９，９−ビスブロモメチルフルオレン、２，７−ビスクロロメチルフルオレン、２，７−ビスクロロメチル−９，９−ジメチルフルオレン、２，７−ビスクロロメチル−９，９−ジエチルフルオレン、２，７−ビスクロロメチル−９，９−ジ−ｎ−プロピルフルオレン、２，７−ビスクロロメチル−９，９−ジイソプロピルフルオレン、２，７−ビスクロロメチル−９，９−ジ−ｎ−ブチルフルオレン、２，７−ビスクロロメチル−９，９−ジイソブチルフルオレン、２，７−ビスクロロメチル−９，９−ジ−sec−ブチルフルオレン、２，７−ビスクロロメチル−９，９−ジ−tert−ブチルフルオレン、２，７−ビスブロモメチルフルオレン、２，７−ビスブロモメチル−９，９−ジメチルフルオレン、２，７−ビスブロモメチル−９，９−ジエチルフルオレン、２，７−ビスブロモメチル−９，９−ジ−ｎ−プロピルフルオレン、２，７−ビスブロモメチル−９，９−ジイソプロピルフルオレン、２，７−ビスブロモメチル−９，９−ジ−ｎ−ブチルフルオレン、２，７−ビスブロモメチル−９，９−ジイソブチルフルオレン、２，７−ビスブロモメチル−９，９−ジ−sec−ブチルフルオレン、２，７−ビスブロモメチル−９，９−ジ−tert−ブチルフルオレン、２，７−ビスヨードメチルフルオレン、２，７−ビスヨードメチル−９，９−ジメチルフルオレン、２，７−ビスヨードメチル−９，９−ジエチルフルオレン、２，７−ビスヨードメチル−９，９−ジ−ｎ−プロピルフルオレン、２，７−ビスヨードメチル−９，９−ジイソプロピルフルオレン、２，７−ビスヨードメチル−９，９−ジ−ｎ−ブチルフルオレン、２，７−ビスヨードメチル−９，９−ジイソブチルフルオレン、２，７−ビスヨードメチル−９，９−ジ−sec−ブチルフルオレン、２，７−ビスヨードメチル−９，９−ジ−tert−ブチルフルオレン、９，９−ビス（４−クロロメチルフェニル）フルオレン、９，９−ビス（３−クロロメチルフェニル）フルオレン、９，９−ビス（２−クロロメチルフェニル）フルオレンなどが挙げられるが、これらに限定されるものではない。特に好ましくは、ｐ−ビスクロロメチルベンゼン、ｍ−ビスクロロメチルベンゼン、ｐ−ビスブロモメチルベンゼン、ｍ−ビスブロモメチルベンゼン、４，４’−ビスクロロメチルビフェニル、４，３’−ビスクロロメチルビフェニル、３，３’−ビスクロロメチルビフェニル、２，２’−ビスクロロメチルビフェニル、４，４’−ビスブロモメチルビフェニル、４，３’−ビスブロモメチルビフェニル、３，３’−ビスブロモメチルビフェニル及び２，２’−ビスブロモメチルビフェニルならびにそれらのメチル置換体及びジメチル置換体である。 Specific examples of the aromatic bishalomethyls represented by the above formula (3) include p-bischloromethylbenzene, m-bischloromethylbenzene, p-bisbromomethylbenzene, m-bisbromomethylbenzene, 4 , 4'-bischloromethylbiphenyl, 4,3'-bischloromethylbiphenyl, 3,3'-bischloromethylbiphenyl, 2,2'-bischloromethylbiphenyl, 4,4'-bisbromomethylbiphenyl, 4, , 3′-bisbromomethylbiphenyl, 3,3′-bisbromomethylbiphenyl, 2,2′-bisbromomethylbiphenyl, 1,4-bischloromethylnaphthalene, 1,5-bischloromethylnaphthalene, 1,6 -Bischloromethylnaphthalene, 2,3-bischloromethylnaphthalene, 2,4-bischloromethylnaphthalene Talene, 2,5-bischloromethylnaphthalene, 2,6-bischloromethylnaphthalene, 2,7-bischloromethylnaphthalene, 1,4-bisbromomethylnaphthalene, 1,5-bisbromomethylnaphthalene, 1,6 -Bisbromomethylnaphthalene, 2,3-bisbromomethylnaphthalene, 2,4-bisbromomethylnaphthalene, 2,5-bisbromomethylnaphthalene, 2,6-bisbromomethylnaphthalene, 2,7-bisbromomethylnaphthalene 9,9-bischloromethylfluorene, 9,9-bisbromomethylfluorene, 2,7-bischloromethylfluorene, 2,7-bischloromethyl-9,9-dimethylfluorene, 2,7-bischloromethyl -9,9-diethylfluorene, 2,7-bischloromethyl-9,9-di-n-propyl Pyrfluorene, 2,7-bischloromethyl-9,9-diisopropylfluorene, 2,7-bischloromethyl-9,9-di-n-butylfluorene, 2,7-bischloromethyl-9,9-diisobutyl Fluorene, 2,7-bischloromethyl-9,9-di-sec-butylfluorene, 2,7-bischloromethyl-9,9-di-tert-butylfluorene, 2,7-bisbromomethylfluorene, 2, , 7-bisbromomethyl-9,9-dimethylfluorene, 2,7-bisbromomethyl-9,9-diethylfluorene, 2,7-bisbromomethyl-9,9-di-n-propylfluorene, 2, 7-bisbromomethyl-9,9-diisopropylfluorene, 2,7-bisbromomethyl-9,9-di-n-butylfluorene, 2,7-bisbromomethyl 9,9-diisobutylfluorene, 2,7-bisbromomethyl-9,9-di-sec-butylfluorene, 2,7-bisbromomethyl-9,9-di-tert-butylfluorene, 2,7-bis Iodomethylfluorene, 2,7-bisiodomethyl-9,9-dimethylfluorene, 2,7-bisiodomethyl-9,9-diethylfluorene, 2,7-bisiodomethyl-9,9-di-n- Propylfluorene, 2,7-bisiodomethyl-9,9-diisopropylfluorene, 2,7-bisiodomethyl-9,9-di-n-butylfluorene, 2,7-bisiodomethyl-9,9-diisobutyl Fluorene, 2,7-bisiodomethyl-9,9-di-sec-butylfluorene, 2,7-bisiodomethyl-9,9-di-tert-butylfluorene, 9,9- (9)-(4-chloromethylphenyl) fluorene, 9,9-bis (3-chloromethylphenyl) fluorene, 9,9-bis (2-chloromethylphenyl) fluorene, etc. Absent. Particularly preferably, p-bischloromethylbenzene, m-bischloromethylbenzene, p-bisbromomethylbenzene, m-bisbromomethylbenzene, 4,4′-bischloromethylbiphenyl, 4,3′-bischloromethyl Biphenyl, 3,3′-bischloromethylbiphenyl, 2,2′-bischloromethylbiphenyl, 4,4′-bisbromomethylbiphenyl, 4,3′-bisbromomethylbiphenyl, 3,3′-bisbromomethyl Biphenyl and 2,2′-bisbromomethylbiphenyl and their methyl and dimethyl substituents.
式（１）中、ｐ、ｑは各々独立に０〜２の整数を表す。R1、R2は各々独立に、炭素数１〜５０の炭化水素基を表すが、好ましくは炭素数１〜１２の脂肪族炭化水素基又は炭素数６〜１２の芳香族炭化水素基であり、より好ましくは炭素数１〜１２のアルキル基である。 In formula (1), p and q each independently represent an integer of 0 to 2. R 1 and R 2 each independently represents a hydrocarbon group having 1 to 50 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. More preferably, it is a C1-C12 alkyl group.
芳香族架橋剤と反応させるビスフェノールフルオレン系化合物としては、下記式（５）で表される化合物が好適である。
（式中、Ｒ１、Ｒ２、ｐ及びｑは式（１）と同じ意味を有する。）
As the bisphenolfluorene compound to be reacted with the aromatic crosslinking agent, a compound represented by the following formula (5) is suitable.
(In the formula, R 1 , R 2 , p and q have the same meaning as in formula (1).)
式（５）で表されるビスフェノールフルオレン系化合物をさらに具体的に例示すると、９，９−ビス（４−ヒドロキシフェニル）フルオレン；９，９−ビス（４−ヒドロキシ−２−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−エチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−ｔ−ブチルフェニル）フルオレンなどの９，９−ビス（アルキルヒドロキシフェニル）フルオレン；９，９−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−２，６−ジメチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３，５−ジ−tert−ブチルフェニル）フルオレンなどの９，９−ビス（ジアルキルヒドロキシフェニル）フルオレン；９，９−ビス（４−ヒドロキシ−３−シクロヘキシルフェニル）フルオレンなどの９，９−ビス（シクロアルキルヒドロキシフェニル）フルオレン；９，９−ビス（４−ヒドロキシ−３−フェニルフェニル）フルオレンなどの９，９−ビス（アリールヒドロキシフェニル）フルオレンなどが挙げられるが、これらに限定されるものではない。好ましくは、９，９−ビス（４−ヒドロキシフェニル）フルオレン；９，９−ビス（４−ヒドロキシ−２−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）フルオレンである。 Specific examples of the bisphenolfluorene compound represented by the formula (5) include 9,9-bis (4-hydroxyphenyl) fluorene; 9,9-bis (4-hydroxy-2-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-t-butylphenyl) ) 9,9-bis (alkylhydroxyphenyl) fluorene such as fluorene; 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-2,6-dimethyl) 9,9-bis (phenyl) fluorene, 9,9-bis (4-hydroxy-3,5-di-tert-butylphenyl) fluorene Dialkylhydroxyphenyl) fluorene; 9,9-bis (cycloalkylhydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene; 9,9-bis (4-hydroxy-3-phenyl) Examples include, but are not limited to, 9,9-bis (arylhydroxyphenyl) fluorene such as phenyl) fluorene. Preferably, 9,9-bis (4-hydroxyphenyl) fluorene; 9,9-bis (4-hydroxy-2-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene.
本発明の式（１）の芳香族ビスハロメチル化合物は、好適には芳香族ビスハロメチル類と式（５）のビスフェノールフルオレン系化合物とを反応させて合成される（工程A）。 The aromatic bishalomethyl compound of the formula (1) of the present invention is preferably synthesized by reacting an aromatic bishalomethyl compound with a bisphenol fluorene compound of the formula (5) (step A).
この工程Aでは、式（３）の芳香族ビスハロメチル類と式（５）のビスフェノールフルオレン系化合物との使用割合は、当量比（ハロメチル：ＯＨのモル比）で１００：２０〜１００：９９であることが好ましい。この範囲内であると、ビスフェノールフルオレン系化合物の全量に近い量が芳香族ビスハロメチル類と反応し、両末端に芳香族ビスハロメチル類中のハロメチル基が残ったモノマー又はオリゴマーとなる。そして、上記当量比を制御することでｎの数を制御することができる。このｎの値は、１〜１０であり更に好ましくは、１．２〜１０、更に好ましくは１．２〜８、特に好ましくは１．２〜５である。なお、ｎは通常、平均値である。本明細書において、平均値の場合は数平均を意味する。 In this step A, the use ratio of the aromatic bishalomethyl compound of the formula (3) and the bisphenolfluorene compound of the formula (5) is 100: 20 to 100: 99 as an equivalent ratio (molar ratio of halomethyl: OH). It is preferable. Within this range, an amount close to the total amount of the bisphenol fluorene compound reacts with the aromatic bishalomethyls, resulting in a monomer or oligomer in which the halomethyl groups in the aromatic bishalomethyls remain at both ends. And the number of n is controllable by controlling the said equivalence ratio. The value of n is 1 to 10, more preferably 1.2 to 10, more preferably 1.2 to 8, and particularly preferably 1.2 to 5. Note that n is usually an average value. In this specification, the average value means number average.
この工程Aでは、ビスフェノールフルオレン系化合物と芳香族ビスハロメチル化合物との反応を促進させるため、アルカリ金属水酸化物の存在下で反応させることがよい。 In this step A, the reaction between the bisphenolfluorene compound and the aromatic bishalomethyl compound is preferably promoted in the presence of an alkali metal hydroxide.
次に、本発明の式（２）で表されるビス（メタ）アクリロイル末端ベンジルエーテル化合物（以下、式（２）のベンジルエーテル化合物又は本発明のベンジルエーテル化合物ともいう。）について説明する。このビス（メタ）アクリロイル末端ベンジルエーテル化合物の製法は特に限定されるものではないが、式（１）で表される芳香族ビスハロメチル化合物と式（４）で表される（メタ）アクリル系化合物とから合成することが望ましい。式（４）において、Ｚは水素、アルカリ金属または（メタ）アクリロイル基（ＣＨ2＝Ｃ（Ｙ）-Ｃ（Ｏ）-）を表し、Ｙは式（２）と同意である。 Next, the bis (meth) acryloyl-terminated benzyl ether compound represented by the formula (2) of the present invention (hereinafter also referred to as the benzyl ether compound of the formula (2) or the benzyl ether compound of the present invention) will be described. The production method of the bis (meth) acryloyl-terminated benzyl ether compound is not particularly limited, but the aromatic bishalomethyl compound represented by the formula (1) and the (meth) acrylic compound represented by the formula (4) It is desirable to synthesize from In the formula (4), Z represents hydrogen, an alkali metal or a (meth) acryloyl group (CH 2 ═C (Y) —C (O) —), and Y is the same as in the formula (2).
本発明のベンジルエーテル化合物の製造において、工程Aで得られた式（１）で表される芳香族ビスハロメチル化合物と（メタ）アクリレート基部分を与える化合物を反応させるのが工業的に有利である。この反応工程を工程Bという。なお、式（１）で表される芳香族ビスハロメチル化合物は、本発明のベンジルエーテル化合物の中間体として有用であるので、中間体ともいう。 In the production of the benzyl ether compound of the present invention, it is industrially advantageous to react the aromatic bishalomethyl compound represented by the formula (1) obtained in Step A with the compound giving the (meth) acrylate group moiety. This reaction process is referred to as process B. In addition, since the aromatic bishalomethyl compound represented by Formula (1) is useful as an intermediate of the benzyl ether compound of this invention, it is also called an intermediate.
式（４）で表される（メタ）アクリル系化合物としては、メタクリル酸、アクリル酸、無水メタクリル酸、無水アクリル酸及びこれらの塩又はこれらの混合物が使用できる。また、アルカリ金属（メタ）アクリレートであれば、反応がより容易に進行する。この場合は、（メタ）アクリル酸リチウム、（メタ）アクリル酸カリウム、又は（メタ）アクリル酸ナトリウムであってよい。 As the (meth) acrylic compound represented by the formula (4), methacrylic acid, acrylic acid, methacrylic anhydride, acrylic anhydride and salts thereof, or a mixture thereof can be used. Moreover, if it is an alkali metal (meth) acrylate, reaction will advance more easily. In this case, it may be lithium (meth) acrylate, potassium (meth) acrylate, or sodium (meth) acrylate.
式（４）において、ＺがＫである（メタ）アクリル系化合物、例えば（メタ）アクリル酸カリウムを使用するときには、（メタ）アクリル酸エステル類のけん化によって、又は、炭酸カリウムによる（メタ）アクリル酸の中和によって、（メタ）アクリル酸カリウムを調製することが可能であり、前記中和の場合には、炭酸カリウムが（メタ）アクリル酸類に対して過剰であることが好ましい。この場合には、芳香族ビスハロメチル化合物と、（メタ）アクリル酸カリウムとの反応の前に、（メタ）アクリル酸カリウムを単離しなくてもよい。過剰のアルカリは反応を促進する。 In the formula (4), when a (meth) acrylic compound in which Z is K, such as potassium (meth) acrylate, is used, saponification of (meth) acrylic acid esters or (meth) acrylic with potassium carbonate It is possible to prepare potassium (meth) acrylate by neutralization of the acid, and in the case of the neutralization, it is preferable that potassium carbonate is excessive with respect to (meth) acrylic acids. In this case, it is not necessary to isolate potassium (meth) acrylate before the reaction between the aromatic bishalomethyl compound and potassium (meth) acrylate. Excess alkali accelerates the reaction.
工程Bでの式（１）の芳香族ビスハロメチル化合物と式（４）の（メタ）アクリル系化合物との反応は、特に制限されるものではないが、例えばＺがＨである（メタ）アクリル酸類を極性溶剤中で炭酸カリウムで中和してカリウム塩を調製し、このカリウム塩と芳香族ビスハロメチル化合物を反応させ、形成された副生物のアルカリ金属塩化物を濾過によって分離し、目的のビス（メタ）アクリロイル末端ベンジルエーテル化合物を得る方法が挙げられる。 The reaction of the aromatic bishalomethyl compound of formula (1) and the (meth) acrylic compound of formula (4) in step B is not particularly limited, but for example (meth) acrylic acids in which Z is H Is neutralized with potassium carbonate in a polar solvent to prepare a potassium salt, the potassium salt is reacted with an aromatic bishalomethyl compound, the formed by-product alkali metal chloride is separated by filtration, and the desired bis ( A method for obtaining a (meth) acryloyl-terminated benzyl ether compound is mentioned.
芳香族ビスハロメチル化合物と（メタ）アクリル系化合物との配合割合は、当量比（ハロメチル：（メタ）アクリロイル基類のモル比）で１００：９５〜１００：１２０であることが好ましく、より好ましくは、１００：１００〜１００：１１０である。当量比が該範囲内であると、仕込んだ芳香族ビスハロメチル化合物の全量に近い量がアクリル系化合物と反応し、芳香族ビスハロメチル化合物中のハロメチル基が（メタ）アクリレート化され、反応物中にほとんど残存しなくなることにより、これを硬化性樹脂組成物とした場合、硬化反応が十分に進行し、また、良好な誘電特性を示し、熱安定性も良好になるので好ましい。 The blending ratio of the aromatic bishalomethyl compound and the (meth) acrylic compound is preferably 100: 95 to 100: 120 in terms of equivalent ratio (molar ratio of halomethyl: (meth) acryloyl groups), more preferably 100: 100 to 100: 110. When the equivalent ratio is within the above range, an amount close to the total amount of the aromatic bishalomethyl compound charged reacts with the acrylic compound, and the halomethyl group in the aromatic bishalomethyl compound is (meth) acrylated, and is almost completely contained in the reaction product. When this is made into a curable resin composition by not remaining, it is preferable because the curing reaction proceeds sufficiently, exhibits good dielectric properties, and has good thermal stability.
工程Bの反応を行う際には、極性溶剤を使用することがよく、好ましい極性溶剤としては、メタノール、エタノール、プロパノール、ブタノール等のアルコール類、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド系溶剤、ジオキサン、テトラヒドロフラン、エチレングリコールジメチルエーテル、１，３−ジメトキシプロパン、１，２−ジメトキシエタン等のエーテル系溶剤類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、ジメチルスルホキシド、アセトニトリルあるいはその混合溶剤が挙げられる。 When performing the reaction of Step B, it is preferable to use a polar solvent. Preferred polar solvents include alcohols such as methanol, ethanol, propanol and butanol, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Solvents, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ether solvents such as 1,3-dimethoxypropane, 1,2-dimethoxyethane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethyl sulfoxide, acetonitrile Or the mixed solvent is mentioned.
工程Bの反応を行う際には、式（４）のアクリル系化合物のＭをけん化又は中和によってアルカリ金属の塩とし、反応を促進する方法が好んで用いられる。好ましいアルカリ金属の塩としては、（メタ）アクリル酸リチウム、（メタ）アクリル酸カリウム、又は（メタ）アクリル酸ナトリウム、およびこれらの混合物が挙げられる。アルカリ金属の塩を形成する際のアクリル酸エステル類又はアクリル酸類とアルカリ金属化合物の配合割合は、当量比で１．０５〜２．０倍の範囲であることが好ましい。 In carrying out the reaction of the step B, a method of accelerating the reaction by converting M of the acrylic compound of the formula (4) into an alkali metal salt by saponification or neutralization is preferably used. Preferred alkali metal salts include lithium (meth) acrylate, potassium (meth) acrylate, or sodium (meth) acrylate, and mixtures thereof. It is preferable that the blending ratio of the acrylic acid esters or acrylic acids and the alkali metal compound when forming the alkali metal salt is in the range of 1.05 to 2.0 times in terms of equivalent ratio.
工程Bの反応温度および反応時間は、反応に応じ適宜選択すればよいが、それぞれ３０〜１００℃、０．５〜２０時間の範囲であれば十分に反応が進行する。 The reaction temperature and reaction time in step B may be appropriately selected depending on the reaction, but the reaction proceeds sufficiently if they are in the range of 30 to 100 ° C. and 0.5 to 20 hours, respectively.
上記反応により式（３）で表されるビス（メタ）アクリロイル末端ベンジルエーテル化合物を得ることができる。この反応により得られたビス（メタ）アクリロイル末端ベンジルエーテル化合物は、さらに再沈精製あるいは再結晶により精製することにより不純物の含有量を低減できる。 By the above reaction, a bis (meth) acryloyl-terminated benzyl ether compound represented by the formula (3) can be obtained. The content of impurities can be reduced by further purifying the bis (meth) acryloyl-terminated benzyl ether compound obtained by this reaction by reprecipitation purification or recrystallization.
本発明のビス（メタ）アクリロイル末端ベンジルエーテル化合物は、（メタ）アクリロイル基を２つ有するので樹脂原料として有用であり、特に熱硬化性樹脂用の樹脂組成物に配合されるモノマーとして有用である。 The bis (meth) acryloyl-terminated benzyl ether compound of the present invention is useful as a resin raw material because it has two (meth) acryloyl groups, and particularly useful as a monomer blended in a resin composition for a thermosetting resin. .
この樹脂組成物は、ビス（メタ）アクリロイル末端ベンジルエーテル化合物と重合開始剤を必須成分として含むことが望ましい。重合開始剤としては、ビニル化合物の重合開始剤として公知の重合開始剤で良く、紫外線、電子線等の活性エネルギー線の照射またはラジカル重合開始剤を適用できるが、ラジカル重合開始剤（ラジカル重合触媒ともいう。）が好ましい。 This resin composition desirably contains a bis (meth) acryloyl-terminated benzyl ether compound and a polymerization initiator as essential components. The polymerization initiator may be a known polymerization initiator as a polymerization initiator of a vinyl compound, and irradiation with active energy rays such as ultraviolet rays and electron beams or a radical polymerization initiator can be applied. A radical polymerization initiator (radical polymerization catalyst) Also referred to).
本発明のビス（メタ）アクリロイル末端ベンジルエーテル化合物を含む樹脂組成物は、硬化性を有するので、硬化性樹脂組成物ともいう。この硬化性樹脂組成物を硬化させて得られる硬化物は成型物、積層物、注型物、接着剤、塗膜、フィルムとして使用できる。例えば、半導体封止材料の硬化物は注型物又は成型物であり、かかる用途の硬化物を得る方法としては、該化合物を注型、或いはトランスファ−成形機、射出成形機、圧縮成形機などを用いて成形し、さらに８０〜２３０℃で０．５〜１０時間に加熱することにより硬化物を得ることができる。また、この硬化性樹脂組成物は活性エネルギー線照射装置を使用して、活性エネルギー線を照射することにより硬化物を得ることができる。 Since the resin composition containing the bis (meth) acryloyl-terminated benzyl ether compound of the present invention has curability, it is also referred to as a curable resin composition. A cured product obtained by curing the curable resin composition can be used as a molded product, a laminate, a cast product, an adhesive, a coating film, or a film. For example, a cured product of a semiconductor sealing material is a cast or molded product. As a method for obtaining a cured product for such use, the compound is cast, or a transfer molding machine, an injection molding machine, a compression molding machine, etc. A cured product can be obtained by molding at 80 to 230 ° C. for 0.5 to 10 hours. Moreover, this curable resin composition can obtain hardened | cured material by irradiating an active energy ray using an active energy ray irradiation apparatus.
本発明のビス（メタ）アクリロイル末端ベンジルエーテル化合物を含む硬化性樹脂組成物は、上述する硬化方法によって硬化させることにより光学物品として適した硬化物を得ることができる。このような光学物品として適した硬化物は、種々の光学特性に優れた光学物品、例えば光学レンズとなる。 The curable resin composition containing the bis (meth) acryloyl-terminated benzyl ether compound of the present invention can be cured by the above-described curing method to obtain a cured product suitable as an optical article. Hardened | cured material suitable as such an optical article turns into an optical article excellent in various optical characteristics, for example, an optical lens.
以下、実施例により本発明を説明するが、本発明はこれらにより制限されるものではない。なお、各例中の部はいずれも重量部である。また、実施例中の測定結果は以下に示す方法により試料調製及び測定を行ったものである。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited by these. In addition, all the parts in each example are parts by weight. In addition, the measurement results in the examples are those obtained by sample preparation and measurement by the following methods.
１）芳香族ビスハロメチル化合物、及びビス（メタ）アクリロイル末端ベンジルエーテル化合物のＧＰＣ純度
分子量及び分子量分布測定はＧＰＣ（東ソー製、ＨＬＣ−８１２０ＧＰＣ）を使用し、溶媒：テトラヒドロフラン（ＴＨＦ）、流量：１．０ｍｌ／ｍｉｎ、カラム温度：４０℃で行った。ＵＶ検出器（波長：２５４ｎｍ）で検出された各ピークの面積比により算出した。分子量は単分散ポリスチレンによる検量線を用い、ポリスチレン換算分子量として測定を行った。
1) GPC purity of aromatic bishalomethyl compound and bis (meth) acryloyl-terminated benzyl ether compound GPC (manufactured by Tosoh Corporation, HLC-8120GPC) was used for molecular weight and molecular weight distribution measurement, solvent: tetrahydrofuran (THF), flow rate: 1. It was carried out at 0 ml / min and column temperature: 40 ° C. It calculated by the area ratio of each peak detected with the UV detector (wavelength: 254 nm). The molecular weight was measured as a polystyrene-converted molecular weight using a calibration curve of monodisperse polystyrene.
２）芳香族ビスハロメチル化合物、及びビス（メタ）アクリロイル末端ベンジルエーテル化合物の構造
日本電子製ＪＮＭ−ＬＡ６００型核磁気共鳴分光装置を用い、１３Ｃ−ＮＭＲ及び１Ｈ−ＮＭＲ分析により決定した。溶媒としてクロロホルム−ｄ１を使用した。ＮＭＲ測定溶媒であるテトラクロロエタン−ｄ２の共鳴線を内部標準として使用した。
2) Structure of aromatic bishalomethyl compound and bis (meth) acryloyl-terminated benzyl ether compound Using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL, the structure was determined by 13 C-NMR and 1 H-NMR analysis. Chloroform-d 1 was used as a solvent. The resonance line of tetrachloroethane -d 2 is an NMR measurement solvent was used as an internal standard.
３）粘度
ビス（メタ）アクリロイル末端ベンジルエーテル化合物を含む硬化性樹脂組成物の粘度は、Ｅ型粘度計を使用して、２５℃の温度で測定を行った。
3) Viscosity The viscosity of the curable resin composition containing a bis (meth) acryloyl-terminated benzyl ether compound was measured at a temperature of 25 ° C. using an E-type viscometer.
４）誘電率及び誘電正接
硬化性樹脂組成物ワニスを０．２ｍｍ厚のスペーサーを挟んだ２枚のガラス板の間に流し込み、高圧水銀ランプを備えたＵＶ照射装置で、照射強度：３０ｍＷ／ｃｍ２、ＵＶ照射量：６，０００ｍＪ／ｃｍ２でＵＶ硬化を行った。ＵＶ硬化を行って得られた平板サンプルをさらに２００℃のオーブンで３０分間ポストキュアを行い、得られた硬化物平板について諸特性を測定した。また、この厚み０．２ｍｍの平板硬化物を０．３ｃｍ×１０ｃｍに切り出して試験片を作成し、ＪＩＳ Ｃ２５６５規格に準拠し、株式会社エーイーティー製、空洞共振器法誘電率測定装置により、絶乾後２３℃、湿度５０％の室内に２４時間保管した後の、２．０ＧＨｚの誘電率と誘電正接を測定した。
4) Dielectric constant and dielectric loss tangent A curable resin composition varnish was poured between two glass plates sandwiched by a 0.2 mm thick spacer, and a UV irradiation device equipped with a high-pressure mercury lamp. Irradiation intensity: 30 mW / cm 2 UV curing was performed at a UV irradiation amount of 6,000 mJ / cm 2 . The flat plate sample obtained by performing UV curing was further post-cured in an oven at 200 ° C. for 30 minutes, and various properties of the obtained cured flat plate were measured. Moreover, this flat plate cured product having a thickness of 0.2 mm was cut out to 0.3 cm × 10 cm to create a test piece, conforming to the JIS C2565 standard, manufactured by ATE Co., Ltd., using a cavity resonator method dielectric constant measuring device, The dielectric constant and dielectric loss tangent of 2.0 GHz were measured after storing for 24 hours in a room at 23 ° C. and 50% humidity after absolute drying.
５）線膨張係数（ＣＴＥ）及びガラス転移温度（Ｔｇ）測定用試験片の調製及び測定
硬化性樹脂組成物をシリコンゴム製の200μｍ厚のスペーサーを介した２枚のガラス基板からなる型の間に流し込むことによって、注型サンプルを作成し、減圧下、気泡を取り除いた。その後、熱硬化型サンプルについては、窒素気流下のイナートオーブンに注型サンプルをセットし、段階的に１５分かけて昇温操作を行った後、２００℃で６０分間熱硬化させた。一方、ＵＶ硬化型サンプルについては、高圧水銀ランプを光源とするコンベア式ＵＶ照射装置を使用して、ＵＶ照射量：６，０００ｍＪ／ｃｍ２でＵＶ硬化を行った。熱硬化サンプル及びＵＶ硬化サンプルのいずれについても、空気気流下、イナートオーブンを使用して、２００℃で３０分間、ポストキュアを行った。得られた２００μｍ厚の平板から３ｍｍ幅の平板サンプルを作成し、ＣＴＥ測定（ＴＭＡ法）及びＴｇ測定（ＤＭＡ法）用の試験片として使用した。
ＣＴＥ測定（ＴＭＡ法）は、上記の方法で作成した試験片をＴＭＡ（熱機械分析装置）測定装置の分析用プローブにセットし、窒素気流下、昇温速度１０℃／分で３０℃から３６０℃までスキャンさせることにより測定を行い、０〜４０℃の温度範囲に於ける平均線膨張係数を求めた。
一方、上記の方法で作成した硬化試験片のＴｇの測定は動的粘弾性測定装置を使用し、昇温速度２℃／ｍｉｎで測定を行い、損失弾性率のピークより決定した。
5) Preparation and measurement of test piece for measurement of linear expansion coefficient (CTE) and glass transition temperature (Tg) Between molds consisting of two glass substrates through a 200 μm thick spacer made of silicon rubber with a curable resin composition A cast sample was made by pouring into a vacuum, and bubbles were removed under reduced pressure. Then, about the thermosetting type | mold sample, the casting sample was set to the inert oven under nitrogen stream, and after performing temperature rising operation over 15 minutes in steps, it was thermoset at 200 degreeC for 60 minutes. On the other hand, the UV curing type sample was UV cured at a UV irradiation amount of 6,000 mJ / cm 2 using a conveyor type UV irradiation apparatus using a high-pressure mercury lamp as a light source. Both the thermosetting sample and the UV curing sample were post-cured at 200 ° C. for 30 minutes using an inert oven under an air stream. A plate sample having a width of 3 mm was prepared from the obtained plate having a thickness of 200 μm and used as a test piece for CTE measurement (TMA method) and Tg measurement (DMA method).
In CTE measurement (TMA method), the test piece prepared by the above method is set on an analysis probe of a TMA (thermomechanical analyzer) measuring device, and from 30 ° C to 360 ° C at a temperature rising rate of 10 ° C / min in a nitrogen stream. The measurement was carried out by scanning up to 0 ° C., and the average linear expansion coefficient in the temperature range of 0 to 40 ° C. was obtained.
On the other hand, the Tg of the cured test piece prepared by the above method was measured using a dynamic viscoelasticity measuring device at a temperature rising rate of 2 ° C./min and determined from the peak of the loss elastic modulus.
６）難燃性の測定
線膨張係数（ＣＴＥ）及びガラス転移温度（Ｔｇ）測定用試験片を作成する際に、作成した平板からサンプリングをおこなった硬化サンプルを用いて、ＴＧＡ（熱天秤）測定装置を使用して、窒素気流下、昇温速度１０℃／分で３０℃から６００℃までスキャンさせることにより測定を行い、５５０℃に於けるチャー（炭化物）生成量により下記の通り、難燃性を求めた。
難燃性Ａ：チャー生成量＞４０ｗｔ％
難燃性Ｂ：２５ｗｔ％＜チャー生成量≦４０ｗｔ％
難燃性Ｃ：１８ｗｔ％＜チャー生成量≦２５ｗｔ％
難燃性Ｄ：１０ｗｔ％＜チャー生成量≦１８ｗｔ％
難燃性Ｅ：チャー生成量≦１０ｗｔ％
6) Measurement of flame retardancy TGA (thermobalance) measurement using a cured sample sampled from the prepared flat plate when preparing a test piece for measuring linear expansion coefficient (CTE) and glass transition temperature (Tg) Using a device, measurement is performed by scanning from 30 ° C. to 600 ° C. at a heating rate of 10 ° C./min under a nitrogen stream, and the flame retardancy is as follows according to the amount of char (carbide) produced at 550 ° C. Seeking sex.
Flame retardancy A: Char production> 40wt%
Flame retardancy B: 25 wt% <Char generation amount ≤ 40 wt%
Flame retardancy C: 18 wt% <Char generation amount ≤ 25 wt%
Flame retardancy D: 10 wt% <char generation amount ≤ 18 wt%
Flame retardancy E: Char generation amount ≦ 10wt%
７）ＹＩ、Ｈａｚｅ及び全光線透過率の測定
ＹＩ、Ｈａｚｅ及び全光線透過率の測定は、調製した硬化性樹脂組成物ワニスを１．０ｍｍ厚のスペーサーを挟んだ２枚のガラス板の間に流し込み、高圧水銀ランプを備えたＵＶ照射装置で、照射強度：３０ｍＷ／ｃｍ２、ＵＶ照射量：６，０００ｍＪ／ｃｍ２でＵＶ硬化を行った。ＵＶ硬化を行って得られた平板サンプルをさらに２００℃のオーブンで３０分間ポストキュアを行い、得られた硬化物平板について、濁度計及び色差計を使用して測定した。
7) Measurement of YI, Haze, and total light transmittance YI, Haze, and total light transmittance were measured by pouring the prepared curable resin composition varnish between two glass plates with a spacer of 1.0 mm in thickness, UV curing was performed with a UV irradiation apparatus equipped with a high-pressure mercury lamp at irradiation intensity: 30 mW / cm 2 and UV irradiation amount: 6,000 mJ / cm 2 . The plate sample obtained by UV curing was further post-cured in an oven at 200 ° C. for 30 minutes, and the obtained cured plate was measured using a turbidimeter and a color difference meter.
８）屈折率及びアッベ数の測定
屈折率及びアッベ数の測定は、調製した硬化性樹脂組成物ワニスを１．０ｍｍ厚のスペーサーを挟んだ２枚のガラス板の間に流し込み、高圧水銀ランプを備えたＵＶ照射装置で、照射強度：３０ｍＷ／ｃｍ２、ＵＶ照射量：６，０００ｍＪ／ｃｍ２でＵＶ硬化を行った。ＵＶ硬化を行って得られた平板サンプルをさらに２００℃のオーブンで３０分間ポストキュアを行い、硬化物平板を得た。得られた硬化物平板の端面をプリズム加工し、真空乾燥器で、60℃で5時間乾燥させた後、20℃、60%RHの恒温恒湿器の槽内に２日間以上置き、状態調節を行った。カルニュー屈折率計KPR-2000（島津デバイス製造社製）を用いて、25℃にて、屈折率を測定し、得られた屈折率データよりアッベ数を算出した。
8) Measurement of refractive index and Abbe number The refractive index and Abbe number were measured by pouring the prepared curable resin composition varnish between two glass plates with a 1.0 mm-thick spacer between them and equipped with a high-pressure mercury lamp. UV curing was performed with a UV irradiation apparatus at an irradiation intensity of 30 mW / cm 2 and an UV irradiation amount of 6,000 mJ / cm 2 . The flat plate sample obtained by performing UV curing was further post-cured in an oven at 200 ° C. for 30 minutes to obtain a cured product flat plate. The end face of the resulting cured flat plate is prism processed, dried in a vacuum dryer at 60 ° C for 5 hours, and then placed in a thermo-hygrostat bath at 20 ° C and 60% RH for 2 days or more to adjust the condition. Went. Using a Karnew refractometer KPR-2000 (manufactured by Shimadzu Device Manufacturing Co., Ltd.), the refractive index was measured at 25 ° C., and the Abbe number was calculated from the obtained refractive index data.
９）成形性
銅箔光沢面に黒化処理を行った銅張り積層板（銅箔層／コア層＝３５μｍ／３００μｍ）の黒化処理を行った銅箔面の上に、硬化性樹脂組成物の未硬化フィルムを積層し、真空ラミネーターを用いて、温度：１１０℃、プレス圧：０．１ＭＰａで真空ラミネートを行い、黒化処理銅箔とフィルムの接着状態により評価を行った。評価は黒化処理銅箔とフィルムの接着状態が良好であったものを「○」、黒化処理銅箔とフィルムとが容易に剥離することができる接着状態のものを「×」として評価した。
9) Formability A curable resin composition is formed on the copper foil surface of the copper-clad laminate (copper foil layer / core layer = 35 μm / 300 μm) subjected to the blackening treatment on the glossy surface of the copper foil. The uncured film was laminated, vacuum lamination was performed at a temperature of 110 ° C. and a press pressure of 0.1 MPa using a vacuum laminator, and evaluation was performed based on the adhesion state between the blackened copper foil and the film. Evaluation was evaluated as “◯” when the adhesion state of the blackened copper foil and the film was good, and “x” when the blackened copper foil and the film could be easily peeled off. .
実施例１
反応容器に９，９−ビス（４−ヒドロキシフェニル）フルオレン１４０．１６ｇ（０．４０モル）、４，４’−ビス（クロロメチル）ビフェニル１４１．４０ｇ（０．８８モル）、及び、アセトン１２００ｍｌを加え攪拌しながら７８℃に昇温した。次いで、７８℃に保った反応容器にＫＯＨ−ＭｅＯＨ（ＫＯＨ：０．８８モル）を３０分かけて滴下した。滴下終了後、さらに７８℃で４ｈ攪拌を継続した。４ｈ後、室温まで冷却し、トルエン９００ｍｌを加え、さらに１０％ＨＣｌを加えて中和した。その後、水相を分液することにより分離し、さらに水３００ｍｌで３回分液洗浄した。
Example 1
In the reaction vessel, 140.16 g (0.40 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 141.40 g (0.88 mol) of 4,4′-bis (chloromethyl) biphenyl, and 1200 ml of acetone The mixture was heated to 78 ° C. with stirring. Next, KOH-MeOH (KOH: 0.88 mol) was added dropwise to the reaction vessel maintained at 78 ° C. over 30 minutes. After completion of the dropwise addition, stirring was further continued at 78 ° C. for 4 hours. After 4 hours, the mixture was cooled to room temperature, 900 ml of toluene was added, and further 10% HCl was added for neutralization. Thereafter, the aqueous phase was separated by liquid separation, and further separated and washed with 300 ml of water three times.
得られた有機相を蒸留することにより濃縮し、メタノールを加えて生成物を再沈殿した。沈殿を濾過・乾燥し、９，９−ビス（４−ヒドロキシフェニル）フルオレンと４，４’−ビス（クロロメチル）ビフェニルとの反応生成物である芳香族ビスクロロメチル化合物Ａ（２ＣＭ−ＤＭＢＰ−ＢＰＦＺ）１６９．３３ｇを得た。得られた２ＣＭ−ＤＭＢＰ−ＢＰＦＺは白色紛体であった。 The resulting organic phase was concentrated by distillation and methanol was added to reprecipitate the product. The precipitate was filtered and dried, and aromatic bischloromethyl compound A (2CM-DMBP-), which is a reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and 4,4′-bis (chloromethyl) biphenyl. BPFZ) 169.33 g was obtained. The obtained 2CM-DMBP-BPFZ was a white powder.
生成物の確認をゲル浸透クロマトグラフ（ＧＰＣ）、赤外線スペクトル（ＩＲ）、１Ｈ核磁気共鳴スペクトル（１Ｈ−ＮＭＲ）で行った。その結果、１）ＧＰＣ測定の結果より、回収された反応生成物では、原料に由来するピークが消失し、高分子量側に新しいピークが生成していること、２）ＩＲ測定結果より、フェノール性水酸基に由来するピークが減少していること、３）１Ｈ−ＮＭＲ測定結果に於いて、４，４’−ビス（クロロメチル）ビフェニルのクロロメチル基に由来するプロトンの共鳴線が減少し、代わりに、５．０２ｐｐｍ付近にベンジルエーテル基に由来するプロトンの共鳴線が生成していることが確認され、芳香族ビスクロロメチル化合物Ａ（２ＣＭ−ＤＭＢＰ−ＢＰＦＺ）が得られていることを確認した。 The product was confirmed by gel permeation chromatography (GPC), infrared spectrum (IR), and 1 H nuclear magnetic resonance spectrum ( 1 H-NMR). As a result, 1) From the results of GPC measurement, in the recovered reaction product, the peak derived from the raw material disappeared and a new peak was generated on the high molecular weight side. 2) From the IR measurement result, phenolic 3) In the 1 H-NMR measurement results, the proton resonance line derived from the chloromethyl group of 4,4′-bis (chloromethyl) biphenyl is reduced, and the peak derived from the hydroxyl group is reduced. Instead, it was confirmed that a proton resonance line derived from the benzyl ether group was generated around 5.02 ppm, and it was confirmed that the aromatic bischloromethyl compound A (2CM-DMBP-BPFZ) was obtained. did.
図１に２ＣＭ−ＤＭＢＰ−ＢＰＦＺ及び原料である９，９−ビス（４−ヒドロキシフェニル）フルオレンのＧＰＣチャートのＧＰＣチャートを示す。２ＣＭ−ＤＭＢＰ−ＢＰＦＺは実線で示し、９，９−ビス（４−ヒドロキシフェニル）フルオレンは点線で示す。
図１の２ＣＭ−ＤＭＢＰ−ＢＰＦＺのＧＰＣ溶出曲線から原料である９，９−ビス（４−ヒドロキシフェニル）フルオレンのピークは消失し、高分子量側にシフトしているのがわかる。
FIG. 1 shows a GPC chart of a GPC chart of 2CM-DMBP-BPFZ and 9,9-bis (4-hydroxyphenyl) fluorene as a raw material. 2CM-DMBP-BPFZ is indicated by a solid line, and 9,9-bis (4-hydroxyphenyl) fluorene is indicated by a dotted line.
It can be seen from the GPC elution curve of 2CM-DMBP-BPFZ in FIG. 1 that the peak of 9,9-bis (4-hydroxyphenyl) fluorene, which is a raw material, disappears and is shifted to the high molecular weight side.
そして、２ＣＭ−ＤＭＢＰ−ＢＰＦＺのｎ＝１以上の成分のＧＰＣ純度（面積比）は、下記の通りであった。
ｎ＝１成分：７．８％
ｎ＝２成分：２７．２％
ｎ＝３成分：３０．６％
ｎ＝４成分：１８．２％
ｎ＝５以上の成分：１５．１％
その他の成分（低分子量成分）：１．２％
And the GPC purity (area ratio) of the component more than n = 1 of 2CM-DMBP-BPFZ was as follows.
n = 1 component: 7.8%
n = 2 components: 27.2%
n = 3 components: 30.6%
n = 4 components: 18.2%
n = 5 or more: 15.1%
Other components (low molecular weight components): 1.2%
また、２ＣＭ−ＤＭＢＰ−ＢＰＦＺのＴＧＡ測定を行ったところ、ＴＧＡ測定結果に於ける示差熱分析（ＤＴＡ）曲線には、２２０℃と２７１℃に発熱ピークが観察された。そして、２２０℃の発熱ピークでは０．７５ｗｔ％、２７１℃の発熱ピークでは、４．８８ｗｔ％の重量減少が観察された。また、６００℃に於ける、炭化物生成量は、６２．２ｗｔ％であった。 Further, when TGA measurement of 2CM-DMBP-BPFZ was performed, exothermic peaks were observed at 220 ° C. and 271 ° C. in the differential thermal analysis (DTA) curve in the TGA measurement results. A weight loss of 0.75 wt% was observed at the exothermic peak at 220 ° C. and 4.88 wt% at the exothermic peak at 271 ° C. Moreover, the carbide | carbonized_material production amount in 600 degreeC was 62.2 wt%.
実施例２
反応容器に９，９−ビス（４−ヒドロキシフェニル）フルオレン１４０．１６ｇ（０．４０モル）、α，α’−ジクロロ−ｐ−キシレン１５７．２０ｇ（０．８８モル）、及び、ＭＥＫ１２００ｍｌを加え攪拌しながら７８℃に昇温した。次いで、７８℃に保った反応容器にＫＯＨ−ＭｅＯＨ（ＫＯＨ：０．８８モル）を３０分かけて滴下した。滴下終了後、さらに７８℃で４ｈ攪拌を継続した。４ｈ後、室温まで冷却し、トルエン９００ｍｌを加え、さらに１０％ＨＣｌを加えて中和した。その後、水相を分液することにより分離し、さらに水３００ｍｌで３回分液洗浄した。
Example 2
To the reaction vessel were added 140.16 g (0.40 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 157.20 g (0.88 mol) of α, α′-dichloro-p-xylene, and 1200 ml of MEK. The temperature was raised to 78 ° C. with stirring. Next, KOH-MeOH (KOH: 0.88 mol) was added dropwise to the reaction vessel maintained at 78 ° C. over 30 minutes. After completion of the dropwise addition, stirring was further continued at 78 ° C. for 4 hours. After 4 hours, the mixture was cooled to room temperature, 900 ml of toluene was added, and further 10% HCl was added for neutralization. Thereafter, the aqueous phase was separated by liquid separation, and further separated and washed with 300 ml of water three times.
得られた有機相を蒸留することにより濃縮し、メタノールを加えて生成物を再沈殿した。沈殿を濾過・乾燥し、９，９−ビス（４−ヒドロキシフェニル）フルオレンとα，α’−ジクロロ−ｐ−キシレンとの反応生成物である芳香族ビスクロロメチル化合物Ｂ（２ＣＭ−Ｘｙ−ＢＰＦＺ）１２３．５７ｇを得た。 The resulting organic phase was concentrated by distillation and methanol was added to reprecipitate the product. The precipitate was filtered and dried, and aromatic bischloromethyl compound B (2CM-Xy-BPFZ) which is a reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and α, α′-dichloro-p-xylene. ) 123.57 g was obtained.
生成物の確認をゲル浸透クロマトグラフ（ＧＰＣ）、赤外線スペクトル（ＩＲ）、１Ｈ核磁気共鳴スペクトル（１Ｈ−ＮＭＲ）で行った。その結果、１）ＧＰＣ測定の結果より、回収された反応生成物では、原料に由来するピークが消失し、高分子量側に新しいピークが生成していること、２）ＩＲ測定結果より、フェノール性水酸基に由来するピークが減少していること、３）１Ｈ−ＮＭＲで、α，α’−ジクロロ−ｐ−キシレンのクロロメチル基に由来するプロトンの共鳴線が減少し、代わりに、５．０２ｐｐｍ付近にベンジルエーテル基に由来するプロトンの共鳴線が生成していることが確認され、芳香族ビスクロロメチル化合物Ｂ（２ＣＭ−Ｘｙ−ＢＰＦＺ）が得られていることを確認した。
The product was confirmed by gel permeation chromatography (GPC), infrared spectrum (IR), and 1H nuclear magnetic resonance spectrum ( 1 H-NMR). As a result, 1) From the results of GPC measurement, in the recovered reaction product, the peak derived from the raw material disappeared and a new peak was generated on the high molecular weight side. 2) From the IR measurement result,
図２に２ＣＭ−Ｘｙ−ＢＰＦＺ及び原料である９，９−ビス（４−ヒドロキシフェニル）フルオレンのＧＰＣチャートのＧＰＣチャートを示す。２ＣＭ−Ｘｙ−ＢＰＦＺは実線で示し、９，９−ビス（４−ヒドロキシフェニル）フルオレンは点線で示す。
図２のＧＰＣ溶出曲線から、原料である９，９−ビス（４−ヒドロキシフェニル）フルオレンのピークは消失し、高分子量側にシフトしているのが確認された。そして、２ＣＭ−Ｘｙ−ＢＰＦＺのｎ＝１以上の成分のＧＰＣ純度は、下記の通りであった。
ｎ＝１成分：３６．３％
ｎ＝２成分：２８．５％
ｎ＝３成分：１９．６％
ｎ＝４成分：１０．６％
ｎ＝５以上の成分：４．１％
その他の成分（低分子量成分）：０．９％
FIG. 2 shows a GPC chart of a GPC chart of 2CM-Xy-BPFZ and 9,9-bis (4-hydroxyphenyl) fluorene as a raw material. 2CM-Xy-BPFZ is indicated by a solid line, and 9,9-bis (4-hydroxyphenyl) fluorene is indicated by a dotted line.
From the GPC elution curve of FIG. 2, it was confirmed that the peak of 9,9-bis (4-hydroxyphenyl) fluorene, which is a raw material, disappeared and shifted to the high molecular weight side. And the GPC purity of the component more than n = 1 of 2CM-Xy-BPFZ was as follows.
n = 1 component: 36.3%
n = 2 components: 28.5%
n = 3 components: 19.6%
n = 4 components: 10.6%
n = 5 or more: 4.1%
Other components (low molecular weight components): 0.9%
２ＣＭ−Ｘｙ−ＢＰＦＺのＴＧＡ測定を行ったところ、ＴＧＡ測定結果に於ける、示差熱分析（ＤＴＡ）曲線には、２１９℃と２６８℃に発熱ピークが観察された。そして、２１９℃の発熱ピークでは０．８１ｗｔ％、２７１℃の発熱ピークでは、５．２１ｗｔ％の重量減少が観察された。また、６００℃に於ける、炭化物生成量は、５７．８ｗｔ％であった。 When TGA measurement of 2CM-Xy-BPFZ was performed, exothermic peaks were observed at 219 ° C. and 268 ° C. in the differential thermal analysis (DTA) curve in the TGA measurement results. A weight loss of 0.81 wt% was observed at the exothermic peak at 219 ° C. and 5.21 wt% at the exothermic peak at 271 ° C. Moreover, the carbide | carbonized_material production amount in 600 degreeC was 57.8 wt%.
実施例３
反応容器に、炭酸カリウム１５．２８ｇ（０．１１モル）とＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）５００ｍｌを入れ、加熱・撹拌を行う。反応容器の内温が８０℃に達したら、メタクリル酸１９．１３ｇ（０．２２モル）をＤＭＦ５０ｍｌに溶解させた溶液を３０分かけて滴下する。そのままの温度を維持して、１時間反応させる。次に、実施例１で得た２ＣＭ−ＤＭＢＰ−ＢＰＦＺ５８．２７ｇをＤＭＦ５００ｍｌに溶解させた溶液を３０分かけて滴下した。滴下終了後、さらに８０℃で３ｈ攪拌を継続した。３ｈ後、室温まで冷却し、固体の析出物を濾別した。そして、反応溶液にトルエン２０００ｍｌを加えた。その後、反応溶液を水で４回洗浄し、油相を硫酸マグネシウムで乾燥させ、ろ過を行った。得られた有機相を水／メタノールの混合溶媒により、生成物を再沈殿した。
沈殿を濾過・乾燥し、２ＣＭ−ＤＭＢＰ−ＢＰＦＺとメタクリル酸との反応生成物である２ＭＡ−ＤＭＢＰ−ＢＰＦＺ５２．６４ｇを得た。
Example 3
In a reaction vessel, 15.28 g (0.11 mol) of potassium carbonate and 500 ml of N, N-dimethylformamide (DMF) are placed and heated and stirred. When the internal temperature of the reaction vessel reaches 80 ° C., a solution prepared by dissolving 19.13 g (0.22 mol) of methacrylic acid in 50 ml of DMF is added dropwise over 30 minutes. The reaction is continued for 1 hour while maintaining the temperature as it is. Next, a solution prepared by dissolving 58.27 g of 2CM-DMBP-BPFZ obtained in Example 1 in 500 ml of DMF was added dropwise over 30 minutes. After completion of dropping, stirring was further continued at 80 ° C. for 3 hours. After 3 h, the mixture was cooled to room temperature, and the solid precipitate was filtered off. Then, 2000 ml of toluene was added to the reaction solution. Thereafter, the reaction solution was washed four times with water, and the oil phase was dried over magnesium sulfate and filtered. The resulting organic phase was reprecipitated with a mixed solvent of water / methanol.
The precipitate was filtered and dried to obtain 52.64 g of 2MA-DMBP-BPFZ which is a reaction product of 2CM-DMBP-BPFZ and methacrylic acid.
生成物の確認をゲル浸透クロマトグラフ（ＧＰＣ）、赤外線スペクトル（ＩＲ）、１Ｈ核磁気共鳴スペクトル（１Ｈ−ＮＭＲ）で行った。その結果、１）ＧＰＣ測定の結果より、回収された反応生成物では、原料に由来するピークが消失し、高分子量側に新しいピークが生成していること、２）ＩＲ測定結果より、カルボニル基が生成していること、１Ｈ−ＮＭＲで、メタクリル基に由来するプロトンの共鳴線を有することが確認され、２ＭＡ−ＤＭＢＰ−ＢＰＦＺが得られていることを確認した。 The product was confirmed by gel permeation chromatography (GPC), infrared spectrum (IR), and 1 H nuclear magnetic resonance spectrum ( 1 H-NMR). As a result, 1) From the results of GPC measurement, in the recovered reaction product, the peak derived from the raw material disappeared and a new peak was generated on the high molecular weight side. 2) From the IR measurement result, the carbonyl group It was confirmed by 1 H-NMR that it had a proton resonance line derived from a methacryl group, and 2MA-DMBP-BPFZ was obtained.
実施例４
反応容器に、炭酸カリウム１４．５９ｇ（０．１０５モル）とＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）５００ｍｌを入れ、加熱・撹拌を行う。反応容器の内温が８０℃に達したら、メタクリル酸１８．２６ｇ（０．２１モル）をＤＭＦ５０ｍｌに溶解させた溶液を３０分かけて滴下する。そのままの温度を維持して、１時間反応させる。次に、実施例２で得た２ＣＭ−Ｘｙ−ＢＰＦＺ ６２．７６ｇをＤＭＦ５００ｍｌに溶解させた溶液を３０分かけて滴下した。滴下終了後、さらに８０℃で３ｈ攪拌を継続した。３ｈ後、室温まで冷却し、固体の析出物を濾別した。そして、反応溶液にトルエン２０００ｍｌを加えた。その後、反応溶液を水で４回洗浄し、油相を硫酸マグネシウムで乾燥させ、ろ過を行った。得られた有機相を水／メタノールの混合溶媒により、生成物を再沈殿した。
沈殿を濾過・乾燥し、２ＣＭ−Ｘｙ−ＢＰＦＺとメタクリル酸との反応生成物である２ＭＡ−Ｘｙ−ＢＰＦＺ６９．５３ｇを得た。
Example 4
A reaction vessel is charged with 14.59 g (0.105 mol) of potassium carbonate and 500 ml of N, N-dimethylformamide (DMF), and heated and stirred. When the internal temperature of the reaction vessel reaches 80 ° C., a solution prepared by dissolving 18.26 g (0.21 mol) of methacrylic acid in 50 ml of DMF is added dropwise over 30 minutes. The reaction is continued for 1 hour while maintaining the temperature as it is. Next, a solution prepared by dissolving 62.76 g of 2CM-Xy-BPFZ obtained in Example 2 in 500 ml of DMF was added dropwise over 30 minutes. After completion of dropping, stirring was further continued at 80 ° C. for 3 hours. After 3 h, the mixture was cooled to room temperature, and the solid precipitate was filtered off. Then, 2000 ml of toluene was added to the reaction solution. Thereafter, the reaction solution was washed four times with water, and the oil phase was dried over magnesium sulfate and filtered. The resulting organic phase was reprecipitated with a mixed solvent of water / methanol.
The precipitate was filtered and dried to obtain 69.53 g of 2MA-Xy-BPFZ which is a reaction product of 2CM-Xy-BPFZ and methacrylic acid.
生成物の確認をゲル浸透クロマトグラフ（ＧＰＣ）、赤外線スペクトル（ＩＲ）、１Ｈ核磁気共鳴スペクトル（１Ｈ−ＮＭＲ）で行った。その結果、１）ＧＰＣ測定の結果より、回収された反応生成物では、原料に由来するピークが消失し、高分子量側に新しいピークが生成していること、２）ＩＲ測定結果より、カルボニル基が生成していること、１Ｈ−ＮＭＲで、メタクリル基に由来するプロトンの共鳴線を有することが確認され、２ＭＡ−Ｘｙ−ＢＰＦＺが得られていることを確認した。 The product was confirmed by gel permeation chromatography (GPC), infrared spectrum (IR), and 1 H nuclear magnetic resonance spectrum ( 1 H-NMR). As a result, 1) From the results of GPC measurement, in the recovered reaction product, the peak derived from the raw material disappeared and a new peak was generated on the high molecular weight side. 2) From the IR measurement result, the carbonyl group It was confirmed by 1 H-NMR that it has a proton resonance line derived from a methacryl group, and 2MA-Xy-BPFZ was obtained.
合成例１
５００ｍｌ四つ口フラスコ中にビスフェノールフルオレン型エポキシ樹脂２３１ｇ（エポキシ当量２３１）と、トリエチルベンジルアンモニウムクロライド４５０ｍｇと、２，６−ジ−イソブチルフェノール１００ｍｇと、アクリル酸７２．０ｇを仕込んで混合し、空気を毎分２５ｍｌの速度で吹き込みながら９０〜１００℃で加熱して溶解させた。この溶液は白濁していたがそのまま徐々に昇温し、１２０℃に加熱して完全に溶解させた。溶液は次第に透明粘稠になったがそのまま攪拌し続け、この間に酸価を測定して酸価が２．０ｍｇＫＯＨ／ｇ未満になるまでこの加熱攪拌を継続した。酸価が目標（酸価０．８）に達するまで８時間を要した。その後、室温まで冷却し、無色透明な固体のビスフェノールフルオレン型エポキシアクリレート樹脂２４３．６ｇを得た。
Synthesis example 1
In a 500 ml four-necked flask, 231 g of bisphenolfluorene type epoxy resin (epoxy equivalent 231), 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-di-isobutylphenol, and 72.0 g of acrylic acid are mixed and mixed. Was dissolved at 90-100 ° C. while blowing at a rate of 25 ml per minute. Although this solution was cloudy, the temperature was gradually raised as it was, and the solution was heated to 120 ° C. to be completely dissolved. Although the solution gradually became transparent and viscous, the stirring was continued as it was, and during this time, the acid value was measured, and this heating and stirring was continued until the acid value became less than 2.0 mgKOH / g. It took 8 hours for the acid value to reach the target (acid value 0.8). Then, it cooled to room temperature and obtained 243.6 g of colorless and transparent solid bisphenolfluorene type epoxy acrylate resins.
実施例５
実施例３で得られた２ＭＡ−ＤＭＢＰ−ＢＰＦＺ ８ｇと反応性希釈剤としてｏ−フェニル−フェノキシエチルアクリレート（新中村化学（株）製、商品名：ＮＫエステル Ａ−ＬＥＮ−１０）１２ｇ、及び、光重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン）（チバ・スペシャリティケミカルズ製、商品名：イルガキュア１８４）０．４０ｇを混合・溶解し硬化性組成物（ワニスＡ）を得た。
Example 5
8 g of 2MA-DMBP-BPFZ obtained in Example 3 and 12 g of o-phenyl-phenoxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-LEN-10) as a reactive diluent, and 0.40 g of 1-hydroxycyclohexyl phenyl ketone (product name: Irgacure 184, manufactured by Ciba Specialty Chemicals) was mixed and dissolved as a photopolymerization initiator to obtain a curable composition (varnish A).
調製したワニスＡを０．２ｍｍ厚のスペーサーを挟んだ２枚のガラス板の間に流し込み、高圧水銀ランプを備えたＵＶ照射装置で、照射強度：３０ｍＷ／ｃｍ２、ＵＶ照射量：６，０００ｍＪ／ｃｍ２でＵＶ硬化を行った。ＵＶ硬化を行って得られた平板サンプルをさらに２００℃のオーブンで３０分間ポストキュアを行い、得られた硬化物平板について諸特性を測定した。また、この厚み０．２ｍｍの平板硬化物を０．３ｃｍ×１０ｃｍに切り出して試験片を作成し、２．０ＧＨｚの誘電率と誘電正接を測定した。これら測定により得られた結果を表１に示した。 The prepared varnish A was poured between two glass plates with a spacer having a thickness of 0.2 mm, and a UV irradiation apparatus equipped with a high-pressure mercury lamp. Irradiation intensity: 30 mW / cm 2 , UV irradiation amount: 6,000 mJ / cm 2 was UV cured. The flat plate sample obtained by performing UV curing was further post-cured in an oven at 200 ° C. for 30 minutes, and various properties of the obtained cured flat plate were measured. Moreover, this flat-plate hardened | cured material with a thickness of 0.2 mm was cut out to 0.3 cm x 10 cm, the test piece was created, and the dielectric constant and dielectric loss tangent of 2.0 GHz were measured. The results obtained from these measurements are shown in Table 1.
比較例１
合成例１で得られたビスフェノールフルオレン型エポキシアクリレート樹脂８ｇと反応性希釈剤としてｏ−フェニル−フェノキシエチルアクリレート（新中村化学（株）製、商品名：ＮＫエステル Ａ−ＬＥＮ−１０）１２ｇ、及び、光重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン）（チバ・スペシャリティケミカルズ製、商品名：イルガキュア１８４）０．４０ｇを混合・溶解し硬化性組成物（ワニスＢ）を得た。
Comparative Example 1
8 g of the bisphenolfluorene-type epoxy acrylate resin obtained in Synthesis Example 1 and 12 g of o-phenyl-phenoxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-LEN-10) as a reactive diluent, and Then, 0.40 g of 1-hydroxycyclohexyl phenyl ketone (product name: Irgacure 184, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator was mixed and dissolved to obtain a curable composition (varnish B).
調製したワニスＢを０．２ｍｍ厚のスペーサーを挟んだ２枚のガラス板の間に流し込み、高圧水銀ランプを備えたＵＶ照射装置で、照射強度：３０ｍＷ／ｃｍ２、ＵＶ照射量：６，０００ｍＪ／ｃｍ２でＵＶ硬化を行った。ＵＶ硬化を行って得られた平板サンプルをさらに２００℃のオーブンで３０分間ポストキュアを行い、得られた硬化物平板について諸特性を測定した。また、この厚み０．２ｍｍの平板硬化物を０．３ｃｍ×１０ｃｍに切り出して試験片を作成し、２．０ＧＨｚの誘電率と誘電正接を測定した。これら測定により得られた結果を表１に示した。
表中、ＢＰＦ樹脂は、ビスフェノールフルオレン型エポキシアクリレート樹脂である。
The prepared varnish B was poured between two glass plates with a spacer having a thickness of 0.2 mm, and a UV irradiation device equipped with a high-pressure mercury lamp. Irradiation intensity: 30 mW / cm 2 , UV irradiation amount: 6,000 mJ / cm 2 was UV cured. The flat plate sample obtained by performing UV curing was further post-cured in an oven at 200 ° C. for 30 minutes, and various properties of the obtained cured flat plate were measured. Moreover, this flat-plate hardened | cured material with a thickness of 0.2 mm was cut out to 0.3 cm x 10 cm, the test piece was created, and the dielectric constant and dielectric loss tangent of 2.0 GHz were measured. The results obtained from these measurements are shown in Table 1.
In the table, BPF resin is a bisphenolfluorene type epoxy acrylate resin.
実施例６
反応容器に、炭酸カリウム１５．２８ｇ（０．１１モル）とＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）５００ｍｌを入れ、加熱・撹拌を行う。反応容器の内温が８０℃に達したら、アクリル酸１５．８５ｇ（０．２２モル）をＤＭＦ５０ｍｌに溶解させた溶液を３０分かけて滴下する。そのままの温度を維持して、１時間反応させる。次に、９，９−ビス（４−ヒドロキシフェニル）フルオレンと４，４’−ビス（クロロメチル）ビフェニルとの反応生成物である芳香族ビスクロロメチル化合物（実施例１の２ＣＭ−ＤＭＢＰ−ＢＰＦＺ）５８．２７ｇをＤＭＦ５００ｍｌに溶解させた溶液を３０分かけて滴下した。滴下終了後、さらに８０℃で３ｈ攪拌を継続した。３ｈ後、室温まで冷却し、固体の析出物を濾別した。そして、反応溶液にトルエン２０００ｍｌを加えた。その後、反応溶液を水で４回洗浄し、油相を硫酸マグネシウムで乾燥させ、ろ過を行った。得られた有機相を水／メタノールの混合溶媒により、生成物を再沈殿した。
沈殿を濾過・乾燥し、２ＣＭ−ＤＭＢＰ−ＢＰＦＺとアクリル酸との反応生成物である２Ａ−ＤＭＢＰ−ＢＰＦＺ４９．８７ｇを得た。
Example 6
In a reaction vessel, 15.28 g (0.11 mol) of potassium carbonate and 500 ml of N, N-dimethylformamide (DMF) are placed and heated and stirred. When the internal temperature of the reaction vessel reaches 80 ° C., a solution prepared by dissolving 15.85 g (0.22 mol) of acrylic acid in 50 ml of DMF is added dropwise over 30 minutes. The reaction is continued for 1 hour while maintaining the temperature as it is. Next, an aromatic bischloromethyl compound (2CM-DMBP-BPFZ of Example 1) which is a reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and 4,4′-bis (chloromethyl) biphenyl. ) A solution obtained by dissolving 58.27 g in 500 ml of DMF was added dropwise over 30 minutes. After completion of dropping, stirring was further continued at 80 ° C. for 3 hours. After 3 h, the mixture was cooled to room temperature, and the solid precipitate was filtered off. Then, 2000 ml of toluene was added to the reaction solution. Thereafter, the reaction solution was washed four times with water, and the oil phase was dried over magnesium sulfate and filtered. The resulting organic phase was reprecipitated with a mixed solvent of water / methanol.
The precipitate was filtered and dried to obtain 49.87 g of 2A-DMBP-BPFZ which is a reaction product of 2CM-DMBP-BPFZ and acrylic acid.
生成物の確認をゲル浸透クロマトグラフ（ＧＰＣ）、赤外線スペクトル（ＩＲ）、１Ｈ核磁気共鳴スペクトル（１Ｈ−ＮＭＲ）で行ったところ、ＧＰＣより回収された反応生成物では、原料に由来するピークが消失し、高分子量側に新しいピークが生成していること、ＩＲよりカルボニル基が生成していること、１Ｈ−ＮＭＲで、アクリル基に由来するプロトンの共鳴線を有することが確認され、２Ａ−ＤＭＢＰ−ＢＰＦＺが得られていることを確認した。 When the product was confirmed by gel permeation chromatography (GPC), infrared spectrum (IR), and 1 H nuclear magnetic resonance spectrum ( 1 H-NMR), the reaction product recovered from GPC is derived from the raw material. The peak disappeared, a new peak was generated on the high molecular weight side, a carbonyl group was generated from IR, and 1 H-NMR confirmed that it had a proton resonance line derived from an acrylic group. It was confirmed that 2A-DMBP-BPFZ was obtained.
実施例７
反応容器に、炭酸カリウム１４．５９ｇ（０．１０５モル）とＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）５００ｍｌを入れ、加熱・撹拌を行う。反応容器の内温が８０℃に達したら、アクリル酸１５．１３ｇ（０．２１モル）をＤＭＦ５０ｍｌに溶解させた溶液を３０分かけて滴下する。そのままの温度を維持して、１時間反応させる。次に、９，９−ビス（４−ヒドロキシフェニル）フルオレンとα，α’−ジクロロ−ｐ−キシレンとの反応生成物である芳香族ビスクロロメチル化合物（実施例２の２ＣＭ−Ｘｙ−ＢＰＦＺ）６２．７６ｇをＤＭＦ５００ｍｌに溶解させた溶液を３０分かけて滴下した。滴下終了後、さらに８０℃で３ｈ攪拌を継続した。３ｈ後、室温まで冷却し、固体の析出物を濾別した。そして、反応溶液にトルエン２０００ｍｌを加えた。その後、反応溶液を水で４回洗浄し、油相を硫酸マグネシウムで乾燥させ、ろ過を行った。得られた有機相を水／メタノールの混合溶媒により、生成物を再沈殿した。
沈殿を濾過・乾燥し、２ＣＭ−Ｘｙ−ＢＰＦＺとメタクリル酸との反応生成物である２Ａ−Ｘｙ−ＢＰＦＺ５４．３ｇを得た。
Example 7
A reaction vessel is charged with 14.59 g (0.105 mol) of potassium carbonate and 500 ml of N, N-dimethylformamide (DMF), and heated and stirred. When the internal temperature of the reaction vessel reaches 80 ° C., a solution prepared by dissolving 15.13 g (0.21 mol) of acrylic acid in 50 ml of DMF is added dropwise over 30 minutes. The reaction is continued for 1 hour while maintaining the temperature as it is. Next, an aromatic bischloromethyl compound (2CM-Xy-BPFZ of Example 2) which is a reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and α, α′-dichloro-p-xylene A solution obtained by dissolving 62.76 g in 500 ml of DMF was added dropwise over 30 minutes. After completion of dropping, stirring was further continued at 80 ° C. for 3 hours. After 3 h, the mixture was cooled to room temperature, and the solid precipitate was filtered off. Then, 2000 ml of toluene was added to the reaction solution. Thereafter, the reaction solution was washed four times with water, and the oil phase was dried over magnesium sulfate and filtered. The resulting organic phase was reprecipitated with a mixed solvent of water / methanol.
The precipitate was filtered and dried to obtain 54.3 g of 2A-Xy-BPFZ which is a reaction product of 2CM-Xy-BPFZ and methacrylic acid.
生成物の確認をゲル浸透クロマトグラフ（ＧＰＣ）、赤外線スペクトル（ＩＲ）、１Ｈ核磁気共鳴スペクトル（１Ｈ−ＮＭＲ）で行ったところ、ＧＰＣより回収された反応生成物では、原料に由来するピークが消失し、高分子量側に新しいピークが生成していること、ＩＲよりカルボニル基が生成していること、１Ｈ−ＮＭＲで、アクリル基に由来するプロトンの共鳴線を有することが確認され、２Ａ−Ｘｙ−ＢＰＦＺが得られていることを確認した。 When the product was confirmed by gel permeation chromatography (GPC), infrared spectrum (IR), and 1 H nuclear magnetic resonance spectrum ( 1 H-NMR), the reaction product recovered from GPC is derived from the raw material. The peak disappeared, a new peak was generated on the high molecular weight side, a carbonyl group was generated from IR, and 1 H-NMR confirmed that it had a proton resonance line derived from an acrylic group. It was confirmed that 2A-Xy-BPFZ was obtained.
実施例８
実施例６で得られた２Ａ−ＤＭＢＰ−ＢＰＦＺ ８ｇと反応性希釈剤としてｏ−フェニル−フェノキシエチルアクリレート（新中村化学（株）製、商品名：ＮＫエステル Ａ−ＬＥＮ−１０）１２ｇ、及び、光重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン）（チバ・スペシャリティケミカルズ製、商品名：イルガキュア１８４）０．４０ｇを混合・溶解し硬化性組成物（ワニスＣ）を得た。
Example 8
8 g of 2A-DMBP-BPFZ obtained in Example 6 and 12 g of o-phenyl-phenoxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-LEN-10) as a reactive diluent, and 0.40 g of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator was mixed and dissolved to obtain a curable composition (varnish C).
調製したワニスＣを実施例５と同様の手順により、硬化物平板を作成し、諸特性を測定した。また、厚み０．２ｍｍの平板硬化物から０．３ｃｍ×１０ｃｍの試験片を作成し、２．０ＧＨｚの誘電率と誘電正接を測定した。これら測定により得られた結果を表２に示した。 A cured product flat plate was prepared from the prepared varnish C in the same manner as in Example 5, and various properties were measured. Moreover, a 0.3 cm × 10 cm test piece was prepared from a cured flat plate having a thickness of 0.2 mm, and a dielectric constant and a dielectric loss tangent of 2.0 GHz were measured. The results obtained by these measurements are shown in Table 2.
実施例９
実施例７で得られた２Ａ−Ｘｙ−ＢＰＦＺ ８ｇと反応性希釈剤としてｏ−フェニル−フェノキシエチルアクリレート（新中村化学（株）製、商品名：ＮＫエステル Ａ−ＬＥＮ−１０）１２ｇ、及び、光重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン）（チバ・スペシャリティケミカルズ製、商品名：イルガキュア１８４）０．４０ｇを混合・溶解し硬化性組成物（ワニスＤ）を得た。
Example 9
8 g of 2A-Xy-BPFZ obtained in Example 7 and 12 g of o-phenyl-phenoxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-LEN-10) as a reactive diluent, and 0.40 g of 1-hydroxycyclohexyl phenyl ketone (product name: Irgacure 184, manufactured by Ciba Specialty Chemicals) was mixed and dissolved as a photopolymerization initiator to obtain a curable composition (varnish D).
調製したワニスＤを実施例５と同様の手順により、硬化物平板を作成し、諸特性を測定した。また、厚み０．２ｍｍの平板硬化物から０．３ｃｍ×１０ｃｍの試験片を作成し、２．０ＧＨｚの誘電率と誘電正接を測定した。これら測定により得られた結果を表２に示した。 A cured product flat plate was prepared from the prepared varnish D in the same manner as in Example 5, and various properties were measured. Moreover, a 0.3 cm × 10 cm test piece was prepared from a cured flat plate having a thickness of 0.2 mm, and a dielectric constant and a dielectric loss tangent of 2.0 GHz were measured. The results obtained by these measurements are shown in Table 2.
実施例１０
実施例３で得られた２ＭＡ−ＤＭＢＰ−ＢＰＦＺ １１ｇと反応性希釈剤としてジビニルベンゼン（新日鐵化学（株）製、商品名：ＤＶＢ９６０）２ｇ、9,9-ビス［4-(2-アクリロイルオキシエトキシ）フェニル］フルオレン（大阪ガスケミカル（株）製、商品名：オグソールＥＡ−０２００）１ｇ及び、フェニルチオエチルアクリレート（ＢＩＭＡＸ社製、商品名：ＢＸ−ＰＴＥＡ）６ｇ、光重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン（チバ・スペシャリティケミカルズ製、商品名：イルガキュア１８４）０．４０ｇ、及び、ｔ−ブチルパーオキシ−２−エチルヘキサノエート（日油（株）製、商品名：パーブチルＯ）０．０４ｇを混合・溶解し硬化性組成物（ワニスＥ）を得た。
Example 10
11 g of 2MA-DMBP-BPFZ obtained in Example 3 and 2 g of divinylbenzene (manufactured by Nippon Steel Chemical Co., Ltd., trade name: DVB960) as a reactive diluent, 9,9-bis [4- (2-acryloyl) 1 g of oxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd., trade name: Ogsol EA-0200) and 6 g of phenylthioethyl acrylate (trade name: BX-PTEA, manufactured by BIMAX Co., Ltd.) -Hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) 0.40 g and t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, trade name: perbutyl O) 0.04 g was mixed and dissolved to obtain a curable composition (varnish E).
調製したワニスＥを実施例５と同様の手順により、硬化物平板を作成し、諸特性を測定した。また、厚み０．２ｍｍの平板硬化物から０．３ｃｍ×１０ｃｍの試験片を作成し、２．０ＧＨｚの誘電率と誘電正接を測定した。これら測定により得られた結果を表３に示した。 A cured product flat plate was prepared from the prepared varnish E in the same procedure as in Example 5, and various properties were measured. Moreover, a 0.3 cm × 10 cm test piece was prepared from a cured flat plate having a thickness of 0.2 mm, and a dielectric constant and a dielectric loss tangent of 2.0 GHz were measured. The results obtained by these measurements are shown in Table 3.
実施例１１
実施例４で得られた２ＭＡ−Ｘｙ−ＢＰＦＺ １１ｇと反応性希釈剤としてジビニルベンゼン（新日鐵化学（株）製、商品名：ＤＶＢ９６０）２ｇ、9,9-ビス［4-(2-アクリロイルオキシエトキシ）フェニル］フルオレン（大阪ガスケミカル（株）製、商品名：オグソールＥＡ−０２００）１ｇ及び、フェニルチオエチルアクリレート（ＢＩＭＡＸ社製、商品名：ＢＸ−ＰＴＥＡ）６ｇ、光重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン（チバ・スペシャリティケミカルズ製、商品名：イルガキュア１８４）０．４０ｇ、及び、ｔ−ブチルパーオキシ−２−エチルヘキサノエート（日油（株）製、商品名：パーブチルＯ）０．０４ｇを混合・溶解し硬化性組成物（ワニスＦ）を得た。
Example 11
11 g of 2MA-Xy-BPFZ obtained in Example 4 and 2 g of divinylbenzene (manufactured by Nippon Steel Chemical Co., Ltd., trade name: DVB960) as a reactive diluent, 9,9-bis [4- (2-acryloyl) 1 g of oxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd., trade name: Ogsol EA-0200) and 6 g of phenylthioethyl acrylate (trade name: BX-PTEA, manufactured by BIMAX Co., Ltd.) -Hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) 0.40 g and t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, trade name: perbutyl O) 0.04 g was mixed and dissolved to obtain a curable composition (varnish F).
調製したワニスＦを実施例５と同様の手順により、硬化物平板を作成し、諸特性を測定した。また、厚み０．２ｍｍの平板硬化物から０．３ｃｍ×１０ｃｍの試験片を作成し、２．０ＧＨｚの誘電率と誘電正接を測定した。これら測定により得られた結果を表３に示した。 A cured product flat plate was prepared from the prepared varnish F in the same procedure as in Example 5, and various properties were measured. Moreover, a 0.3 cm × 10 cm test piece was prepared from a cured flat plate having a thickness of 0.2 mm, and a dielectric constant and a dielectric loss tangent of 2.0 GHz were measured. The results obtained by these measurements are shown in Table 3.
Claims (2)
（式中、Ａｒ1は炭素数６〜５０の芳香族炭化水素基を表し、Ｙは水素またはメチル基を表し、ｎは１〜１０の数を表し、Ｒ1及びＲ2は独立に炭素数１〜５０の炭化水素基を表す。ｐ、ｑは独立に０〜２の整数を表す。） A bis (meth) acryloyl-terminated benzyl ether compound represented by the following formula (2):
(In the formula, Ar 1 represents an aromatic hydrocarbon group having 6 to 50 carbon atoms, Y represents hydrogen or a methyl group, n represents a number of 1 to 10, and R 1 and R 2 independently represent the number of carbon atoms. And represents a hydrocarbon group of 1 to 50. p and q independently represent an integer of 0 to 2.)
（式中、Ａｒ 1 は炭素数６〜５０の芳香族炭化水素基を表し、Ｘはハロゲン元素を表し、ｎは１〜１０の数を表し、Ｒ 1 及びＲ 2 は独立に炭素数１〜５０の炭化水素基を表す。ｐ、ｑは独立に０〜２の整数を表す。）
（式中、Ｙは水素またはメチル基を表し、Ｚは水素、アルカリ金属、または（メタ）アクリロイル基を表す。） The bis (meth) acryloyl according to claim 1, wherein an aromatic bishalomethyl compound represented by the following formula (1) is reacted with a (meth) acrylic compound represented by the following formula (4): A method for producing a terminal benzyl ether compound.
(In the formula, Ar 1 represents an aromatic hydrocarbon group having 6 to 50 carbon atoms, X represents a halogen element, n represents a number of 1 to 10, and R 1 and R 2 are independently 1 to 1 carbon atoms. Represents a hydrocarbon group of 50. p and q independently represent an integer of 0 to 2.)
(In the formula, Y represents hydrogen or a methyl group, and Z represents hydrogen, an alkali metal, or a (meth) acryloyl group.)
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| TW102146069A TWI600681B (en) | 2012-12-17 | 2013-12-13 | Diethyl ether compounds and resin compositions having a tau skeleton |
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