JP5672475B2 - (Meth) acrylic acid ester, resin composition and cured product thereof - Google Patents
(Meth) acrylic acid ester, resin composition and cured product thereof Download PDFInfo
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- JP5672475B2 JP5672475B2 JP2010097787A JP2010097787A JP5672475B2 JP 5672475 B2 JP5672475 B2 JP 5672475B2 JP 2010097787 A JP2010097787 A JP 2010097787A JP 2010097787 A JP2010097787 A JP 2010097787A JP 5672475 B2 JP5672475 B2 JP 5672475B2
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- Prior art keywords
- meth
- acrylate
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- compound
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- 239000011342 resin composition Substances 0.000 title description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title description 10
- 150000001875 compounds Chemical class 0.000 claims description 38
- 125000004434 sulfur atom Chemical group 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004957 naphthylene group Chemical group 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 82
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- -1 acrylic acid halide Chemical class 0.000 description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 239000010410 layer Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 150000003613 toluenes Chemical class 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- INUNLMUAPJVRME-UHFFFAOYSA-N 3-chloropropanoyl chloride Chemical compound ClCCC(Cl)=O INUNLMUAPJVRME-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 125000003003 spiro group Chemical group 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GUJZISPOCRVAMW-UHFFFAOYSA-N 2-[1-(2-hydroxyphenyl)-9h-fluoren-2-yl]phenol Chemical class OC1=CC=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=CC=C1O GUJZISPOCRVAMW-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical class C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- SLKXGYYUITVNDF-UHFFFAOYSA-N 2,2-bis(sulfanylmethyl)propane-1,3-diol Chemical compound OCC(CO)(CS)CS SLKXGYYUITVNDF-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- QBCQGEXLWDKMGN-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-2-phenoxyethanol Chemical compound OCCOC(CO)OC1=CC=CC=C1 QBCQGEXLWDKMGN-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、光学材料として利用可能な（メタ）アクリル酸エステル、樹脂組成物及びその硬化物に関する。 The present invention relates to a (meth) acrylic acid ester that can be used as an optical material, a resin composition, and a cured product thereof.
現在、液晶テレビ、ノートパソコン、携帯ゲーム機、携帯電話等の表示に使用される液晶表示素子において小型化、高耐光性、高輝度化が要求されている。特に、高輝度化の実現にはプリズムシートの高屈折率化が不可欠である。
屈折率の高い材料を提供するため、フルオレン骨格を持つ化合物が提案されている。フルオレン骨格を持つ化合物は耐熱性が高く高屈折率であるとして注目されており、特許文献1においては化合物自体が固体であって、硬化物の屈折率が１．６０を超えるビス（ヒドロキシフェニル）フルオレンの誘導体が提供されている。しかし、ビス（ヒドロキシフェニル）フルオレンの誘導体は一般に固体または高粘度であり、プリズムシートなどの賦形材料に用いる場合には、適当な粘度になるよう低粘度モノマー等で希釈しないと使用できないという課題があった。また、ハンドリング性を改良したビス（ヒドロキシフェニル）フルオレンの誘導体が特許文献２で提示されているが、提示されている粘度は３３０１０ｍＰａ・ｓとやはり高粘度であり、実際の使用には十分でなかった。
Currently, liquid crystal display elements used for display of liquid crystal televisions, notebook computers, portable game machines, mobile phones, and the like are required to be small in size, high in light resistance, and high in brightness. In particular, it is essential to increase the refractive index of the prism sheet in order to achieve high brightness.
In order to provide a material having a high refractive index, a compound having a fluorene skeleton has been proposed. A compound having a fluorene skeleton attracts attention as having high heat resistance and a high refractive index. In Patent Document 1, the compound itself is a solid, and the refractive index of the cured product exceeds 1.60. Bis (hydroxyphenyl) Derivatives of fluorene are provided. However, bis (hydroxyphenyl) fluorene derivatives are generally solid or high-viscosity, and cannot be used unless diluted with low-viscosity monomers to achieve an appropriate viscosity when used in shaping materials such as prism sheets. was there. In addition, a bis (hydroxyphenyl) fluorene derivative with improved handling properties is presented in Patent Document 2, but the presented viscosity is as high as 33010 mPa · s, which is not sufficient for actual use. It was.
本発明の課題は、その硬化物が高屈折率であって、光学材料として利用可能な低粘度の新規（メタ）アクリル酸エステルとその樹脂組成物、及び硬化物を提供することである。 An object of the present invention is to provide a novel (meth) acrylic acid ester having a high refractive index and a low viscosity that can be used as an optical material, a resin composition thereof, and a cured product.
すなわち、本発明では、下記式（１）で表される化合物。 That is, in the present invention, a compound represented by the following formula (1).
（式中、X及びYは、それぞれ独立して炭素原子、窒素原子、酸素原子又は硫黄原子を表し、Ｘ及びＹが炭素原子又は窒素原子のときは、Ｒ１及びＲ２はそれぞれ独立して水素原子又は下記式（２） (In the formula, X and Y each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. When X and Y are a carbon atom or a nitrogen atom, R 1 and R 2 are each independently Hydrogen atom or the following formula (2)
（式中、Ｑは酸素原子又は硫黄原子を表し、R3は水素原子又は−CH３基を表し、ｎは１〜５のいずれかの整数を表す）で表される基であり、酸素原子又は硫黄原子のときは、Ｒ１及びＲ２は結合しておらず、 (Wherein Q represents an oxygen atom or a sulfur atom, R 3 represents a hydrogen atom or —CH 3 group, and n represents an integer of 1 to 5), and an oxygen atom Or when it is a sulfur atom, R 1 and R 2 are not bonded,
Ｚは、−（CH２）ｎ−（式中、ｎは１〜５のいずれかの整数を表す）で表される2価の基、フェニレン基又はナフチレン基であり、Ｚ中の少なくとも一つの水素原子は式（２）で表される基で置換されていてもよく、式（１）で表される化合物は、式（２）で表される基を少なくとも一つ有する。）
により、上記課題を解決することができる。
Z is a divalent group represented by — (CH 2 ) n — (wherein n represents an integer of 1 to 5), a phenylene group or a naphthylene group, and at least one of Z The hydrogen atom may be substituted with a group represented by Formula (2), and the compound represented by Formula (1) has at least one group represented by Formula (2). )
Thus, the above problem can be solved.
即ち、本発明では、上記式（１）で表される新規の（メタ）アクリル酸エステル化合物は高屈折率かつ液状の化合物であり、上記式（１）で表される（メタ）アクリル酸エステルの樹脂組成物は、高屈折率を有する硬化物を与えることができる。 That is, in the present invention, the novel (meth) acrylic acid ester compound represented by the above formula (1) is a high refractive index and liquid compound, and the (meth) acrylic acid ester represented by the above formula (1). This resin composition can give a cured product having a high refractive index.
本発明によれば、その硬化物が高屈折率であって、光学材料として利用が可能な低粘性かつハロゲンフリーの新規（メタ）アクリル酸エステルを提供することができる。 According to the present invention, it is possible to provide a novel (meth) acrylic acid ester having a low refractive index and a halogen-free, which has a high refractive index and can be used as an optical material.
本発明で提供される（メタ）アクリル酸エステルは、フルオレンに対しスピロ炭素で環状構造が結合したスピロ環化合物であり、フルオレンを含む平面とスピロ炭素に結合する環状構造内の原子を含む平面が異なる平面に存在することから結晶性を引き下げつつ高屈折率な重合性モノマーを供給できる。 The (meth) acrylic acid ester provided in the present invention is a spiro ring compound in which a cyclic structure is bonded to fluorene by a spiro carbon, and a plane including atoms in the cyclic structure bonded to the spiro carbon and a plane including the fluorene. Since it exists in a different plane, it is possible to supply a polymerizable monomer having a high refractive index while lowering the crystallinity.
上記式（１）におけるＸ及びＹはそれぞれ独立して炭素原子、窒素原子、酸素原子又は硫黄原子を表しており、ＸまたはＹがそれぞれ独立して硫黄原子または窒素原子であることが好ましく、ＸとＹのどちらかが硫黄原子であることがさらに好ましい。また、Ｘ、Ｙ、Ｚを含む環状構造は４員環から８員環まで構成でき、５員環構造及び６員環構造が好ましい。Ｚはフェニレン基またはナフチレン基でも良く、この場合、環状構造はＸ及びＹを含む縮合環構造を構成する。 X and Y in the formula (1) each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and X or Y is preferably independently a sulfur atom or a nitrogen atom, More preferably, either Y or Y is a sulfur atom. Moreover, the cyclic structure containing X, Y, Z can be comprised from a 4-membered ring to an 8-membered ring, and a 5-membered ring structure and a 6-membered ring structure are preferable. Z may be a phenylene group or a naphthylene group, and in this case, the cyclic structure constitutes a condensed ring structure containing X and Y.
上記式（１）において、Ｘ及びＹが酸素原子または硫黄原子のときはＲ1、Ｒ2は結合していないが、Ｘ及びＹが炭素原子または窒素原子のときはＲ1及びＲ2が結合しており、Ｒ1およびＲ2はそれぞれ独立して水素原子又は式（２）で表される基である。 In the above formula (1), when X and Y are oxygen atoms or sulfur atoms, R 1 and R 2 are not bonded, but when X and Y are carbon atoms or nitrogen atoms, R 1 and R 2 are bonded. R 1 and R 2 are each independently a hydrogen atom or a group represented by the formula (2).
上記式（２）においては、式中Qは酸素原子または硫黄原子を表し、R3は水素原子または−CH3基を表し、ｎは１〜５のいずれかを表すものであって、上記式（２）の好ましい構造としては下記のような構造が挙げられる。 In the formula (2), Q represents an oxygen atom or a sulfur atom, R 3 represents a hydrogen atom or a —CH 3 group, n represents any one of 1 to 5, and The following structure is mentioned as a preferable structure of (2).
上記式（２）で表される基は、上記式（１）中に少なくとも一つ存在し、上記式（１）中のＲ1及びＲ2に結合しているか、Ｚ中の少なくとも一つの水素原子が式（２）で表される基で置換されているかしている。 At least one group represented by the above formula (2) is present in the above formula (1) and is bonded to R 1 and R 2 in the above formula (1) or at least one hydrogen in Z. It is assumed that the atom is substituted with a group represented by the formula (2).
上記式（１）において、上記式（２）が二つ以上存在しても良く、その場合上記式（１）で表される化合物は多官能（メタ）アクリル酸エステルとなり、架橋重合物が生成可能になるなど産業上有用である。 In the above formula (1), two or more of the above formula (2) may exist, in which case the compound represented by the above formula (1) becomes a polyfunctional (meth) acrylic acid ester, and a crosslinked polymer is formed. It is useful in the industry such as becoming possible.
上記式（１）におけるＸとＹはどちらかが硫黄原子であることがさらに好ましく、ＸとＹがともに硫黄原子であるかまたはＸが硫黄原子でＹが窒素原子または酸素原子であることがより好ましい。ＸとＹがともに硫黄原子であるとき、好ましい例として下記のような構造が挙げられる。このとき、式（１）のＺに相当する部分の少なくとも一つの水素原子が式（２）で表される基で置換されている。 More preferably, either X or Y in the formula (1) is a sulfur atom, and X and Y are both sulfur atoms, or X is a sulfur atom and Y is a nitrogen atom or an oxygen atom. preferable. When X and Y are both sulfur atoms, preferred examples include the following structures. At this time, at least one hydrogen atom in the portion corresponding to Z in the formula (1) is substituted with a group represented by the formula (2).
更に好ましくは、 More preferably,
が挙げられる。 Is mentioned.
上記式（１）におけるＸが硫黄原子でＹが窒素原子であるときの好ましい例として、 As a preferable example when X in the above formula (1) is a sulfur atom and Y is a nitrogen atom,
が挙げられ、式（１）のＺに相当する部分の少なくとも一つの水素原子が式（２）で表される基で置換されている。更に好ましくは、 And at least one hydrogen atom corresponding to Z in the formula (1) is substituted with a group represented by the formula (2). More preferably,
が挙げられる。 Is mentioned.
上記式（１）におけるＸが硫黄原子でＹが酸素原子であるときの好ましい例として、 As a preferable example when X in the above formula (1) is a sulfur atom and Y is an oxygen atom,
が挙げられ、式（１）のＺに相当する部分の少なくとも一つの水素原子が式（２）で表される基で置換されている。更に好ましくは、 And at least one hydrogen atom corresponding to Z in the formula (1) is substituted with a group represented by the formula (2). More preferably,
が挙げられる。 Is mentioned.
上記式（１）で表される化合物に含まれる構造の内、スピロフルオレン環は、９−フルオレノンを出発原料とした反応によって得ることができる。このとき、触媒として、塩酸、硫酸、リン酸に代表される無機酸や、ｐ−トルエンスルホン酸、酢酸に代表される有機酸や塩化アルミニウム、三フッ化ホウ素、塩化錫、塩化亜鉛に代表されるルイス酸を使用することができる。また、ヨウ素を使用することもできる。 Of the structures contained in the compound represented by the above formula (1), the spirofluorene ring can be obtained by a reaction using 9-fluorenone as a starting material. At this time, the catalyst is typically an inorganic acid typified by hydrochloric acid, sulfuric acid or phosphoric acid, an organic acid typified by p-toluenesulfonic acid or acetic acid, aluminum chloride, boron trifluoride, tin chloride or zinc chloride. Lewis acids can be used. Iodine can also be used.
一般式（１）におけるＲ１またはＲ２で表される基が、上記式（ｉ）〜（Ｖｉｉｉ）で表される何れかの基である場合には、アクリル酸と対応するアルコール若しくはチオールとの脱水縮合反応を行うか、塩基性物質の存在下にアクリル酸ハライドと対応するアルコール若しくはチオールとの脱ハロゲン化水素反応を行えばよい。また、アクリル酸低級アルキルエステルと該アルコールとのエステル交換反応によっても得ることができる。さらには、３−クロロプロピオン酸クロリドのようなハロゲン化アルキル酸クロリドを用いても得ることができる。 When the group represented by R 1 or R 2 in the general formula (1) is any group represented by the above formulas (i) to (Viii), the corresponding alcohol or thiol and acrylic acid Or a dehydrohalogenation reaction between an acrylic acid halide and the corresponding alcohol or thiol in the presence of a basic substance. It can also be obtained by a transesterification reaction between the lower alkyl ester of acrylic acid and the alcohol. Furthermore, it can be obtained by using a halogenated alkyl acid chloride such as 3-chloropropionic acid chloride.
脱水縮合反応の場合には、公知の方法により、ｐ−トルエンスルホン酸又は硫酸等のエステル化触媒及びハイドロキノン、ｐ−メトキシフェノール、フェノチアジン等の重合禁止剤の存在下に、好ましくは溶剤類（例えば、トルエン、ベンゼン、シクロヘキサン、ｎ−ヘキサン、ｎ−ヘプタン等）の存在下に、好ましくは７０〜１５０℃の温度で反応させることにより得ることができる。アクリル酸の使用割合は、該アルコール１モルに対して１〜５モル、好ましくは１．０５〜２モルである。エステル化触媒は、使用するアクリル酸に対して０．１〜１５モル％、好ましくは１〜６モル％の濃度で存在させる。 In the case of the dehydration condensation reaction, a solvent is preferably used in the presence of an esterification catalyst such as p-toluenesulfonic acid or sulfuric acid and a polymerization inhibitor such as hydroquinone, p-methoxyphenol, or phenothiazine. , Toluene, benzene, cyclohexane, n-hexane, n-heptane, etc.), and preferably at a temperature of 70 to 150 ° C. The ratio of acrylic acid used is 1 to 5 mol, preferably 1.05 to 2 mol, per 1 mol of the alcohol. The esterification catalyst is present at a concentration of 0.1 to 15 mol%, preferably 1 to 6 mol%, based on the acrylic acid used.
また、塩基性物質の存在下の脱ハロゲン化水素反応では、例えばアクリル酸クロリドと対応するアルコールと反応せしめることにより得ることができる。その際、トリエチルアミン、ピリジン等のアミン系塩基性物質を加えておくことが好ましい。溶剤類（例えば、トルエン、ベンゼン、シクロヘキサン、ｎ−ヘキサン、ｎ−ヘプタン、アセトン、テトラヒドロフラン等）の存在下に、好ましくは０〜１００℃の温度で反応させることにより得ることができる。 In the dehydrohalogenation reaction in the presence of a basic substance, it can be obtained, for example, by reacting acrylic acid chloride with a corresponding alcohol. At that time, it is preferable to add an amine basic substance such as triethylamine or pyridine. It can obtain by making it react at the temperature of 0-100 degreeC preferably in presence of solvents (for example, toluene, benzene, a cyclohexane, n-hexane, n-heptane, acetone, tetrahydrofuran, etc.).
更には、通常公知のエステル交換触媒の存在下に、例えば、アクリル酸メチル或いはアクリル酸エチル等の低級アルキルエステルと該アルコールとのエステル交換反応によっても得ることができる。 Furthermore, it can also be obtained by a transesterification reaction of the alcohol with a lower alkyl ester such as methyl acrylate or ethyl acrylate in the presence of a commonly known transesterification catalyst.
本発明における樹脂組成物は、上記式（１）で表される化合物を含有するものであって、その他の共重合可能な反応性単量体化合物や反応性オリゴマーを含んでも良い。 The resin composition in the present invention contains a compound represented by the above formula (1), and may contain other copolymerizable reactive monomer compounds and reactive oligomers.
反応性単量体としては、例えば、アクリレート系単量体やビニル系単量体が挙げられ、アクリレート系単量体としては、単官能アクリレート、二官能アクリレート、多官能アクリレートが挙げられる。 Examples of reactive monomers include acrylate monomers and vinyl monomers, and examples of acrylate monomers include monofunctional acrylates, bifunctional acrylates, and polyfunctional acrylates.
単官能アクリレートとしては、アクリロイルモルホリン、２−エチルヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、２−フェノキシジエチレングリオール（メタ）アクリレート、ノニルフェノキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェニルオキシプロピル（メタ）アクリレート、ｉｓｏオクチル（メタ）アクリレート、ｉｓｏステアリル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、グリシジル（メタ）アクリレート、アリル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート
４−ヒドロキシブチル（メタ）アクリレート、２−メトキシエトキシエチル（メタ）アクリレート、２−エトキシエトキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリロイルホスフェート、テトラヒドロフルフリル（メタ）アクリレート、ジシクロペンタジエニル（メタ）アクリレート、ジシクロペンタジエンエトキシ（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、トリシクロデカニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、２−エチルヘキシルカルビトール（メタ）アクリレート、メトキシプロピレンモノアクリレート、無水フタル酸−２−ＨＥＡ付加物、無水テトラヒドロフタル酸−２−ＨＰＡ付加物、無水ヘキサヒドロフタル酸−２−ＨＰＡ付加物、トリブロモフェニル（メタ）アクリレート、フェニルチオエチル（メタ）アクリレート、ｏ−フェニルフェノキシエチル（メタ）アクリレート、ｏ−フェニルフェニルオキシエチルオキシエチル（メタ）アクリレート、２−ヒドロキシ−３−（ジブロモフェニル）オキシプロピル（メタ）アクリレート、２−（２−ナフチロキシ）エチル（メタ）アクリレート、２−（２−ナフタレニルチオ）エチル（メタ）アクリレートが挙げられる。
Monofunctional acrylates include acryloylmorpholine, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxydiethyleneglycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxy Ethyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, isooctyl (meth) acrylate, isostearyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl ( (Meth) acrylate, lauryl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate Rate, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 4-hydroxybutyl (meth) Acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (meth) Acryloyl phosphate, tetrahydrofurfuryl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentadiene ethoxy (meth) acrylate, tricyclodecanyl (meth) Addition of acrylate, tricyclodecanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, methoxypropylene monoacrylate, phthalic anhydride-2-HEA , Tetrahydrophthalic anhydride-2-HPA adduct, hexahydrophthalic anhydride-2-HPA adduct, tribromophenyl (meth) acrylate, phenylthioethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate , O-phenylphenyloxyethyloxyethyl (meth) acrylate, 2-hydroxy-3- (dibromophenyl) oxypropyl (meth) acrylate, 2- (2-naphthyloxy) ethyl (meth) acrylate And 2- (2-naphthalenylthio) ethyl (meth) acrylate.
二官能性アクリレートとしては、１，３−ブタンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ネオペンチルジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＦジ（メタ）アクリレート、ビスフェノールＳジ（メタ）アクリレート、ＥＯ変性ビスフェノールＡジ（メタ）アクリレート、ＥＯ変性ビスフェノールＦジ（メタ）アクリレート、ＥＯ変性ビスフェノールＳジ（メタ）アクリレート、ＥＯ変性テトラブロモビスフェノールＡジ（メタ）アクリレート、ＰＯ変性ビスフェノールＡジ（メタ）アクリレート、ＰＯ変性ビスフェノールＳジ（メタ）アクリレート、ＰＯ変性テトラブロモビスフェノールＡジ（メタ）アクリレート、ＥＣＨ変性ビスフェノールＡジ（メタ）アクリレート、トリシクロデカンジメチロールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリエチレングリオールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、イソシアヌル酸ＥＯ変性ジ（メタ）アクリレート、９，９−ビス［４−（２−（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン、ビスフェノールＳジチオール（メタ）アクリレート、３−メチルペンタンジオールジ（メタ）アクリレートが挙げられる。 Examples of the bifunctional acrylate include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (Meth) acrylate, neopentyl di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate EO modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, EO modified bisphenol S di (meth) acrylate, EO modified tetrabromobisphenol A di (meth) acrylate , PO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol S di (meth) acrylate, PO-modified tetrabromobisphenol A di (meth) acrylate, ECH-modified bisphenol A di (meth) acrylate, tricyclodecane dimethylol di ( (Meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethyleneglycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, isocyanuric acid EO-modified di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bisphenol S dithiol (meth) acrylate 3-methyl-pentanediol di (meth) acrylate.
多官能性アクリレートとしては、ＰＯ変性グリセリントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンＥＯ変性トリ（メタ）アクリレート、トリメチロールプロパンＰＯ変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタアクリレート
が挙げられる。
Polyfunctional acrylates include PO-modified glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol pentaacrylate.
ビニル系単量体としては、スチレン、α−メチルスチレン、クロロスチレン、ビニルフェノール、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクトン、Ｎ−ビニルカルバゾール、ビニルナフタレン、ジビニルベンゼンが挙げられる。 Examples of the vinyl monomer include styrene, α-methylstyrene, chlorostyrene, vinylphenol, N-vinylpyrrolidone, N-vinylcaprolactone, N-vinylcarbazole, vinylnaphthalene, and divinylbenzene.
反応性オリゴマーとしては、例えばエポキシ樹脂類と（メタ）アクリル酸との反応物であるエポキシ（メタ）アクリレート系オリゴマーが挙げられ、ビスフェノールＡ−エピクロルヒドリン型／アクリル酸系オリゴマー、フェノールノボラック−エピクロルヒドリン型／アクリル酸系オリゴマー、脂環型／アクリル酸オリゴマーが挙げられる。 Examples of reactive oligomers include epoxy (meth) acrylate oligomers which are reaction products of epoxy resins and (meth) acrylic acid, and include bisphenol A-epichlorohydrin type / acrylic acid oligomer, phenol novolac-epichlorohydrin type / Acrylic acid oligomers and alicyclic / acrylic acid oligomers may be mentioned.
その他の反応性オリゴマーとしては、ポリオール類と有機ポリイソシアネート類と水酸基含有（メタ）アクリレート類の反応物であるウレタン（メタ）アクリレート等の（メタ）アクリレート系の反応性オリゴマー、ポリエステル（メタ）アクリレート系の反応性オリゴマー、ポリエーテル（メタ）アクリレート系の反応性オリゴマー、メラミン（メタ）アクリレート系の反応性オリゴマー、シリコン（メタ）アクリレート系の反応性オリゴマーなどが挙げられる。 Other reactive oligomers include (meth) acrylate-based reactive oligomers such as urethane (meth) acrylate, which is a reaction product of polyols, organic polyisocyanates, and hydroxyl group-containing (meth) acrylates, and polyester (meth) acrylates. Reactive oligomers based on polyether, reactive oligomers based on polyether (meth) acrylate, reactive oligomers based on melamine (meth) acrylate, reactive oligomers based on silicon (meth) acrylate, and the like.
本発明における組成物には、組成物の塗布作業性を改良するために、組成物の粘度を調製することを目的として有機溶剤を含有させてもよい。配合量としては発明の効果を損なわない範囲であればよく、本発明の化合物と反応性単量体および反応性オリゴマーの合計を１００質量部としたときに、０．０１質量部から５００質量部の範囲が好ましい。有機溶剤としては、Ｎ−メチル−２−ピロリドン、ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメトキシアセトアミド、１，３−ジメチル−２−イミダゾリジノン、Ｎ−メチルカプロラクタム、１，２−ジメトキシエタン、ビス（２−メトキシエチル）エーテル、１，２−ビス（２−メトキシエトキシ）エタン、ビス〔２−（２−メトキシエトキシ）エチル〕エーテル、１，３−ジオキサン、１，４−ジオキサン、ピリジン、ピコリン、ジメチルスルホキシド、ジメチルスルホン、テトラメチル尿素、ヘキサメチルホスホルアミド、ベンゼン、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、ｍ−クレゾール酸、ｐ−クロロフェノール、アニソール、アセトン、アセチルアセトン、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、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｔ−ブタノール、３−メトキシ−１−ブタノール、３−メトキシ−２−ブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノ−ｎ−ブチルエーテル、２−エトキシエタノール、１−メトキシ−２−プロパノール、ジアセトンアルコール、プロピレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、２−エトキシエチルアセテート、ブチルアセテート、イソアミルアセテート、テトラヒドロフラン、メチルピロリドンなどが挙げられる。これらの有機溶剤は、単独で用いても、２種類以上を併用してもよい。 In order to improve the coating workability of the composition, the composition in the present invention may contain an organic solvent for the purpose of adjusting the viscosity of the composition. The blending amount may be in a range that does not impair the effects of the invention. When the total of the compound of the present invention, the reactive monomer and the reactive oligomer is 100 parts by mass, 0.01 part by mass to 500 parts by mass The range of is preferable. Examples of the organic solvent include N-methyl-2-pyrrolidone, dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethoxyacetamide, 1,3-dimethyl-2-imidazolidinone, N -Methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, 1,3 -Dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethyl urea, hexamethyl phosphoramide, benzene, toluene, o-xylene, m-xylene, p-xylene, phenol, o-cresol , M-cresol, p-cresol, m-cresol P-chlorophenol, anisole, acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 3-methoxy-1-butanol, 3 -Methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol Monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate, isoamyl acetate, Rahidorofuran, like methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.
本発明の樹脂組成物は、公知慣用の硬化法により硬化させることができる。紫外線（ＵＶ）、電子線（ＥＢ）等の活性エネルギー線照射による硬化法、及び加熱による硬化法を用いることができる。 The resin composition of the present invention can be cured by a known and commonly used curing method. A curing method by irradiation with active energy rays such as ultraviolet rays (UV) and electron beams (EB) and a curing method by heating can be used.
本発明の樹脂組成物に紫外線を照射して硬化させる場合、光重合開始剤を使用するのが好ましい。光重合開始剤としては、例えば１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチルプロピオフェノン、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド等があげられる。これらは単独、または２種類以上を組み合わせて用いることができる。 When the resin composition of the present invention is cured by irradiation with ultraviolet rays, it is preferable to use a photopolymerization initiator. Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. These can be used alone or in combination of two or more.
市販の光ラジカル重合開始剤としては、イルガキュア６５１、イルガキュア１８４、イルガキュア８１９、イルガキュア９０７、イルガキュア１８７０、イルガキュア５００、イルガキュア３６９、イルガキュア１１７３、イルガキュア２９５９、イルガキュア４２６５、イルガキュア４２６３、ダロキュアＴＰＯ、イルガキュアＯＸＥ０１等（チバ・スペシャルティ・ケミカルズ株式会社製）が挙げられる。また、イルガキュア２５０等のカチオン系光重合開始剤も使用することができる。 Commercially available radical photopolymerization initiators include Irgacure 651, Irgacure 184, Irgacure 819, Irgacure 907, Irgacure 1870, Irgacure 500, Irgacure 369, Irgacure 1173, Irgacure 2959, Irgacure 4265, Irgacure 4263, Darocure OPO 01, Erugac Ciba Specialty Chemicals Co., Ltd.). A cationic photopolymerization initiator such as Irgacure 250 can also be used.
本発明の樹脂組成物を熱硬化させる場合、熱重合開始剤を使用することもできる。ラジカル重合開始剤として一般的に知られるものが使用でき、例えば２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス−（２，４−ジメチルバレロニトリル）、２，２’−アゾビス−（４−メトキシ−２，４−ジメチルバレロニトリル）等のアゾ化合物、ベンゾイルペルオキシド、ラウロイルペルオキシド、ｔ−ブチルペルオキシピバレート、１，１’−ビス−（ｔ−ブチルペルオキシ）シクロヘキサン、ｔ−アミルペルオキシ−２−エチルヘキサノエート、ｔ−ヘキシルペルオキシ−２−エチルヘキサノエート等の有機過酸化物が挙げられる。また、これらの重合開始剤は単独、または２種以上を組み合わせて用いることができる。 When thermosetting the resin composition of the present invention, a thermal polymerization initiator can also be used. Those generally known as radical polymerization initiators can be used, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'- Azo compounds such as azobis- (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane, t- Organic peroxides such as amylperoxy-2-ethylhexanoate and t-hexylperoxy-2-ethylhexanoate can be mentioned. Moreover, these polymerization initiators can be used alone or in combination of two or more.
光重合開始剤に加えて、光増感剤を用いてもよい。光増感剤の具体例として、ｎ−ブチルアミン、トリエチルアミン、トリ−ｎ−ブチルホスフィン、ミヒラーケトン及びチオキサントンなどを挙げることができる。更にアジド化合物、チオ尿素化合物、メルカプト化合物などの助剤を１種以上組み合わせて用いてもよい。 In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.
本発明の樹脂組成物は、前記成分以外に界面活性剤、レベリング剤、離型剤、消泡剤、光安定剤（例えばヒンダードアミンなど）、紫外線吸収剤、酸化防止剤、重合禁止剤、帯電防止剤、着色剤（例えば染料、顔料など）、抗菌剤、シランカップリング剤、無機フィラー、有機フィラーなどの各種添加剤を併用してもよい。 In addition to the above components, the resin composition of the present invention includes a surfactant, a leveling agent, a release agent, an antifoaming agent, a light stabilizer (such as a hindered amine), an ultraviolet absorber, an antioxidant, a polymerization inhibitor, and an antistatic agent. Various additives such as an agent, a colorant (for example, a dye, a pigment, etc.), an antibacterial agent, a silane coupling agent, an inorganic filler, and an organic filler may be used in combination.
界面活性剤としては、市販されているものをそのまま使用することができる。界面活性剤の例としては、例えば、ＳＨ２８ＰＡ、ＳＦ８４２８、ＤＣ５７、ＤＣ１９０、ＢＹ１６−００４（東レダウコーニング社製）、ペインタッド１９、５４（東レダウコーニング社製、ジメチルポリシロキサンポリオキシアルキレン共重合体）、ＢＹＫ ＵＶ３５００、ＵＶ３５１０、ＵＶ３５３０、Ｄｉｓｐｅｒｂｙｋ−１８０（ビックケミー社製）、サイラプレーンＦＭ−４４１１、ＦＭ−４４２１、ＦＭ−４４２５、ＦＭ−７７１１、ＦＭ−７７２１、ＦＭ−７７２５、ＦＭ−０４１１、ＦＭ−０４２１、ＦＭ−０４２５、ＦＭ−ＤＡ１１、ＦＭ−ＤＡ２１、ＦＭ−ＤＡ２６、ＦＭ０７１１、ＦＭ０７２１、ＦＭ−０７２５、ＴＭ−０７０１、ＴＭ−０７０１Ｔ（チッソ社製）、ＶＰＳ−１００１（和光純薬製）、Ｔｅｇｏ Ｒａｄ ２３００、２２００Ｎ（テゴ・ケミー社製）、メガファックＦ−１１４、Ｆ４１０、Ｆ４１１、Ｆ４５０、Ｆ４９３、Ｆ４９４、Ｆ４４３、Ｆ４４４、Ｆ４４５、Ｆ４４６、Ｆ４７０、Ｆ４７１、Ｆ４７２ＳＦ、Ｆ４７４、Ｆ４７５、Ｒ３０、Ｆ４７７、Ｆ４７８、Ｆ４７９、Ｆ４８０ＳＦ、Ｆ４８２、Ｆ４８３、Ｆ４８４、Ｆ４８６、Ｆ４８７、Ｆ１７２Ｄ、Ｆ１７８Ｋ、Ｆ１７８ＲＭ、ＥＳＭ−１、ＭＣＦ３５０ＳＦ、ＢＬ２０、Ｒ０８、Ｒ６１、Ｒ９０（ＤＩＣ社製）、ディスパロンＬＦ−１９８０、ＬＦ−１９８２、ＬＦ−１９８３，ＬＦ−１９８４，ＬＦ−１９８５（楠本化成株式会社製）などが挙げられる。 As the surfactant, a commercially available one can be used as it is. Examples of the surfactant include, for example, SH28PA, SF8428, DC57, DC190, BY16-004 (manufactured by Toray Dow Corning), Paintad 19, 54 (manufactured by Toray Dow Corning, dimethylpolysiloxane polyoxyalkylene copolymer) , BYK UV3500, UV3510, UV3530, Disperbyk-180 (manufactured by Big Chemie), Silaplane FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM-0411, FM-0421 , FM-0425, FM-DA11, FM-DA21, FM-DA26, FM0711, FM0721, FM-0725, TM-0701, TM-0701T (manufactured by Chisso Corporation), VPS-1001 (manufactured by Wako Pure Chemical Industries), Tego R d 2300, 2200N (manufactured by Tego Chemie), Megafuck F-114, F410, F411, F450, F493, F494, F443, F444, F445, F446, F470, F471, F472SF, F474, F475, R30, F477, F478, F479, F480SF, F482, F483, F484, F486, F487, F172D, F178K, F178RM, ESM-1, MCF350SF, BL20, R08, R61, R90 (manufactured by DIC), Disparon LF-1980, LF-1982, LF-1983, LF-1984, LF-1985 (manufactured by Enomoto Kasei Co., Ltd.) and the like.
本発明の樹脂組成物において、重合開始剤、光増感剤および各種添加剤は発明の効果を損なわない程度であればよく、本発明の化合物と反応性単量体および反応性オリゴマーの合計を１００質量部としたときに、０．０１〜５０質量部の範囲内が好ましい。 In the resin composition of the present invention, the polymerization initiator, photosensitizer and various additives may be of a level that does not impair the effects of the invention, and the total of the compound of the present invention, the reactive monomer and the reactive oligomer. When it is 100 parts by mass, the range of 0.01 to 50 parts by mass is preferable.
本発明における樹脂組成物は、液晶テレビ、ノートパソコン、カーナビゲーションシステム、携帯電話、携帯用ゲーム機などの液晶表示パネルの輝度向上を目的とした集光フィルム（プリズムシート）の成形に好適に使用できる。また、フレネルレンズ、レンチキュラーレンズ、レンズアレイ、マイクロレンズ、グレーティングレンズ、眼鏡レンズ、コンタクトレンズ、人口水晶体レンズ、眼科用レンズ、カメラレンズなどプラスチックレンズ用途にも好適に使用できる。また、光ディスク用コーティング材、光ファイバー用コーティング材、ホログラム、光造形、導光板、光半導体、光部品用接着剤、光回路、太陽電池用部材、照明装置用部材などにも好適に使用可能である。 The resin composition in the present invention is suitably used for forming a light-collecting film (prism sheet) for the purpose of improving the brightness of liquid crystal display panels such as liquid crystal televisions, notebook computers, car navigation systems, mobile phones, and portable game machines. it can. Further, it can be suitably used for plastic lens applications such as Fresnel lenses, lenticular lenses, lens arrays, micro lenses, grating lenses, spectacle lenses, contact lenses, artificial lens lenses, ophthalmic lenses, and camera lenses. It can also be suitably used for optical disk coating materials, optical fiber coating materials, holograms, stereolithography, light guide plates, optical semiconductors, optical component adhesives, optical circuits, solar cell members, lighting device members, and the like. .
以下、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらの実施例のみに限定されるものではない。なお、以下ことわりのない場合、「％」は「質量％」を、「部」は「質量部」をそれぞれ示すものとする。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited only to these Examples. Unless otherwise specified, “%” indicates “mass%” and “part” indicates “mass part”.
（実施例１）化合物（A）の合成
攪拌機、温度計、還流管を備えた５００ｍＬ４つ口フラスコに、９−フルオレノン４５．４部とジクロロメタン３００部と２，３−ジメルカプト−１−プロパノール２５．０部を仕込み、室温下で溶解させた。塩化アルミニウム（ＩＩＩ）１０．１部を分割添加で仕込み、３時間撹拌を続けた。その後、蒸留水３００部を添加し、さらに３０分撹拌した。静置分離後、水層を除去し、水層が中性になるまで水洗を繰り返した。得られた有機層を濃縮し、トルエンに再溶解した後、シリカゲルカラムクロマトグラフィーにより精製した。主成分を含む分画を集め、溶媒を留去して固体を得た（収量：２９．５部）。
攪拌機、温度計、還流管を備えた２００ｍＬ４つ口フラスコに、先に得た固体２９．５部と脱水トルエン２００部とトリエチルアミン５．９部、ｐ−メトキシフェノール０．００５６部を仕込み、室温下で溶解させた。滴下ロートにアクリル酸クロリド５．３部を仕込み、アイスバスでフラスコ内温を０〜１０℃に維持しながら３０分掛けてアクリル酸クロリドの全量を滴下した。滴下終了後、室温まで戻し、１時間撹拌を続けた。その後、蒸留水２００部を添加し、さらに３０分撹拌した。引き続き、５ｗｔ％水酸化ナトリウム水溶液２００部を添加し、１０分間撹拌した。静置分離後、水層を除去した。飽和食塩水２００部を添加し、１０分間撹拌した。静置分離後、水層を除去し、水層が中性になるまで飽和食塩水による水洗を繰り返した。得られた有機層を減圧濃縮し、シリカゲルカラムクロマトグラフィーにより精製した。主成分を含む分画を集め、ｐ−メトキシフェノール０．００４３部を添加して、トルエンを減圧留去して粘調液体を得た（収量：１１．７部、収率：３６％）。
屈折率（ｎＤ，２５℃）：１．６５９
１Ｈ−ＮＭＲ（３００ＭＨｚ）：δ（ＣＤＣｌ３、内部標準ＴＭＳ）３．６６（ｄ、１Ｈ）、３．８１（ｄ、１Ｈ）、４．５０−４．７０（ｍ、３Ｈ）、５．８８（ｄ、１Ｈ）、６．１７（ｑ、１Ｈ）、６．５０（ｄ、１Ｈ），７．２３−７．７３（ｍ、８Ｈ）
ＧＣ−ＭＳ（ＣＩ）：ｍ／ｚ＝３４１［Ｍ＋Ｈ］＋
Example 1 Synthesis of Compound (A) In a 500 mL four-necked flask equipped with a stirrer, a thermometer and a reflux tube, 45.4 parts of 9-fluorenone, 300 parts of dichloromethane and 2,3-dimercapto-1-propanol 25. 0 parts was charged and dissolved at room temperature. 10.1 parts of aluminum (III) chloride was charged in portions, and stirring was continued for 3 hours. Thereafter, 300 parts of distilled water was added and the mixture was further stirred for 30 minutes. After stationary separation, the aqueous layer was removed, and washing with water was repeated until the aqueous layer became neutral. The obtained organic layer was concentrated, redissolved in toluene, and purified by silica gel column chromatography. The fractions containing the main component were collected and the solvent was distilled off to obtain a solid (yield: 29.5 parts).
A 200 mL four-necked flask equipped with a stirrer, a thermometer and a reflux tube was charged with 29.5 parts of the previously obtained solid, 200 parts of dehydrated toluene, 5.9 parts of triethylamine, and 0.0056 part of p-methoxyphenol at room temperature. And dissolved. Into the dropping funnel, 5.3 parts of acrylic acid chloride was charged, and the whole amount of acrylic acid chloride was dropped over 30 minutes while maintaining the temperature in the flask at 0 to 10 ° C. with an ice bath. After completion of dropping, the temperature was returned to room temperature and stirring was continued for 1 hour. Thereafter, 200 parts of distilled water was added and the mixture was further stirred for 30 minutes. Subsequently, 200 parts of a 5 wt% aqueous sodium hydroxide solution was added and stirred for 10 minutes. After stationary separation, the aqueous layer was removed. 200 parts of saturated brine was added and stirred for 10 minutes. After stationary separation, the aqueous layer was removed, and washing with saturated saline was repeated until the aqueous layer became neutral. The obtained organic layer was concentrated under reduced pressure and purified by silica gel column chromatography. Fractions containing the main component were collected, 0.0043 parts of p-methoxyphenol was added, and toluene was distilled off under reduced pressure to obtain a viscous liquid (yield: 11.7 parts, yield: 36%).
Refractive index (nD, 25 ° C.): 1.659
1 H-NMR (300 MHz): δ (CDCl 3 , internal standard TMS) 3.66 (d, 1H), 3.81 (d, 1H), 4.50-4.70 (m, 3H), 5. 88 (d, 1H), 6.17 (q, 1H), 6.50 (d, 1H), 7.23-7.73 (m, 8H)
GC-MS (CI): m / z = 341 [M + H] +
（実施例２）化合物（B）の合成
攪拌機、温度計、還流管を備えた１０００ｍＬ４つ口フラスコに、９−フルオレノン５０部とジクロロメタン５００部とｏ−アミノベンゼンチオール３１．３部を仕込み、室温下で溶解させた。塩化アルミニウム（ＩＩＩ）１１．１部を分割添加で仕込み、３時間撹拌を続けた。その後、蒸留水５００部を添加し、さらに３０分撹拌した。静置分離後、水層を除去し、水層が中性になるまで水洗を繰り返した。得られた有機層を濃縮し、トルエンに再溶解した後、シリカゲルカラムクロマトグラフィーにより精製した。主成分を含む分画を集め、溶媒を留去して固体を得た（収量：２６部）。
攪拌機、温度計、還流管を備えた５００ｍＬ４つ口フラスコに、先に得た固体２６部と乾燥Ｎ，Ｎ−ジメチルホルムアミド２００部と水酸化カリウム７．３部とエチレンカーボネート１１．４部を仕込み、８０℃で1時間撹拌した。その後、室温まで冷却し、トルエン２５０部と蒸留水２５０部を添加し、さらに３０分撹拌した。静置分離後、水層を除去し水層が中性になるまで水洗を繰り返した。得られた有機層を濃縮し、固体を得た（収量：１５部）。
攪拌機、温度計、還流管を備えた２００ｍＬ４つ口フラスコに、先に得た固体１５部と脱水トルエン７７部とトリエチルアミン５．７部、ｐ−メトキシフェノール０．００５４部を仕込み、室温下で溶解させた。滴下ロートにアクリル酸クロリド５．１部を仕込み、アイスバスでフラスコ内温を０〜１０℃に維持しながら３０分掛けてアクリル酸クロリドの全量を滴下した。滴下終了後、室温まで戻し、１時間撹拌を続けた。その後、蒸留水１６７部を添加し、さらに３０分撹拌した。静置分離後、水層を除去し、以後、水層が中性になるまで水洗を繰り返した。得られた有機層を減圧濃縮した。トルエンに溶解させた後、シリカゲルカラムクロマトグラフィーにより精製した。主成分を含む分画を集め、ｐ−メトキシフェノール０．００１６部を添加して、トルエンを減圧留去して粘調液体を得た（収量：３．５部、収率：２．３％）。
屈折率（ｎＤ，２５℃）：１．６８０
粘度（ｍＰａ・ｓ，５０℃）：３９８０
１Ｈ−ＮＭＲ（３００ＭＨｚ）：δ（ＣＤＣｌ３、内部標準ＴＭＳ）３．１１（ｔ、２Ｈ）、４．２８（ｔ、２Ｈ）、５．７７（ｄ、１Ｈ）、６．０３（ｑ、１Ｈ）、６．３３（ｄ、１Ｈ）、６．８９−７．９８（ｍ、１２Ｈ）
ＧＣ−ＭＳ（ＣＩ）：ｍ／ｚ＝３８６［Ｍ＋Ｈ］＋
Example 2 Synthesis of Compound (B) A 1000 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux tube was charged with 50 parts of 9-fluorenone, 500 parts of dichloromethane and 31.3 parts of o-aminobenzenethiol at room temperature. Dissolved below. 11.1 parts of aluminum (III) chloride was charged in portions, and stirring was continued for 3 hours. Thereafter, 500 parts of distilled water was added and the mixture was further stirred for 30 minutes. After stationary separation, the aqueous layer was removed, and washing with water was repeated until the aqueous layer became neutral. The obtained organic layer was concentrated, redissolved in toluene, and purified by silica gel column chromatography. Fractions containing the main component were collected and the solvent was distilled off to obtain a solid (yield: 26 parts).
A 500 mL four-necked flask equipped with a stirrer, a thermometer and a reflux tube is charged with 26 parts of the previously obtained solid, 200 parts of dry N, N-dimethylformamide, 7.3 parts of potassium hydroxide and 11.4 parts of ethylene carbonate. And stirred at 80 ° C. for 1 hour. Then, it cooled to room temperature, 250 parts of toluene and 250 parts of distilled water were added, and also it stirred for 30 minutes. After stationary separation, the aqueous layer was removed, and washing with water was repeated until the aqueous layer became neutral. The obtained organic layer was concentrated to obtain a solid (yield: 15 parts).
A 200 mL four-necked flask equipped with a stirrer, thermometer and reflux tube is charged with 15 parts of the previously obtained solid, 77 parts of dehydrated toluene, 5.7 parts of triethylamine, and 0.0054 part of p-methoxyphenol, and dissolved at room temperature. I let you. Into the dropping funnel, 5.1 parts of acrylic acid chloride was charged, and the whole amount of acrylic acid chloride was dropped over 30 minutes while maintaining the flask internal temperature at 0 to 10 ° C. with an ice bath. After completion of dropping, the temperature was returned to room temperature and stirring was continued for 1 hour. Thereafter, 167 parts of distilled water was added, and the mixture was further stirred for 30 minutes. After standing and separation, the aqueous layer was removed, and thereafter water washing was repeated until the aqueous layer became neutral. The obtained organic layer was concentrated under reduced pressure. After dissolving in toluene, it was purified by silica gel column chromatography. Fractions containing the main component were collected, 0.0016 part of p-methoxyphenol was added, and toluene was distilled off under reduced pressure to obtain a viscous liquid (yield: 3.5 parts, yield: 2.3%). ).
Refractive index (nD, 25 ° C.): 1.680
Viscosity (mPa · s, 50 ° C.): 3980
1 H-NMR (300 MHz): δ (CDCl 3 , internal standard TMS) 3.11 (t, 2H), 4.28 (t, 2H), 5.77 (d, 1H), 6.03 (q, 1H), 6.33 (d, 1H), 6.89-7.98 (m, 12H)
GC-MS (CI): m / z = 386 [M + H] +
（実施例３）化合物（C）の合成
攪拌機、温度計、還流管を備えた５００ｍＬ４つ口フラスコに、９−フルオレノン５０部とクロロホルム２５０部と２−アミノエタンチオール２１．４部を仕込み、室温下で溶解させた。三フッ化ホウ素・ジエチルエーテル酢体１．６３部を仕込み、３９時間還流させた。その後、蒸留水２００部を添加し、さらに３０分撹拌した。静置分離後、水層を除去し、水層が中性になるまで水洗を繰り返した。得られた有機層を濃縮し、トルエンに再溶解した後、シリカゲルカラムクロマトグラフィーにより精製した。主成分を含む分画を集め、溶媒を留去して固体を得た（収量：４４部）。
攪拌機、温度計、還流管を備えた５００ｍＬ４つ口フラスコに、先に得た固体２５部と乾燥Ｎ，Ｎ−ジメチルホルムアミド２５０部と２−ブロモエタノール２６．１部とトリエチルアミン２１．１部を仕込み、１００℃で1２時間撹拌した。その後、室温まで冷却し、トルエン２５０部と蒸留水２５０部を添加し、さらに３０分撹拌した。静置分離後、水層を除去し水層が中性になるまで飽和食塩水で洗浄を繰り返した。得られた有機層を濃縮し、トルエンに再溶解した後、シリカゲルカラムクロマトグラフィーにより精製した。主成分を含む分画を集め、溶媒を留去して液体を得た（収量：１２．９部）。
攪拌機、温度計、還流管を備えた２００ｍＬ４つ口フラスコに、先に得た液体１２．９部と脱水トルエン６４．６部とトリエチルアミン５．５部、ｐ−メトキシフェノール０．００５０部を仕込み、室温下で溶解させた。滴下ロートにアクリル酸クロリド５．０部を仕込み、アイスバスでフラスコ内温を０〜１０℃に維持しながら３０分掛けてアクリル酸クロリドの全量を滴下した。滴下終了後、室温まで戻し、２時間撹拌を続けた。その後、蒸留水１００部を添加し、さらに３０分撹拌した。静置分離後、水層を除去し、以後、水層が中性になるまで飽和食塩水で洗浄を繰り返した。得られた有機層を減圧濃縮した。トルエンに溶解させた後、シリカゲルカラムクロマトグラフィーにより精製した。主成分を含む分画を集め、ｐ−メトキシフェノール０．００２２部を添加して、トルエンを減圧留去して粘調液体を得た（収量：４．９部、収率：９％）。
屈折率（ｎＤ，２５℃）：１．６２９
粘度（ｍＰａ・ｓ，５０℃）：１６８０
１Ｈ−ＮＭＲ（３００ＭＨｚ）：δ（ＣＤＣｌ３、内部標準ＴＭＳ） ２．２４（ｔ、２Ｈ）、３．３８（ｔ、２Ｈ）、３．６７（ｔ、２Ｈ）、３．９７（ｔ、２Ｈ）、５．７８（ｄ、１Ｈ），６．００（ｑ、１Ｈ）、６．３０（ｄ、１Ｈ）、７．２４−７．５９（ｍ、８Ｈ）
ＧＣ−ＭＳ（ＣＩ）：ｍ／ｚ＝３３８［Ｍ＋Ｈ］＋
Example 3 Synthesis of Compound (C) A 500 mL four-necked flask equipped with a stirrer, a thermometer and a reflux tube was charged with 50 parts of 9-fluorenone, 250 parts of chloroform and 21.4 parts of 2-aminoethanethiol at room temperature. Dissolved below. Boron trifluoride / diethyl ether vinegar (1.63 parts) was charged and refluxed for 39 hours. Thereafter, 200 parts of distilled water was added and the mixture was further stirred for 30 minutes. After stationary separation, the aqueous layer was removed, and washing with water was repeated until the aqueous layer became neutral. The obtained organic layer was concentrated, redissolved in toluene, and purified by silica gel column chromatography. Fractions containing the main component were collected and the solvent was distilled off to obtain a solid (yield: 44 parts).
A 500 mL four-necked flask equipped with a stirrer, a thermometer and a reflux tube is charged with 25 parts of the previously obtained solid, 250 parts of dry N, N-dimethylformamide, 26.1 parts of 2-bromoethanol, and 21.1 parts of triethylamine. And stirred at 100 ° C. for 12 hours. Then, it cooled to room temperature, 250 parts of toluene and 250 parts of distilled water were added, and also it stirred for 30 minutes. After stationary separation, the aqueous layer was removed, and washing with saturated brine was repeated until the aqueous layer became neutral. The obtained organic layer was concentrated, redissolved in toluene, and purified by silica gel column chromatography. The fractions containing the main component were collected and the solvent was distilled off to obtain a liquid (yield: 12.9 parts).
A 200 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux tube was charged with 12.9 parts of the liquid obtained previously, 64.6 parts of dehydrated toluene, 5.5 parts of triethylamine, and 0.0050 part of p-methoxyphenol. It was dissolved at room temperature. A dropping funnel was charged with 5.0 parts of acrylic acid chloride, and the entire amount of acrylic acid chloride was added dropwise over 30 minutes while maintaining the flask internal temperature at 0 to 10 ° C. with an ice bath. After completion of dropping, the temperature was returned to room temperature and stirring was continued for 2 hours. Thereafter, 100 parts of distilled water was added and the mixture was further stirred for 30 minutes. After standing and separation, the aqueous layer was removed, and thereafter, washing with saturated brine was repeated until the aqueous layer became neutral. The obtained organic layer was concentrated under reduced pressure. After dissolving in toluene, it was purified by silica gel column chromatography. Fractions containing the main component were collected, 0.0022 part of p-methoxyphenol was added, and toluene was distilled off under reduced pressure to obtain a viscous liquid (yield: 4.9 parts, yield: 9%).
Refractive index (nD, 25 ° C.): 1.629
Viscosity (mPa · s, 50 ° C.): 1680
1 H-NMR (300 MHz): δ (CDCl 3, internal standard TMS) 2.24 (t, 2 H), 3.38 (t, 2 H), 3.67 (t, 2 H), 3.97 (t, 2 H ), 5.78 (d, 1H), 6.00 (q, 1H), 6.30 (d, 1H), 7.24-7.59 (m, 8H)
GC-MS (CI): m / z = 338 [M + H] +
（実施例４）化合物（Ｄ）の合成
攪拌機、温度計を備えた５００ｍＬ３つ口フラスコに、９−フルオレノン１０．０部とクロロホルム１５０部と１，２，３−トリメルカプトプロパン９．０部とヨウ素１．５２部を仕込み、室温下で１８時間撹拌した。その後、トルエンから再結晶し、白色固体を得た（収量：５．０部）。
攪拌機、温度計、還流管を備えた２００ｍＬ４つ口フラスコに、先に得た白色固体５．０部と脱水トルエン５０部を仕込み、室温下で溶解させ、その後、窒素雰囲気下で５０℃に加熱した。滴下ロートに３−クロロプロピオン酸クロリド２．８部を仕込み、３０分掛けて３−クロロプロピオン酸クロリドの全量を滴下した。滴下終了後、室温まで戻し、３０時間撹拌を続けた。その後、炭酸水素ナトリウム水を添加し、３０分撹拌した。静置分離後、水層を除去し、炭酸水素ナトリウムで乾燥させた。ろ過後、減圧濃縮し、濃縮物をアセトンに溶解させ、過剰のトリエチルアミンを添加し、一昼夜撹拌した。その後、蒸留水を添加し、１０分間撹拌した。静置分離後、水層を除去し、クエン酸水溶液と炭酸水素ナトリウム水で洗浄した。静置分離後、水層を除去し、有機層を硫酸ナトリウムで乾燥させ、ろ過後、濃縮した。濃縮物をトルエンを用いたシリカゲルカラムクロマトグラフィーによって精製した。主成分を含む分画を集め、ｐ−メトキシフェノール０．００４部を添加して、トルエンを減圧留去して粘調液体を得た（収量：２．２部、収率：３４％）。
屈折率（ｎＤ，２５℃）：１．６７８
粘度（ｍＰａ・ｓ，５０℃）：１５３０
１Ｈ−ＮＭＲ（３００ＭＨｚ）：δ（ＣＤＣｌ３、内部標準ＴＭＳ） ３．５５−３．９４（ｍ、４Ｈ）、４．４５（ｍ、１Ｈ）、５．７８（ｄ、１Ｈ）、６．４０（ｍ，２Ｈ）、７．２８−７．８７（ｍ、８Ｈ）
ＧＣ−ＭＳ（ＣＩ）：ｍ／ｚ＝３５７［Ｍ＋Ｈ］＋
Example 4 Synthesis of Compound (D) In a 500 mL three-necked flask equipped with a stirrer and a thermometer, 10.0 parts of 9-fluorenone, 150 parts of chloroform, and 9.0 parts of 1,2,3-trimercaptopropane 1.52 parts of iodine was charged and stirred at room temperature for 18 hours. Thereafter, it was recrystallized from toluene to obtain a white solid (yield: 5.0 parts).
A 200 mL four-necked flask equipped with a stirrer, thermometer, and reflux tube is charged with 5.0 parts of the previously obtained white solid and 50 parts of dehydrated toluene, dissolved at room temperature, and then heated to 50 ° C. under a nitrogen atmosphere. did. The dropping funnel was charged with 2.8 parts of 3-chloropropionic acid chloride, and the entire amount of 3-chloropropionic acid chloride was added dropwise over 30 minutes. After completion of the dropping, the temperature was returned to room temperature and stirring was continued for 30 hours. Then, sodium hydrogen carbonate water was added and stirred for 30 minutes. After stationary separation, the aqueous layer was removed and dried over sodium bicarbonate. After filtration, the filtrate was concentrated under reduced pressure, the concentrate was dissolved in acetone, excess triethylamine was added, and the mixture was stirred overnight. Then, distilled water was added and stirred for 10 minutes. After stationary separation, the aqueous layer was removed and washed with an aqueous citric acid solution and aqueous sodium hydrogen carbonate. After stationary separation, the aqueous layer was removed, and the organic layer was dried over sodium sulfate, filtered and concentrated. The concentrate was purified by silica gel column chromatography using toluene. Fractions containing the main component were collected, 0.004 part of p-methoxyphenol was added, and toluene was distilled off under reduced pressure to obtain a viscous liquid (yield: 2.2 parts, yield: 34%).
Refractive index (nD, 25 ° C.): 1.678
Viscosity (mPa · s, 50 ° C.): 1530
1 H-NMR (300 MHz): δ (CDCl 3 , internal standard TMS) 3.55-3.94 (m, 4H), 4.45 (m, 1H), 5.78 (d, 1H), 6. 40 (m, 2H), 7.28-7.87 (m, 8H)
GC-MS (CI): m / z = 357 [M + H] +
（実施例５）化合物（Ｅ）の合成
実施例１と同様の方法で、２，３−ジメルカプト−１−プロパノールの代わりに１−チオグリセロールを用いて、４−アクリロキシメチル−スピロ［［１，３］オキソチオラン−２，９‘−フルオレン］を合成した（収量：１０．２部、収率：３３％）
屈折率（ｎＤ，２５℃）：１．６３７
１Ｈ−ＮＭＲ（３００ＭＨｚ）：δ（ＣＤＣｌ３、内部標準ＴＭＳ） ３．５５（ｄ、２Ｈ）、３．７２−４．２５（ｍ、３Ｈ）、５．８０（ｄ、１Ｈ）、６．１０（ｑ，Ｈ）、６．３３（ｄ、１Ｈ）、７．２０−７．８５（ｍ、８Ｈ）
ＧＣ−ＭＳ（ＣＩ）：ｍ／ｚ＝３２５［Ｍ＋Ｈ］＋
(Example 5) Synthesis of Compound (E) In the same manner as in Example 1, 4-acryloxymethyl-spiro [[1 was used by using 1-thioglycerol instead of 2,3-dimercapto-1-propanol. , 3] oxothiolane-2,9′-fluorene] (yield: 10.2 parts, yield: 33%).
Refractive index (nD, 25 ° C.): 1.637
1 H-NMR (300 MHz): δ (CDCl 3 , internal standard TMS) 3.55 (d, 2H), 3.72-4.25 (m, 3H), 5.80 (d, 1H), 6. 10 (q, H), 6.33 (d, 1H), 7.20-7.85 (m, 8H)
GC-MS (CI): m / z = 325 [M + H] +
（実施例６）化合物（Ｆ）の合成
実施例１と同様の方法で、２，３−ジメルカプト−１−プロパノールの代わりに２，２−ビス（メルカプトメチル）−１，３−プロパンジオールを用いて、５，５―ジアクリロキシメチル−スピロ［［１，３］ジチオラン−２，９‘−フルオレン］を合成した（収量：７．５部、収率：１８％）
屈折率（ｎＤ，２５℃）：１．６４１
１Ｈ−ＮＭＲ（３００ＭＨｚ）：δ（ＣＤＣｌ３、内部標準ＴＭＳ）３．３３（ｓ、４Ｈ）、４．０５（ｓ、４Ｈ），５．５５（ｄ、２Ｈ），６．０３（ｑ、２Ｈ），６．３０（ｄ、２Ｈ）、７．２５―７．８５（ｍ、８Ｈ）
ＧＣ−ＭＳ（ＣＩ）：ｍ／ｚ＝４３９［Ｍ＋Ｈ］＋
Example 6 Synthesis of Compound (F) In the same manner as in Example 1, 2,2-bis (mercaptomethyl) -1,3-propanediol was used instead of 2,3-dimercapto-1-propanol. 5,5-Diacryloxymethyl-spiro [[1,3] dithiolane-2,9′-fluorene] was synthesized (yield: 7.5 parts, yield: 18%).
Refractive index (nD, 25 ° C.): 1.641
1 H-NMR (300 MHz): δ (CDCl 3 , internal standard TMS) 3.33 (s, 4H), 4.05 (s, 4H), 5.55 (d, 2H), 6.03 (q, 2H), 6.30 (d, 2H), 7.25-7.85 (m, 8H)
GC-MS (CI): m / z = 439 [M + H] +
（実施例７）
実施例１で得られた化合物５０部とオグソールＥＡ−０２００（化合物名：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式会社）５０部とシクロヘキサノン２４６部を配合して組成物を得た。
この組成物にイルガキュア１８４（チバスペシャリティ・ケミカルズ社製）の６部とディスパロンＬＦ−１９８５（楠本化成株式会社製）２部を配合し、７６μｍのアプリケーターを用いてＰＥＴ基材上に塗布し、５００ｍＪ／ｃｍ２の高圧水銀灯を用いて紫外線を照射することにより、硬化物を得た。硬化性は良好であった。硬化物の屈折率（ｎＤ、２５℃）は１．６３９であった。
(Example 7)
50 parts of the compound obtained in Example 1 and 50 parts of Ogsol EA-0200 (compound name: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, Osaka Gas Chemical Co., Ltd.) and 246 parts of cyclohexanone. Was added to obtain a composition.
To this composition, 6 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals) and 2 parts of Disparon LF-1985 (manufactured by Enomoto Kasei Co., Ltd.) are blended and applied onto a PET substrate using a 76 μm applicator. A cured product was obtained by irradiating with ultraviolet rays using a high-pressure mercury lamp of / cm 2 . The curability was good. The refractive index (nD, 25 ° C.) of the cured product was 1.639.
（実施例８）〜（実施例１２）
実施例７の実施例１で得られた化合物５０部の替わりに、表１に記載のアクリル酸エステル誘導体を用いる他は、実施例７と同様にして実施例８〜１２を行った。得られた硬化物の屈折率を表１に示す。
(Example 8) to (Example 12)
Examples 8 to 12 were carried out in the same manner as in Example 7 except that 50 parts of the compound obtained in Example 1 of Example 7 was used instead of the acrylate derivatives shown in Table 1. The refractive index of the obtained cured product is shown in Table 1.
以上の結果より、本発明の化合物は低粘度かつ高屈折率であり、本発明の硬化物は高屈折率であった。特許文献１のフルオレン化合物は固体であり、特許文献２のフルオレン化合物は３３０１０ｍＰａ・ｓと高粘度であることから、本発明の化合物が高屈折かつ低粘度の化合物であることは明白であり、光学材料用途として有用である。 From the above results, the compound of the present invention has a low viscosity and a high refractive index, and the cured product of the present invention has a high refractive index. Since the fluorene compound of Patent Document 1 is a solid and the fluorene compound of Patent Document 2 has a high viscosity of 33010 mPa · s, it is clear that the compound of the present invention is a compound having a high refraction and a low viscosity. It is useful as a material application.
本発明における新規（メタ）アクリル酸エステルは、光学材料として利用可能である。 The novel (meth) acrylic acid ester in the present invention can be used as an optical material.
Claims (5)
Ｚは、−（CH２）ｎ−（式中、ｎは１〜５のいずれかの整数を表す）で表される2価の基、フェニレン基又はナフチレン基であり、
Ｚ中の少なくとも一つの水素原子は式（２）で表される基で置換されていてもよく、
式（１）で表される化合物は、式（２）で表される基を少なくとも一つ有する。） A compound represented by the following formula (1).
Z is a divalent group represented by — (CH 2 ) n — (wherein n represents any integer of 1 to 5), a phenylene group, or a naphthylene group,
At least one hydrogen atom in Z may be substituted with a group represented by the formula (2),
The compound represented by the formula (1) has at least one group represented by the formula (2). )
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