WO2015068839A1 - Polymerizable compound, resin composition using same, cured resin, and optical material - Google Patents
Polymerizable compound, resin composition using same, cured resin, and optical material Download PDFInfo
- Publication number
- WO2015068839A1 WO2015068839A1 PCT/JP2014/079728 JP2014079728W WO2015068839A1 WO 2015068839 A1 WO2015068839 A1 WO 2015068839A1 JP 2014079728 W JP2014079728 W JP 2014079728W WO 2015068839 A1 WO2015068839 A1 WO 2015068839A1
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- WIPO (PCT)
- Prior art keywords
- group
- carbon atoms
- meth
- polymerizable compound
- acrylate
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 192
- 229920005989 resin Polymers 0.000 title claims abstract description 91
- 239000011347 resin Substances 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 86
- 230000003287 optical effect Effects 0.000 title claims abstract description 45
- 239000011342 resin composition Substances 0.000 title claims abstract description 36
- 125000003118 aryl group Chemical group 0.000 claims abstract description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 17
- 125000005110 aryl thio group Chemical group 0.000 claims abstract description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 10
- -1 thioalkylene group Chemical group 0.000 claims description 128
- 125000004432 carbon atom Chemical group C* 0.000 claims description 73
- 239000011159 matrix material Substances 0.000 claims description 57
- 125000001424 substituent group Chemical group 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- 125000004434 sulfur atom Chemical group 0.000 claims description 12
- 125000004414 alkyl thio group Chemical group 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000004104 aryloxy group Chemical group 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 8
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 8
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 135
- 238000006243 chemical reaction Methods 0.000 description 84
- 239000012043 crude product Substances 0.000 description 58
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- 239000000203 mixture Substances 0.000 description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- 239000002904 solvent Substances 0.000 description 37
- 230000015572 biosynthetic process Effects 0.000 description 30
- 238000003786 synthesis reaction Methods 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 24
- 239000002274 desiccant Substances 0.000 description 23
- 239000012044 organic layer Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 19
- 239000004593 Epoxy Substances 0.000 description 18
- 238000000746 purification Methods 0.000 description 18
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 16
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical class OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- 230000035945 sensitivity Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000003505 polymerization initiator Substances 0.000 description 15
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 150000001491 aromatic compounds Chemical class 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical class OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 description 9
- 239000012279 sodium borohydride Substances 0.000 description 9
- NADUDFSNHZPLIN-UHFFFAOYSA-N 2-ethenylbenzenethiol Chemical compound SC1=CC=CC=C1C=C NADUDFSNHZPLIN-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 8
- PZUGJLOCXUNFLM-UHFFFAOYSA-N n-ethenylaniline Chemical compound C=CNC1=CC=CC=C1 PZUGJLOCXUNFLM-UHFFFAOYSA-N 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- 239000007870 radical polymerization initiator Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- QEWHNJPLPZOEKU-UHFFFAOYSA-N 1-(2,4-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1F QEWHNJPLPZOEKU-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical group C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- MRLUWCIEBHJONW-UHFFFAOYSA-N 1-phenyl-2-phenylsulfanylethanone Chemical compound C=1C=CC=CC=1C(=O)CSC1=CC=CC=C1 MRLUWCIEBHJONW-UHFFFAOYSA-N 0.000 description 4
- 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 4
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical class C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000013307 optical fiber Substances 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- BMNPSNUIGOGEDS-UHFFFAOYSA-N 1-[2,4-bis(phenylsulfanyl)phenyl]ethanol Chemical compound OC(C)C1=C(C=C(C=C1)SC1=CC=CC=C1)SC1=CC=CC=C1 BMNPSNUIGOGEDS-UHFFFAOYSA-N 0.000 description 3
- CFKNYGPNWDOHRT-UHFFFAOYSA-N 1-ethenyl-2,4-bis(phenylsulfanyl)benzene Chemical compound C1(=CC=CC=C1)SC1=C(C=C)C=CC(=C1)SC1=CC=CC=C1 CFKNYGPNWDOHRT-UHFFFAOYSA-N 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000012663 cationic photopolymerization Methods 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- RKPWOUFGYKPCEI-UHFFFAOYSA-N 1-(2-naphthalen-2-ylsulfanyl-4-phenylsulfanylphenyl)ethanol Chemical compound OC(C)C1=C(C=C(C=C1)SC1=CC=CC=C1)SC1=CC2=CC=CC=C2C=C1 RKPWOUFGYKPCEI-UHFFFAOYSA-N 0.000 description 2
- XUDYHODVSUXRPW-UHFFFAOYSA-N 1-(4-phenylsulfanylphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1SC1=CC=CC=C1 XUDYHODVSUXRPW-UHFFFAOYSA-N 0.000 description 2
- YCQIGDVJBOVZKY-UHFFFAOYSA-N 1-[2,4,6-tris(phenylsulfanyl)phenyl]ethanol Chemical compound OC(C)C1=C(C=C(C=C1SC1=CC=CC=C1)SC1=CC=CC=C1)SC1=CC=CC=C1 YCQIGDVJBOVZKY-UHFFFAOYSA-N 0.000 description 2
- AYJITJSQKMVMBL-UHFFFAOYSA-N 1-[2,4-bis(naphthalen-2-ylsulfanyl)phenyl]ethanol Chemical compound OC(C)C1=C(C=C(C=C1)SC1=CC2=CC=CC=C2C=C1)SC1=CC2=CC=CC=C2C=C1 AYJITJSQKMVMBL-UHFFFAOYSA-N 0.000 description 2
- JAOKCZRGVVWGAM-UHFFFAOYSA-N 1-[2,4-bis[(4-methylsulfanylphenyl)sulfanyl]phenyl]ethanol Chemical compound OC(C)C1=C(C=C(C=C1)SC1=CC=C(C=C1)SC)SC1=CC=C(C=C1)SC JAOKCZRGVVWGAM-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 2
- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- PTGSABHWFWZJSO-UHFFFAOYSA-N 2-(2-ethenyl-5-naphthalen-2-ylsulfanylphenyl)sulfanylnaphthalene Chemical compound C1=C(C=CC2=CC=CC=C12)SC1=C(C=C)C=CC(=C1)SC1=CC2=CC=CC=C2C=C1 PTGSABHWFWZJSO-UHFFFAOYSA-N 0.000 description 2
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical class C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/30—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a heterocyclic ring containing sulfur
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/2403—Layers; Shape, structure or physical properties thereof
- G11B7/24035—Recording layers
- G11B7/24044—Recording layers for storing optical interference patterns, e.g. holograms; for storing data in three dimensions, e.g. volume storage
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H2001/026—Recording materials or recording processes
- G03H2001/0264—Organic recording material
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/245—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing a polymeric component
Definitions
- the present invention relates to a polymerizable compound having a high refractive index and excellent in transparency, handling properties, and the like, a resin composition using the same, a cured resin and an optical material, particularly a holographic recording material and a holographic recording medium It is about.
- optical resins have been actively used in various optical fields, and (meth) acrylic resins such as polymethylmethacrylate are well known as materials thereof.
- optical resin materials typified by (meth) acrylic resins have lightness, safety, and design properties, but have a disadvantage of low refractive index. Therefore, in recent years, there has been an increasing demand for optical resins having a high refractive index, such as liquid crystal display panels, color filters, spectacle lenses, Fresnel lenses, lenticular lenses, TFT prism lens sheets, aspherical lenses, optical fibers.
- Studies on optical waveguides, optical recording materials, and the like have been actively conducted.
- optical recording materials particularly holographic recording materials
- the development of high refractive index materials for achieving a high degree of refractive index modulation, a large M # (M number), and high sensitivity has become a major issue.
- a high refractive index monomer as a raw material polymerizable compound (hereinafter also referred to as a monomer). It is theoretically known that introduction of halogen atoms (chlorine, bromine, iodine), sulfur atoms and heavy metal atoms is effective.
- monomers having an aromatic ring in the molecular structure for example, those having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene and anthracene in addition to a benzene ring are known (Patent Documents 1 and 2, etc.).
- the refractive index of a monomer having a single benzene ring in the molecular structure is not sufficient.
- monomers having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene, and anthracene in the molecular structure are expected to have a high refractive index, but in most cases become a high-viscosity liquid or a crystalline solid. There is a problem that handling property is lowered. Furthermore, there is a problem that not only the transparency is lowered but also the photocurability and the weather resistance are lowered by increasing the absorption wavelength.
- a monomer having a diphenyl sulfide structure in the molecular structure has a higher refractive index than a monomer having a single benzene ring.
- the higher the viscosity and the longer the absorption wavelength the less the monomer having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene, anthracene, etc., handling properties such as solubility, transparency, photocurability, weather resistance
- the advantage that there are few problems of the fall of can be expected.
- Patent Documents 3 to 6, etc. So far, several polymerizable compounds having a diphenyl sulfide structure in the molecular structure have been synthesized (Patent Documents 3 to 6, etc.). However, even the polymerizable compounds disclosed in the patent documents listed here are insufficient in terms of high refractive index, transparency and handling properties, and further creation of improved polymerizable compounds is required. ing.
- Holographic recording is performed by recording interference fringes generated by simultaneously irradiating reference light together with signal light having image information on a recording medium as a diffraction grating (hereinafter also referred to as a grating).
- the reproduction from the recording medium is performed by irradiating the recording medium on which the image information is recorded with reference light and reading out the image information as reproduction signal light from the diffraction grating.
- the above-mentioned image information can be recorded and reproduced as a single page in a batch, and multiple pages can be recorded at the same location on the medium. Therefore, bit-by-bit used in conventional CDs, DVDs, and Blu-ray discs. This technology is expected as a high transfer rate and large capacity optical recording system that replaces the bit recording system.
- a holographic recording material As a holographic recording material, a photopolymer in which a recording polymerizable compound and a photopolymerization initiator are dispersed in a matrix resin is used in consideration of the convenience of recording medium production and diversity of raw material selection. There are many cases.
- a holographic recording medium using a photopolymer a write-once type in which interference fringes are recorded as a refractive index modulation diffraction grating is generally used.
- M # is an index representing the multiplex recording performance, and is a numerical value represented by the following formula (I) when the diffraction efficiency of the i-th page is ⁇ i in the m-multiplex recorded signal.
- a high recording sensitivity is required because it is necessary to obtain a sufficient diffraction efficiency with a short recording exposure in order to achieve a high transfer rate.
- Holographic recording is performed by irradiating a photopolymer with interference fringes (light contrast) obtained by crossing coherent light. Photopolymerization occurs in the bright part of the interference fringes during light irradiation, and the polymerizable compound is consumed to produce a polymer. The polymerizable compound is supplied by diffusion transfer from the dark part to the bright part of the interference fringes so as to compensate for the concentration gradient of the polymerizable compound generated at this time. In this way, the interference fringe pattern is fixed in the photopolymer as a refractive index distribution (Non-Patent Document 1).
- the matrix resin and the polymerizable compound are advantageous to select so that the difference in refractive index is as large as possible.
- the polymerizable compound should have a refractive index as high as possible. It is desirable to use it.
- examples of the high refractive index polymerizable compound include condensed (hetero) aryl groups and bromine-substituted aryl groups such as N-vinylcarbazole, bromostyrene, and tribromophenyl acrylate described in Patent Documents 7 to 9. There are those that have.
- Patent Documents 10 to 12 report that a holographic recording material and a recording medium having high diffraction efficiency and sensitivity can be obtained by using a polymerizable compound having a sulfur-containing fused ring structure.
- the difference in refractive index and the compatibility are in a trade-off relationship.
- the refractive index of the polymerizable compound is improved to improve the diffraction efficiency, the matrix resin and the polymerizable compound or a polymer thereof are not affected. Compatibility is deteriorated.
- Even the polymerizable compounds disclosed in the patent documents listed here are insufficient from the viewpoint of diffraction efficiency, light transmittance, and compatibility, and the creation of further improved polymerizable compounds is demanded.
- JP-A-5-170702 JP 2004-83855 A Japanese Patent Laid-Open No. 2-113005 JP 2005-145861 A JP 2010-186979 A Korean Patent No. 1254325 (KR2012-40799A) JP-A-10-105030 Japanese Patent Laid-Open No. 11-352303 JP 2005-502918 A JP 2005-43507 A JP 2005-114848 A JP 2010-18606 A
- the diffraction efficiency of the holographic recording medium is proportional to the recording density per medium surface, and the value can be expressed by the refractive index modulation degree from the Kogelnik theory of the following equation (II).
- ⁇ is the diffraction efficiency
- ⁇ n is the refractive index modulation degree
- ⁇ is the reproduction wavelength
- ⁇ B is the reproduction angle.
- the degree of modulation of the refractive index is the difference in refractive index between the light irradiated part and the non-irradiated part.
- the holographic recording medium before recording is uniformly dispersed in a state where the polymerizable compound is compatible with the matrix resin.
- this holographic recording medium is irradiated with interference fringes for recording, photopolymerization starts in the bright part of the interference fringes, and the polymerizable compound is consumed to produce a polymer.
- the polymerizable compound is supplied by diffusion transfer from the dark part to the bright part of the interference fringes, and the polymerization continues, and the polymerization causes an increase in density.
- the concentration of the polymerizable compound decreases in the dark part of the interference fringes.
- the refractive index of the polymerizable compound when the refractive index of the polymerizable compound is higher than the refractive index of the matrix resin, the refractive index increases with respect to the non-irradiated portion due to the increase in density due to polymerization and the concentration of the polymerizable compound in the light irradiated portion.
- the refractive index in the non-irradiated portion, the refractive index is further lowered than the state before recording due to the decrease in the polymerizable compound concentration. Therefore, a refractive index difference is formed between the light irradiation part and the non-irradiation part.
- the refractive index of the polymerizable compound When the refractive index of the polymerizable compound is lower than the refractive index of the matrix resin, the refractive index increases in the light-irradiated part than in the non-irradiated part due to polymerization. The width is suppressed. Furthermore, since the refractive index increases due to a decrease in the concentration of the polymerizable compound in the non-irradiated part, the difference in refractive index between the light-irradiated part and the non-irradiated part is larger than that when the polymerizable compound has a higher refractive index than the matrix resin. Smaller.
- the refractive index of the polymerizable compound is larger than the refractive index of the matrix resin and that the difference is large.
- M # increases as the multiplicity increases. Further, M # is calculated from the diffraction efficiency, and it can be seen from the formula (II) that the diffraction efficiency increases as the refractive index modulation degree increases. From these facts, the diffraction efficiency can be increased as the difference in the refractive index between the light-irradiated portion and the non-irradiated portion is increased, and further, improvement in M # can be achieved.
- the present invention provides a polymerizable compound having a high refractive index, a high light transmittance, and a low viscosity, and a resin composition, a cured resin and an optical material using the polymerizable compound, and further when used as a holographic recording material. It is an object to provide a holographic recording material containing the polymerizable compound capable of obtaining a large M # and high sensitivity, and a holographic recording medium capable of realizing a large capacity (high density) and a high transfer rate using the material. To do.
- R 1 to R 5 are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a carbon atom having 6 to 10 carbon atoms.
- X 1 is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms, wherein the alkylene group, oxyalkylene group, thioalkylene group, alkyleneoxy group and alkylenethio group may have a substituent,
- the substituent of is a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a carbon number 6 to 10 arylthio groups.
- R 6 is a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, an optionally substituted vinylaryl group or a vinylaryloyl group.
- the -S-Ar Ar 1 of 1 represents an aryl group or ring members 5-14 heterocyclic aryl group ring members 6-14, also may have combined two or more rings are condensed, substituted It may be.
- the substituent is chlorine atom, bromine atom, alkyl group having 1 to 4 carbon atoms, alkyloxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, phenyloxy group or phenylthio group. In the case where these are a phenyloxy group or a phenylthio group, they may further have a substituent similar to the substituent.
- R 1 ⁇ R 5 it is -S-Ar 1, or two or but three R 1 ⁇ R 5, more excellent If it is -S-Ar 1 It becomes a polymerizable compound.
- the present invention also includes a resin composition characterized by containing the polymerizable compound, a resin cured product obtained by curing the resin composition, and the resin composition or resin cured product. It is an optical material characterized by this.
- the present invention relates to a holographic recording material containing the polymerizable compound.
- the holographic recording material may be a holographic recording material containing A) the polymerizable compound, B) a matrix resin or a matrix resin forming component, and C) a photopolymerization initiator.
- one of R 1 to R 5 is —S—Ar 1
- two or three of R 1 to R 5 are —S—Ar 1
- a refractive index n D at 25 ° C. of the compound of 1.60 or more gives a better holographic recording material.
- Examples of the matrix resin include isocyanate-hydroxyl polyadducts, and examples of the matrix resin forming material include materials containing polyisocyanate and polyol.
- the present invention also provides a holographic recording medium comprising a recording layer containing the holographic recording material.
- the polymerizable compound of the present invention is higher in refractive index, transparency and handling than conventional polymerizable compounds, glass substitute materials for lens applications, and protective film materials for color filters for liquid crystal displays.
- Resin compositions useful for various optical materials such as coating materials for protecting optical products, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, optical recording materials for hologram recording media, and curing Can give things.
- the optical material as used in the present invention means a material used for light transmitting or reflecting light, and is preferably an optical material for light transmission such as for lenses and light transmission films. More preferably, it is an optical material for lens use.
- the polymerizable compound used in the holographic recording material of the present invention is compatible with the refractive index modulation and compatibility, and without causing turbidity or scattering, the holographic recording material using the polymerizable compound is , Large M #, high sensitivity.
- the polymerizable compound of the present invention is represented by the general formula (1).
- R 1 to R 5 are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms.
- one, two or three of R 1 to R 5 are the arylthio group.
- the number of monovalent groups other than hydrogen atoms or arylthio groups in R 1 to R 5 is 0 to 4, preferably 0 to 2, and more preferably 0 or 1.
- a monovalent group other than a hydrogen atom or an arylthio group for example, a chlorine atom, a bromine atom, an alkyl group having 1 to 2 carbon atoms, an alkyloxy group having 1 to 2 carbon atoms, or an alkylthio group having 1 to 2 carbon atoms
- an aryloxy group having 6 to 7 carbon atoms, an aryloxy group having 6 to 7 carbon atoms, or an aralkyl group having 7 to 9 carbon atoms preferably a bromine atom, methyl group, methoxy group, methylthio group, phenyl group, phenoxy A group, a benzyl group, a 1-phenylethyl group, or a 2-phenylpropan-2-yl group is more preferable.
- X 1 is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms.
- the oxyalkylene group, thioalkylene group, alkyleneoxy group or alkylenethio group is represented by YC n H 2n or C n H 2n Y, Y is O or S, and n is a number from 1 to 4. It is.
- the alkylene group, oxyalkylene group (or alkyleneoxy group), and thioalkylene group (or alkylenethio group) may have a substituent.
- preferred substituents include a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 6 to 6 carbon atoms.
- 10 aryloxy group or arylthio group having 6 to 10 carbon atoms, and the aryl group, aryloxy group or arylthio group may have a substituent which Ar1 described later may have.
- R 6 represents a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, a vinyl aryl group which may have a substituent, or a vinyl aryloyl group.
- the vinyl aryl group preferably has 8 to 20 carbon atoms, and the vinyl aryloyl group preferably has 9 to 20 carbon atoms.
- a vinyl aryl group Preferred examples of the substituent for the case of having a substituent include the substituents cited as preferred substituents in the description of X 1.
- Ar 1 of -S-Ar 1 represents a ring members 6-14 aryl group or ring members 5-14 heterocyclic aryl group may have a substituent, and two or more rings condensed You may do it.
- Ar 1 may be a monocyclic structure or a condensed ring structure, and the number of rings constituting Ar 1 is 1 to 4, preferably 1 to 3, and more preferably 1 to 2.
- the coloring is small in order to ensure not only a decrease in transparency but also photocurability and weather resistance. From this point, Ar 1 is an aryl group. It is preferable that The substituent in the case of having a substituent will be described later.
- —S—Ar 1 When used as a holographic recording material, the number of —S—Ar 1 is one, R 1 , R 2 , R 4 , R 5 are hydrogen atoms, and R 3 is —S—Ar 1 .
- Ar 1 is a phenyl group, it is desirable to exclude those in which X 1 is a direct bond and R 6 is a vinyl group.
- ⁇ Aryl group> 6-16 preferably 6 carbon atoms such as benzene, indene, naphthalene, azulene, fluorene, acenaphthene, anthracene, phenanthrene, fluoranthene, pyrene, and the like -14 aryl groups.
- the number of carbon atoms is more preferably 6 to 10, and particularly preferably a benzene ring group and a naphthalene ring group.
- the benzene ring group is a group formed by taking one H from benzene, and the other groups are the same.
- the heteroatom contained in the heteroaryl group is not particularly limited, and each atom such as S, O, N, and P can be used, but each atom of S, O, and N is preferable from the viewpoint of ensuring compatibility, Each atom of S or O is more preferable, and S atom is particularly preferable from the viewpoint of improving the refractive index. From the viewpoint of high transmittance and compatibility, the number of heteroatoms is preferably 1 to 3, more preferably 1 to 2, in the heteroaryl group.
- Ar 1 may have a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group, an alkylthio group, a phenyloxy group, and a phenylthio group.
- Preferred substituents are a chlorine atom, a bromine atom, an alkylthio group having 1 to 4 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms.
- the polymerizable compound represented by the general formula (1) can be produced by a known method.
- a compound in which R 6 is a vinyl group can be produced, for example, by a dehydration reaction using a compound having a hydroxyethyl group as a precursor.
- a compound in which R 6 is a (meth) acryloyl group can be produced, for example, by a reaction between a compound having active hydrogen and (meth) acrylic acids.
- a compound in which R 6 is a glycidyl group can be produced, for example, by a reaction between a compound having active hydrogen and epichlorohydrin.
- the molecular weight of the polymerizable compound represented by the general formula (1) described above is usually 1000 or less, preferably 800 or less, from the viewpoint of shrinkage reduction due to crosslinking during light irradiation or recording sensitivity and compatibility. More preferably, it is 600 or less, especially 500 or less, and is usually 200 or more, preferably 220 or more, more preferably 250 or more.
- the polymerizable compound represented by the general formula (1) has a refractive index n D at 25 ° C. of 1.50 or more, preferably 1.55 or more, more preferably 1.60 or more, and particularly preferably 1.62 or more. It is.
- n D refractive index
- the refractive index n D is 1.60 or more. It is preferable.
- the refractive index is excessively high, the difference in refractive index from the matrix resin becomes too large, which may cause scattering.
- a refractive index shows a large value when evaluated at a short wavelength
- a sample showing a relatively large refractive index at a short wavelength shows a relatively large refractive index even at a long wavelength, and its order is not reversed. . Therefore, the refractive index can be evaluated at a wavelength other than the recording wavelength, and the value at the recording wavelength can be predicted.
- the compound When the polymerizable compound is solid and it is difficult to directly measure the refractive index, the compound is dissolved in an appropriate solvent to form a solution, and the refractive index of this solution is measured.
- the refractive index can be obtained by extrapolation.
- the polymerizable compound represented by the general formula (1) has a viscosity at 60 ° C. of 5000 mPa ⁇ s or less, preferably 3000 mPa ⁇ s or less, more preferably 1000 mPa ⁇ s or less, and particularly preferably 500 mPa ⁇ s or less. is there.
- the resin composition of the present invention contains the polymerizable compound, but preferably contains a polymerization initiator.
- the polymerization initiator may be a known polymerization initiator and is not particularly limited as long as the polymerization is initiated by heating or irradiation with ultraviolet rays.
- a thermal radical polymerization initiator a photo radical polymerization initiator, etc. may be mentioned.
- a radical photopolymerization initiator is preferred because it can be rapidly cured at room temperature.
- thermal radical polymerization initiator examples include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert -Butylperoxy) -2-methylcyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) cyclohexane, 1,1 -Peroxyketals such as bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, hydroperoxides such as p-menthane hydroperoxide, ⁇ , ⁇ '-bis (tert-butylperoxy) ) Diiso Dialkyl peroxides such as propylbenzene, dicum
- diacyl peroxides peroxycarbonates, peroxyesters, and azo compounds are preferable from the viewpoints of curability, transparency, and heat resistance.
- photo radical polymerization initiator examples include benzyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl.
- ⁇ -hydroxyacetophenones such as propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2-benzyl-2-dimethylamino-1 ⁇ -aminoacetophenones such as-(4-morpholinophenyl) -butan-1-one and 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1- [ Oxime esters such as 4- (phenylthio) phenyl] -1,2-octadione and 2- (O-benzoyl) oxime Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Phosphine oxides such as fin oxide, 2- (o-
- thermal and photo radical polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.
- the photosensitizer is not particularly limited, and specifically, tertiary amines such as triethylamine and triethanolamine, alkylphosphine such as triphenylphosphine, ⁇ -thiodiglycol and the like Thioethers are exemplified, and the blending amount is recommended to be about 0.01 to 5% by weight with respect to the total amount of the resin composition.
- examples of the polymerization initiator include a thermal cationic polymerization initiator and a photo cationic polymerization initiator.
- a photocationic polymerization initiator is preferred because it can be rapidly cured at room temperature.
- thermal cationic polymerization initiator examples include benzylsulfonium salts such as p-alkoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-p-cyanopyridinium hexafluoroantimonate, 1-naphthylmethyl-o-cyanopyridinium hexafluoroantimonate.
- pyridinium salts such as cinnamyl-o-cyanopyridinium hexafluoroantimonate and benzylammonium salts such as benzyldimethylphenylammonium hexafluoroantimonate.
- benzylsulfonium salts are preferred from the viewpoints of curability, transparency, and heat resistance.
- Examples of the cationic photopolymerization initiator include aryl diazonium salts such as p-methoxybenzenediazonium hexafluorophosphate, diaryliodonium salts such as diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfone Triarylsulfonium such as phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium pentafluorohydroxyantimonate Salts, triphenyl acetate Triarylselenonium salt
- triarylsulfonium salts are preferred from the viewpoints of curability, transparency, and heat resistance.
- thermal and photocationic polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.
- the amount of the polymerization initiator used is 0.01 to 10% by weight based on the total amount of the resin composition, although it varies depending on the presence or absence of the polymerization inhibitor and the type and amount of the polymerization inhibitor used. More preferably, it is 0.02 to 5% by weight, and further preferably 0.03 to 3% by weight. However, since the amount used varies greatly depending on the type of polymerization initiator used, it is necessary to appropriately determine the optimum conditions.
- a known polymerization inhibitor can be added for storage of the resin composition.
- the type and amount of addition vary greatly depending on the type and amount of polymerization initiator and polymerizable compound to be used, it is necessary to appropriately determine the optimum conditions.
- the resin composition of this invention can contain other polymeric compounds (henceforth other polymeric compounds) other than the polymeric compound represented by General formula (1) as needed. . Even when other polymerizable compounds are included, the polymerizable compound represented by the general formula (1) is preferably 10% by weight or more, more preferably 50% by weight based on the total amount of the resin composition. % Or more.
- the other polymerizable compound a known polymerizable compound may be used, and any of monofunctional, bifunctional, polyfunctional, and polymerizable oligomers may be used. You may use together.
- the polymerizable compound by heat or light it is preferable to use either a thermally polymerizable compound or a photopolymerizable compound depending on the application.
- a compound having a radical polymerizable group such as a (meth) acryloyl group or a vinylaryl group
- a known radical polymerizable compound can be used as the other polymerizable compound.
- Examples of monofunctional (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and butoxyethyl (meth) acrylate.
- bifunctional (meth) acrylate compound examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth).
- trifunctional or higher polyfunctional (meth) acrylate compound examples include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated propoxy.
- (Meth) acrylate-based polymerizable oligomers include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polybutadiene oligomer (meth) acrylate, polyamide-type (meth) acryl oligomer, melamine (meth) acrylate , Cyclopentadiene oligomer (meth) acrylate, silicone oligomer (meth) acrylate, and the like.
- Another polymerizable oligomer is a copolymer obtained by copolymerizing a bifunctional compound having two unsaturated double bonds and a chain transfer agent, and a reaction derived from the bifunctional compound in the side chain.
- An oligomer having a pendant structure having a sex group can be mentioned.
- Preferred functional groups at this time are a vinyl group and an allyl group, and the bifunctional compound includes a branched structure, an alicyclic structure, or a substituent having an unsaturated double bond in a monocyclic or condensed aromatic ring. May be partially substituted with oxygen, nitrogen, or sulfur atoms.
- a compound having a cationic polymerizable group such as a glycidyl group is used as the polymerizable compound of the present invention
- a known cationic polymerizable compound can be used as the other polymerizable compound.
- Examples of the cationic polymerizable compound used as the other polymerizable compound include alkenyl ethers such as vinyl ether compounds and propenyl ether compounds, alkenyl thioethers such as vinyl thioether compounds and propenyl thioether compounds, vinyl ester compounds, and O-propenyl ester compounds.
- N-alkenylamides such as N-vinylamide compounds and N-propenylamide compounds
- cyclic ethers such as epoxy (oxirane) compounds, oxetane compounds and oxolane compounds
- cyclic compounds such as ethylene sulfide (thiirane) compounds Thioethers, cyclic acetal compounds, lactone compounds, spiroorthoester compounds, N-vinylimidazole compounds, N-vinylcarbazole compounds, etc.
- Rukoto can.
- vinyl ether compounds, epoxy compounds, and oxetane compounds are preferable.
- Particularly preferable other polymerizable compounds include a resin composition having a high refractive index and a low viscosity, which contains a polymerizable functional group capable of copolymerization and is a compound represented by the following general formula (2). It is suitable for giving.
- Y represents an n-valent ring-containing group having 2 to 7, preferably 2 to 5, 5- or 6-membered rings, where n is an integer of 2 to 4.
- the plurality of rings of the ring-containing group are (a) those directly connected to each other by a single bond, (b) an alkylene group having 1 to 3 carbon atoms, an oxygen atom (ether group), a sulfur atom (sulfide group)
- the rings are bonded via any of the above, or (c) the rings are condensed, and have two or more types of bonds (a), (b) and (c) above. It may be what you are doing.
- Y is not particularly limited, but an n-valent ring-containing group having a structure represented by the following formulas (Y-1) to (Y-17) is preferable.
- the compound represented by the general formula (2) is obtained by substituting these n-valent ring-containing groups with n atomic groups -ZA.
- n-valent ring-containing groups having the structures of the above formulas (Y-1) to (Y-11) are preferable from the viewpoint of improving the refractive index, and the above formulas (Y-12) to (Y An n-valent ring-containing group having the structure of Y-17) is preferred from the viewpoint of reducing the viscosity.
- Z represents a direct bond, an oxygen atom, a sulfur atom, or an alkylene group having 1 to 4 carbon atoms, an oxyalkylene group, a thioalkylene group, an alkyleneoxy group, or an alkylenethio group.
- A represents a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, a vinylaryl group or a vinylaryloyl group.
- n is an integer of 2 to 4, but a compound in which n is 2 is more preferable because of the availability of materials.
- the type and content of the other polymerizable compound represented by the general formula (2) can be appropriately determined depending on the type and amount of the other constituents in the resin composition, but preferably to obtain a sufficient effect. In addition, 5% by weight, preferably 10% by weight or more is added to the total amount of the resin composition.
- fillers such as fillers, fibers, coupling agents, flame retardants, mold release agents, and foaming agents can be added to the resin composition of the present invention as necessary.
- the filler used in this case is polyethylene powder, polypropylene powder, quartz, silica, silicate, calcium carbonate, magnesium carbonate, gypsum, bentonite, fluorite, titanium dioxide, carbon black, graphite, iron oxide, aluminum powder, iron powder. , Talc, mica, kaolin clay and the like.
- the fiber include cellulose fiber, glass fiber, carbon fiber, and aramid fiber.
- the coupling agent include a silane coupling agent and a titanium coupling agent.
- Examples of the flame retardant include brominated bisphenol A, antimony trioxide, and phosphorus compounds.
- Examples of the release agent include stearates, silicones, waxes and the like.
- Freon, dichloroethane, butane, pentane, dinitropentamethylenetetramine, p-toluenesulfonyl hydrazide, or freon, dichloroethane, butane, pentane, etc. are vinyl chloride-vinylidene chloride copolymer or styrene- (meth) acrylic. Examples thereof include expandable thermoplastic resin particles filled in an acid ester copolymer shell.
- the resin composition of the present invention can be dissolved in a solvent and diluted for use.
- specific examples of the diluent solvent that can be used include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, etc., and the amount used is based on the total amount of the resin composition and the diluent solvent. It is preferable that it is 70 weight% or less, More preferably, it is 60 weight% or less.
- other polymerizable compounds having a low viscosity can also be used as a reactive diluent for reducing the viscosity of the resin composition.
- the low viscosity is 500 mPa ⁇ s or less, preferably 200 mPa ⁇ s or less.
- the resin composition of the present invention can be easily made into a cured resin or molded product by a method similar to a conventionally known method. For example, a thermal polymerization initiator or a photopolymerization initiator is added to the polymerizable compound of the present invention, and other polymerizable compounds and other additives are further added as necessary, and an extruder, kneader, roll, stirrer, etc. And mixed well to obtain a resin composition.
- the resin composition is molded using a roll coater, a cast after casting or a transfer molding machine, and further heated to 60 to 200 ° C. or irradiated with light. A cured product can be obtained.
- a prepreg obtained by impregnating the resin composition of the present invention into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating is subjected to hot press molding to obtain a cured product.
- a thermal polymerization initiator is added to the polymerizable compound of the present invention, another polymerizable compound or other additive is further added as necessary, a solvent is further added, and the resin composition diluent is stirred.
- a glass cloth laminate can be produced by impregnating a glass cloth and heating and semi-drying (devolatilization) and prepressing the prepreg obtained by heating at 60 to 200 ° C.
- the substrate is preferably a transparent material.
- the substrate is opaque with respect to the wavelength of the light to be reflected / diffused.
- the resin composition thus obtained and its cured product are excellent in high refractive index, excellent in transparency, handling properties, etc., glass substitute materials for lens applications, protective film materials for color filters for liquid crystal displays, optical It is suitably used for various optical materials such as coating materials for product protection, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, and optical recording materials for hologram recording media.
- the holographic recording material of the present invention comprises A) a polymerizable compound, B) a matrix resin or a matrix resin forming component, and C) a photopolymerization initiator.
- the polymerizable compound the polymerizable compound represented by the general formula (1) is used.
- A) polymerizable compound, B) matrix resin or matrix resin forming component, and C) photopolymerization initiator are also referred to as A component, B component, and C component, respectively.
- the matrix resin As the matrix resin, a resin that can be dissolved in a solvent may be used, or a three-dimensionally cross-linked resin may be used, and a three-dimensional cross-linked resin is preferably used from the viewpoint of recording characteristics.
- the holographic recording material may be blended with a matrix resin, but may be blended as a matrix resin forming component (such as a monomer) that forms the matrix resin. When the matrix resin forming component is blended, it is preferable that polymerization of the polymerizable compound does not occur when forming the matrix resin.
- the three-dimensional crosslinked resin examples include isocyanate-hydroxyl polyadducts, isocyanate-amine polyadducts, isocyanate-thiol polyadducts, epoxy-amine polyadducts, epoxy-thiol polyadducts, episulfide-amine polyadducts, and Episulfide-thiol polyadduct, etc. can be mentioned, and it is an isocyanate-hydroxyl polyadduct capable of reacting under a relatively mild temperature condition, having excellent optical characteristics of the resulting matrix resin, and having a relatively low odor. It is preferable.
- the polyisocyanate component constituting the isocyanate-hydroxyl polyadduct a compound having two or more isocyanate groups in one molecule or a mixture thereof is used.
- a compound having two or more hydroxyl groups in one molecule or a mixture thereof is used as the polyol component constituting the isocyanate-hydroxyl polyadduct.
- diols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, butanediol, pentanediol, hexanediol, heptanediol, tetramethylene glycol; bisphenols;
- triols such as methylolpropane, butanetriol, pentanetriol, hexanetriol and decanetriol; compounds obtained by modifying the hydroxyl group of these compounds with a polyethyleneoxy chain or a polypropyleneoxy chain.
- the matrix resin may contain a unit derived from a reactive aromatic compound having an aromatic ring and having a polymerization reactive group and a hydroxyl group as a part of the constituent unit of the matrix resin.
- it can be part of the structural unit of the matrix resin via the hydroxyl group, and an aromatic ring is present in the matrix resin, so that the hollow resin containing the high refractive index polymerizable compound having the aromatic ring is present.
- the compatibility is high and turbidity hardly occurs, and a relatively large amount of polymerizable compound can be contained.
- the refractive index difference between the matrix resin and the polymerizable compound or polymer thereof can be increased, and as a result, the refractive index modulation can be increased.
- a plurality of diffraction gratings can be formed with high contrast by the refractive index modulation structure, and a plurality of page information corresponding to the plurality of diffraction gratings can be obtained. It can be recorded and played back with a high SNR.
- Examples of the reactive aromatic compound include those represented by the formula (5), (6) or (7).
- Ar5 represents a monovalent or divalent group having one or more aromatic rings
- Z 1 and Z 2 each independently represents a hydrogen atom or a methyl group
- L 1 represents an oxygen atom, a sulfur atom or — (OZ 3 ) nO—
- Z 3 is an alkylene group having 1 to 4 carbon atoms, n is an integer of 1 to 4
- L 2 is a divalent divalent alkyl group which may have an aromatic ring.
- m represents an integer of 1 to 2.
- Z 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- L 3 represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, or an alkylene group having 1 to 4 carbon atoms. Or represents a 9,9-fluorenylene group.
- Z 1 and L 1 are the same as in formula (5).
- L 2 represents a single bond or a divalent group which may have an aromatic ring.
- Z 1 , Z 2 , and L 1 are the same as in formula (6).
- Examples of the reactive aromatic compound represented by the formula (5) or (6) include (meth) acrylic acid adducts, 3-butenoic acid adducts, and vinyl benzoic acid adducts of bisphenol A type epoxy resins. , Vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, bisphenol F type epoxy resin (meth) acrylic acid adduct, 3-butenoic acid adduct, vinyl benzoic acid adduct, Vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, (meth) acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether, 3-butenoic acid adduct, Vinyl benzoic acid adduct, vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, 9,9- (Meth) acrylic acid adducts, 3-butenoic acid
- the reactive aromatic compound is preferably 0.1 to 20% by weight, more preferably 0.2 to 10% by weight, based on the total of the matrix resin or the matrix resin forming component (including the reactive aromatic compound), More preferably, it is 0.3-5% by mass. If the content of the reactive aromatic compound is too high, the viscosity of the precursor becomes high and the production of the holographic recording material may become complicated. On the other hand, if the reactive aromatic compound is not contained or if the content is too low, the compatibility between the matrix resin and the polymerizable compound or polymer thereof is lowered, and the holographic recording material may be turbid. .
- Examples of the compound having a polymerization reactive group and a hydroxyl group represented by the formula (7) include 9,9-bis (4-hydroxy) among the reactive aromatic compounds represented by the formula (5) or (6).
- the main component of the acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether is that R 1 in formula (7) is a hydrogen atom, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a single bond.
- the main components of the methacrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether are as follows: R 1 in formula (7) is a methyl group, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a single bond.
- R 1 in formula (7) is a hydrogen atom
- R 2 is a hydrogen atom
- L 1 is an oxygen atom
- L 2 is a compound represented by a methylene group.
- the main component of the vinyl benzoic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether is as follows: R 1 in formula (7) is a hydrogen atom, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a phenylene group.
- Component A polymerizable compound
- the blending amount of the polymerizable compound is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 1.5 to 10% by mass with respect to the entire holographic recording material. Moreover, if necessary, a small amount of other polymerizable compounds can be used in combination for the purpose of adjusting the refractive index.
- the photopolymerization initiator is not particularly limited as long as it initiates polymerization of the polymerizable compound of component A by irradiation with ultraviolet rays or the like.
- a radical photopolymerization initiator can be used.
- any known radical radical polymerization initiator can be used.
- Examples include azo compounds, azide compounds, organic peroxides, organoborates, onium salts, bisimidazole derivatives, titanocene compounds, iodonium salts, organic thiol compounds, halogenated hydrocarbon derivatives, ⁇ -hydroxyketone compounds. , ⁇ -aminoketone compounds, acylphosphine oxide compounds, oxime ester compounds, and the like are used. Any one of these may be used alone, or two or more may be used in any combination and ratio. Of these, titanocene compounds, acylphosphine oxide compounds, oxime ester compounds, and the like are preferable because a polymerization reaction occurs in the visible light region without requiring a sensitizer.
- titanocene compound is not particularly limited, but specific examples thereof include biscyclopentadienyl-Ti-dichloride, biscyclopentadienyl-Ti-diphenyl, biscyclopentadienyl-Ti-bis (2 , 3,4,5,6-pentafluorophenyl), biscyclopentadienyl-Ti-bis (2,3,5,6-tetrafluorophenyl), biscyclopentadienyl-Ti-bis (2,4 , 6-trifluorophenyl), biscyclopentadienyl-Ti-bis (2,6-difluorophenyl), biscyclopentadienyl-Ti-bis (2,4-difluorophenyl), bis (methylcyclopentadi) Enyl) -Ti-bis (2,3,4,5,6-pentafluorophenyl), bis (methylcyclopentadienyl) -Ti-bis (2,3,
- the acyl phosphine oxide compound is not particularly limited, but specific examples include triphenyl phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and 2,6-dichlorobenzoyl diphenyl.
- Phosphine oxide bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichloro) And benzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and the like.
- the type of the oxime ester compound is not particularly limited, but specific examples thereof include 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) -1,2-octanedione, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -2- (O-benzoyloxime) -3-cyclopentyl-1,2-propanedione, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] And -2- (O-acetyloxime) -4-cyclopentyl-1,2-butanedione.
- any one of these various photo radical polymerization initiators may be used alone, or two or more of them may be used in any combination and ratio.
- a photocationic polymerization initiator can be used as the photopolymerization initiator.
- Any known cationic photopolymerization initiator can be used as the cationic photopolymerization initiator.
- Examples include aryl diazonium salts, diaryl iodonium salts, triaryl sulfonium salts, triaryl selenonium salts, dialkylphenacyl sulfonium salts, dialkyl-4-hydroxy salts, sulfonic acid esters, and the like. Any one of these may be used alone, or two or more may be used in any combination and ratio.
- the holographic recording material of the present invention includes a photosensitizer, a plasticizer, a compatibilizer, a chain transfer agent, a polymerization accelerator, a polymerization inhibitor, a polymerization inhibitor, a radical scavenger, and a surfactant as necessary.
- a silane coupling agent, an antifoaming agent, a release agent, a stabilizer, an antioxidant, a flame retardant and the like may be further included. These additives may be used alone, or two or more of them may be used in any combination and ratio.
- a matrix resin forming component for example, a polyisocyanate component and a polyol component constituting an isocyanate-hydroxyl polyadduct, a polymerizable compound, a photopolymerization initiator, and, if necessary, represented by the formula (5)
- a reactive aromatic compound is blended.
- a matrix resin is formed by causing polymerization by a reaction other than a reaction in which the polymerizable reactive group of the polymerizable compound or the reactive aromatic compound is polymerized with respect to the matrix resin forming component.
- the matrix resin can be formed by polymerizing a matrix resin forming component in the presence of a polymerizable compound and a photopolymerization initiator.
- a holographic recording material contains a high refractive index polymerizable compound in addition to a low refractive index matrix resin, and forms a diffraction grating as a refractive index modulation structure in the medium by polymerizing the polymerizable compound during recording. It is preferable.
- the holographic recording material includes (1) matrix forming components (isocyanate, polyol, reaction catalyst (tin-containing catalyst), etc.), (2) polymerizable compound, (3) photopolymerization initiator, (4) other components, Are mixed and dissolved as appropriate, and (1) only the matrix-forming components are allowed to react independently.
- a polymerizable compound (3) a photopolymerization initiator, (4) other components Is basically unaffected and is preferably dispersed in the matrix resin as it is.
- a material in which the holographic recording material is sandwiched between two substrates is called a holographic recording medium.
- a photopolymerization initiator is cleaved to form polymerization initiation species (radicals, etc.), and (2) polymerization Compound is polymerized.
- the polymerizable compound or the photopolymerization initiator decreases due to reaction, the performance as a holographic recording material is lowered. Therefore, it is preferable to form a matrix resin without reducing these. Therefore, it is preferable to mix a reaction catalyst or adjust the reaction temperature so that polymerization in a reaction form different from the reaction in which the polymerizable compound is polymerized preferentially occurs.
- reaction catalyst for example, as a catalyst for isocyanate-hydroxyl polyaddition reaction, a tin-containing catalyst, a titanium-containing catalyst, a zinc-containing catalyst, a zirconium-containing catalyst, an aluminum-containing catalyst, a cobalt-containing catalyst, a nickel-containing catalyst, a copper-containing catalyst, and Various metal-containing catalysts such as iron-containing catalysts can be used. Of these, tin-containing catalysts are preferred from the viewpoint of reaction rate.
- a tin-containing catalyst such as dimethyltin dilaurate or dibutyltin dilaurate can be used.
- Non-metal-containing catalysts include 1,4-diazabicyclo [2,2,2] octane (DABCO), imidazole derivatives, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine. Tertiary amine compounds such as can be used. These catalysts may be used alone or in combination of two or more.
- the holographic recording medium of the present invention includes a recording layer containing the holographic recording material described above.
- the holographic recording medium of the present invention can have other layers such as an upper substrate, a lower substrate, and a reflective film as necessary.
- the holographic recording medium of the present invention may be either a transmission type or a reflection type.
- each substrate and recording layer that can be included in the holographic recording medium of the present invention.
- the substrate material glass, ceramics, resin and the like are usually used, but resin is preferable from the viewpoint of moldability and cost.
- the resin include polycarbonate resin, acrylic resin, polycycloolefin resin, epoxy resin, polystyrene resin, acrylonitrile-styrene copolymer, ABS resin, polyethylene resin, polypropylene resin, silicone resin, fluorine resin, and urethane resin.
- polycarbonate resin, acrylic resin, and polycycloolefin resin are particularly preferable in terms of moldability, optical characteristics, and cost.
- a substrate provided with a reflective layer in advance can also be used according to the recording / reproducing method.
- the recording layer is made of the holographic recording material, and information can be recorded using the holographic recording.
- those obtained by subjecting the surface of the recording layer to a hard coat treatment with a UV curable resin or the like and those subjected to an antireflection treatment can be used as appropriate.
- the holographic recording medium of the present invention is preferably used for holographic recording / reproduction, but any method can be used for the holographic recording / reproduction method.
- a holographic recording / reproducing method based on the two-beam interference method, a coaxial holographic recording / reproducing method in which reference light and information light are arranged on the same axis and condensed are preferably used.
- FIG. 3 shows a schematic configuration diagram of an optical system for multiple recording.
- Laser light emitted from a laser generator (a semiconductor laser having a wavelength of 405 nm) 1 is reflected by a mirror 2 and is a half-wave plate (HWP).
- HWP half-wave plate
- the beam diameter is enlarged by the beam expander 5, and then passed through the shutter 6 to be stopped.
- the beam diameter is narrowed by 7 (opening diameter 6 mm ⁇ ), and reaches the PBS 9 through the HWP 8.
- the laser light is divided into two, and one of the divided lights passes through the shutter 10, is reflected by the mirror 11, and is applied to the holographic recording medium S as the recording signal light Ls.
- the other light split by the PBS 9 passes through the quarter wave plate (QWP) 12 and is reflected by the mirror 13, and then passes through the QWP 12 and PBS 9 again to irradiate the holographic recording medium S as the recording reference light Lw. Is done.
- the angle ⁇ of the rotary stage 14 to which the holographic recording medium S is attached is set to a predetermined value, the shutter 6 is opened for a predetermined time and exposed, and the first hologram is recorded on the holographic recording medium S. .
- ⁇ is set to the next predetermined value
- the shutter 6 is opened for a predetermined time and exposed, and a second hologram is recorded in the same location of the holographic recording medium S.
- multiplex recording can be performed by repeating the above operation until a predetermined multiplicity is reached.
- HWP3 is for adjusting the power of the entire optical system
- HWP8 is for adjusting the power ratio of the signal light and the reference light.
- the QWP 12 is for adjusting the polarization axis of the recording reference light Lw (or reproduction reference light Lr described later).
- FIG. 4 is a schematic configuration diagram of the reproducing optical system, and the same symbols as those in FIG. 3 have the same meaning.
- Laser light emitted from the laser generator 1 reaches the PBS 9 via the mirror 2, the HWP 3, the PBS 4, the beam expander 5, the shutter 6, and the diaphragm 7.
- the PBS 9 the laser light is divided into two, and one of the divided lights is blocked by the shutter 10.
- the other light divided by the PBS 9 is reflected by the mirror 13 through the QWP 12, and then passes again through the QWP 12 and the PBS 9, and the beam diameter is narrowed by the aperture 15 (opening diameter 2.7 mm ⁇ ), and the reproduction reference light Lr To the holographic recording medium S.
- the angle ⁇ of the rotary stage 14 to which the holographic recording medium S is attached is set to a value corresponding to a predetermined (reproduced) hologram, the shutter 6 is opened for a predetermined time, and the reproduction reference light Lr is irradiated onto the medium.
- the intensity of the light (reproduced signal light) diffracted by the recorded hologram is measured by the optical power meter 16, and the intensity of the light transmitted through the medium (transmitted light) is measured by the optical power meter 17.
- Example 1 1- (I): Synthesis of 4-acetyldiphenyl sulfide 25.0 g (0.136 mol) of diphenyl sulfide was dissolved in 300 ml of dichloromethane and cooled to 0 ° C. under a nitrogen atmosphere. 149 mol) was added slowly and the mixture was stirred for 15 minutes. A solution prepared by dissolving 11.9 g (0.149 mol) of acetyl chloride in 50 ml of dichloromethane was added dropwise, stirred for 30 minutes, warmed to room temperature, and further stirred for 1 hour.
- the organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product.
- the obtained crude product was purified by column chromatography to obtain 3.0 g of the objective compound as a colorless transparent liquid (yield 48%).
- DMF dimethylformamide
- the organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 68.7 g of a crude product.
- the obtained crude product was used in the next reaction without further purification.
- DMF dimethylformamide
- Example 9 9- (I): Synthesis of 4- (2-naphthylthio) -2-phenylthioacetophenone 2,4-difluoroacetophenone 24.4 g (0.156 mol), 2-naphthalenethiol 25 g (0.156 mol), potassium carbonate 43 .13 g (0.312 mol) was dissolved in 300 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 1 hour. Subsequently, after 17.2 g (0.156 mol) of thiophenol was added little by little, the mixture was further stirred at 130 ° C. for 1 hour.
- DMF dimethylformamide
- the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (500 ml).
- the organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 20.1 g of a crude product.
- the obtained crude product was used in the next reaction without further purification.
- Example 10 10- (I): Synthesis of 2- (2-naphthylthio) -4-phenylthioacetophenone 2,4-difluoroacetophenone 24.4 g (0.156 mol), thiophenol 17.2 g (0.156 mol), potassium carbonate 43 .13 g (0.312 mol) was dissolved in 300 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 1 hour. Next, 25 g (0.156 mol) of 2-naphthalenethiol was added little by little, and the mixture was further stirred at 130 ° C. for 1 hour.
- DMF dimethylformamide
- DMF dimethylformamide
- the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (500 ml).
- the organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 94.1 g of a crude product.
- the obtained crude product was used in the next reaction without further purification.
- the refractive index of each of the compounds obtained in Examples 1 to 11 was determined according to the following procedure. For measurement, an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. was used, and the temperature was adjusted to 25 ° C. at a wavelength of 589 nm. Since the compound obtained in Example 4 was a solid, the refractive index of a compound dissolved in a solvent having a known refractive index was measured using the above apparatus, and the value extrapolated to 100% of the substrate The refractive index of the compound was used. In this case, N-methylpyrrolidone was used as a solvent, and the substrate concentrations were 10% by mass, 20% by mass, and 30% by mass. The results of refractive index measurement are shown in Table 1.
- ultraviolet / visible absorption spectra were measured according to the following procedures.
- the above compound was dissolved in acetonitrile to make a 0.001% by weight solution, and an absorption spectrum was measured in a wavelength region of 500 to 200 nm using an ultraviolet-visible spectrophotometer V-650 manufactured by JASCO Corporation.
- FIG. 1 is an ultraviolet / visible absorption spectrum of the compounds obtained in Examples 1 to 3, 9, and 11. In any sample, it was confirmed that there was no absorption in the visible region of 400 nm or more, and the transparency was high.
- FIG. 2 is an infrared absorption spectrum of the compounds obtained in Examples 1 to 3.
- the inset in FIG. 2 is an enlarged view of the wave number range of 500 to 1000 cm ⁇ 1 .
- Example 12 99.5 parts by weight of 2,4-bis (phenylthio) styrene obtained in Example 2 as a polymerizable compound and 0.5 parts by weight of azobisisobutyronitrile as a thermal radical polymerization initiator are stirred and mixed at 40 ° C. Thus, a resin composition was obtained. Furthermore, this resin composition was introduced into a gap formed by bonding two glass substrates (50 mm ⁇ 50 mm) coated with a release agent through silicon film spacers (thickness 1.0 mm). After heat treatment at 60 ° C. for 15 hours, the glass substrate was peeled off to obtain a colorless and transparent sheet-like resin cured product.
- Example 13 A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 1- [2,4-bis (phenylthio) phenyl] ethyl acrylate obtained in Example 3 was used as the polymerizable compound. It was.
- Example 14 A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 4,4′-bis (phenylthio) phenylmethyl acrylate obtained in Example 8 was used as the polymerizable compound.
- Example 15 A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12, except that 2- (2-naphthylthio) -4-phenylthiostyrene obtained in Example 10 was used as the polymerizable compound.
- Example 16 A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 2- (2-naphthylthio) -4-phenylthiobenzophenone obtained in Example 11 was used as the polymerizable compound.
- Comparative Example 1 A pale yellow transparent sheet-like cured resin was obtained in the same manner as in Example 9 except that phenylthioethyl acrylate (manufactured by BIMAX, BX-PTEA) was used as the polymerizable compound.
- Comparative Example 2 A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 9, except that benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester BZ) was used as the polymerizable compound.
- Comparative Example 3 A light yellow transparent sheet-like resin cured product was obtained in the same manner as in Example 9 except that ethoxylated o-phenylphenol acrylate (Miramer M1142 manufactured by MIWON) was used as the polymerizable compound.
- ethoxylated o-phenylphenol acrylate (Miramer M1142 manufactured by MIWON) was used as the polymerizable compound.
- Samples having a length of 20 mm, a width of 5 mm, and a thickness of 1.0 mm were cut out from the sheet-like resin cured products obtained in Examples 12 to 16 and Comparative Examples 1 to 3, and the refractive index was measured. The results are shown in Table 2.
- an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. was used, and the temperature was adjusted to 25 ° C. at a wavelength of 589 nm.
- the polymerizable compound of the present invention, the resin composition using the same, and the cured product thereof are excellent in high refractive index and excellent in transparency, and are used for glass substitute materials for lens applications, liquid crystal displays, and the like.
- Suitable for various optical materials such as protective film materials for color filters, coating materials for protecting optical products, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, optical recording materials for hologram recording media, etc. Used for.
- holographic recording materials examples are shown below.
- the abbreviations and the like in the preparation examples of the holographic recording material are as follows.
- Matrix resin forming catalyst Dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
- Photopolymerization initiator 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -2- (O-
- Example 17 Compound having a polymerizable reactive group containing 34.2 parts (parts by mass) of HMDI, 45.8 parts of G-400, 10.0 parts of OFHDO, and 0.06 parts of matrix resin-forming catalyst as matrix resin-forming components 9 parts of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether 3-butenoic acid adduct (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 2 parts obtained as a polymerizable compound in Example 2 , 4-bis (phenylthio) styrene (3.0 parts by mass), photopolymerization initiator (0.05 parts), and plasticizer (6.0 parts) were blended to prepare a holographic recording material.
- matrix resin-forming catalyst 9 parts of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether 3-butenoic acid adduct (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 2
- This holographic recording material was introduced into the gap between two glass substrates (30 mm ⁇ 30 mm) bonded together via a silicon film spacer (thickness 0.5 mm).
- Holographic recording medium in which a matrix resin is formed by heat treatment at 60 ° C. for 2 hours in a nitrogen atmosphere, and a recording layer made of a holographic recording material is formed between two glass substrates to a thickness of 0.5 mm Got.
- Example 18 As a matrix resin forming component, 33.7 parts of HMDI, 44.9 parts of G-400, and 1- [2,4-bis (phenylthio) phenyl] ethyl 4-vinylbenzoate obtained in Example 4 as a polymerizable compound A holographic recording medium was obtained in the same manner as in Example 17 except that 4.4 parts were used.
- Example 19 As the matrix resin forming component, 33.9 parts of HMDI, 45.2 parts of G-400, and 4.0 parts of 2,4-bis (2-naphthylthio) styrene obtained in Example 5 as a polymerizable compound were used. A holographic recording medium was obtained in the same manner as Example 17 except for the above.
- Example 20 As a matrix resin forming component, 33.8 parts of HMDI, 45.5 parts of G-400, and 3.5 parts of 4- (2-naphthylthio) -2-phenylthiostyrene obtained in Example 9 as a polymerizable compound were used. A holographic recording medium was obtained in the same manner as in Example 17 except that it was used.
- Table 3 shows the compositions of the holographic recording material precursors of Examples 17 to 20 and Comparative Examples 4 and 5.
- the number of the compounding amount in Table 3 is part by mass.
- Holographic recording / reproduction evaluation was performed using a holographic recording / reproduction evaluation machine based on the two-beam interference method. Multiple recording was performed using angle multiplexing.
- Diffraction efficiency ( ⁇ ) [diffracted light intensity / (transmitted light intensity + diffracted light intensity)] ⁇ 100 (%)
- M # M number
- the recording sensitivity was calculated by the formula (III), and the maximum value was defined as the maximum sensitivity.
- ⁇ diffraction efficiency E is exposure energy [mJ / cm 2 ]
- L is the media thickness [cm] Represents.
- FIG. 5 is an integrated value of M # with respect to the recording exposure energy. It can be seen that the media according to Examples 17 to 20 all have a higher M # than the media according to Comparative Examples 4 and 5 and are excellent in multiplex recording properties.
- FIG. 6 shows the sensitivity to the recording exposure energy. All the media according to Examples 17 to 20 have higher sensitivity than the media according to Comparative Examples 4 and 5, and a high data transfer rate can be realized.
- Table 4 shows the results of numerical comparison of M # obtained by plane wave measurement, maximum sensitivity, refractive index of polymerizable compound, and number of molecules per gram of material.
- the polymerizable compound since the polymerizable compound is responsible for forming a refractive index modulation structure when holographic recording is performed, increasing the content improves M # and sensitivity, but on the other hand, it tends to cause polymerization shrinkage. Become. Generally, it is known that the polymerization shrinkage of vinyl monomers is proportional to the inverse of the molecular weight. By aligning the number of molecules of the polymerizable compound contained in the material, it is possible to polymerize with the same shrinkage of the recording medium. The performance between compounds can be compared. It can be seen from Table 4 that when the shrinkage ratios are set to the same level, the medium according to the example clearly has higher M # and sensitivity than the medium according to the comparative example.
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Abstract
Provided are a polymerizable compound having a high refractive index, high light transmittance, and low viscosity, a resin composition using the same, a cured resin, and an optical material. A polymerizable compound represented by general formula (1). Here, R1-R5 are a hydrogen atom or a monovalent group such as an arylthio group, alkyl group, or the like, but 1-3 thereof are arylthio groups represented by –S-Ar1; X1 is a direct bond, oxygen atom, or a divalent group such as an alkylene group or the like; R6 is a polymerizable group such as a glycidyl group, acryloyl group, or the like; and the Ar1 of -S-Ar1 is an aryl group or heteroaryl group.
Description
本発明は、高屈折率を有するとともに、透明性、ハンドリング性等に優れた重合性化合物、それを用いた樹脂組成物、樹脂硬化物及び光学材料、特にホログラフィック記録用材料及びホログラフィック記録媒体に関するものである。
The present invention relates to a polymerizable compound having a high refractive index and excellent in transparency, handling properties, and the like, a resin composition using the same, a cured resin and an optical material, particularly a holographic recording material and a holographic recording medium It is about.
最近、様々な光学分野において光学樹脂が盛んに用いられているが、その材料としてはポリメチルメタクリレートなどの(メタ)アクリル樹脂がよく知られている。一般的に(メタ)アクリル樹脂に代表される光学樹脂材料は、軽量性、安全性、意匠性を有している反面、屈折率が低いという欠点がある。そこで、近年、高屈折率を有する光学樹脂に対する要望が高くなってきており、液晶ディスプレイ用パネル、カラーフィルタ、眼鏡レンズ、フレネルレンズ、レンチキュラーレンズ、TFT用のプリズムレンズシート、非球面レンズ、光ファイバー、光導波路、光記録材料などへの検討が盛んに行われている。なかでも光記録材料、特にホログラフィック記録用材料において、大きな屈折率変調度・大きなM#(エムナンバー)・高い感度を達成するための高屈折率材料の開発が大きな課題となっている。
Recently, optical resins have been actively used in various optical fields, and (meth) acrylic resins such as polymethylmethacrylate are well known as materials thereof. In general, optical resin materials typified by (meth) acrylic resins have lightness, safety, and design properties, but have a disadvantage of low refractive index. Therefore, in recent years, there has been an increasing demand for optical resins having a high refractive index, such as liquid crystal display panels, color filters, spectacle lenses, Fresnel lenses, lenticular lenses, TFT prism lens sheets, aspherical lenses, optical fibers, Studies on optical waveguides, optical recording materials, and the like have been actively conducted. In particular, for optical recording materials, particularly holographic recording materials, the development of high refractive index materials for achieving a high degree of refractive index modulation, a large M # (M number), and high sensitivity has become a major issue.
光学樹脂の屈折率を高めるためには、原料となる重合性化合物(以下、モノマーともいう。)として高屈折率モノマーを使用することが有利であり、モノマー分子構造中への芳香環、フッ素を除くハロゲン原子(塩素、臭素、ヨウ素)、硫黄原子や重金属原子の導入が有効であることが理論的に知られている。
In order to increase the refractive index of the optical resin, it is advantageous to use a high refractive index monomer as a raw material polymerizable compound (hereinafter also referred to as a monomer). It is theoretically known that introduction of halogen atoms (chlorine, bromine, iodine), sulfur atoms and heavy metal atoms is effective.
分子構造中に芳香環を有するモノマーとしては、例えば、ベンゼン環のほか、ビフェニル、ナフタレン、フルオレン、アントラセンなどの多環芳香環を有するものが知られている(特許文献1、2など)。しかし、分子構造中に単一のベンゼン環を有するモノマーでは、屈折率が十分でない。また、分子構造中にビフェニル、ナフタレン、フルオレン、アントラセンなどの多環芳香環を有するモノマーは、高屈折率が期待されるものの、殆どの場合に高粘度液体または結晶固体になるため溶解性などのハンドリング性が低下する問題がある。さらには、吸収波長の長波長化により、透明性の低下だけでなく、光硬化性や耐候性が低下するという問題もある。
As monomers having an aromatic ring in the molecular structure, for example, those having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene and anthracene in addition to a benzene ring are known ( Patent Documents 1 and 2, etc.). However, the refractive index of a monomer having a single benzene ring in the molecular structure is not sufficient. In addition, monomers having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene, and anthracene in the molecular structure are expected to have a high refractive index, but in most cases become a high-viscosity liquid or a crystalline solid. There is a problem that handling property is lowered. Furthermore, there is a problem that not only the transparency is lowered but also the photocurability and the weather resistance are lowered by increasing the absorption wavelength.
一方、分子構造中にジフェニルスルフィド構造を有するモノマーでは、単一のベンゼン環を有するモノマーに比べて屈折率は高くなる。また、ビフェニル、ナフタレン、フルオレン、アントラセンなどの多環芳香環を有するモノマーほど粘度の上昇や吸収波長の長波長化を生じないため、溶解性などのハンドリング性、透明性、光硬化性、耐侯性の低下の問題が少ないという利点が期待できる。
On the other hand, a monomer having a diphenyl sulfide structure in the molecular structure has a higher refractive index than a monomer having a single benzene ring. In addition, the higher the viscosity and the longer the absorption wavelength, the less the monomer having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene, anthracene, etc., handling properties such as solubility, transparency, photocurability, weather resistance The advantage that there are few problems of the fall of can be expected.
これまでに、分子構造中にジフェニルスルフィド構造を有する重合性化合物が幾つか合成されている(特許文献3~6など)。しかしながら、ここに挙げた特許文献で開示された重合性化合物であっても、高屈折率性、透明性、ハンドリング性の点から不十分であり、更に改善された重合性化合物の創出が求められている。
So far, several polymerizable compounds having a diphenyl sulfide structure in the molecular structure have been synthesized (Patent Documents 3 to 6, etc.). However, even the polymerizable compounds disclosed in the patent documents listed here are insufficient in terms of high refractive index, transparency and handling properties, and further creation of improved polymerizable compounds is required. ing.
ホログラフィック記録は、イメージ情報を持った信号光とともに参照光を同時に照射して生じる干渉縞を、記録媒体に回折格子(以下、グレーティングともいう。)として記録することにより行われる。記録媒体からの再生は、イメージ情報が記録された記録媒体に参照光を照射して、イメージ情報を回折格子からの再生信号光として読み出すことによって行われる。
ホログラフィック記録は、上記イメージ情報を1ページとして、ページ単位で一括記録、再生でき、かつ、媒体の同一箇所にページを多重記録できることから、従来のCD、DVD、ブルーレイディスクで用いられるビット・バイ・ビットの記録方式に替わる高転送レートかつ大容量の光記録方式として期待される技術である。 Holographic recording is performed by recording interference fringes generated by simultaneously irradiating reference light together with signal light having image information on a recording medium as a diffraction grating (hereinafter also referred to as a grating). The reproduction from the recording medium is performed by irradiating the recording medium on which the image information is recorded with reference light and reading out the image information as reproduction signal light from the diffraction grating.
In holographic recording, the above-mentioned image information can be recorded and reproduced as a single page in a batch, and multiple pages can be recorded at the same location on the medium. Therefore, bit-by-bit used in conventional CDs, DVDs, and Blu-ray discs. This technology is expected as a high transfer rate and large capacity optical recording system that replaces the bit recording system.
ホログラフィック記録は、上記イメージ情報を1ページとして、ページ単位で一括記録、再生でき、かつ、媒体の同一箇所にページを多重記録できることから、従来のCD、DVD、ブルーレイディスクで用いられるビット・バイ・ビットの記録方式に替わる高転送レートかつ大容量の光記録方式として期待される技術である。 Holographic recording is performed by recording interference fringes generated by simultaneously irradiating reference light together with signal light having image information on a recording medium as a diffraction grating (hereinafter also referred to as a grating). The reproduction from the recording medium is performed by irradiating the recording medium on which the image information is recorded with reference light and reading out the image information as reproduction signal light from the diffraction grating.
In holographic recording, the above-mentioned image information can be recorded and reproduced as a single page in a batch, and multiple pages can be recorded at the same location on the medium. Therefore, bit-by-bit used in conventional CDs, DVDs, and Blu-ray discs. This technology is expected as a high transfer rate and large capacity optical recording system that replaces the bit recording system.
ホログラフィック記録用材料としては、記録媒体製造の簡便性、原料選択の多様性などが考慮され、マトリックス樹脂中に記録用の重合性化合物と光重合開始剤とを分散させたフォトポリマーが用いられる場合が多い。フォトポリマーを用いたホログラフィック記録媒体では、干渉縞が屈折率変調回折格子として記録されるライトワンス型が一般的である。
As a holographic recording material, a photopolymer in which a recording polymerizable compound and a photopolymerization initiator are dispersed in a matrix resin is used in consideration of the convenience of recording medium production and diversity of raw material selection. There are many cases. In a holographic recording medium using a photopolymer, a write-once type in which interference fringes are recorded as a refractive index modulation diffraction grating is generally used.
ホログラフィック記録媒体において、大容量化のためには大きなM#が必要である。M#とは多重記録性能を表す指標であり、m多重記録された信号においてiページ目の回折効率をηiとしたとき、次式(I)で表される数値である。
In a holographic recording medium, a large M # is necessary for increasing the capacity. M # is an index representing the multiplex recording performance, and is a numerical value represented by the following formula (I) when the diffraction efficiency of the i-th page is η i in the m-multiplex recorded signal.
また、ホログラフィック記録媒体において、高転送レート化のためには短時間の記録露光で十分な回折効率が得られる必要があるため、高い記録感度が求められる。
Further, in a holographic recording medium, a high recording sensitivity is required because it is necessary to obtain a sufficient diffraction efficiency with a short recording exposure in order to achieve a high transfer rate.
ホログラフィック記録はコヒーレントな光を交差させることで得られる干渉縞(光の明暗)をフォトポリマーに照射することによって行われる。光照射時に干渉縞の明部では光重合が生じ、重合性化合物が消費されて重合物が生成する。このとき生じる重合性化合物の濃度勾配を補う形で、干渉縞の暗部から明部へと拡散移動によって重合性化合物が供給される。このようにして、干渉縞パターンが屈折率の分布としてフォトポリマー内に固定される(非特許文献1)。
Holographic recording is performed by irradiating a photopolymer with interference fringes (light contrast) obtained by crossing coherent light. Photopolymerization occurs in the bright part of the interference fringes during light irradiation, and the polymerizable compound is consumed to produce a polymer. The polymerizable compound is supplied by diffusion transfer from the dark part to the bright part of the interference fringes so as to compensate for the concentration gradient of the polymerizable compound generated at this time. In this way, the interference fringe pattern is fixed in the photopolymer as a refractive index distribution (Non-Patent Document 1).
マトリックス樹脂と重合性化合物は屈折率差がなるべく大きくなるように選択することが有利であり、マトリックス樹脂に低屈折率のものを用いた場合は重合性化合物にはできるだけ高い屈折率を有するものを用いることが望ましい。
It is advantageous to select the matrix resin and the polymerizable compound so that the difference in refractive index is as large as possible. When a matrix resin having a low refractive index is used, the polymerizable compound should have a refractive index as high as possible. It is desirable to use it.
従来、高屈折率の重合性化合物としては、例えば、特許文献7~9に記載されるN-ビニルカルバゾールやブロモスチレン、トリブロモフェニルアクリレートなど、縮合(複素)アリール基や臭素置換されたアリール基を有するものなどが知られている。
Conventionally, examples of the high refractive index polymerizable compound include condensed (hetero) aryl groups and bromine-substituted aryl groups such as N-vinylcarbazole, bromostyrene, and tribromophenyl acrylate described in Patent Documents 7 to 9. There are those that have.
また、特許文献10~12には、含硫黄縮合環構造を持つ重合性化合物を用いることにより、回折効率と感度の高いホログラフィック記録用材料及び記録媒体が得られることが報告されている。しかし、一般的に、屈折率差と相溶性とはトレードオフの関係にあり、回折効率向上のために重合性化合物の屈折率を向上させるとマトリックス樹脂と該重合性化合物やその重合物との相溶性が悪化する。ここに挙げた特許文献で開示された重合性化合物であっても、回折効率、光透過率、相溶性の点から不十分であり更に改善された重合性化合物の創出が求められている。
Patent Documents 10 to 12 report that a holographic recording material and a recording medium having high diffraction efficiency and sensitivity can be obtained by using a polymerizable compound having a sulfur-containing fused ring structure. However, in general, the difference in refractive index and the compatibility are in a trade-off relationship. When the refractive index of the polymerizable compound is improved to improve the diffraction efficiency, the matrix resin and the polymerizable compound or a polymer thereof are not affected. Compatibility is deteriorated. Even the polymerizable compounds disclosed in the patent documents listed here are insufficient from the viewpoint of diffraction efficiency, light transmittance, and compatibility, and the creation of further improved polymerizable compounds is demanded.
ホログラフィック記録媒体の回折効率は、媒体表面当たりの記録密度と比例しており、その値は次式(II)のKogelnik理論から屈折率の変調度で表わすことができる。ここでηは回折効率、Δnは屈折率変調度、λは再生波長、θBは再生角度である。
The diffraction efficiency of the holographic recording medium is proportional to the recording density per medium surface, and the value can be expressed by the refractive index modulation degree from the Kogelnik theory of the following equation (II). Here, η is the diffraction efficiency, Δn is the refractive index modulation degree, λ is the reproduction wavelength, and θ B is the reproduction angle.
屈折率の変調度は、光照射部と非照射部の屈折率の差のことである。記録前のホログラフィック記録媒体は、重合性化合物がマトリックス樹脂に相溶した状態で均一に分散されている。このホログラフィック記録媒体に、記録のための干渉縞を照射すると、干渉縞の明部では光重合が開始し、重合性化合物が消費されて重合物が生成する。このとき生じる重合性化合物の濃度勾配を補う形で、干渉縞の暗部から明部へと拡散移動によって重合性化合物が供給され重合が継続するとともに、重合により密度の上昇が起こる。一方で干渉縞の暗部では重合性化合物の濃度が減少する。
The degree of modulation of the refractive index is the difference in refractive index between the light irradiated part and the non-irradiated part. The holographic recording medium before recording is uniformly dispersed in a state where the polymerizable compound is compatible with the matrix resin. When this holographic recording medium is irradiated with interference fringes for recording, photopolymerization starts in the bright part of the interference fringes, and the polymerizable compound is consumed to produce a polymer. In order to compensate for the concentration gradient of the polymerizable compound generated at this time, the polymerizable compound is supplied by diffusion transfer from the dark part to the bright part of the interference fringes, and the polymerization continues, and the polymerization causes an increase in density. On the other hand, the concentration of the polymerizable compound decreases in the dark part of the interference fringes.
よって、重合性化合物の屈折率がマトリックス樹脂の屈折率よりも高い場合、光照射部では重合による密度増加と重合性化合物の濃度増加により、非照射部に対して屈折率が上昇する。一方、非照射部分では重合性化合物濃度減少により、記録前の状態よりも更に屈折率が低下する。そのため、光照射部と非照射部に屈折率差が形成される。
Therefore, when the refractive index of the polymerizable compound is higher than the refractive index of the matrix resin, the refractive index increases with respect to the non-irradiated portion due to the increase in density due to polymerization and the concentration of the polymerizable compound in the light irradiated portion. On the other hand, in the non-irradiated portion, the refractive index is further lowered than the state before recording due to the decrease in the polymerizable compound concentration. Therefore, a refractive index difference is formed between the light irradiation part and the non-irradiation part.
重合性化合物の屈折率がマトリックス樹脂の屈折率よりも低い場合、光照射部分では重合により非照射部分より屈折率が上昇するものの、重合性化合物濃度の増加は屈折率低下に働くため、その上昇幅は抑制される。更に、非照射部分では重合性化合物の濃度減少により屈折率が上昇するため、光照射部と非照射部の屈折率の差は、重合性化合物がマトリックス樹脂よりも屈折率が大きい場合に比べてより小さくなる。従って、光照射部と未照射部の屈折率差を大きくするためには、重合性化合物の屈折率がマトリックス樹脂の屈折率よりも大きいこと、またその差が大きいことが重要である。
When the refractive index of the polymerizable compound is lower than the refractive index of the matrix resin, the refractive index increases in the light-irradiated part than in the non-irradiated part due to polymerization. The width is suppressed. Furthermore, since the refractive index increases due to a decrease in the concentration of the polymerizable compound in the non-irradiated part, the difference in refractive index between the light-irradiated part and the non-irradiated part is larger than that when the polymerizable compound has a higher refractive index than the matrix resin. Smaller. Therefore, in order to increase the refractive index difference between the light irradiated portion and the unirradiated portion, it is important that the refractive index of the polymerizable compound is larger than the refractive index of the matrix resin and that the difference is large.
前記式(I)より、M#は多重度が大きいほど大きくなる。また、M#は回折効率から計算され、回折効率は前記式(II)より屈折率変調度が大きいほど大きくなることがわかる。これらのことから、光照射部と未照射部の屈折率の差がより大きいほど回折効率を大きくすることができ、更にはM#の向上を達成することが出来る。
From the above formula (I), M # increases as the multiplicity increases. Further, M # is calculated from the diffraction efficiency, and it can be seen from the formula (II) that the diffraction efficiency increases as the refractive index modulation degree increases. From these facts, the diffraction efficiency can be increased as the difference in the refractive index between the light-irradiated portion and the non-irradiated portion is increased, and further, improvement in M # can be achieved.
従って、本発明は高い屈折率、高い光透過率、低い粘度を有する重合性化合物と、それを用いた樹脂組成物、樹脂硬化物および光学材料、さらにはホログラフィック記録用材料として用いた場合に大きなM#、高い感度が得られる前記重合性化合物を含むホログラフィック記録用材料、それを用いた大容量(高密度)、高転送レートを実現可能なホログラフィック記録媒体を提供することを目的とする。
Therefore, the present invention provides a polymerizable compound having a high refractive index, a high light transmittance, and a low viscosity, and a resin composition, a cured resin and an optical material using the polymerizable compound, and further when used as a holographic recording material. It is an object to provide a holographic recording material containing the polymerizable compound capable of obtaining a large M # and high sensitivity, and a holographic recording medium capable of realizing a large capacity (high density) and a high transfer rate using the material. To do.
一般に有機物の屈折率を高くする手段として、芳香環の導入や、硫黄原子、臭素原子などの重原子の導入が挙げられる。そこで、本発明者らは、重合性基を有するベンゼン環に硫黄原子を介して芳香族環を導入することで高屈折率化と高相溶性化の両立を図ることが可能な化合物を創出し、これを使用することにより、大きなM#、高い感度を示す高性能なホログラフィック記録用材料が得られることを見出し、本発明を完成するに至った。
Generally, as means for increasing the refractive index of organic substances, introduction of aromatic rings and introduction of heavy atoms such as sulfur atoms and bromine atoms can be mentioned. Therefore, the present inventors have created a compound that can achieve both high refractive index and high compatibility by introducing an aromatic ring through a sulfur atom into a benzene ring having a polymerizable group. By using this, it has been found that a high-performance holographic recording material exhibiting a large M # and high sensitivity can be obtained, and the present invention has been completed.
すなわち、本発明は下記一般式(1)で表される重合性化合物である。
ここで、
R1~R5は水素原子、又は塩素原子、臭素原子、炭素数1~4のアルキル基、炭素数1~4のアルキルオキシ基、炭素数1~4のアルキルチオ基、炭素数6~10のアリール基、炭素数6~10のアリールオキシ基、炭素数7~11のアラルキル基、及び-S-Ar1で表わされるアリールチオ基からなる群れから選ばれる1価の基を表し、その内1つ、2つまたは3つが該アリールチオ基である。
X1は直接結合、酸素原子、硫黄原子、炭素数1~4のアルキレン基、炭素数1~4のオキシアルキレン基、炭素数1~4のチオアルキレン基、炭素数1~4のアルキレンオキシ基または炭素数1~4のアルキレンチオ基を表し、ここで、アルキレン基、オキシアルキレン基、チオアルキレン基、アルキレンオキシ基及びアルキレンチオ基は、置換基を有してもよく、置換基を有する場合の置換基は塩素原子、臭素原子、炭素数1~4のアルキルオキシ基、炭素数1~4のアルキルチオ基、炭素数6~10のアリール基、炭素数6~10のアリールオキシ基または炭素数6~10のアリールチオ基である。
R6はグリシジル基、アクリロイル基、メタクリロイル基、ビニル基、置換基を有していてもよいビニルアリール基またはビニルアリーロイル基である。
上記-S-Ar1のAr1は環員数6~14のアリール基または環員数5~14の複素アリール基を表わし、また2つ以上の環が縮合していてもよく、置換基を有していてもよい。置換基を有する場合の置換基は塩素原子、臭素原子、炭素数1~4のアルキル基、炭素数1~4のアルキルオキシ基または炭素数1~4のアルキルチオ基、フェニルオキシ基またはフェニルチオ基であり、これらがフェニルオキシ基またはフェニルチオ基である場合は更に該置換基と同様な置換基を有してもよい。 That is, the present invention is a polymerizable compound represented by the following general formula (1).
here,
R 1 to R 5 are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a carbon atom having 6 to 10 carbon atoms. Represents a monovalent group selected from the group consisting of an aryl group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an arylthio group represented by —S—Ar 1 , one of which Two or three are the arylthio groups.
X 1 is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms, wherein the alkylene group, oxyalkylene group, thioalkylene group, alkyleneoxy group and alkylenethio group may have a substituent, The substituent of is a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or acarbon number 6 to 10 arylthio groups.
R 6 is a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, an optionally substituted vinylaryl group or a vinylaryloyl group.
The -S-Ar Ar 1 of 1 represents an aryl group or ring members 5-14 heterocyclic aryl group ring members 6-14, also may have combined two or more rings are condensed, substituted It may be. In the case of having a substituent, the substituent is chlorine atom, bromine atom, alkyl group having 1 to 4 carbon atoms, alkyloxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, phenyloxy group or phenylthio group. In the case where these are a phenyloxy group or a phenylthio group, they may further have a substituent similar to the substituent.
R1~R5は水素原子、又は塩素原子、臭素原子、炭素数1~4のアルキル基、炭素数1~4のアルキルオキシ基、炭素数1~4のアルキルチオ基、炭素数6~10のアリール基、炭素数6~10のアリールオキシ基、炭素数7~11のアラルキル基、及び-S-Ar1で表わされるアリールチオ基からなる群れから選ばれる1価の基を表し、その内1つ、2つまたは3つが該アリールチオ基である。
X1は直接結合、酸素原子、硫黄原子、炭素数1~4のアルキレン基、炭素数1~4のオキシアルキレン基、炭素数1~4のチオアルキレン基、炭素数1~4のアルキレンオキシ基または炭素数1~4のアルキレンチオ基を表し、ここで、アルキレン基、オキシアルキレン基、チオアルキレン基、アルキレンオキシ基及びアルキレンチオ基は、置換基を有してもよく、置換基を有する場合の置換基は塩素原子、臭素原子、炭素数1~4のアルキルオキシ基、炭素数1~4のアルキルチオ基、炭素数6~10のアリール基、炭素数6~10のアリールオキシ基または炭素数6~10のアリールチオ基である。
R6はグリシジル基、アクリロイル基、メタクリロイル基、ビニル基、置換基を有していてもよいビニルアリール基またはビニルアリーロイル基である。
上記-S-Ar1のAr1は環員数6~14のアリール基または環員数5~14の複素アリール基を表わし、また2つ以上の環が縮合していてもよく、置換基を有していてもよい。置換基を有する場合の置換基は塩素原子、臭素原子、炭素数1~4のアルキル基、炭素数1~4のアルキルオキシ基または炭素数1~4のアルキルチオ基、フェニルオキシ基またはフェニルチオ基であり、これらがフェニルオキシ基またはフェニルチオ基である場合は更に該置換基と同様な置換基を有してもよい。 That is, the present invention is a polymerizable compound represented by the following general formula (1).
R 1 to R 5 are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a carbon atom having 6 to 10 carbon atoms. Represents a monovalent group selected from the group consisting of an aryl group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an arylthio group represented by —S—Ar 1 , one of which Two or three are the arylthio groups.
X 1 is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms, wherein the alkylene group, oxyalkylene group, thioalkylene group, alkyleneoxy group and alkylenethio group may have a substituent, The substituent of is a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a
R 6 is a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, an optionally substituted vinylaryl group or a vinylaryloyl group.
The -S-Ar Ar 1 of 1 represents an aryl group or ring members 5-14 heterocyclic aryl group ring members 6-14, also may have combined two or more rings are condensed, substituted It may be. In the case of having a substituent, the substituent is chlorine atom, bromine atom, alkyl group having 1 to 4 carbon atoms, alkyloxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, phenyloxy group or phenylthio group. In the case where these are a phenyloxy group or a phenylthio group, they may further have a substituent similar to the substituent.
上記一般式(1)において、R1~R5の1つが、-S-Ar1であること、またはR1~R5の2つ又は3つが、-S-Ar1であるとより優れた重合性化合物となる。
In the general formula (1), one of R 1 ~ R 5, it is -S-Ar 1, or two or but three R 1 ~ R 5, more excellent If it is -S-Ar 1 It becomes a polymerizable compound.
また、本発明は、上記の重合性化合物含むことを特徴とする樹脂組成物、この樹脂組成物を硬化させてなることを特徴とする樹脂硬化物、およびこの樹脂組成物または樹脂硬化物を含むことを特徴とする光学材料である。
The present invention also includes a resin composition characterized by containing the polymerizable compound, a resin cured product obtained by curing the resin composition, and the resin composition or resin cured product. It is an optical material characterized by this.
さらに、本発明は、上記の重合性化合物を含むホログラフィック記録用材料に関する。このホログラフィック記録用材料は、A)上記重合性化合物、B)マトリックス樹脂又はマトリックス樹脂形成成分及びC)光重合開始剤を含むホログラフィック記録用材料であってもよい。
Furthermore, the present invention relates to a holographic recording material containing the polymerizable compound. The holographic recording material may be a holographic recording material containing A) the polymerizable compound, B) a matrix resin or a matrix resin forming component, and C) a photopolymerization initiator.
一般式(1)において、R1~R5の1つが、-S-Ar1であること、R1~R5の2つまたは3つが、-S-Ar1であること、または前記重合性化合物の25℃における屈折率nDが、1.60以上であることは、より良いホログラフィック記録用材料を与える。
In the general formula (1), one of R 1 to R 5 is —S—Ar 1 , two or three of R 1 to R 5 are —S—Ar 1 , or the polymerizable property A refractive index n D at 25 ° C. of the compound of 1.60 or more gives a better holographic recording material.
前記マトリックス樹脂としては、イソシアネート-ヒドロキシル重付加物が挙げられ、マトリックス樹脂形成材料としては、ポリイソシアネートとポリオールを含む材料が挙げられる。
Examples of the matrix resin include isocyanate-hydroxyl polyadducts, and examples of the matrix resin forming material include materials containing polyisocyanate and polyol.
また、本発明は前記のホログラフィック記録用材料を含有する記録層を備えることを特徴とするホログラフィック記録媒体である。
The present invention also provides a holographic recording medium comprising a recording layer containing the holographic recording material.
本発明の重合性化合物は、従来知られている重合性化合物と比較して高屈折率性、透明性、ハンドリング性に優れ、レンズ用途等のガラス代替材料、液晶ディスプレイ用カラーフィルタの保護膜材料、光学製品の保護用コーティング材料、電子ペーパーや液晶ディスプレイ等のスペーサ用微粒子、光ディスクや光ファイバー等用の接着剤、ホログラム記録媒体用の光記録材料等の各種光学材料に有用な樹脂組成物及び硬化物を与えることができる。
The polymerizable compound of the present invention is higher in refractive index, transparency and handling than conventional polymerizable compounds, glass substitute materials for lens applications, and protective film materials for color filters for liquid crystal displays. Resin compositions useful for various optical materials such as coating materials for protecting optical products, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, optical recording materials for hologram recording media, and curing Can give things.
本発明でいう光学材料は、光を透過させる用途、又は光を反射させる用途に使用される材料を意味し、好適にはレンズ用、光透過膜用等の光透過性用の光学材料であり、更に好適にはレンズ用途の光学材料である。
The optical material as used in the present invention means a material used for light transmitting or reflecting light, and is preferably an optical material for light transmission such as for lenses and light transmission films. More preferably, it is an optical material for lens use.
また、本発明のホログラフィック記録用材料に使用した重合性化合物は、屈折率変調度と相溶性の両立が図られ、濁りや散乱を生じさせることなく、これを使用したホログラフィック記録用材料は、大きなM#、高い感度を示す。
In addition, the polymerizable compound used in the holographic recording material of the present invention is compatible with the refractive index modulation and compatibility, and without causing turbidity or scattering, the holographic recording material using the polymerizable compound is , Large M #, high sensitivity.
以下、本発明の詳細並びにその他の特徴について、実施の形態に関連させて詳細に説明するが、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々に変更して実施することができる。
Hereinafter, the details and other features of the present invention will be described in detail in connection with the embodiments. However, the present invention is not limited to the following embodiments, and variously within the scope of the gist of the present invention. It can be changed and implemented.
まず、本発明の重合性化合物について、説明する。
本発明の重合性化合物は、上記一般式(1)で表される。 First, the polymerizable compound of the present invention will be described.
The polymerizable compound of the present invention is represented by the general formula (1).
本発明の重合性化合物は、上記一般式(1)で表される。 First, the polymerizable compound of the present invention will be described.
The polymerizable compound of the present invention is represented by the general formula (1).
一般式(1)において、R1~R5は水素原子、又は塩素原子、臭素原子、炭素数1~4のアルキル基、炭素数1~4のアルキルオキシ基、炭素数1~4のアルキルチオ基、炭素数6~10のアリール基、炭素数6~10のアリールオキシ基、炭素数7~11のアラルキル基、及び-S-Ar1で表わされるアリールチオ基からなる群れから選ばれる1価の基を表し、R1~R5の内1つ、2つまたは3つが該アリールチオ基である。
In the general formula (1), R 1 to R 5 are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms. A monovalent group selected from the group consisting of an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an arylthio group represented by -S-Ar 1 And one, two or three of R 1 to R 5 are the arylthio group.
R1~R5が、水素原子又はアリールチオ基以外の1価の基の数は、0~4であるが、0~2が好ましく、0又は1がより好ましい。水素原子又はアリールチオ基以外の1価の基である場合、例えば、塩素原子、臭素原子、炭素数1~2のアルキル基、炭素数1~2のアルキルオキシ基または炭素数1~2のアルキルチオ基、炭素数6~7のアリール基、炭素数6~7のアリールオキシ基、又は炭素数7~9のアラルキル基が好ましく挙げられ、臭素原子、メチル基、メトキシ基、メチルチオ基、フェニル基、フェノキシ基、ベンジル基、1-フェニルエチル基、又は2-フェニルプロパン-2-イル基がより好ましい。
The number of monovalent groups other than hydrogen atoms or arylthio groups in R 1 to R 5 is 0 to 4, preferably 0 to 2, and more preferably 0 or 1. In the case of a monovalent group other than a hydrogen atom or an arylthio group, for example, a chlorine atom, a bromine atom, an alkyl group having 1 to 2 carbon atoms, an alkyloxy group having 1 to 2 carbon atoms, or an alkylthio group having 1 to 2 carbon atoms And an aryloxy group having 6 to 7 carbon atoms, an aryloxy group having 6 to 7 carbon atoms, or an aralkyl group having 7 to 9 carbon atoms, preferably a bromine atom, methyl group, methoxy group, methylthio group, phenyl group, phenoxy A group, a benzyl group, a 1-phenylethyl group, or a 2-phenylpropan-2-yl group is more preferable.
X1は直接結合、酸素原子、硫黄原子、炭素数1~4のアルキレン基、炭素数1~4のオキシアルキレン基、炭素数1~4のチオアルキレン基、炭素数1~4のアルキレンオキシ基または炭素数1~4のアルキレンチオ基を表す。ここで、オキシアルキレン基、チオアルキレン基、アルキレンオキシ基またはアルキレンチオ基は、YCnH2n又はCnH2nYで表わされ、YはO又はSであり、nは1~4の数である。また、アルキレン基、オキシアルキレン基(又はアルキレンオキシ基)、チオアルキレン基(又はアルキレンチオ基)は、置換基を有してもよい。
置換基を有する場合の好ましい置換基としては、塩素原子、臭素原子、炭素数1~4のアルキルオキシ基、炭素数1~4のアルキルチオ基、炭素数6~10のアリール基、炭素数6~10のアリールオキシ基または炭素数6~10のアリールチオ基が挙げられ、上記アリール基、アリールオキシ基またはアリールチオ基は、後記するAr1が有していてもよい置換基を有していてもよい。 X 1 is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms. Here, the oxyalkylene group, thioalkylene group, alkyleneoxy group or alkylenethio group is represented by YC n H 2n or C n H 2n Y, Y is O or S, and n is a number from 1 to 4. It is. The alkylene group, oxyalkylene group (or alkyleneoxy group), and thioalkylene group (or alkylenethio group) may have a substituent.
In the case of having a substituent, preferred substituents include a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 6 to 6 carbon atoms. 10 aryloxy group or arylthio group having 6 to 10 carbon atoms, and the aryl group, aryloxy group or arylthio group may have a substituent which Ar1 described later may have.
置換基を有する場合の好ましい置換基としては、塩素原子、臭素原子、炭素数1~4のアルキルオキシ基、炭素数1~4のアルキルチオ基、炭素数6~10のアリール基、炭素数6~10のアリールオキシ基または炭素数6~10のアリールチオ基が挙げられ、上記アリール基、アリールオキシ基またはアリールチオ基は、後記するAr1が有していてもよい置換基を有していてもよい。 X 1 is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms. Here, the oxyalkylene group, thioalkylene group, alkyleneoxy group or alkylenethio group is represented by YC n H 2n or C n H 2n Y, Y is O or S, and n is a number from 1 to 4. It is. The alkylene group, oxyalkylene group (or alkyleneoxy group), and thioalkylene group (or alkylenethio group) may have a substituent.
In the case of having a substituent, preferred substituents include a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 6 to 6 carbon atoms. 10 aryloxy group or arylthio group having 6 to 10 carbon atoms, and the aryl group, aryloxy group or arylthio group may have a substituent which Ar1 described later may have.
R6はグリシジル基、アクリロイル基、メタクリロイル基、ビニル基、置換基を有していてもよいビニルアリール基またはビニルアリーロイル基を表わす。ビニルアリール基の炭素数は8~20が好ましく、ビニルアリーロイル基の炭素数は9~20が好ましい。また、ビニルアリール基が置換基を有する場合の好ましい置換基としては、X1の説明における好ましい置換基として挙げられた置換基が挙げられる。
R 6 represents a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, a vinyl aryl group which may have a substituent, or a vinyl aryloyl group. The vinyl aryl group preferably has 8 to 20 carbon atoms, and the vinyl aryloyl group preferably has 9 to 20 carbon atoms. Further, a vinyl aryl group Preferred examples of the substituent for the case of having a substituent include the substituents cited as preferred substituents in the description of X 1.
上記-S-Ar1のAr1は環員数6~14のアリール基または環員数5~14の複素アリール基を表わし、置換基を有していてもよく、また2つ以上の環が縮環していてもよい。Ar1は単環構造であっても縮合環構造であってもよく、Ar1を構成する環の数は1~4、好ましくは1~3、更に好ましくは1~2である。また、光学樹脂用途、特にホログラフィク記録に用いる場合、透明性の低下だけでなく、光硬化性や耐候性を確保するためには、着色が少ないことが好ましく、この点からAr1はアリール基であることが好ましい。置換基を有する場合の置換基は、後記する。
It said Ar 1 of -S-Ar 1 represents a ring members 6-14 aryl group or ring members 5-14 heterocyclic aryl group may have a substituent, and two or more rings condensed You may do it. Ar 1 may be a monocyclic structure or a condensed ring structure, and the number of rings constituting Ar 1 is 1 to 4, preferably 1 to 3, and more preferably 1 to 2. In addition, when used for optical resin applications, particularly for holographic recording, it is preferable that the coloring is small in order to ensure not only a decrease in transparency but also photocurability and weather resistance. From this point, Ar 1 is an aryl group. It is preferable that The substituent in the case of having a substituent will be described later.
ただし、一般式(1)において、-S-Ar1の数が1つである場合で、(d)R1、R2、R4、R5が水素原子で、(e)R3が-S-Ar1で、かつ(f)Ar1がフェニル基であるとき、下記(a)、(b)または(c)を満足するものは除くことが望ましい。
(a) X1が直接結合で、かつR6がビニル基、
(b) X1が酸素原子で、かつR6がアクリロイル基またはメタクリロイル基、
(c) X1が置換基を有さないオキシメチレン基、かつR6がアクリロイル基またはメタクリロイル基。 However, in the general formula (1), when —S—Ar 1 is one, (d) R 1 , R 2 , R 4 , R 5 are hydrogen atoms, and (e) R 3 is — When S-Ar 1 and (f) Ar 1 is a phenyl group, those satisfying the following (a), (b) or (c) are preferably excluded.
(A) X 1 is a direct bond and R 6 is a vinyl group,
(B) X 1 is an oxygen atom, and R 6 is an acryloyl group or a methacryloyl group,
(C) X 1 is an oxymethylene group having no substituent, and R 6 is an acryloyl group or a methacryloyl group.
(a) X1が直接結合で、かつR6がビニル基、
(b) X1が酸素原子で、かつR6がアクリロイル基またはメタクリロイル基、
(c) X1が置換基を有さないオキシメチレン基、かつR6がアクリロイル基またはメタクリロイル基。 However, in the general formula (1), when —S—Ar 1 is one, (d) R 1 , R 2 , R 4 , R 5 are hydrogen atoms, and (e) R 3 is — When S-Ar 1 and (f) Ar 1 is a phenyl group, those satisfying the following (a), (b) or (c) are preferably excluded.
(A) X 1 is a direct bond and R 6 is a vinyl group,
(B) X 1 is an oxygen atom, and R 6 is an acryloyl group or a methacryloyl group,
(C) X 1 is an oxymethylene group having no substituent, and R 6 is an acryloyl group or a methacryloyl group.
しかし、一般式(1)において、-S-Ar1の数が2つ又は3つである場合は、上記(d)~(f)と、(a)、(b)または(c)を満足するものであっても除かれない。
However, in the general formula (1), when the number of —S—Ar 1 is 2 or 3, the above (d) to (f) and (a), (b) or (c) are satisfied. It is not excluded even if it is something to do.
また、ホログラフィック記録用材料として使用する場合は、-S-Ar1の数が1つで、R1、R2、R4、R5が水素原子で、R3が-S-Ar1で、かつAr1がフェニル基であるとき、X1が直接結合で、かつR6がビニル基であるものは除くことが望ましい。
When used as a holographic recording material, the number of —S—Ar 1 is one, R 1 , R 2 , R 4 , R 5 are hydrogen atoms, and R 3 is —S—Ar 1 . When Ar 1 is a phenyl group, it is desirable to exclude those in which X 1 is a direct bond and R 6 is a vinyl group.
本明細書でいう用語は、特段の断りがない限り、次の意味を有する。
The terms used in this specification have the following meanings unless otherwise specified.
<アリール基>
ベンゼン環基、インデン環基、ナフタレン環基、アズレン環基、フルオレン環基、アセナフテン環基、アントラセン環基、フェナントレン環基、フルオランテン環基、ピレン環基などの炭素数6~16、好ましくは6~14のアリール基が挙げられる。着色回避、相溶性の点から、更に好ましくは炭素数6~10であり、特に好ましくはベンゼン環基、ナフタレン環基である。なお、ベンゼン環基はベンゼンから1つのHを取って生じる基であり、他の基も同様である。 <Aryl group>
6-16, preferably 6 carbon atoms such as benzene, indene, naphthalene, azulene, fluorene, acenaphthene, anthracene, phenanthrene, fluoranthene, pyrene, and the like -14 aryl groups. From the viewpoint of avoiding coloring and compatibility, the number of carbon atoms is more preferably 6 to 10, and particularly preferably a benzene ring group and a naphthalene ring group. The benzene ring group is a group formed by taking one H from benzene, and the other groups are the same.
ベンゼン環基、インデン環基、ナフタレン環基、アズレン環基、フルオレン環基、アセナフテン環基、アントラセン環基、フェナントレン環基、フルオランテン環基、ピレン環基などの炭素数6~16、好ましくは6~14のアリール基が挙げられる。着色回避、相溶性の点から、更に好ましくは炭素数6~10であり、特に好ましくはベンゼン環基、ナフタレン環基である。なお、ベンゼン環基はベンゼンから1つのHを取って生じる基であり、他の基も同様である。 <Aryl group>
6-16, preferably 6 carbon atoms such as benzene, indene, naphthalene, azulene, fluorene, acenaphthene, anthracene, phenanthrene, fluoranthene, pyrene, and the like -14 aryl groups. From the viewpoint of avoiding coloring and compatibility, the number of carbon atoms is more preferably 6 to 10, and particularly preferably a benzene ring group and a naphthalene ring group. The benzene ring group is a group formed by taking one H from benzene, and the other groups are the same.
<複素アリール基>
複素アリール基に含まれるヘテロ原子としては特に限定されず、S、O、N、Pなどの各原子を用いることができるが、相溶性確保の点からS,O,Nの各原子が好ましく、SまたはOの各原子がより好ましく、中でも屈折率向上の点からS原子が特に好ましい。また、高透過率、相溶性の点からヘテロ原子の数は当該複素アリール基中に1~3であることが好ましく、1~2であることがより好ましい。 <Heteroaryl group>
The heteroatom contained in the heteroaryl group is not particularly limited, and each atom such as S, O, N, and P can be used, but each atom of S, O, and N is preferable from the viewpoint of ensuring compatibility, Each atom of S or O is more preferable, and S atom is particularly preferable from the viewpoint of improving the refractive index. From the viewpoint of high transmittance and compatibility, the number of heteroatoms is preferably 1 to 3, more preferably 1 to 2, in the heteroaryl group.
複素アリール基に含まれるヘテロ原子としては特に限定されず、S、O、N、Pなどの各原子を用いることができるが、相溶性確保の点からS,O,Nの各原子が好ましく、SまたはOの各原子がより好ましく、中でも屈折率向上の点からS原子が特に好ましい。また、高透過率、相溶性の点からヘテロ原子の数は当該複素アリール基中に1~3であることが好ましく、1~2であることがより好ましい。 <Heteroaryl group>
The heteroatom contained in the heteroaryl group is not particularly limited, and each atom such as S, O, N, and P can be used, but each atom of S, O, and N is preferable from the viewpoint of ensuring compatibility, Each atom of S or O is more preferable, and S atom is particularly preferable from the viewpoint of improving the refractive index. From the viewpoint of high transmittance and compatibility, the number of heteroatoms is preferably 1 to 3, more preferably 1 to 2, in the heteroaryl group.
具体的には、ピロール環基、フラン環基、チオフェン環基、イミダゾール環基、オキサゾール環基、チアゾール環基、ピリジン環基、ピラジン環基、ピリミジン環基、トリアジン環基、インドール環基、ベンゾフラン環基、ベンゾチオフェン環基、ベンゾイミダゾール環基、ベンゾオキサゾール環基、ベンゾチアゾール環基、キノリン環基、イソキノリン環基、カルバゾール環基、ジベンゾフラン環基、ジベンゾチオフェン環基、アクリジン環基、ベンゾカルバゾール環基、ベンゾナフトフラン環基、ベンゾナフトチオフェン環基などの炭素数5~17、好ましくは5~14の複素アリール基が挙げられる。中でもチオフェン環基、ベンゾチオフェン環基、ジベンゾチオフェン環基が好ましい。
Specifically, pyrrole ring group, furan ring group, thiophene ring group, imidazole ring group, oxazole ring group, thiazole ring group, pyridine ring group, pyrazine ring group, pyrimidine ring group, triazine ring group, indole ring group, benzofuran Ring group, benzothiophene ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, quinoline ring group, isoquinoline ring group, carbazole ring group, dibenzofuran ring group, dibenzothiophene ring group, acridine ring group, benzocarbazole Examples thereof include heteroaryl groups having 5 to 17 carbon atoms, preferably 5 to 14 carbon atoms, such as a cyclic group, a benzonaphthofuran ring group, and a benzonaphththiophene ring group. Of these, a thiophene ring group, a benzothiophene ring group, and a dibenzothiophene ring group are preferable.
<Ar1が有していてもよい置換基>
Ar1はハロゲン原子、炭素数1~4のアルキル基、アルキルオキシ基、アルキルチオ基、フェニルオキシ基及びフェニルチオ基から選ばれる置換基を有していてもよい。好ましい置換基は、塩素原子、臭素原子、炭素数1~4のアルキルチオ基、炭素数6~10のアリールオキシ基、炭素数7~11のアラルキル基である。但し、合成上の容易さの観点からは無置換であることが有利である。 <Substituent Ar 1 may have>
Ar 1 may have a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group, an alkylthio group, a phenyloxy group, and a phenylthio group. Preferred substituents are a chlorine atom, a bromine atom, an alkylthio group having 1 to 4 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms. However, from the viewpoint of ease of synthesis, it is advantageous that it is unsubstituted.
Ar1はハロゲン原子、炭素数1~4のアルキル基、アルキルオキシ基、アルキルチオ基、フェニルオキシ基及びフェニルチオ基から選ばれる置換基を有していてもよい。好ましい置換基は、塩素原子、臭素原子、炭素数1~4のアルキルチオ基、炭素数6~10のアリールオキシ基、炭素数7~11のアラルキル基である。但し、合成上の容易さの観点からは無置換であることが有利である。 <Substituent Ar 1 may have>
Ar 1 may have a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group, an alkylthio group, a phenyloxy group, and a phenylthio group. Preferred substituents are a chlorine atom, a bromine atom, an alkylthio group having 1 to 4 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms. However, from the viewpoint of ease of synthesis, it is advantageous that it is unsubstituted.
上記一般式(1)で表される化合物の具体例を以下に示すが、本発明はその要旨をこえない限りこれらに限定されるものではない。
Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited to these unless it exceeds the gist.
上記一般式(1)で表される重合性化合物は、公知の方法によって製造することができる。R6がビニル基である化合物は、例えば、ヒドロキシエチル基を有する化合物を前駆体として脱水反応によって製造することができる。R6が(メタ)アクリロイル基である化合物は、例えば、活性水素を有する化合物と(メタ)アクリル酸類との反応によって製造することができる。R6がグリシジル基である化合物は、例えば、活性水素を有する化合物とエピクロルヒドリンとの反応によって製造することができる。
The polymerizable compound represented by the general formula (1) can be produced by a known method. A compound in which R 6 is a vinyl group can be produced, for example, by a dehydration reaction using a compound having a hydroxyethyl group as a precursor. A compound in which R 6 is a (meth) acryloyl group can be produced, for example, by a reaction between a compound having active hydrogen and (meth) acrylic acids. A compound in which R 6 is a glycidyl group can be produced, for example, by a reaction between a compound having active hydrogen and epichlorohydrin.
以上に説明した一般式(1)で表わされる重合性化合物の分子量は、光照射時の架橋に伴う収縮率低減の点あるいは記録感度や相溶性の点から、通常1000以下、好ましくは800以下、更に好ましくは600以下、中でも500以下であって、通常200以上、好ましくは220以上、更に好ましくは250以上である。
The molecular weight of the polymerizable compound represented by the general formula (1) described above is usually 1000 or less, preferably 800 or less, from the viewpoint of shrinkage reduction due to crosslinking during light irradiation or recording sensitivity and compatibility. More preferably, it is 600 or less, especially 500 or less, and is usually 200 or more, preferably 220 or more, more preferably 250 or more.
上記一般式(1)で表される重合性化合物は、25℃における屈折率nDが1.50以上、好ましくは1.55以上、更に好ましくは1.60以上、特に好ましくは1.62以上である。ホログラフィック記録用材料やホログラフィック記録媒体に用いる場合、屈折率が過度に低いと、回折効率が大きくならず、十分な多重度が得られないため、屈折率nDは1.60以上であることが好ましい。一方、屈折率が過度に高いと、マトリックス樹脂との屈折率の差が大きくなり過ぎ、散乱を生じる場合がある。なお、屈折率は短い波長で評価すると大きい値を示すが、短波長で相対的に大きい屈折率を示すサンプルは、長波長でも相対的に大きい屈折率を示し、その序列が逆転することはない。従って、記録波長以外の波長で屈折率を評価し、記録波長での値を予測することができる。
The polymerizable compound represented by the general formula (1) has a refractive index n D at 25 ° C. of 1.50 or more, preferably 1.55 or more, more preferably 1.60 or more, and particularly preferably 1.62 or more. It is. When used for a holographic recording material or a holographic recording medium, if the refractive index is excessively low, the diffraction efficiency does not increase and sufficient multiplicity cannot be obtained, so the refractive index n D is 1.60 or more. It is preferable. On the other hand, if the refractive index is excessively high, the difference in refractive index from the matrix resin becomes too large, which may cause scattering. In addition, although a refractive index shows a large value when evaluated at a short wavelength, a sample showing a relatively large refractive index at a short wavelength shows a relatively large refractive index even at a long wavelength, and its order is not reversed. . Therefore, the refractive index can be evaluated at a wavelength other than the recording wavelength, and the value at the recording wavelength can be predicted.
重合性化合物が固体であり、屈折率を直接測定することが困難な場合は、適当な溶媒に当該化合物を溶解して溶液とし、この溶液の屈折率を測定し、化合物が100%の場合の屈折率を外挿により求めることができる。
When the polymerizable compound is solid and it is difficult to directly measure the refractive index, the compound is dissolved in an appropriate solvent to form a solution, and the refractive index of this solution is measured. The refractive index can be obtained by extrapolation.
また、上記一般式(1)で表される重合性化合物は、60℃における粘度が5000mPa・s以下、好ましくは3000mPa・s以下、更に好ましくは1000mPa・s以下、特に好ましくは500mPa・s以下である。
The polymerizable compound represented by the general formula (1) has a viscosity at 60 ° C. of 5000 mPa · s or less, preferably 3000 mPa · s or less, more preferably 1000 mPa · s or less, and particularly preferably 500 mPa · s or less. is there.
本発明の樹脂組成物は、上記重合性化合物を含むものであるが、重合開始剤を含むことが好ましい。重合開始剤としては、公知の重合開始剤で良く、加熱又は紫外線などの照射によって重合を開始させるものであれば特に制限はない。
The resin composition of the present invention contains the polymerizable compound, but preferably contains a polymerization initiator. The polymerization initiator may be a known polymerization initiator and is not particularly limited as long as the polymerization is initiated by heating or irradiation with ultraviolet rays.
例えば、本発明の重合性化合物として(メタ)アクリロイル基、ビニル基などのラジカル重合性基を有する化合物を用いる場合、熱ラジカル重合開始剤、光ラジカル重合開始剤などが挙げられるが、硬化速度が速く常温硬化が可能なことから、光ラジカル重合開始剤であることが好ましい。
For example, when a compound having a radical polymerizable group such as a (meth) acryloyl group or a vinyl group is used as the polymerizable compound of the present invention, a thermal radical polymerization initiator, a photo radical polymerization initiator, etc. may be mentioned. A radical photopolymerization initiator is preferred because it can be rapidly cured at room temperature.
熱ラジカル重合開始剤としては、例えば、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイドなどのケトンパーオキサイド類、1,1-ビス(tert-ブチルパーオキシ)シクロヘキサン、1,1-ビス(tert-ブチルパーオキシ)-2-メチルシクロヘキサン、1,1-ビス(tert-ブチルパーオキシ)-3,3,5-トリメチルシクロヘキサン、1,1-ビス(tert-ヘキシルパーオキシ)シクロヘキサン、1,1-ビス(tert-ヘキシルパーオキシ)-3,3,5-トリメチルシクロヘキサンなどのパーオキシケタール類、p-メンタンハイドロパーオキサイドなどのハイドロパーオキサイド類、α,α’-ビス(tert-ブチルパーオキシ)ジイソプロピルベンゼン、ジクミルパーオキサイド、tert-ブチルクミルパーオキサイド、ジ-tert-ブチルパーオキサイドなどのジアルキルパーオキサイド類、ジオクタノイルパーオキサイド、ジラウロイルパーオキサイド、ジステアリルパーオキサイド、ジベンゾイルパーオキサイドなどのジアシルパーオキサイド類、ビス(4-tert-ブチルシクロヘキシル)パーオキシジカーボネート、ジ-2-エトキシエチルパーオキシジカーボネート、ジ-2-エチルヘキシルパーオキシジカーボネート、ジ-3-メトキシブチルパーオキシジカーボネートなどのパーオキシジカーボネート類、tert-ブチルパーオキシイソプロピルモノカーボネート、tert-ヘキシルパーオキシイソプロピルモノカーボネート、tert-ブチルパーオキシ-2-エチルヘキシルモノカーボネート、などのパーオキシカーボネート類、tert-ブチルパーオキシピバレート、tert-ヘキシルパーオキシピバレート、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、2,5-ジメチル-2,5-ビス(2-エチルヘキサノイルパーオキシ)ヘキサン、tert-ヘキシルパーオキシ-2-エチルヘキサノエート、tert-ブチルパーオキシ-2-エチルヘキサノエート、tert-ブチルパーオキシイソブチレート、tert-ブチルパーオキシ-3,5,5-トリメチルヘキサノエート、tert-ブチルパーオキシラウリレート、tert-ブチルパーオキシベンゾエート、tert-ヘキシルパーオキシベンゾエート、2,5-ジメチル-2,5-ビス(ベンゾイルパーオキシ)ヘキサン、tert-ブチルパーオキシアセテートなどのパーオキシエステル類、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’-ジメチルバレロニトリル)などのアゾ化合物などが挙げられる。
Examples of the thermal radical polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert -Butylperoxy) -2-methylcyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) cyclohexane, 1,1 -Peroxyketals such as bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, hydroperoxides such as p-menthane hydroperoxide, α, α'-bis (tert-butylperoxy) ) Diiso Dialkyl peroxides such as propylbenzene, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, distearyl peroxide, dibenzoyl peroxide Diacyl peroxides, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutylperoxydi Peroxydicarbonates such as carbonate, tert-butyl peroxyisopropyl monocarbonate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl Peroxycarbonates such as oxy-2-ethylhexyl monocarbonate, tert-butyl peroxypivalate, tert-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexano 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, tert-butylperoxybenzoate, tert-hexylperoxybenzoate, 2, 5-dimethyl-2 Peroxyesters such as 5-bis (benzoylperoxy) hexane and tert-butylperoxyacetate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) And azo compounds such as 2,2′-azobis (4-methoxy-2′-dimethylvaleronitrile).
これらの中で、硬化性、透明性、及び耐熱性の観点から、ジアシルパーオキサイド類、パーオキシカーボネート類、パーオキシエステル類、アゾ化合物であることが好ましい。
Of these, diacyl peroxides, peroxycarbonates, peroxyesters, and azo compounds are preferable from the viewpoints of curability, transparency, and heat resistance.
光ラジカル重合開始剤としては、例えば、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オンなどのベンジルケタール類、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-1-フェニルプロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)フェニル]-2-ヒドロキシ-2-メチルプロパン-1-オンなどのα-ヒドロキシアセトフェノン類、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタン-1-オン、1,2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オンなどのα-アミノアセトフェノン類、1-[4-(フェニルチオ)フェニル]-1,2-オクタジオン,2-(O-ベンゾイル)オキシムなどのオキシムエステル類、ビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルフォスフィンオキサイド、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイドなどのフォスフィンオキサイド類、2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-クロロフェニル)-4,5-ジ(メトキシフェニル)イミダゾール二量体、2-(o-フルオロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体、2-(p-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体などの2,4,5-トリアリールイミダゾール二量体、ベンゾフェノン、N,N’-テトラメチル-4,4’-ジアミノベンゾフェノン、N,N’-テトラエチル-4,4’-ジアミノベンゾフェノン、4-メトキシ-4’-ジメチルアミノベンゾフェノンなどのベンゾフェノン類、2-エチルアントラキノン、フェナントレンキノン、2-tert-ブチルアントラキノン、オクタメチルアントラキノン、1,2-ベンズアントラキノン、2,3-ベンズアントラキノン、2-フェニルアントラキノン、2,3-ジフェニルアントラキノン、1-クロロアントラキノン、2-メチルアントラキノン、1,4-ナフトキノン、9,10-フェナントレンキノン、2-メチル-1,4-ナフトキノン、2,3-ジメチルアントラキノンなどのキノン類、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインフェニルエーテルなどのベンゾインエーテル類、ベンゾイン、メチルベンゾイン、エチルベンゾインなどのベンゾイン類、9-フェニルアクリジン、1,7-ビス(9-アクリジニル)ヘプタンなどのアクリジン類、N-フェニルグリシン、クマリンなどが挙げられる。
Examples of the photo radical polymerization initiator include benzyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl. Α-hydroxyacetophenones such as propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2-benzyl-2-dimethylamino-1 Α-aminoacetophenones such as-(4-morpholinophenyl) -butan-1-one and 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1- [ Oxime esters such as 4- (phenylthio) phenyl] -1,2-octadione and 2- (O-benzoyl) oxime Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Phosphine oxides such as fin oxide, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2 -(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5- 2,4,5-triarylimidazole dimer such as diphenylimidazole dimer, benzo Benzophenones such as enone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2- Ethyl anthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2- Quinones such as methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether Benzoin ethers such as benzoin phenyl ether, benzoins such as benzoin, methylbenzoin, and ethylbenzoin, acridines such as 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, N-phenylglycine, coumarin, etc. Is mentioned.
これらの中で、硬化性、透明性および耐熱性の観点から、α-ヒドロキシアセトフェノン類、フォスフィンオキサイド類であることが好ましい。これらの熱及び光ラジカル重合開始剤は、単独でまたは2種類以上を組み合わせて使用することができる。さらに、適切な増感剤と組み合わせて用いることもできる。
Among these, α-hydroxyacetophenones and phosphine oxides are preferable from the viewpoints of curability, transparency and heat resistance. These thermal and photo radical polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.
光増感剤としては、特に限定されるものではなく、具体的には、トリエチルアミン、トリエタノールアミンなどの3級アミン類、トリフェニルフォスフィン等のアルキルフォスフィン類、β-チオジグリコール等のチオエーテル類などが例示され、その配合量としては、樹脂組成物の合計量に対して0.01~5重量%程度が推奨される。
The photosensitizer is not particularly limited, and specifically, tertiary amines such as triethylamine and triethanolamine, alkylphosphine such as triphenylphosphine, β-thiodiglycol and the like Thioethers are exemplified, and the blending amount is recommended to be about 0.01 to 5% by weight with respect to the total amount of the resin composition.
また、本発明の重合性化合物としてグリシジル基などのカチオン重合性基を有する化合物を用いる場合、重合開始剤としては、熱カチオン重合開始剤や光カチオン重合開始剤などが挙げられるが、硬化速度が速く常温硬化が可能なことから、光カチオン重合開始剤であることが好ましい。
Further, when a compound having a cationic polymerizable group such as a glycidyl group is used as the polymerizable compound of the present invention, examples of the polymerization initiator include a thermal cationic polymerization initiator and a photo cationic polymerization initiator. A photocationic polymerization initiator is preferred because it can be rapidly cured at room temperature.
熱カチオン重合開始剤としては、例えば、p-アルコキシフェニルベンジルメチルスルホニウムヘキサフルオロアンチモネートなどのベンジルスルホニウム塩類、ベンジル-p-シアノピリジニウムヘキサフルオロアンチモネート、1-ナフチルメチル-o-シアノピリジニウムヘキサフルオロアンチモネート、シンナミル-o-シアノピリジニウムヘキサフルオロアンチモネートなどのピリジニウム塩類、ベンジルジメチルフェニルアンモニウムヘキサフルオロアンチモネートなどのベンジルアンモニウム塩類などが挙げられる。
Examples of the thermal cationic polymerization initiator include benzylsulfonium salts such as p-alkoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-p-cyanopyridinium hexafluoroantimonate, 1-naphthylmethyl-o-cyanopyridinium hexafluoroantimonate. And pyridinium salts such as cinnamyl-o-cyanopyridinium hexafluoroantimonate and benzylammonium salts such as benzyldimethylphenylammonium hexafluoroantimonate.
これらの中で、硬化性、透明性、及び耐熱性の観点から、ベンジルスルホニウム塩類であることが好ましい。
Of these, benzylsulfonium salts are preferred from the viewpoints of curability, transparency, and heat resistance.
光カチオン重合開始剤としては、例えば、p-メトキシベンゼンジアゾニウムヘキサフルオロホスフェートなどのアリールジアゾニウム塩類、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネートなどのジアリールヨードニウム塩類、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、ジフェニル-4-チオフェノキシフェニルスルホニウムヘキサフルオロホスフェート、ジフェニル-4-チオフェノキシフェニルスルホニウムヘキサフルオロアンチモネート、ジフェニル-4-チオフェノキシフェニルスルホニウムペンタフルオロヒドロキシアンチモネートなどのトリアリールスルホニウム塩類、トリフェニルセレノニウムヘキサフルオロホスフェート、トリフェニルセレノニウムテトラフルオロボレート、トリフェニルセレノニウムヘキサフルオロアンチモネートなどのトリアリールセレノニウム塩類、ジメチルフェナシルスルホニウムヘキサフルオロアンチモネート、ジエチルフェナシルスルホニウムヘキサフルオロアンチモネートなどのジアルキルフェナシルスルホニウム塩類、4-ヒドロキシフェニルジメチルスルホニウムヘキサフルオロアンチモネート、4-ヒドロキシフェニルベンジルメチルスルホニウムヘキサフルオロアンチモネートなどのジアルキル-4-ヒドロキシ塩類、α-ヒドロキシメチルベンゾインスルホン酸エステル、N-ヒドロキシイミドスルホネート、α-スルホニロキシケトン、β-スルホニロキシケトンなどのスルホン酸エステルなどが挙げられる。
Examples of the cationic photopolymerization initiator include aryl diazonium salts such as p-methoxybenzenediazonium hexafluorophosphate, diaryliodonium salts such as diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfone Triarylsulfonium such as phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium pentafluorohydroxyantimonate Salts, triphenyl acetate Triarylselenonium salts such as nonium hexafluorophosphate, triphenylselenonium tetrafluoroborate, triphenylselenonium hexafluoroantimonate, dialkyl such as dimethylphenacylsulfonium hexafluoroantimonate, diethylphenacylsulfonium hexafluoroantimonate Dialkyl-4-hydroxy salts such as phenacylsulfonium salts, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate, α-hydroxymethylbenzoin sulfonate, N-hydroxyimide sulfonate , Α-sulfonyloxy ketone, β-sulfonyloxy ketone, etc. An acid ester.
これらの中で、硬化性、透明性、及び耐熱性の観点から、トリアリールスルホニウム塩類であることが好ましい。これらの熱及び光カチオン重合開始剤は、単独で又は2種類以上組み合わせて用いることができる。さらに、適切な増感剤と組み合わせて用いることもできる。
Of these, triarylsulfonium salts are preferred from the viewpoints of curability, transparency, and heat resistance. These thermal and photocationic polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.
これら重合開始剤の使用量は、重合禁止剤の使用の有無、使用する場合の重合禁止剤の種類や量により異なるが、樹脂組成物の合計量に対して0.01~10重量%であることがよく、より好ましくは0.02~5重量%であり、さらに好ましくは0.03~3重量%である。但し、この使用量は使用する重合開始剤の種類により大きく変化するので最適条件を適宜決定することが必要である。
The amount of the polymerization initiator used is 0.01 to 10% by weight based on the total amount of the resin composition, although it varies depending on the presence or absence of the polymerization inhibitor and the type and amount of the polymerization inhibitor used. More preferably, it is 0.02 to 5% by weight, and further preferably 0.03 to 3% by weight. However, since the amount used varies greatly depending on the type of polymerization initiator used, it is necessary to appropriately determine the optimum conditions.
本発明の樹脂組成物は、樹脂組成物の保存等のために、公知の重合禁止剤を添加することができる。但し、この種類及び添加量は使用する重合開始剤並びに重合性化合物の種類及び量により大きく変化するので最適条件を適宜決定することが必要である。
In the resin composition of the present invention, a known polymerization inhibitor can be added for storage of the resin composition. However, since the type and amount of addition vary greatly depending on the type and amount of polymerization initiator and polymerizable compound to be used, it is necessary to appropriately determine the optimum conditions.
また、本発明の樹脂組成物は、必要に応じて一般式(1)で表される重合性化合物以外の他の重合性化合物(以下、他の重合性化合物とも言う。)を含むことができる。他の重合性化合物を含む場合であっても、一般式(1)で表される重合性化合物は樹脂組成物の合計量に対して10重量%以上であることが好ましく、より好ましくは50重量%以上である。
Moreover, the resin composition of this invention can contain other polymeric compounds (henceforth other polymeric compounds) other than the polymeric compound represented by General formula (1) as needed. . Even when other polymerizable compounds are included, the polymerizable compound represented by the general formula (1) is preferably 10% by weight or more, more preferably 50% by weight based on the total amount of the resin composition. % Or more.
他の重合性化合物としては、公知の重合性化合物で良く、単官能のもの、二官能のもの、多官能のもの又は重合性オリゴマーのいずれも用いることができ、また、単独でも2種以上を併用してもよい。熱又は光による重合性化合物は、熱重合性化合物と光重合性化合物を用途に応じて使い分けることが好ましい。
As the other polymerizable compound, a known polymerizable compound may be used, and any of monofunctional, bifunctional, polyfunctional, and polymerizable oligomers may be used. You may use together. As the polymerizable compound by heat or light, it is preferable to use either a thermally polymerizable compound or a photopolymerizable compound depending on the application.
本発明の重合性化合物として(メタ)アクリロイル基、ビニルアリール基などのラジカル重合性基を有する化合物を用いる場合、他の重合性化合物としては公知のラジカル重合性化合物を用いることができ、具体的には、(メタ)アクリレート化合物、ハロゲン化ビニリデン化合物、ビニルエーテル化合物、ビニルエステル化合物、ビニルピリジン化合物、ビニルアミド化合物、ビニルアリール化合物などが挙げられる。これらのうち透明性の観点から、(メタ)アクリレート化合物やビニルアリール化合物であることが好ましい。
When a compound having a radical polymerizable group such as a (meth) acryloyl group or a vinylaryl group is used as the polymerizable compound of the present invention, a known radical polymerizable compound can be used as the other polymerizable compound. (Meth) acrylate compounds, vinylidene halide compounds, vinyl ether compounds, vinyl ester compounds, vinyl pyridine compounds, vinyl amide compounds, vinyl aryl compounds, and the like. Of these, a (meth) acrylate compound and a vinylaryl compound are preferable from the viewpoint of transparency.
単官能(メタ)アクリレート化合物としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、イソアミル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、オクチルヘプチル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ウンデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、トリデシル(メタ)アクリレート、テトラデシル(メタ)アクリレート、ペンタデシル(メタ)アクリレート、ヘキサデシル(メタ)アクリレート、ステアリル(メタ)アクリレート、ベヘニル(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、3-クロロ-2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、エトキシポリエチレングリコール(メタ)アクリレート、メトキシポリプロピレングリコール(メタ)アクリレート、エトキシポリプロピレングリコール(メタ)アクリレート、モノ(2-(メタ)アクリロイロキシエチル)スクシネートなどの脂肪族(メタ)アクリレート類、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ノルボルニル(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、ジシクロペンテニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、モノ(2-(メタ)アクリロイロキシエチル)テトラヒドロフタレート、モノ(2-(メタ)アクリロイロキシエチル)ヘキサヒドロフタレートなどの脂環式(メタ)アクリレート類、ベンジル(メタ)アクリレート、フェニル(メタ)アクリレート、o-ビフェニル(メタ)アクリレート、1-ナフチル(メタ)アクリレート、2-ナフチル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、p-クミルフェノキシエチル(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、1-ナフトキシエチル(メタ)アクリレート、2-ナフトキシエチル(メタ)アクリレート、フェノキシポリエチレングリコール(メタ)アクリレート、ノニルフェノキシポリエチレングリコール(メタ)アクリレート、フェノキシポリプロピレングリコール(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、2-ヒドロキシ-3-(o-フェニルフェノキシ)プロピル(メタ)アクリレート、2-ヒドロキシ-3-(1-ナフトキシ)プロピル(メタ)アクリレート、2-ヒドロキシ-3-(2-ナフトキシ)プロピル(メタ)アクリレートなどの芳香族(メタ)アクリレート類、2-テトラヒドロフルフリル(メタ)アクリレート、N-(メタ)アクリロイロキシエチルヘキサヒドロフタルイミド、2-(メタ)アクリロイロキシエチル-N-カルバゾールなどの複素環式(メタ)アクリレート類、これらのカプロラクトン変性体などが挙げられる。
Examples of monofunctional (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and butoxyethyl (meth) acrylate. , Isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) Acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, Allyl (meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Fats such as acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, mono (2- (meth) acryloyloxyethyl) succinate Group (meth) acrylates, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopenta Ru (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate, mono (2- (meth) acryloyloxyethyl) hexahydrophthalate Alicyclic (meth) acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, phenoxyethyl ( (Meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 1-naphthoxyethyl (meth) acrylate, 2-naphthoxyethyl (meth) acrylate, phenoxypolyethylene Lenglycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl Aromatic (meth) acrylates such as (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy-3- (2-naphthoxy) propyl (meth) acrylate, 2- Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, 2- (meth) acryloyloxyethyl-N-carbazole, Such Rorakuton modified products thereof.
2官能(メタ)アクリレート化合物としては、例えば、エチレングリコールジ(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、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(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、プロピレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(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、テトラプロピレングリコールジ(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、エトキシ化ポリプロピレングリコールジ(メタ)アクリレート、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、ネオペンチルグリコールジ(メタ)アクリレート、3-メチル-1,5-ペンタンジオールジ(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、2-ブチル-2-エチル-1,3-プロパンジオールジ(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、1,10-デカンジオールジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、エトキシ化2-メチル-1,3-プロパンジオールジ(メタ)アクリレートなどの脂肪族ジ(メタ)アクリレート類、シクロヘキサンジメタノールジ(メタ)アクリレート、エトキシ化シクロヘキサンジメタノールジ(メタ)アクリレート、プロポキシ化シクロヘキサンジメタノールジ(メタ)アクリレート、エトキシ化プロポキシ化シクロヘキサンジメタノールジ(メタ)アクリレート、トリシクロデカンジメタノールジ(メタ)アクリレート、エトキシ化トリシクロデカンジメタノールジ(メタ)アクリレート、プロポキシ化トリシクロデカンジメタノールジ(メタ)アクリレート、エトキシ化プロポキシ化トリシクロデカンジメタノールジ(メタ)アクリレート、エトキシ化水添ビスフェノールAジ(メタ)アクリレート、プロポキシ化水添ビスフェノールAジ(メタ)アクリレート、エトキシ化プロポキシ化水添ビスフェノールAジ(メタ)アクリレート、エトキシ化水添ビスフェノールFジ(メタ)アクリレート、プロポキシ化水添ビスフェノールFジ(メタ)アクリレート、エトキシ化プロポキシ化水添ビスフェノールFジ(メタ)アクリレートなどの脂環式ジ(メタ)アクリレート類、エトキシ化ビスフェノールAジ(メタ)アクリレート、プロポキシ化ビスフェノールAジ(メタ)アクリレート、エトキシ化プロポキシ化ビスフェノールAジ(メタ)アクリレート、エトキシ化ビスフェノールFジ(メタ)アクリレート、プロポキシ化ビスフェノールFジ(メタ)アクリレート、エトキシ化プロポキシ化ビスフェノールFジ(メタ)アクリレート、エトキシ化ビスフェノールAFジ(メタ)アクリレート、プロポキシ化ビスフェノールAFジ(メタ)アクリレート、エトキシ化プロポキシ化ビスフェノールAFジ(メタ)アクリレート、エトキシ化フルオレン型ジ(メタ)アクリレート、プロポキシ化フルオレン型ジ(メタ)アクリレート、エトキシ化プロポキシ化フルオレン型ジ(メタ)アクリレートなどの芳香族ジ(メタ)アクリレート類、エトキシ化イソシアヌル酸ジ(メタ)アクリレート、プロポキシ化イソシアヌル酸ジ(メタ)アクリレート、エトキシ化プロポキシ化イソシアヌル酸ジ(メタ)アクリレートなどの複素環式ジ(メタ)アクリレート類、これらのカプロラクトン変性体、ネオペンチルグリコール型エポキシジ(メタ)アクリレートなどの脂肪族エポキシジ(メタ)アクリレート類、シクロヘキサンジメタノール型エポキシジ(メタ)アクリレート、水添ビスフェノールA型エポキシジ(メタ)アクリレート、水添ビスフェノールF型エポキシジ(メタ)アクリレートなどの脂環式エポキシジ(メタ)アクリレート類、レゾルシノール型エポキシジ(メタ)アクリレート、ビスフェノールA型エポキシジ(メタ)アクリレート、ビスフェノールF型エポキシジ(メタ)アクリレート、ビスフェノールAF型エポキシジ(メタ)アクリレート、フルオレン型エポキシジ(メタ)アクリレートなどの芳香族エポキシジ(メタ)アクリレート類などが挙げられる。
Examples of the bifunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth). ) Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated polypropylene glycol Di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ne Pentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, ethoxylated 2-methyl-1,3-propanediol di Aliphatic di (meth) acrylates such as (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, propoxylated cyclohexanedimethanol di (meth) acrylate, ethoxylated propoxylation Cyclohexane Methanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethoxylated tricyclodecane dimethanol di (meth) acrylate, propoxylated tricyclodecane dimethanol di (meth) acrylate, ethoxylated propoxylated tricyclo Decandimethanol di (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated water Cycloaliphatic di (meth) acrylates such as bisphenol F di (meth) acrylate, propoxylated hydrogenated bisphenol F di (meth) acrylate, ethoxylated propoxy hydrogenated bisphenol F di (meth) acrylate Ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, ethoxylated propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, propoxylated bisphenol F Di (meth) acrylate, ethoxylated propoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol AF di (meth) acrylate, propoxylated bisphenol AF di (meth) acrylate, ethoxylated propoxylated bisphenol AF di (meth) acrylate, Fragrances such as ethoxylated fluorene type di (meth) acrylate, propoxylated fluorene type di (meth) acrylate, ethoxylated propoxylated fluorene type di (meth) acrylate Heterocyclic di (meth) acrylates such as di (meth) acrylates, ethoxylated isocyanuric acid di (meth) acrylate, propoxylated isocyanuric acid di (meth) acrylate, ethoxylated propoxylated isocyanuric acid di (meth) acrylate, These modified caprolactones, aliphatic epoxy di (meth) acrylates such as neopentyl glycol type epoxy di (meth) acrylate, cyclohexanedimethanol type epoxy di (meth) acrylate, hydrogenated bisphenol A type epoxy di (meth) acrylate, hydrogenated bisphenol Alicyclic epoxy di (meth) acrylates such as F type epoxy di (meth) acrylate, resorcinol type epoxy di (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, Phenol F type epoxy di (meth) acrylate, bisphenol AF type epoxy di (meth) acrylate, and aromatic epoxy di (meth) acrylates such as fluorene epoxy di (meth) acrylate.
3官能以上の多官能(メタ)アクリレート化合物としては、例えば、トリメチロールプロパントリ(メタ)アクリレート、エトキシ化トリメチロールプロパントリ(メタ)アクリレート、プロポキシ化トリメチロールプロパントリ(メタ)アクリレート、エトキシ化プロポキシ化トリメチロールプロパントリ(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、エトキシ化ペンタエリスリトールトリ(メタ)アクリレート、プロポキシ化ペンタエリスリトールトリ(メタ)アクリレート、エトキシ化プロポキシ化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、エトキシ化ペンタエリスリトールテトラ(メタ)アクリレート、プロポキシ化ペンタエリスリトールテトラ(メタ)アクリレート、エトキシ化プロポキシ化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アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレートなどの脂肪族多官能(メタ)アクリレート類、エトキシ化イソシアヌル酸トリ(メタ)アクリレート、プロポキシ化イソシアヌル酸トリ(メタ)アクリレート、エトキシ化プロポキシ化イソシアヌル酸トリ(メタ)アクリレートなどの複素環式多官能(メタ)アクリレート類、これらのカプロラクトン変性体、フェノールノボラック型エポキシ(メタ)アクリレート、クレゾールノボラック型エポキシ(メタ)アクリレートなどの芳香族エポキシ(メタ)アクリレート類などが挙げられる。
Examples of the trifunctional or higher polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated propoxy. Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated propoxylated pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol Aliphatic polyfunctional (meth) such as tiger (meth) acrylate, ethoxylated propoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Heterocyclic polyfunctional (meth) acrylates such as acrylates, ethoxylated isocyanuric acid tri (meth) acrylate, propoxylated isocyanuric acid tri (meth) acrylate, ethoxylated propoxylated isocyanuric acid tri (meth) acrylate, and these caprolactones Modified products, aromatic epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, etc. And the like.
(メタ)アクリレート系重合性オリゴマーとしては、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレート、ポリブタジエンオリゴマーの(メタ)アクリレート、ポリアミド型(メタ)アクリルオリゴマー、メラミン(メタ)アクリレート、シクロペンタジエンオリゴマーの(メタ)アクリレート、シリコーンオリゴマーの(メタ)アクリレートなどが挙げられる。
(Meth) acrylate-based polymerizable oligomers include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polybutadiene oligomer (meth) acrylate, polyamide-type (meth) acryl oligomer, melamine (meth) acrylate , Cyclopentadiene oligomer (meth) acrylate, silicone oligomer (meth) acrylate, and the like.
また、他の重合性オリゴマーとしては、不飽和二重結合を二つ有する2官能化合物と、連鎖移動剤を共重合して得られる共重合体であって、側鎖に2官能化合物由来の反応性基を有するペンダント構造のオリゴマーが挙げられる。この時の好ましい官能基としてはビニル基、アリル基であり、2官能性化合物としては、分岐構造、脂環構造、又は単環若しくは縮環した芳香環等に不飽和二重結合を有する置換基を2個有する化合物であって、一部が酸素、窒素、硫黄原子で置換されていても良い。
Another polymerizable oligomer is a copolymer obtained by copolymerizing a bifunctional compound having two unsaturated double bonds and a chain transfer agent, and a reaction derived from the bifunctional compound in the side chain. An oligomer having a pendant structure having a sex group can be mentioned. Preferred functional groups at this time are a vinyl group and an allyl group, and the bifunctional compound includes a branched structure, an alicyclic structure, or a substituent having an unsaturated double bond in a monocyclic or condensed aromatic ring. May be partially substituted with oxygen, nitrogen, or sulfur atoms.
本発明の重合性化合物としてグリシジル基などのカチオン重合性基を有する化合物を用いる場合、他の重合性化合物としては公知のカチオン重合性化合物を用いることができる。
When a compound having a cationic polymerizable group such as a glycidyl group is used as the polymerizable compound of the present invention, a known cationic polymerizable compound can be used as the other polymerizable compound.
他の重合性化合物として用いるカチオン重合性化合物としては、例えば、ビニルエーテル化合物、プロペニルエーテル化合物などのアルケニルエーテル類、ビニルチオエーテル化合物、プロペニルチオエーテル化合物などのアルケニルチオエーテル類、ビニルエステル化合物、O-プロペニルエステル化合物などのアルケニルエステル類、N-ビニルアミド化合物、N-プロペニルアミド化合物などのN-アルケニルアミド類、エポキシ(オキシラン)化合物、オキセタン化合物、オキソラン化合物などの環状エーテル類、エチレンスルフィド(チイラン)化合物などの環状チオエーテル類、環状アセタール化合物、ラクトン化合物、スピロオルトエステル化合物、N-ビニルイミダゾール化合物、N-ビニルカルバゾール化合物などを挙げることができる。これらのカチオン重合性化合物の中では、ビニルエーテル化合物、エポキシ化合物、オキセタン化合物が好ましい。
Examples of the cationic polymerizable compound used as the other polymerizable compound include alkenyl ethers such as vinyl ether compounds and propenyl ether compounds, alkenyl thioethers such as vinyl thioether compounds and propenyl thioether compounds, vinyl ester compounds, and O-propenyl ester compounds. N-alkenylamides such as N-vinylamide compounds and N-propenylamide compounds, cyclic ethers such as epoxy (oxirane) compounds, oxetane compounds and oxolane compounds, and cyclic compounds such as ethylene sulfide (thiirane) compounds Thioethers, cyclic acetal compounds, lactone compounds, spiroorthoester compounds, N-vinylimidazole compounds, N-vinylcarbazole compounds, etc. Rukoto can. Among these cationically polymerizable compounds, vinyl ether compounds, epoxy compounds, and oxetane compounds are preferable.
特に好ましい他の重合性化合物としては、共重合が可能な重合性官能基を含み、下記一般式(2)で表される化合物であることが、高屈折率、低粘度を有する樹脂組成物を与えるため好適である。
Particularly preferable other polymerizable compounds include a resin composition having a high refractive index and a low viscosity, which contains a polymerizable functional group capable of copolymerization and is a compound represented by the following general formula (2). It is suitable for giving.
一般式(2)において、Yは5又は6員環を2~7個、好ましくは2~5個有するn価の環含有基を表し、ここでnは2~4の整数である。この環含有基の複数の環は、(a)単結合により環同士直接結合しているもの、(b)炭素数1~3のアルキレン基、酸素原子(エーテル基)、硫黄原子(スルフィド基)のいずれかを介して環同士が結合しているもの、又は(c)環同士が縮合しているものがあり、上記(a)、(b)及び(c)の2種類以上の結合を有しているものであってもよい。
In the general formula (2), Y represents an n-valent ring-containing group having 2 to 7, preferably 2 to 5, 5- or 6-membered rings, where n is an integer of 2 to 4. The plurality of rings of the ring-containing group are (a) those directly connected to each other by a single bond, (b) an alkylene group having 1 to 3 carbon atoms, an oxygen atom (ether group), a sulfur atom (sulfide group) There are those in which the rings are bonded via any of the above, or (c) the rings are condensed, and have two or more types of bonds (a), (b) and (c) above. It may be what you are doing.
Yの構造としては、特に限定されるものではないが、下記式(Y-1)~(Y-17)で示される構造を有するn価の環含有基が好ましい。一般式(2)で表わされる化合物は、これらn価の環含有基にn個の原子団-Z-Aが置換したものである。
The structure of Y is not particularly limited, but an n-valent ring-containing group having a structure represented by the following formulas (Y-1) to (Y-17) is preferable. The compound represented by the general formula (2) is obtained by substituting these n-valent ring-containing groups with n atomic groups -ZA.
本発明の樹脂組成物において、上記式(Y-1)~(Y-11)の構造を有するn価の環含有基は屈折率を向上させる点で好ましく、上記式(Y-12)~(Y-17)の構造を有するn価の環含有基は粘度を低下させる点で好ましい。
In the resin composition of the present invention, n-valent ring-containing groups having the structures of the above formulas (Y-1) to (Y-11) are preferable from the viewpoint of improving the refractive index, and the above formulas (Y-12) to (Y An n-valent ring-containing group having the structure of Y-17) is preferred from the viewpoint of reducing the viscosity.
一般式(2)において、Zは直接結合、酸素原子、硫黄原子、または炭素数1~4のアルキレン基、オキシアルキレン基、チオアルキレン基、アルキレンオキシ基もしくはアルキレンチオ基を表す。Aはグリシジル基、アクリロイル基、メタクリロイル基、ビニル基、ビニルアリール基またはビニルアリーロイル基を表わす。
In the general formula (2), Z represents a direct bond, an oxygen atom, a sulfur atom, or an alkylene group having 1 to 4 carbon atoms, an oxyalkylene group, a thioalkylene group, an alkyleneoxy group, or an alkylenethio group. A represents a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, a vinylaryl group or a vinylaryloyl group.
一般式(2)において、nは2~4の整数であるが、nが2である化合物は、材料の入手の容易さからさらに好適である。
In the general formula (2), n is an integer of 2 to 4, but a compound in which n is 2 is more preferable because of the availability of materials.
一般式(2)で表わされる他の重合性化合物の種類及び含有量は、樹脂組成物における他の構成成分の種類及び量により適宜決定することができるが、好ましくは、十分な効果を得るために、樹脂組成物の合計量に対して5重量%、好ましくは10重量%以上添加するのが良い。
The type and content of the other polymerizable compound represented by the general formula (2) can be appropriately determined depending on the type and amount of the other constituents in the resin composition, but preferably to obtain a sufficient effect. In addition, 5% by weight, preferably 10% by weight or more is added to the total amount of the resin composition.
本発明の樹脂組成物には、必要に応じて充填剤、繊維、カップリング剤、難燃剤、離型剤、発泡剤等のその他の成分を添加することができる。この際の充填剤としては、ポリエチレン粉末、ポリプロピレン粉末、石英、シリカ、珪酸塩、炭酸カルシウム、炭酸マグネシウム、石膏、ベントナイト、蛍石、二酸化チタン、カーボンブラック、黒鉛、酸化鉄、アルミニウム粉末、鉄粉、タルク、マイカ、カオリンクレー等が挙げられる。繊維としては、セルロース繊維、ガラス繊維、炭素繊維、アラミド繊維等が挙げられる。カップリング剤としては、シランカップリング剤、チタンカップリング剤等が挙げられる。難燃剤としては、臭素化ビスフェノールA、三酸化アンチモン、燐系化合物等が挙げられる。離型剤としては、ステアリン酸塩、シリコーン、ワックス等が挙げられる。発泡剤としては、フロン、ジクロロエタン、ブタン、ペンタン、ジニトロペンタメチレンテトラミン、パラトルエンスルホニルヒドラジッド、あるいは、フロン、ジクロロエタン、ブタン、ペンタン等が塩化ビニル-塩化ビニリデン共重合体やスチレン-(メタ)アクリル酸エステル共重合体の殻内に充填されている膨張性熱可塑性樹脂粒子等が挙げられる。
Other components such as fillers, fibers, coupling agents, flame retardants, mold release agents, and foaming agents can be added to the resin composition of the present invention as necessary. The filler used in this case is polyethylene powder, polypropylene powder, quartz, silica, silicate, calcium carbonate, magnesium carbonate, gypsum, bentonite, fluorite, titanium dioxide, carbon black, graphite, iron oxide, aluminum powder, iron powder. , Talc, mica, kaolin clay and the like. Examples of the fiber include cellulose fiber, glass fiber, carbon fiber, and aramid fiber. Examples of the coupling agent include a silane coupling agent and a titanium coupling agent. Examples of the flame retardant include brominated bisphenol A, antimony trioxide, and phosphorus compounds. Examples of the release agent include stearates, silicones, waxes and the like. As the blowing agent, Freon, dichloroethane, butane, pentane, dinitropentamethylenetetramine, p-toluenesulfonyl hydrazide, or freon, dichloroethane, butane, pentane, etc. are vinyl chloride-vinylidene chloride copolymer or styrene- (meth) acrylic. Examples thereof include expandable thermoplastic resin particles filled in an acid ester copolymer shell.
本発明の樹脂組成物を溶剤に溶解させ、希釈して使用することもできる。この際、用いうる希釈用溶剤の具体例としては、トルエン、キシレン、メチルエチルケトン、メチルイソブチルケトン、メチルセロソルブ等が挙げられ、その使用量は、樹脂組成物と該希釈用溶剤の合計量に対して70重量%以下であることがよく、より好ましくは60重量%以下である。
また、低粘度の他の重合性化合物を、樹脂組成物の粘度を低下させるための反応性希釈剤として使用することもできる。ここで、低粘度とは、500mPa・s以下であり、好ましくは200mPa・s以下である。 The resin composition of the present invention can be dissolved in a solvent and diluted for use. In this case, specific examples of the diluent solvent that can be used include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, etc., and the amount used is based on the total amount of the resin composition and the diluent solvent. It is preferable that it is 70 weight% or less, More preferably, it is 60 weight% or less.
In addition, other polymerizable compounds having a low viscosity can also be used as a reactive diluent for reducing the viscosity of the resin composition. Here, the low viscosity is 500 mPa · s or less, preferably 200 mPa · s or less.
また、低粘度の他の重合性化合物を、樹脂組成物の粘度を低下させるための反応性希釈剤として使用することもできる。ここで、低粘度とは、500mPa・s以下であり、好ましくは200mPa・s以下である。 The resin composition of the present invention can be dissolved in a solvent and diluted for use. In this case, specific examples of the diluent solvent that can be used include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, etc., and the amount used is based on the total amount of the resin composition and the diluent solvent. It is preferable that it is 70 weight% or less, More preferably, it is 60 weight% or less.
In addition, other polymerizable compounds having a low viscosity can also be used as a reactive diluent for reducing the viscosity of the resin composition. Here, the low viscosity is 500 mPa · s or less, preferably 200 mPa · s or less.
本発明の樹脂組成物は従来知られている方法と同様の方法で容易に樹脂硬化物又は成形体とすることができる。例えば、本発明の重合性化合物に熱重合開始剤又は光重合開始剤を添加し、必要に応じてさらに他の重合性化合物やその他の添加剤を加え、押出機、ニーダ、ロール、攪拌機等を用いて充分に混合して樹脂組成物を得、その樹脂組成物をロールコーター、溶融後注型あるいはトランスファー成形機などを用いて成形し、さらに60~200℃に加熱又は光照射することにより樹脂硬化物を得ることができる。
The resin composition of the present invention can be easily made into a cured resin or molded product by a method similar to a conventionally known method. For example, a thermal polymerization initiator or a photopolymerization initiator is added to the polymerizable compound of the present invention, and other polymerizable compounds and other additives are further added as necessary, and an extruder, kneader, roll, stirrer, etc. And mixed well to obtain a resin composition. The resin composition is molded using a roll coater, a cast after casting or a transfer molding machine, and further heated to 60 to 200 ° C. or irradiated with light. A cured product can be obtained.
また、本発明の樹脂組成物を、ガラス繊維、カーボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙などの基材に含浸させ加熱乾燥して得たプリプレグを熱プレス成形して硬化物を得ることもできる。例えば、本発明の重合性化合物に熱重合開始剤を添加し、必要に応じてさらに他の重合性化合物やその他の添加剤を加え、さらに溶剤を加えて撹拌することで樹脂組成物希釈液を得、それをガラスクロスに含浸させ加熱半乾燥(脱揮)して得られるプリプレグを、必要枚数重ねて60~200℃で加熱プレスすることによりガラスクロス積層板を作製することができる。ただし、本発明の光学材料を光を透過させる用途に使用する場合は、上記基材が透明材料であることが好ましい。一方、本発明の光学材料を光を反射・拡散させる用途に使用する場合は、上記基材が、上記反射・拡散させる光の波長について不透明であることが好ましい。
In addition, a prepreg obtained by impregnating the resin composition of the present invention into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating is subjected to hot press molding to obtain a cured product. You can also For example, a thermal polymerization initiator is added to the polymerizable compound of the present invention, another polymerizable compound or other additive is further added as necessary, a solvent is further added, and the resin composition diluent is stirred. A glass cloth laminate can be produced by impregnating a glass cloth and heating and semi-drying (devolatilization) and prepressing the prepreg obtained by heating at 60 to 200 ° C. However, when the optical material of the present invention is used for an application of transmitting light, the substrate is preferably a transparent material. On the other hand, when the optical material of the present invention is used for the purpose of reflecting / diffusing light, it is preferable that the substrate is opaque with respect to the wavelength of the light to be reflected / diffused.
こうして得られる樹脂組成物およびその硬化物は、高屈折率性に優れるとともに、透明性、ハンドリング性等に優れており、レンズ用途等のガラス代替材料、液晶ディスプレイ用カラーフィルタの保護膜材料、光学製品の保護用コーティング材料、電子ペーパーや液晶ディスプレイ等のスペーサ用微粒子、光ディスクや光ファイバー等用の接着剤、ホログラム記録媒体用の光記録材料等の各種光学材料に好適に使用される。
The resin composition thus obtained and its cured product are excellent in high refractive index, excellent in transparency, handling properties, etc., glass substitute materials for lens applications, protective film materials for color filters for liquid crystal displays, optical It is suitably used for various optical materials such as coating materials for product protection, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, and optical recording materials for hologram recording media.
次に、本発明のホログラフィック記録用材料について説明する。本発明のホログラフィック記録用材料は、A)重合性化合物、B)マトリックス樹脂又はマトリックス樹脂形成成分及びC)光重合開始剤を含む。重合性化合物としては、上記一般式(1)の重合性化合物を使用する。以下、A)重合性化合物、B)マトリックス樹脂又はマトリックス樹脂形成成分及びC)光重合開始剤を、それぞれA成分、B成分及びC成分ともいう。
Next, the holographic recording material of the present invention will be described. The holographic recording material of the present invention comprises A) a polymerizable compound, B) a matrix resin or a matrix resin forming component, and C) a photopolymerization initiator. As the polymerizable compound, the polymerizable compound represented by the general formula (1) is used. Hereinafter, A) polymerizable compound, B) matrix resin or matrix resin forming component, and C) photopolymerization initiator are also referred to as A component, B component, and C component, respectively.
(B成分:マトリックス樹脂)
マトリックス樹脂としては、溶剤に溶解可能な樹脂を用いても、三次元架橋させた樹脂を用いてもよく、記録特性の点では三次元架橋させた樹脂を用いることが好ましい。ホログラフィック記録用材料には、マトリックス樹脂が配合されてもよいが、マトリックス樹脂を形成するマトリックス樹脂形成成分(モノマー等)として配合されてもよい。マトリックス樹脂形成成分を配合する場合は、マトリックス樹脂を形成させる際に、重合性化合物の重合が起こらないようにすることがよい。 (B component: Matrix resin)
As the matrix resin, a resin that can be dissolved in a solvent may be used, or a three-dimensionally cross-linked resin may be used, and a three-dimensional cross-linked resin is preferably used from the viewpoint of recording characteristics. The holographic recording material may be blended with a matrix resin, but may be blended as a matrix resin forming component (such as a monomer) that forms the matrix resin. When the matrix resin forming component is blended, it is preferable that polymerization of the polymerizable compound does not occur when forming the matrix resin.
マトリックス樹脂としては、溶剤に溶解可能な樹脂を用いても、三次元架橋させた樹脂を用いてもよく、記録特性の点では三次元架橋させた樹脂を用いることが好ましい。ホログラフィック記録用材料には、マトリックス樹脂が配合されてもよいが、マトリックス樹脂を形成するマトリックス樹脂形成成分(モノマー等)として配合されてもよい。マトリックス樹脂形成成分を配合する場合は、マトリックス樹脂を形成させる際に、重合性化合物の重合が起こらないようにすることがよい。 (B component: Matrix resin)
As the matrix resin, a resin that can be dissolved in a solvent may be used, or a three-dimensionally cross-linked resin may be used, and a three-dimensional cross-linked resin is preferably used from the viewpoint of recording characteristics. The holographic recording material may be blended with a matrix resin, but may be blended as a matrix resin forming component (such as a monomer) that forms the matrix resin. When the matrix resin forming component is blended, it is preferable that polymerization of the polymerizable compound does not occur when forming the matrix resin.
前記三次元架橋樹脂としては、イソシアネート-ヒドロキシル重付加物、イソシアネート-アミン重付加物、イソシアネート-チオール重付加物、エポキシ-アミン重付加物、エポキシ-チオール重付加物、エピスルフィド-アミン重付加物及びエピスルフィド-チオール重付加物などを挙げることができ、特に比較的穏やかな温度条件下での反応が可能で、生じるマトリックス樹脂の光学特性に優れ、臭気が比較的少ないイソシアネート-ヒドロキシル重付加物であることが好ましい。
Examples of the three-dimensional crosslinked resin include isocyanate-hydroxyl polyadducts, isocyanate-amine polyadducts, isocyanate-thiol polyadducts, epoxy-amine polyadducts, epoxy-thiol polyadducts, episulfide-amine polyadducts, and Episulfide-thiol polyadduct, etc. can be mentioned, and it is an isocyanate-hydroxyl polyadduct capable of reacting under a relatively mild temperature condition, having excellent optical characteristics of the resulting matrix resin, and having a relatively low odor. It is preferable.
イソシアネート-ヒドロキシル重付加物を構成するポリイソシアネート成分としては、1分子中に2以上のイソシアネート基を有する化合物またはその混合物が使用される。例えば、トリレンジイソシアネート(TDI)、ジフェニルメタン-4,4’-ジイソシアネート(MDI)、キシリレンジイソシアネート(XDI)、テトラメチルキシリレンジイソシアネート(TMXDI)、ナフチレン-1,5-ジイソシアネート(NDI)、トリフェニルメタン-4,4’,4”-トリイソシアネート、ジシクロヘキシルメタン-4,4’-ジイソシアネート(H12MDI)、水素化キシリレンジイソシアネート(H6XDI)、ヘキサメチレンジイソシアネート(HDI)、トリメチルヘキサメチレンジイソシアネート(TMHDI)、イソホロンジイソシアネート(IPDI)、ノルボルナンジイソシアネート(NBDI)、シクロヘキサン-1,3,5-トリイソシアネート及びこれらのイソシアネート化合物から得られる三量体、ビウレット体、アダクト体、プレポリマーなどが挙げられる。これらの1分子中に2以上のイソシアネート基を有する化合物は、単独で用いても2種以上を組み合わせて用いてもよい。
As the polyisocyanate component constituting the isocyanate-hydroxyl polyadduct, a compound having two or more isocyanate groups in one molecule or a mixture thereof is used. For example, tolylene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthylene-1,5-diisocyanate (NDI), triphenyl Methane-4,4 ′, 4 ″ -triisocyanate, dicyclohexylmethane-4,4′-diisocyanate (H12MDI), hydrogenated xylylene diisocyanate (H6XDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), Isophorone diisocyanate (IPDI), norbornane diisocyanate (NBDI), cyclohexane-1,3,5-triisocyanate and their isocyanateation Trimers obtained from products, biurets, adducts, prepolymers, etc. These compounds having two or more isocyanate groups in one molecule may be used alone or in combination of two or more. Also good.
イソシアネート-ヒドロキシル重付加物を構成するポリオール成分としては、1分子中に2以上のヒドロキシル基を有する化合物またはその混合物が使用される。例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ポリプロピレングリコール、ネオペンチルグリコール、ブタンジオール、ペンタンジオール、ヘキサンジオール、ヘプタンジオール、テトラメチレングリコールなどのジオール類;ビスフェノール類;グリセリン、トリメチロールプロパン、ブタントリオール、ペンタントリオール、ヘキサントリオール、デカントリオールなどのトリオール類;これらの化合物のヒドロキシル基をポリエチレンオキシ鎖やポリプロピレンオキシ鎖で修飾した化合物、などが挙げられる。これらの1分子中に2以上のヒドロキシル基を有する化合物は、単独で用いても2種以上を組み合わせて用いてもよい。
As the polyol component constituting the isocyanate-hydroxyl polyadduct, a compound having two or more hydroxyl groups in one molecule or a mixture thereof is used. For example, diols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, butanediol, pentanediol, hexanediol, heptanediol, tetramethylene glycol; bisphenols; Examples include triols such as methylolpropane, butanetriol, pentanetriol, hexanetriol and decanetriol; compounds obtained by modifying the hydroxyl group of these compounds with a polyethyleneoxy chain or a polypropyleneoxy chain. These compounds having two or more hydroxyl groups in one molecule may be used alone or in combination of two or more.
別の好ましい態様としてマトリックス樹脂は、芳香環を有し、かつ重合反応性基及びヒドロキシル基を有する反応性芳香族化合物から生じる単位をマトリックス樹脂の構成単位の一部として含むことができる。
この場合、ヒドロキシル基を介してマトリックス樹脂の構成単位の一部とすることができ、マトリックス樹脂中に芳香環が存在するようになるので、芳香環を有する高屈折率の重合性化合物を含むホログラフィック記録用材料の場合でも相溶性が高く濁りを生じにくくなり、比較的多くの重合性化合物を含有させることができると実験的に確認されている。その結果、マトリックス樹脂と重合性化合物やその重合体との屈折率差を大きくすることができ、結果として屈折率変調度を高めることが可能となる。 As another preferred embodiment, the matrix resin may contain a unit derived from a reactive aromatic compound having an aromatic ring and having a polymerization reactive group and a hydroxyl group as a part of the constituent unit of the matrix resin.
In this case, it can be part of the structural unit of the matrix resin via the hydroxyl group, and an aromatic ring is present in the matrix resin, so that the hollow resin containing the high refractive index polymerizable compound having the aromatic ring is present. Even in the case of graphic recording materials, it has been experimentally confirmed that the compatibility is high and turbidity hardly occurs, and a relatively large amount of polymerizable compound can be contained. As a result, the refractive index difference between the matrix resin and the polymerizable compound or polymer thereof can be increased, and as a result, the refractive index modulation can be increased.
この場合、ヒドロキシル基を介してマトリックス樹脂の構成単位の一部とすることができ、マトリックス樹脂中に芳香環が存在するようになるので、芳香環を有する高屈折率の重合性化合物を含むホログラフィック記録用材料の場合でも相溶性が高く濁りを生じにくくなり、比較的多くの重合性化合物を含有させることができると実験的に確認されている。その結果、マトリックス樹脂と重合性化合物やその重合体との屈折率差を大きくすることができ、結果として屈折率変調度を高めることが可能となる。 As another preferred embodiment, the matrix resin may contain a unit derived from a reactive aromatic compound having an aromatic ring and having a polymerization reactive group and a hydroxyl group as a part of the constituent unit of the matrix resin.
In this case, it can be part of the structural unit of the matrix resin via the hydroxyl group, and an aromatic ring is present in the matrix resin, so that the hollow resin containing the high refractive index polymerizable compound having the aromatic ring is present. Even in the case of graphic recording materials, it has been experimentally confirmed that the compatibility is high and turbidity hardly occurs, and a relatively large amount of polymerizable compound can be contained. As a result, the refractive index difference between the matrix resin and the polymerizable compound or polymer thereof can be increased, and as a result, the refractive index modulation can be increased.
また、この場合、マトリックス樹脂中に重合反応性基が存在するようになるので、光照射時に、重合性化合物の少なくとも一部がマトリックス樹脂に存在する重合反応性基と反応し、共重合していると考えられる。結果として、相溶性が高まり透明性が向上するとともに、形成された屈折率変調構造が安定化されていると推察される。
Further, in this case, since a polymerization reactive group is present in the matrix resin, at the time of light irradiation, at least a part of the polymerizable compound reacts with the polymerization reactive group present in the matrix resin and is copolymerized. It is thought that there is. As a result, compatibility is improved and transparency is improved, and it is presumed that the formed refractive index modulation structure is stabilized.
したがって、上記反応性芳香族化合物をホログラフィック記録用材料に添加した場合、屈折率変調構造によって複数の回折格子を高いコントラストで形成することができ、複数の回折格子に応じた複数のページ情報を高いSNRで記録し、再生することができる。
Therefore, when the reactive aromatic compound is added to the holographic recording material, a plurality of diffraction gratings can be formed with high contrast by the refractive index modulation structure, and a plurality of page information corresponding to the plurality of diffraction gratings can be obtained. It can be recorded and played back with a high SNR.
上記反応性芳香族化合物としては、例えば式(5)、(6)または(7)に示すようなものがある。
Examples of the reactive aromatic compound include those represented by the formula (5), (6) or (7).
式(5)中、Ar5は1以上の芳香環を有する1または2価の基を表し、Z1、Z2はそれぞれ独立して水素原子またはメチル基を表し、L1は酸素原子、硫黄原子または-(OZ3)nO-(Z3は炭素数1~4のアルキレン基であり、nは1~4の整数である。)を表し、L2は芳香環を有してもよい2価の基を表し、mは1~2の整数を表わす。
式(6)中、Z2はそれぞれ独立して水素原子または炭素数1~4のアルキル基を表し、L3は単結合、酸素原子、硫黄原子、スルホニル基、炭素数1~4のアルキレン基または9,9-フルオレニレン基を表す。Z1、L1は式(5)と同意である。
式(7)中、L2は単結合、または芳香環を有してもよい2価の基を表す。Z1、Z2、L1は式(6)と同意である。 In the formula (5), Ar5 represents a monovalent or divalent group having one or more aromatic rings, Z 1 and Z 2 each independently represents a hydrogen atom or a methyl group, andL 1 represents an oxygen atom, a sulfur atom or — (OZ 3 ) nO— (Z 3 is an alkylene group having 1 to 4 carbon atoms, n is an integer of 1 to 4), and L 2 is a divalent divalent alkyl group which may have an aromatic ring. Represents a group, and m represents an integer of 1 to 2.
In formula (6), Z 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and L 3 represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, or an alkylene group having 1 to 4 carbon atoms. Or represents a 9,9-fluorenylene group. Z 1 and L 1 are the same as in formula (5).
In formula (7), L 2 represents a single bond or a divalent group which may have an aromatic ring. Z 1 , Z 2 , and L 1 are the same as in formula (6).
式(6)中、Z2はそれぞれ独立して水素原子または炭素数1~4のアルキル基を表し、L3は単結合、酸素原子、硫黄原子、スルホニル基、炭素数1~4のアルキレン基または9,9-フルオレニレン基を表す。Z1、L1は式(5)と同意である。
式(7)中、L2は単結合、または芳香環を有してもよい2価の基を表す。Z1、Z2、L1は式(6)と同意である。 In the formula (5), Ar5 represents a monovalent or divalent group having one or more aromatic rings, Z 1 and Z 2 each independently represents a hydrogen atom or a methyl group, and
In formula (6), Z 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and L 3 represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, or an alkylene group having 1 to 4 carbon atoms. Or represents a 9,9-fluorenylene group. Z 1 and L 1 are the same as in formula (5).
In formula (7), L 2 represents a single bond or a divalent group which may have an aromatic ring. Z 1 , Z 2 , and L 1 are the same as in formula (6).
式(5)または(6)で表される反応性芳香族化合物としては、例えば、ビスフェノールA型エポキシ樹脂の(メタ)アクリル酸付加物、同3-ブテン酸付加物、同ビニル安息香酸付加物、同ビニルフェノール付加物、同ビニルチオフェノール付加物、同ビニルアニリン付加物、ビスフェノールF型エポキシ樹脂の(メタ)アクリル酸付加物、同3-ブテン酸付加物、同ビニル安息香酸付加物、同ビニルフェノール付加物、同ビニルチオフェノール付加物、同ビニルアニリン付加物、9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルの(メタ)アクリル酸付加物、同3-ブテン酸付加物、同ビニル安息香酸付加物、同ビニルフェノール付加物、同ビニルチオフェノール付加物、同ビニルアニリン付加物、9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレンジグリシジルエーテルの(メタ)アクリル酸付加物、同3-ブテン酸付加物、同ビニル安息香酸付加物、同ビニルフェノール付加物、同ビニルチオフェノール付加物、同ビニルアニリン付加物、9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンジグリシジルエーテルの(メタ)アクリル酸付加物、同3-ブテン酸付加物、同ビニル安息香酸付加物、同ビニルフェノール付加物、同ビニルチオフェノール付加物、同ビニルアニリン付加物などが挙げられる。
Examples of the reactive aromatic compound represented by the formula (5) or (6) include (meth) acrylic acid adducts, 3-butenoic acid adducts, and vinyl benzoic acid adducts of bisphenol A type epoxy resins. , Vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, bisphenol F type epoxy resin (meth) acrylic acid adduct, 3-butenoic acid adduct, vinyl benzoic acid adduct, Vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, (meth) acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether, 3-butenoic acid adduct, Vinyl benzoic acid adduct, vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, 9,9- (Meth) acrylic acid adducts, 3-butenoic acid adducts, vinyl benzoic acid adducts, vinyl phenol adducts, vinyl thiophenol adducts of bis (4-hydroxy-3-methylphenyl) fluorenediglycidyl ether , Vinyl aniline adduct, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorenediglycidyl ether (meth) acrylic acid adduct, 3-butenoic acid adduct, vinyl benzoic acid addition Products, vinyl phenol adducts, vinyl thiophenol adducts, vinyl aniline adducts, and the like.
上記反応性芳香族化合物は、マトリックス樹脂又はマトリックス樹脂形成成分の合計(反応性芳香族化合物を含む)に対して0.1~20質量%が好ましく、0.2~10質量%がより好ましく、0.3~5質量%が更に好ましい。上記反応性芳香族化合物の含有率が高過ぎると、前駆体の粘度が高くなってホログラフィック記録用材料の製造が煩雑になることがある。一方、上記反応性芳香族化合物を含有しないかまたは含有率が低過ぎると、マトリックス樹脂と重合性化合物やその重合体との相溶性が低下し、ホログラフィック記録用材料に濁りを生じる場合がある。
The reactive aromatic compound is preferably 0.1 to 20% by weight, more preferably 0.2 to 10% by weight, based on the total of the matrix resin or the matrix resin forming component (including the reactive aromatic compound), More preferably, it is 0.3-5% by mass. If the content of the reactive aromatic compound is too high, the viscosity of the precursor becomes high and the production of the holographic recording material may become complicated. On the other hand, if the reactive aromatic compound is not contained or if the content is too low, the compatibility between the matrix resin and the polymerizable compound or polymer thereof is lowered, and the holographic recording material may be turbid. .
式(7)で表される重合反応性基及びヒドロキシル基を有する化合物としては、式(5)または(6)で表される反応性芳香族化合物のうち、9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルの(メタ)アクリル酸付加物、同3-ブテン酸付加物、同ビニル安息香酸付加物、同ビニルフェノール付加物、同ビニルチオフェノール付加物、同ビニルアニリン付加物、9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレンジグリシジルエーテルの(メタ)アクリル酸付加物、同3-ブテン酸付加物、同ビニル安息香酸付加物、同ビニルフェノール付加物、同ビニルチオフェノール付加物、同ビニルアニリン付加物、9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンジグリシジルエーテルの(メタ)アクリル酸付加物、同3-ブテン酸付加物、同ビニル安息香酸付加物、同ビニルフェノール付加物、同ビニルチオフェノール付加物、同ビニルアニリン付加物などが挙げられる。
Examples of the compound having a polymerization reactive group and a hydroxyl group represented by the formula (7) include 9,9-bis (4-hydroxy) among the reactive aromatic compounds represented by the formula (5) or (6). (Meth) acrylic acid adduct, phenyl 3-butenoic acid adduct, vinyl benzoic acid adduct, vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, 9 , 9-Bis (4-hydroxy-3-methylphenyl) fluorenedin glycidyl ether, (meth) acrylic acid adduct, 3-butenoic acid adduct, vinylbenzoic acid adduct, vinylphenol adduct, vinyl Thiophenol adduct, vinylaniline adduct, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorange glycidyl a (Meth) acrylic acid adduct of Le, the 3-butenoic acid adduct, the vinyl benzoic acid adducts, the vinyl phenol adduct, the vinylthiophenol adducts, such as the vinyl aniline adduct.
9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルのアクリル酸付加物の主成分は、式(7)中のR1が水素原子、R2が水素原子、L1が酸素原子、L2が単結合で表される化合物である。
9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルのメタクリル酸付加物の主成分は、式(7)中のR1がメチル基、R2が水素原子、L1が酸素原子、L2が単結合で表される化合物である。
9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルの3-ブテン酸付加物の主成分は、式(7)中のR1が水素原子、R2が水素原子、L1が酸素原子、L2がメチレン基で表される化合物である。
9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルのビニル安息香酸付加物の主成分は、式(7)中のR1が水素原子、R2が水素原子、L1が酸素原子、L2がフェニレン基で表される化合物である。 The main component of the acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether is that R 1 in formula (7) is a hydrogen atom, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a single bond.
The main components of the methacrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether are as follows: R 1 in formula (7) is a methyl group, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a single bond.
The main components of the 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether 3-butenoic acid adduct are: R 1 in formula (7) is a hydrogen atom, R 2 is a hydrogen atom, and L 1 is an oxygen atom , L 2 is a compound represented by a methylene group.
The main component of the vinyl benzoic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether is as follows: R 1 in formula (7) is a hydrogen atom, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a phenylene group.
9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルのメタクリル酸付加物の主成分は、式(7)中のR1がメチル基、R2が水素原子、L1が酸素原子、L2が単結合で表される化合物である。
9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルの3-ブテン酸付加物の主成分は、式(7)中のR1が水素原子、R2が水素原子、L1が酸素原子、L2がメチレン基で表される化合物である。
9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルのビニル安息香酸付加物の主成分は、式(7)中のR1が水素原子、R2が水素原子、L1が酸素原子、L2がフェニレン基で表される化合物である。 The main component of the acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether is that R 1 in formula (7) is a hydrogen atom, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a single bond.
The main components of the methacrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether are as follows: R 1 in formula (7) is a methyl group, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a single bond.
The main components of the 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether 3-butenoic acid adduct are: R 1 in formula (7) is a hydrogen atom, R 2 is a hydrogen atom, and L 1 is an oxygen atom , L 2 is a compound represented by a methylene group.
The main component of the vinyl benzoic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether is as follows: R 1 in formula (7) is a hydrogen atom, R 2 is a hydrogen atom, L 1 is an oxygen atom, L 2 is a compound represented by a phenylene group.
(A成分:重合性化合物)
上記重合性化合物の配合量は、ホログラフィック記録用材料の全体に対して0.5~30質量%が好ましく、1~20質量%がより好ましく、1.5~10質量%が更に好ましい。また、必要により、屈折率の調整等の目的で他の重合性化合物の少量の併用もできる。 (Component A: polymerizable compound)
The blending amount of the polymerizable compound is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 1.5 to 10% by mass with respect to the entire holographic recording material. Moreover, if necessary, a small amount of other polymerizable compounds can be used in combination for the purpose of adjusting the refractive index.
上記重合性化合物の配合量は、ホログラフィック記録用材料の全体に対して0.5~30質量%が好ましく、1~20質量%がより好ましく、1.5~10質量%が更に好ましい。また、必要により、屈折率の調整等の目的で他の重合性化合物の少量の併用もできる。 (Component A: polymerizable compound)
The blending amount of the polymerizable compound is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 1.5 to 10% by mass with respect to the entire holographic recording material. Moreover, if necessary, a small amount of other polymerizable compounds can be used in combination for the purpose of adjusting the refractive index.
(C成分:光重合開始剤)
光重合開始剤は、A成分の重合性化合物の重合を紫外線などの照射によって開始させるものであれば特に制限はない。例えば、重合性化合物としてエチレン性不飽和基を有する化合物を用いる場合、光ラジカル重合開始剤を使用することができる。光ラジカル重合開始剤は、公知の光ラジカル重合開始剤であれば、何れを用いることも可能である。例としては、アゾ系化合物、アジド系化合物、有機過酸化物、有機硼素酸塩、オニウム塩類、ビスイミダゾール誘導体、チタノセン化合物、ヨードニウム塩類、有機チオール化合物、ハロゲン化炭化水素誘導体、α-ヒドロキシケトン化合物、α-アミノケトン化合物、アシルフォスフィンオキサイド化合物、オキシムエステル化合物などが用いられる。これらは何れか1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。中でも、増感剤を必要とせずに可視光領域で重合反応が生じるという理由から、チタノセン化合物、アシルフォスフィンオキサイド化合物、オキシムエステル化合物などが好ましい。 (C component: photopolymerization initiator)
The photopolymerization initiator is not particularly limited as long as it initiates polymerization of the polymerizable compound of component A by irradiation with ultraviolet rays or the like. For example, when a compound having an ethylenically unsaturated group is used as the polymerizable compound, a radical photopolymerization initiator can be used. As the radical photopolymerization initiator, any known radical radical polymerization initiator can be used. Examples include azo compounds, azide compounds, organic peroxides, organoborates, onium salts, bisimidazole derivatives, titanocene compounds, iodonium salts, organic thiol compounds, halogenated hydrocarbon derivatives, α-hydroxyketone compounds. , Α-aminoketone compounds, acylphosphine oxide compounds, oxime ester compounds, and the like are used. Any one of these may be used alone, or two or more may be used in any combination and ratio. Of these, titanocene compounds, acylphosphine oxide compounds, oxime ester compounds, and the like are preferable because a polymerization reaction occurs in the visible light region without requiring a sensitizer.
光重合開始剤は、A成分の重合性化合物の重合を紫外線などの照射によって開始させるものであれば特に制限はない。例えば、重合性化合物としてエチレン性不飽和基を有する化合物を用いる場合、光ラジカル重合開始剤を使用することができる。光ラジカル重合開始剤は、公知の光ラジカル重合開始剤であれば、何れを用いることも可能である。例としては、アゾ系化合物、アジド系化合物、有機過酸化物、有機硼素酸塩、オニウム塩類、ビスイミダゾール誘導体、チタノセン化合物、ヨードニウム塩類、有機チオール化合物、ハロゲン化炭化水素誘導体、α-ヒドロキシケトン化合物、α-アミノケトン化合物、アシルフォスフィンオキサイド化合物、オキシムエステル化合物などが用いられる。これらは何れか1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。中でも、増感剤を必要とせずに可視光領域で重合反応が生じるという理由から、チタノセン化合物、アシルフォスフィンオキサイド化合物、オキシムエステル化合物などが好ましい。 (C component: photopolymerization initiator)
The photopolymerization initiator is not particularly limited as long as it initiates polymerization of the polymerizable compound of component A by irradiation with ultraviolet rays or the like. For example, when a compound having an ethylenically unsaturated group is used as the polymerizable compound, a radical photopolymerization initiator can be used. As the radical photopolymerization initiator, any known radical radical polymerization initiator can be used. Examples include azo compounds, azide compounds, organic peroxides, organoborates, onium salts, bisimidazole derivatives, titanocene compounds, iodonium salts, organic thiol compounds, halogenated hydrocarbon derivatives, α-hydroxyketone compounds. , Α-aminoketone compounds, acylphosphine oxide compounds, oxime ester compounds, and the like are used. Any one of these may be used alone, or two or more may be used in any combination and ratio. Of these, titanocene compounds, acylphosphine oxide compounds, oxime ester compounds, and the like are preferable because a polymerization reaction occurs in the visible light region without requiring a sensitizer.
チタノセン化合物としては、その種類は特に限定はされないが、具体例としては、ビスシクロペンタジエニル-Ti-ジクロライド、ビスシクロペンタジエニル-Ti-ジフェニル、ビスシクロペンタジエニル-Ti-ビス(2,3,4,5,6-ペンタフルオロフェニル)、ビスシクロペンタジエニル-Ti-ビス(2,3,5,6-テトラフルオロフェニル)、ビスシクロペンタジエニル-Ti-ビス(2,4,6-トリフルオロフェニル)、ビスシクロペンタジエニル-Ti-ビス(2,6-ジフルオロフェニル)、ビスシクロペンタジエニル-Ti-ビス(2,4-ジフルオロフェニル)、ビス(メチルシクロペンタジエニル)-Ti-ビス(2,3,4,5,6-ペンタフルオロフェニル)、ビス(メチルシクロペンタジエニル)-Ti-ビス(2,3,5,6-テトラフルオロフェニル)、ビス(メチルシクロペンタジエニル)-Ti-ビス(2,6-ジフルオロフェニル)、ビスシクロペンタジエニル-Ti-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)などが挙げられる。
The type of titanocene compound is not particularly limited, but specific examples thereof include biscyclopentadienyl-Ti-dichloride, biscyclopentadienyl-Ti-diphenyl, biscyclopentadienyl-Ti-bis (2 , 3,4,5,6-pentafluorophenyl), biscyclopentadienyl-Ti-bis (2,3,5,6-tetrafluorophenyl), biscyclopentadienyl-Ti-bis (2,4 , 6-trifluorophenyl), biscyclopentadienyl-Ti-bis (2,6-difluorophenyl), biscyclopentadienyl-Ti-bis (2,4-difluorophenyl), bis (methylcyclopentadi) Enyl) -Ti-bis (2,3,4,5,6-pentafluorophenyl), bis (methylcyclopentadienyl) -Ti-bis (2,3,5,6-tetrafluorophenyl), bis (methylcyclopentadienyl) -Ti-bis (2,6-difluorophenyl), biscyclopentadienyl-Ti-bis (2 , 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) and the like.
アシルフォスフィンオキサイド化合物としては、その種類は特に限定されないが、具体例としては、トリフェニルフォスフィンオキサイド、ジフェニル(2,4,6-トリメチルベンゾイル)フォスフィンオキサイド、2,6-ジクロルベンゾイルジフェニルフォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルフォスフィンオキサイド、ビス(2,6-ジクロルベンゾイル)-4-プロピルフェニルフォスフィンオイサイド、ビス(2,6-ジクロルベンゾイル)-2,5-ジメチルフェニルフォスフィンオキサイドなどが挙げられる。
The acyl phosphine oxide compound is not particularly limited, but specific examples include triphenyl phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and 2,6-dichlorobenzoyl diphenyl. Phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichloro) And benzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and the like.
オキシムエステル系化合物としては、その種類は特に限定されないが、具体例としては、1-[4-(フェニルチオ)フェニル]-2-(O-ベンゾイルオキシム)-1,2-オクタンジオン、1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-1-(O-アセチルオキシム)エタノン1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-2-(O-ベンゾイルオキシム)-3-シクロペンチル-1,2-プロパンジオン、1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-2-(O-アセチルオキシム)-4-シクロペンチル-1,2-ブタンジオンなどが挙げられる。
The type of the oxime ester compound is not particularly limited, but specific examples thereof include 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) -1,2-octanedione, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -2- (O-benzoyloxime) -3-cyclopentyl-1,2-propanedione, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] And -2- (O-acetyloxime) -4-cyclopentyl-1,2-butanedione.
上記の各種の光ラジカル重合開始剤は、何れか1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用しても良い。
Any one of these various photo radical polymerization initiators may be used alone, or two or more of them may be used in any combination and ratio.
また、重合性化合物としてグリシジル基を有する化合物などのカチオン重合性を有するものを用いる場合、光重合開始剤としては、光カチオン重合開始剤を使用することができる。
In addition, when a cationically polymerizable compound such as a compound having a glycidyl group is used as the polymerizable compound, a photocationic polymerization initiator can be used as the photopolymerization initiator.
光カチオン重合開始剤としては、公知の光カチオン重合開始剤であれば、何れを用いることも可能である。例としては、アリールジアゾニウム塩類、ジアリールヨードニウム塩類、トリアリールスルホニウム塩類、トリアリールセレノニウム塩類、ジアルキルフェナシルスルホニウム塩類、ジアルキル-4-ヒドロキシ塩類、スルホン酸エステル類などが用いられる。これらは何れか1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
Any known cationic photopolymerization initiator can be used as the cationic photopolymerization initiator. Examples include aryl diazonium salts, diaryl iodonium salts, triaryl sulfonium salts, triaryl selenonium salts, dialkylphenacyl sulfonium salts, dialkyl-4-hydroxy salts, sulfonic acid esters, and the like. Any one of these may be used alone, or two or more may be used in any combination and ratio.
(その他の成分)
本発明のホログラフィック記録用材料は、必要に応じて、光増感剤、可塑剤、相溶化剤、連鎖移動剤、重合促進剤、重合抑制剤、重合禁止剤、ラジカル補足剤、界面活性剤、シランカップリング剤、消泡剤、剥離剤、安定化剤、酸化防止剤、難燃剤などの添加剤を更に含んでもよい。これらの添加剤は単独で用いても良いし、2種以上を任意の組み合わせ及び割合で使用しても良い。 (Other ingredients)
The holographic recording material of the present invention includes a photosensitizer, a plasticizer, a compatibilizer, a chain transfer agent, a polymerization accelerator, a polymerization inhibitor, a polymerization inhibitor, a radical scavenger, and a surfactant as necessary. , A silane coupling agent, an antifoaming agent, a release agent, a stabilizer, an antioxidant, a flame retardant and the like may be further included. These additives may be used alone, or two or more of them may be used in any combination and ratio.
本発明のホログラフィック記録用材料は、必要に応じて、光増感剤、可塑剤、相溶化剤、連鎖移動剤、重合促進剤、重合抑制剤、重合禁止剤、ラジカル補足剤、界面活性剤、シランカップリング剤、消泡剤、剥離剤、安定化剤、酸化防止剤、難燃剤などの添加剤を更に含んでもよい。これらの添加剤は単独で用いても良いし、2種以上を任意の組み合わせ及び割合で使用しても良い。 (Other ingredients)
The holographic recording material of the present invention includes a photosensitizer, a plasticizer, a compatibilizer, a chain transfer agent, a polymerization accelerator, a polymerization inhibitor, a polymerization inhibitor, a radical scavenger, and a surfactant as necessary. , A silane coupling agent, an antifoaming agent, a release agent, a stabilizer, an antioxidant, a flame retardant and the like may be further included. These additives may be used alone, or two or more of them may be used in any combination and ratio.
(ホログラフィック記録用材料の製造)
本発明のホログラフィック記録用材料の製造方法について説明する。最初に、マトリックス樹脂形成成分、例えば、イソシアネート-ヒドロキシル重付加物を構成するポリイソシアネート成分及びポリオール成分、重合性化合物、光重合開始剤、さらには必要に応じて、式(5)等で表わされる反応性芳香族化合物などを配合する。次いで、マトリックス樹脂形成成分に対し、前記重合性化合物あるいは反応性芳香族化合物の重合反応性基が重合する反応以外の反応による重合を生ぜしめてマトリックス樹脂を形成する。この場合、マトリックス樹脂は、マトリックス樹脂形成成分が重合性化合物及び光重合開始剤の共存下で重合することによって形成することができる。 (Manufacture of holographic recording materials)
The method for producing the holographic recording material of the present invention will be described. First, a matrix resin forming component, for example, a polyisocyanate component and a polyol component constituting an isocyanate-hydroxyl polyadduct, a polymerizable compound, a photopolymerization initiator, and, if necessary, represented by the formula (5) A reactive aromatic compound is blended. Next, a matrix resin is formed by causing polymerization by a reaction other than a reaction in which the polymerizable reactive group of the polymerizable compound or the reactive aromatic compound is polymerized with respect to the matrix resin forming component. In this case, the matrix resin can be formed by polymerizing a matrix resin forming component in the presence of a polymerizable compound and a photopolymerization initiator.
本発明のホログラフィック記録用材料の製造方法について説明する。最初に、マトリックス樹脂形成成分、例えば、イソシアネート-ヒドロキシル重付加物を構成するポリイソシアネート成分及びポリオール成分、重合性化合物、光重合開始剤、さらには必要に応じて、式(5)等で表わされる反応性芳香族化合物などを配合する。次いで、マトリックス樹脂形成成分に対し、前記重合性化合物あるいは反応性芳香族化合物の重合反応性基が重合する反応以外の反応による重合を生ぜしめてマトリックス樹脂を形成する。この場合、マトリックス樹脂は、マトリックス樹脂形成成分が重合性化合物及び光重合開始剤の共存下で重合することによって形成することができる。 (Manufacture of holographic recording materials)
The method for producing the holographic recording material of the present invention will be described. First, a matrix resin forming component, for example, a polyisocyanate component and a polyol component constituting an isocyanate-hydroxyl polyadduct, a polymerizable compound, a photopolymerization initiator, and, if necessary, represented by the formula (5) A reactive aromatic compound is blended. Next, a matrix resin is formed by causing polymerization by a reaction other than a reaction in which the polymerizable reactive group of the polymerizable compound or the reactive aromatic compound is polymerized with respect to the matrix resin forming component. In this case, the matrix resin can be formed by polymerizing a matrix resin forming component in the presence of a polymerizable compound and a photopolymerization initiator.
ホログラフィック記録用材料においては、低屈折率のマトリックス樹脂に加えて高屈折率の重合性化合物を含み、記録時に重合性化合物を重合させることによって媒体中に回折格子を屈折率変調構造として形成することが好ましい。ホログラフィック記録用材料は、(1)マトリックス形成成分(イソシアネート、ポリオール、反応触媒(スズ含有触媒)など)、(2)重合性化合物、(3)光重合開始剤、(4)その他の成分、を適宜混合、溶解し、(1)マトリックス形成成分の反応のみを独立して行わせることにより行い、この時、(2)重合性化合物、(3)光重合開始剤、(4)その他の成分は基本的に影響を受けず、そのままの形でマトリックス樹脂中に分散されているようにすることが好ましい。このホログラフィック記録用材料を2枚の基板に挟んだ形のもの等をホログラフィック記録媒体という。このホログラフィック記録用材料またはホログラフィック記録媒体に情報を記録する際、光を照射すると(3)光重合開始剤が開裂するなどして重合開始種(ラジカルなど)が形成され、(2)重合性化合物が重合する。
A holographic recording material contains a high refractive index polymerizable compound in addition to a low refractive index matrix resin, and forms a diffraction grating as a refractive index modulation structure in the medium by polymerizing the polymerizable compound during recording. It is preferable. The holographic recording material includes (1) matrix forming components (isocyanate, polyol, reaction catalyst (tin-containing catalyst), etc.), (2) polymerizable compound, (3) photopolymerization initiator, (4) other components, Are mixed and dissolved as appropriate, and (1) only the matrix-forming components are allowed to react independently. At this time, (2) a polymerizable compound, (3) a photopolymerization initiator, (4) other components Is basically unaffected and is preferably dispersed in the matrix resin as it is. A material in which the holographic recording material is sandwiched between two substrates is called a holographic recording medium. When information is recorded on this holographic recording material or holographic recording medium, when irradiated with light, (3) a photopolymerization initiator is cleaved to form polymerization initiation species (radicals, etc.), and (2) polymerization Compound is polymerized.
一方、重合性化合物や光重合開始剤が反応して減少してしまうと、ホログラフィック記録用材料としての性能が低下するので、これらを減少させることなくマトリックス樹脂を形成させることが好ましい。したがって、前記重合性化合物が重合する反応とは別の反応形態での重合が優先的に生じるように、反応触媒などを配合したり、反応温度を調整したりすることがよい。
On the other hand, when the polymerizable compound or the photopolymerization initiator decreases due to reaction, the performance as a holographic recording material is lowered. Therefore, it is preferable to form a matrix resin without reducing these. Therefore, it is preferable to mix a reaction catalyst or adjust the reaction temperature so that polymerization in a reaction form different from the reaction in which the polymerizable compound is polymerized preferentially occurs.
上記反応触媒としては、例えば、イソシアネート-ヒドロキシル重付加反応の触媒として、スズ含有触媒、チタン含有触媒、亜鉛含有触媒、ジルコニウム含有触媒、アルミニウム含有触媒、コバルト含有触媒、ニッケル含有触媒、銅含有触媒及び鉄含有触媒などの各種金属含有触媒が使用できる。なかでも反応速度の点からスズ含有触媒が好ましい。スズ含有触媒としては、例えば、ジメチルスズジラウレート、ジブチルスズジラウレートなどのスズ含有触媒が使用できる。また、非金属含有触媒としては、1,4-ジアザビシクロ[2,2,2]オクタン(DABCO)、イミダゾール誘導体、2,4,6-トリス(ジメチルアミノメチル)フェノール、N,N-ジメチルベンジルアミンなどの三級アミン化合物などを用いることができる。これらの触媒は、単独で用いても2種以上を組み合わせて用いてもよい。
As the reaction catalyst, for example, as a catalyst for isocyanate-hydroxyl polyaddition reaction, a tin-containing catalyst, a titanium-containing catalyst, a zinc-containing catalyst, a zirconium-containing catalyst, an aluminum-containing catalyst, a cobalt-containing catalyst, a nickel-containing catalyst, a copper-containing catalyst, and Various metal-containing catalysts such as iron-containing catalysts can be used. Of these, tin-containing catalysts are preferred from the viewpoint of reaction rate. As the tin-containing catalyst, for example, a tin-containing catalyst such as dimethyltin dilaurate or dibutyltin dilaurate can be used. Non-metal-containing catalysts include 1,4-diazabicyclo [2,2,2] octane (DABCO), imidazole derivatives, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine. Tertiary amine compounds such as can be used. These catalysts may be used alone or in combination of two or more.
(ホログラフィック記録媒体)
本発明のホログラフィック記録媒体は、上記のホログラフィック記録用材料を含有する記録層を具える。本発明のホログラフィック記録媒体は、必要に応じて、上側基板、下側基板、反射膜などのその他の層を有することができる。
本発明のホログラフィック記録媒体は、透過型及び反射型のいずれであってもよい。 (Holographic recording medium)
The holographic recording medium of the present invention includes a recording layer containing the holographic recording material described above. The holographic recording medium of the present invention can have other layers such as an upper substrate, a lower substrate, and a reflective film as necessary.
The holographic recording medium of the present invention may be either a transmission type or a reflection type.
本発明のホログラフィック記録媒体は、上記のホログラフィック記録用材料を含有する記録層を具える。本発明のホログラフィック記録媒体は、必要に応じて、上側基板、下側基板、反射膜などのその他の層を有することができる。
本発明のホログラフィック記録媒体は、透過型及び反射型のいずれであってもよい。 (Holographic recording medium)
The holographic recording medium of the present invention includes a recording layer containing the holographic recording material described above. The holographic recording medium of the present invention can have other layers such as an upper substrate, a lower substrate, and a reflective film as necessary.
The holographic recording medium of the present invention may be either a transmission type or a reflection type.
以下に、本発明のホログラフィック記録媒体に含まれ得る各基板、記録層の詳細な紹介をする。
基板材料としては、通常、ガラス、セラミックス、樹脂、などが用いられるが、成形性、コストの点から、樹脂が好ましい。樹脂としては、例えば、ポリカーボネート樹脂、アクリル樹脂、ポリシクロオレフィン樹脂、エポキシ樹脂、ポリスチレン樹脂、アクリロニトリル-スチレン共重合体、ABS樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、シリコーン樹脂、フッ素樹脂、ウレタン樹脂、などが挙げられる。これらの中でも、成形性、光学特性、コストの点から、ポリカーボネート樹脂、アクリル樹脂、ポリシクロオレフィン樹脂が特に好ましい。また、基板表面をUV硬化樹脂などでハードコート処理したものや反射防止処理をしたものも適宜使用することができる。また記録再生方式に応じて、予め反射層が設けられた基板を用いることもできる。 The following is a detailed introduction of each substrate and recording layer that can be included in the holographic recording medium of the present invention.
As the substrate material, glass, ceramics, resin and the like are usually used, but resin is preferable from the viewpoint of moldability and cost. Examples of the resin include polycarbonate resin, acrylic resin, polycycloolefin resin, epoxy resin, polystyrene resin, acrylonitrile-styrene copolymer, ABS resin, polyethylene resin, polypropylene resin, silicone resin, fluorine resin, and urethane resin. Can be mentioned. Among these, polycarbonate resin, acrylic resin, and polycycloolefin resin are particularly preferable in terms of moldability, optical characteristics, and cost. Further, those obtained by subjecting the substrate surface to a hard coat treatment with a UV curable resin or the like and those subjected to an antireflection treatment can be used as appropriate. A substrate provided with a reflective layer in advance can also be used according to the recording / reproducing method.
基板材料としては、通常、ガラス、セラミックス、樹脂、などが用いられるが、成形性、コストの点から、樹脂が好ましい。樹脂としては、例えば、ポリカーボネート樹脂、アクリル樹脂、ポリシクロオレフィン樹脂、エポキシ樹脂、ポリスチレン樹脂、アクリロニトリル-スチレン共重合体、ABS樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、シリコーン樹脂、フッ素樹脂、ウレタン樹脂、などが挙げられる。これらの中でも、成形性、光学特性、コストの点から、ポリカーボネート樹脂、アクリル樹脂、ポリシクロオレフィン樹脂が特に好ましい。また、基板表面をUV硬化樹脂などでハードコート処理したものや反射防止処理をしたものも適宜使用することができる。また記録再生方式に応じて、予め反射層が設けられた基板を用いることもできる。 The following is a detailed introduction of each substrate and recording layer that can be included in the holographic recording medium of the present invention.
As the substrate material, glass, ceramics, resin and the like are usually used, but resin is preferable from the viewpoint of moldability and cost. Examples of the resin include polycarbonate resin, acrylic resin, polycycloolefin resin, epoxy resin, polystyrene resin, acrylonitrile-styrene copolymer, ABS resin, polyethylene resin, polypropylene resin, silicone resin, fluorine resin, and urethane resin. Can be mentioned. Among these, polycarbonate resin, acrylic resin, and polycycloolefin resin are particularly preferable in terms of moldability, optical characteristics, and cost. Further, those obtained by subjecting the substrate surface to a hard coat treatment with a UV curable resin or the like and those subjected to an antireflection treatment can be used as appropriate. A substrate provided with a reflective layer in advance can also be used according to the recording / reproducing method.
記録層は、上記ホログラフィック記録用材料からなり、ホログラフィック記録を利用して情報が記録され得るものである。記録層の厚みとしては、特に制限はなく、目的に応じて適宜選択することができる。記録層の厚みが1~3000μmの範囲であれば、記録波長領域350nm~800nmでの透過率が高く有利である。前記基板を用いない場合は、記録層表面にUV硬化樹脂などでハードコート処理したものや反射防止処理を施したものも適宜使用することができる。
The recording layer is made of the holographic recording material, and information can be recorded using the holographic recording. There is no restriction | limiting in particular as thickness of a recording layer, According to the objective, it can select suitably. If the thickness of the recording layer is in the range of 1 to 3000 μm, the transmittance in the recording wavelength region of 350 to 800 nm is high, which is advantageous. In the case where the substrate is not used, those obtained by subjecting the surface of the recording layer to a hard coat treatment with a UV curable resin or the like and those subjected to an antireflection treatment can be used as appropriate.
本発明のホログラフィック記録媒体はホログラフィック記録再生に好ましく用いられるが、ホログラフィック記録再生方法に関してはどの様な方法であっても構わない。例えば、二光束干渉法に基づくホログラフィック記録再生方法や、同軸上に参照光と情報光を配置し集光させるコアキシャルホログラフィック記録再生方法などが好ましく用いられる。
The holographic recording medium of the present invention is preferably used for holographic recording / reproduction, but any method can be used for the holographic recording / reproduction method. For example, a holographic recording / reproducing method based on the two-beam interference method, a coaxial holographic recording / reproducing method in which reference light and information light are arranged on the same axis and condensed are preferably used.
ホログラフィック記録再生装置の一例を図3及び4を参照して説明する。
図3は多重記録用光学系の概略構成図を示すものであり、レーザ発生装置(波長405nmの半導体レーザ)1から発せられたレーザ光は、ミラー2で反射され1/2波長板(HWP)3でパワーの調整を受けた後、一部が偏光ビームスプリッタ(PBS)4で図の下方に向けて反射され、ビームエキスパンダ5でビーム径が拡大された後、シャッタ6を通過して絞り7(開口径6mmφ)でビーム径が狭窄され、HWP8を通ってPBS9に至る。PBS9において、レーザ光は二つに分割され、分割された一方の光はシャッタ10を通過してミラー11で反射され、記録信号光Lsとしてホログラフィック記録媒体Sに照射される。PBS9で分割された他方の光は、1/4波長板(QWP)12を通ってミラー13で反射された後、再度QWP12、PBS9を通過し、記録参照光Lwとしてホログラフィック記録媒体Sに照射される。
この際、ホログラフィック記録媒体Sが取り付けられた回転ステージ14の角度θを所定の値に設定し、所定の時間シャッタ6を開いて露光させ、ホログラフィック記録媒体Sに1つめのホログラムを記録する。次に、θを次の所定の値に設定して、所定の時間シャッタ6を開いて露光させ、ホログラフィック記録媒体Sの同一箇所に2つめのホログラムを記録する。以下、所定の多重度になるまで上記の操作を繰り返すことで多重記録を行うことができる。
HWP3は光学系全体のパワー調整を、HWP8は、信号光と参照光のパワー比率調整を行うためのものである。QWP12は記録参照光Lw(または後述の再生参照光Lr)の偏光軸を調整するためのものである。 An example of the holographic recording / reproducing apparatus will be described with reference to FIGS.
FIG. 3 shows a schematic configuration diagram of an optical system for multiple recording. Laser light emitted from a laser generator (a semiconductor laser having a wavelength of 405 nm) 1 is reflected by amirror 2 and is a half-wave plate (HWP). After the power is adjusted at 3, a part thereof is reflected downward by the polarizing beam splitter (PBS) 4, the beam diameter is enlarged by the beam expander 5, and then passed through the shutter 6 to be stopped. The beam diameter is narrowed by 7 (opening diameter 6 mmφ), and reaches the PBS 9 through the HWP 8. In the PBS 9, the laser light is divided into two, and one of the divided lights passes through the shutter 10, is reflected by the mirror 11, and is applied to the holographic recording medium S as the recording signal light Ls. The other light split by the PBS 9 passes through the quarter wave plate (QWP) 12 and is reflected by the mirror 13, and then passes through the QWP 12 and PBS 9 again to irradiate the holographic recording medium S as the recording reference light Lw. Is done.
At this time, the angle θ of therotary stage 14 to which the holographic recording medium S is attached is set to a predetermined value, the shutter 6 is opened for a predetermined time and exposed, and the first hologram is recorded on the holographic recording medium S. . Next, θ is set to the next predetermined value, the shutter 6 is opened for a predetermined time and exposed, and a second hologram is recorded in the same location of the holographic recording medium S. Thereafter, multiplex recording can be performed by repeating the above operation until a predetermined multiplicity is reached.
HWP3 is for adjusting the power of the entire optical system, and HWP8 is for adjusting the power ratio of the signal light and the reference light. TheQWP 12 is for adjusting the polarization axis of the recording reference light Lw (or reproduction reference light Lr described later).
図3は多重記録用光学系の概略構成図を示すものであり、レーザ発生装置(波長405nmの半導体レーザ)1から発せられたレーザ光は、ミラー2で反射され1/2波長板(HWP)3でパワーの調整を受けた後、一部が偏光ビームスプリッタ(PBS)4で図の下方に向けて反射され、ビームエキスパンダ5でビーム径が拡大された後、シャッタ6を通過して絞り7(開口径6mmφ)でビーム径が狭窄され、HWP8を通ってPBS9に至る。PBS9において、レーザ光は二つに分割され、分割された一方の光はシャッタ10を通過してミラー11で反射され、記録信号光Lsとしてホログラフィック記録媒体Sに照射される。PBS9で分割された他方の光は、1/4波長板(QWP)12を通ってミラー13で反射された後、再度QWP12、PBS9を通過し、記録参照光Lwとしてホログラフィック記録媒体Sに照射される。
この際、ホログラフィック記録媒体Sが取り付けられた回転ステージ14の角度θを所定の値に設定し、所定の時間シャッタ6を開いて露光させ、ホログラフィック記録媒体Sに1つめのホログラムを記録する。次に、θを次の所定の値に設定して、所定の時間シャッタ6を開いて露光させ、ホログラフィック記録媒体Sの同一箇所に2つめのホログラムを記録する。以下、所定の多重度になるまで上記の操作を繰り返すことで多重記録を行うことができる。
HWP3は光学系全体のパワー調整を、HWP8は、信号光と参照光のパワー比率調整を行うためのものである。QWP12は記録参照光Lw(または後述の再生参照光Lr)の偏光軸を調整するためのものである。 An example of the holographic recording / reproducing apparatus will be described with reference to FIGS.
FIG. 3 shows a schematic configuration diagram of an optical system for multiple recording. Laser light emitted from a laser generator (a semiconductor laser having a wavelength of 405 nm) 1 is reflected by a
At this time, the angle θ of the
HWP3 is for adjusting the power of the entire optical system, and HWP8 is for adjusting the power ratio of the signal light and the reference light. The
図4は再生用光学系の概略構成図を示すものであり、図3と同一の記号は同じ意味を有する。レーザ発生装置1から発せられたレーザ光は、ミラー2、HWP3、PBS4、ビームエキスパンダ5、シャッタ6、絞り7を経由してPBS9に至る。PBS9においてレーザ光は二つに分割され、分割された一方の光はシャッタ10によって遮断される。PBS9で分割された他方の光は、QWP12を通ってミラー13で反射された後、再度QWP12、PBS9を通過し、絞り15(開口径2.7mmφ)によりビーム径が狭窄され、再生参照光Lrとしてホログラフィック記録媒体Sに照射される。
この際、ホログラフィック記録媒体Sが取り付けられた回転ステージ14の角度θを所定の(再生したい)ホログラムに対応する値に設定し、所定の時間シャッタ6を開いて再生参照光Lrを媒体に照射する。記録されたホログラムによって回折された光(再生信号光)の強度を光パワーメータ16で、媒体を透過した光(透過光)の強度を光パワーメータ17で、それぞれ測定する。 FIG. 4 is a schematic configuration diagram of the reproducing optical system, and the same symbols as those in FIG. 3 have the same meaning. Laser light emitted from thelaser generator 1 reaches the PBS 9 via the mirror 2, the HWP 3, the PBS 4, the beam expander 5, the shutter 6, and the diaphragm 7. In the PBS 9, the laser light is divided into two, and one of the divided lights is blocked by the shutter 10. The other light divided by the PBS 9 is reflected by the mirror 13 through the QWP 12, and then passes again through the QWP 12 and the PBS 9, and the beam diameter is narrowed by the aperture 15 (opening diameter 2.7 mmφ), and the reproduction reference light Lr To the holographic recording medium S.
At this time, the angle θ of therotary stage 14 to which the holographic recording medium S is attached is set to a value corresponding to a predetermined (reproduced) hologram, the shutter 6 is opened for a predetermined time, and the reproduction reference light Lr is irradiated onto the medium. To do. The intensity of the light (reproduced signal light) diffracted by the recorded hologram is measured by the optical power meter 16, and the intensity of the light transmitted through the medium (transmitted light) is measured by the optical power meter 17.
この際、ホログラフィック記録媒体Sが取り付けられた回転ステージ14の角度θを所定の(再生したい)ホログラムに対応する値に設定し、所定の時間シャッタ6を開いて再生参照光Lrを媒体に照射する。記録されたホログラムによって回折された光(再生信号光)の強度を光パワーメータ16で、媒体を透過した光(透過光)の強度を光パワーメータ17で、それぞれ測定する。 FIG. 4 is a schematic configuration diagram of the reproducing optical system, and the same symbols as those in FIG. 3 have the same meaning. Laser light emitted from the
At this time, the angle θ of the
以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。
Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.
実施例1
1-(I): 4-アセチルジフェニルスルフィドの合成
ジフェニルスルフィド25.0g(0.136mol)をジクロロメタン300mlに溶解させ、窒素雰囲気下0℃に冷却したものに、無水塩化アルミニウム19.9g(0.149mol)をゆっくりと加え、混合物を15分間撹拌した。塩化アセチル11.9g(0.149mol)を50mlのジクロロメタンに溶解させたものを滴下し、30分間撹拌後、室温に昇温してさらに1時間攪拌した。反応終了後、混合物を氷水(200ml)に注ぎ、10分間撹拌後、ジクロロメタン(各100ml)で三回抽出した。有機層をまとめ、水(100ml)と飽和食塩水(100ml)で洗浄し、無水硫酸マグネシウムで乾燥した。乾燥剤を濾別して、溶媒を減圧留去することで粗生成物28.5gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 1
1- (I): Synthesis of 4-acetyldiphenyl sulfide 25.0 g (0.136 mol) of diphenyl sulfide was dissolved in 300 ml of dichloromethane and cooled to 0 ° C. under a nitrogen atmosphere. 149 mol) was added slowly and the mixture was stirred for 15 minutes. A solution prepared by dissolving 11.9 g (0.149 mol) of acetyl chloride in 50 ml of dichloromethane was added dropwise, stirred for 30 minutes, warmed to room temperature, and further stirred for 1 hour. After completion of the reaction, the mixture was poured into ice water (200 ml), stirred for 10 minutes, and extracted three times with dichloromethane (100 ml each). The organic layers were combined, washed with water (100 ml) and saturated brine (100 ml), and dried over anhydrous magnesium sulfate. The desiccant was filtered off and the solvent was distilled off under reduced pressure to obtain 28.5 g of a crude product. The obtained crude product was used in the next reaction without further purification.
1-(I): 4-アセチルジフェニルスルフィドの合成
ジフェニルスルフィド25.0g(0.136mol)をジクロロメタン300mlに溶解させ、窒素雰囲気下0℃に冷却したものに、無水塩化アルミニウム19.9g(0.149mol)をゆっくりと加え、混合物を15分間撹拌した。塩化アセチル11.9g(0.149mol)を50mlのジクロロメタンに溶解させたものを滴下し、30分間撹拌後、室温に昇温してさらに1時間攪拌した。反応終了後、混合物を氷水(200ml)に注ぎ、10分間撹拌後、ジクロロメタン(各100ml)で三回抽出した。有機層をまとめ、水(100ml)と飽和食塩水(100ml)で洗浄し、無水硫酸マグネシウムで乾燥した。乾燥剤を濾別して、溶媒を減圧留去することで粗生成物28.5gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 1
1- (I): Synthesis of 4-acetyldiphenyl sulfide 25.0 g (0.136 mol) of diphenyl sulfide was dissolved in 300 ml of dichloromethane and cooled to 0 ° C. under a nitrogen atmosphere. 149 mol) was added slowly and the mixture was stirred for 15 minutes. A solution prepared by dissolving 11.9 g (0.149 mol) of acetyl chloride in 50 ml of dichloromethane was added dropwise, stirred for 30 minutes, warmed to room temperature, and further stirred for 1 hour. After completion of the reaction, the mixture was poured into ice water (200 ml), stirred for 10 minutes, and extracted three times with dichloromethane (100 ml each). The organic layers were combined, washed with water (100 ml) and saturated brine (100 ml), and dried over anhydrous magnesium sulfate. The desiccant was filtered off and the solvent was distilled off under reduced pressure to obtain 28.5 g of a crude product. The obtained crude product was used in the next reaction without further purification.
1-(II): 4-(1-ヒドロキシエチル)ジフェニルスルフィドの合成
上記の反応にて得た4-アセチルジフェニルスルフィド28.2g(0.124mol)をメタノール150mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム9.3g(0.247mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(300ml)を加え、酢酸エチル(250ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物26.6gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 1- (II): Synthesis of 4- (1-hydroxyethyl) diphenyl sulfide 28.2 g (0.124 mol) of 4-acetyldiphenyl sulfide obtained by the above reaction was dissolved in 150 ml of methanol and cooled to 0 ° C. To the mixture, 9.3 g (0.247 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower, and the mixture was stirred for 1 hour. After completion of the reaction, water (300 ml) was added to the mixture and extracted with ethyl acetate (250 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 26.6 g of a crude product. The obtained crude product was used in the next reaction without further purification.
上記の反応にて得た4-アセチルジフェニルスルフィド28.2g(0.124mol)をメタノール150mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム9.3g(0.247mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(300ml)を加え、酢酸エチル(250ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物26.6gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 1- (II): Synthesis of 4- (1-hydroxyethyl) diphenyl sulfide 28.2 g (0.124 mol) of 4-acetyldiphenyl sulfide obtained by the above reaction was dissolved in 150 ml of methanol and cooled to 0 ° C. To the mixture, 9.3 g (0.247 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower, and the mixture was stirred for 1 hour. After completion of the reaction, water (300 ml) was added to the mixture and extracted with ethyl acetate (250 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 26.6 g of a crude product. The obtained crude product was used in the next reaction without further purification.
1-(III): 1-[4-(フェニルチオ)フェニル]エチル アクリレートの合成
上記の反応にて得た4-(1-ヒドロキシエチル)ジフェニルスルフィド5.0g(0.022mol)とトリエチルアミン8.8g(0.087mol)をジクロロメタン50mlに溶解させ0℃に冷却したものに、アクリロイルクロリドを滴下し、混合物を30分間攪拌後、室温に昇温してさらに1時間攪拌した。反応終了後、水(100ml)を加えジクロロメタン(100ml)で抽出した。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物3.0gを無色透明の液体として得た(収率48%)。
1H-NMR(CDCl3、600MHz ) δ(ppm):7.25-7.36(m,9H);6.42(dd=18.0Hz&1.2Hz,1H);6.14(dd=17.4Hz&10.2Hz,1H);5.92-5.95(q,1H);5.83(dd=10.8Hz&1.2Hz,1H);1.56(d=6.6Hz,3H) 1- (III): Synthesis of 1- [4- (phenylthio) phenyl] ethyl acrylate
A solution obtained by dissolving 5.0 g (0.022 mol) of 4- (1-hydroxyethyl) diphenyl sulfide obtained in the above reaction and 8.8 g (0.087 mol) of triethylamine in 50 ml of dichloromethane and cooling to 0 ° C. was obtained by adding acryloyl Chloride was added dropwise and the mixture was stirred for 30 minutes, then warmed to room temperature and stirred for an additional hour. After completion of the reaction, water (100 ml) was added and extracted with dichloromethane (100 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 3.0 g of the objective compound as a colorless transparent liquid (yield 48%).
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.25-7.36 (m, 9H); 6.42 (dd = 18.0 Hz & 1.2 Hz, 1H); 6.14 (dd = 17 .4 Hz & 10.2 Hz, 1 H); 5.92-5.95 (q, 1 H); 5.83 (dd = 10.8 Hz & 1.2 Hz, 1 H); 1.56 (d = 6.6 Hz, 3 H)
1H-NMR(CDCl3、600MHz ) δ(ppm):7.25-7.36(m,9H);6.42(dd=18.0Hz&1.2Hz,1H);6.14(dd=17.4Hz&10.2Hz,1H);5.92-5.95(q,1H);5.83(dd=10.8Hz&1.2Hz,1H);1.56(d=6.6Hz,3H) 1- (III): Synthesis of 1- [4- (phenylthio) phenyl] ethyl acrylate
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.25-7.36 (m, 9H); 6.42 (dd = 18.0 Hz & 1.2 Hz, 1H); 6.14 (dd = 17 .4 Hz & 10.2 Hz, 1 H); 5.92-5.95 (q, 1 H); 5.83 (dd = 10.8 Hz & 1.2 Hz, 1 H); 1.56 (d = 6.6 Hz, 3 H)
実施例2
2-(I): 2,4-ビス(フェニルチオ)アセトフェノンの合成
2,4-ジフルオロアセトフェノン16.1g(0.103mol)、チオフェノール25g(0.227mol)、炭酸カリウム31.5g(0.227mol)をジメチルホルムアミド(DMF)250mlに溶解させ、130℃で8時間攪拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(200ml)、酢酸エチル(200ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、34.0gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 2
2- (I): Synthesis of 2,4-bis (phenylthio) acetophenone 16.1-g (0.103 mol) 2,4-difluoroacetophenone, 25 g (0.227 mol) thiophenol, 31.5 g (0.227 mol) potassium carbonate ) Was dissolved in 250 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (200 ml) and ethyl acetate (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 34.0 g of a crude product. The obtained crude product was used in the next reaction without further purification.
2-(I): 2,4-ビス(フェニルチオ)アセトフェノンの合成
2,4-ジフルオロアセトフェノン16.1g(0.103mol)、チオフェノール25g(0.227mol)、炭酸カリウム31.5g(0.227mol)をジメチルホルムアミド(DMF)250mlに溶解させ、130℃で8時間攪拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(200ml)、酢酸エチル(200ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、34.0gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 2
2- (I): Synthesis of 2,4-bis (phenylthio) acetophenone 16.1-g (0.103 mol) 2,4-difluoroacetophenone, 25 g (0.227 mol) thiophenol, 31.5 g (0.227 mol) potassium carbonate ) Was dissolved in 250 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (200 ml) and ethyl acetate (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 34.0 g of a crude product. The obtained crude product was used in the next reaction without further purification.
2-(II): 1-(1-ヒドロキシエチル)-2,4-ビス(フェニルチオ)ベンゼンの合成
上記の反応にて得た2,4-ビス(フェニルチオ)アセトフェノン34.0g(0.103mol)をメタノール300mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム5.9g(0.155mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(300ml)を加え、酢酸エチル(200ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物27.0gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 2- (II): Synthesis of 1- (1-hydroxyethyl) -2,4-bis (phenylthio) benzene 34.0 g (0.103 mol) of 2,4-bis (phenylthio) acetophenone obtained by the above reaction Was dissolved in 300 ml of methanol and cooled to 0 ° C., 5.9 g (0.155 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower, and the mixture was stirred for 1 hour. After completion of the reaction, water (300 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 27.0 g of a crude product. The obtained crude product was used in the next reaction without further purification.
上記の反応にて得た2,4-ビス(フェニルチオ)アセトフェノン34.0g(0.103mol)をメタノール300mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム5.9g(0.155mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(300ml)を加え、酢酸エチル(200ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物27.0gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 2- (II): Synthesis of 1- (1-hydroxyethyl) -2,4-bis (phenylthio) benzene 34.0 g (0.103 mol) of 2,4-bis (phenylthio) acetophenone obtained by the above reaction Was dissolved in 300 ml of methanol and cooled to 0 ° C., 5.9 g (0.155 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower, and the mixture was stirred for 1 hour. After completion of the reaction, water (300 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 27.0 g of a crude product. The obtained crude product was used in the next reaction without further purification.
2-(III): 2,4-ビス(フェニルチオ)スチレンの合成
ディーン・スタークトラップを具えた反応容器に、上記の反応にて得た1-(1-ヒドロキシエチル)-2,4-ビス(フェニルチオ)ベンゼン10.0g(0.030mol)、p-トルエンスルホン酸一水和物0.014g(0.070mmol)、トルエン100mlとを加え、混合物をトルエン還流下で7時間攪拌した。反応終了後、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物7.5gを無色透明の液体として得た。
1H-NMR(CDCl3、600MHz) δ(ppm):7.50-7.52(m,1H);7.15-7.33(m,12H);5.69(d=18.0Hz,1H);5.30(d=10.8Hz,1H)。 2- (III): Synthesis of 2,4-bis (phenylthio) styrene
In a reaction vessel equipped with a Dean-Stark trap, 10.0 g (0.030 mol) of 1- (1-hydroxyethyl) -2,4-bis (phenylthio) benzene obtained by the above reaction, p-toluenesulfonic acid 0.014 g (0.070 mmol) of monohydrate and 100 ml of toluene were added, and the mixture was stirred for 7 hours under toluene reflux. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 7.5 g of the objective compound as a colorless transparent liquid.
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.50-7.52 (m, 1H); 7.15-7.33 (m, 12H); 5.69 (d = 18.0 Hz) , 1H); 5.30 (d = 10.8 Hz, 1H).
1H-NMR(CDCl3、600MHz) δ(ppm):7.50-7.52(m,1H);7.15-7.33(m,12H);5.69(d=18.0Hz,1H);5.30(d=10.8Hz,1H)。 2- (III): Synthesis of 2,4-bis (phenylthio) styrene
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.50-7.52 (m, 1H); 7.15-7.33 (m, 12H); 5.69 (d = 18.0 Hz) , 1H); 5.30 (d = 10.8 Hz, 1H).
実施例3
1-[2,4-ビス(フェニルチオ)フェニル]エチル アクリレートの合成
上記、2-(II)の反応で得た1-(1-ヒドロキシエチル)-2,4-ビス(フェニルチオ)ベンゼン5.0g(0.015mol)とトリエチルアミン6.0g(0.059mol)をジクロロメタン50mlに溶解させ0℃に冷却したものに、アクリロイルクロリドを滴下し、混合物を30分間攪拌後、室温に昇温してさらに1時間攪拌した。反応終了後、水(100ml)を加えジクロロメタン(100ml)で抽出した。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物2.9gを無色透明の液体として得た(収率49%)。
1H-NMR(CDCl3、600MHz ) δ(ppm):7.14-7.39(m,13H);6.38-6.41(q,1H);6.13(dd=18.6Hz&10.2Hz,1H);5.82(dd=10.2Hz&1.2Hz,1H);1.51(d=6.0Hz,3H) Example 3
Synthesis of 1- [2,4-bis (phenylthio) phenyl] ethyl acrylate
1- (1-Hydroxyethyl) -2,4-bis (phenylthio) benzene (5.0 g, 0.015 mol) and triethylamine (6.0 g, 0.059 mol) obtained by the above 2- (II) reaction were mixed with dichloromethane. Acryloyl chloride was added dropwise to the solution dissolved in 50 ml and cooled to 0 ° C., and the mixture was stirred for 30 minutes, then warmed to room temperature and further stirred for 1 hour. After completion of the reaction, water (100 ml) was added and extracted with dichloromethane (100 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 2.9 g of the objective compound as a colorless transparent liquid (yield 49%).
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.14-7.39 (m, 13H); 6.38-6.41 (q, 1H); 6.13 (dd = 18.6 Hz & 10 .2 Hz, 1 H); 5.82 (dd = 10.2 Hz & 1.2 Hz, 1 H); 1.51 (d = 6.0 Hz, 3 H)
1-[2,4-ビス(フェニルチオ)フェニル]エチル アクリレートの合成
1H-NMR(CDCl3、600MHz ) δ(ppm):7.14-7.39(m,13H);6.38-6.41(q,1H);6.13(dd=18.6Hz&10.2Hz,1H);5.82(dd=10.2Hz&1.2Hz,1H);1.51(d=6.0Hz,3H) Example 3
Synthesis of 1- [2,4-bis (phenylthio) phenyl] ethyl acrylate
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.14-7.39 (m, 13H); 6.38-6.41 (q, 1H); 6.13 (dd = 18.6 Hz & 10 .2 Hz, 1 H); 5.82 (dd = 10.2 Hz & 1.2 Hz, 1 H); 1.51 (d = 6.0 Hz, 3 H)
実施例4
1-[2,4-ビス(フェニルチオ)フェニル]エチル 4-ビニルベンゾエートの合成
上記、2-(II)の反応で得た1-(1-ヒドロキシエチル)-2,4-ビス(フェニルチオ)ベンゼン3.39g(0.010mol)、4-ビニル安息香酸1.8g(0.012mol)、N,N’-ジシクロヘキシルカルボジイミド2.5g(0.012mol)、N,N-ジメチルアミノピリジン1.5g(0.012mol)とをジクロロメタン100mlに溶解させ、室温で混合物を8時間攪拌した。反応終了後、水(100ml)を加えジクロロメタン(100ml)で抽出した。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物3.9gを白色固体(粉末)として得た(収率83%)。この白色固体は60℃の温浴中で無色透明の液体となった。
1H-NMR(CDCl3、600MHz ) δ(ppm):7.50-7.52(m,2H);7.24-7.46(m,15H);6.75(dd=15.0Hz&10.8Hz,1H);6.53-6.57(q,1H);5.86(d=18Hz,1H);5.38(d=10.8Hz,1H);1.59(d=7.2Hz,3H) Example 4
Synthesis of 1- [2,4-bis (phenylthio) phenyl] ethyl 4-vinylbenzoate
3.39 g (0.010 mol) of 1- (1-hydroxyethyl) -2,4-bis (phenylthio) benzene obtained by the reaction of 2- (II) above, 1.8 g (0. 10 mol) of 4-vinylbenzoic acid. 012 mol), 2.5 g (0.012 mol) of N, N′-dicyclohexylcarbodiimide and 1.5 g (0.012 mol) of N, N-dimethylaminopyridine were dissolved in 100 ml of dichloromethane, and the mixture was stirred at room temperature for 8 hours. . After completion of the reaction, water (100 ml) was added and extracted with dichloromethane (100 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 3.9 g of the target compound as a white solid (powder) (yield 83%). This white solid became a colorless and transparent liquid in a hot bath at 60 ° C.
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.50-7.52 (m, 2H); 7.24-7.46 (m, 15H); 6.75 (dd = 15.0 Hz & 10 8.53, 6.57 (q, 1H); 5.86 (d = 18 Hz, 1H); 5.38 (d = 10.8 Hz, 1H); 1.59 (d = 7) .2Hz, 3H)
1-[2,4-ビス(フェニルチオ)フェニル]エチル 4-ビニルベンゾエートの合成
1H-NMR(CDCl3、600MHz ) δ(ppm):7.50-7.52(m,2H);7.24-7.46(m,15H);6.75(dd=15.0Hz&10.8Hz,1H);6.53-6.57(q,1H);5.86(d=18Hz,1H);5.38(d=10.8Hz,1H);1.59(d=7.2Hz,3H) Example 4
Synthesis of 1- [2,4-bis (phenylthio) phenyl] ethyl 4-vinylbenzoate
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.50-7.52 (m, 2H); 7.24-7.46 (m, 15H); 6.75 (dd = 15.0 Hz & 10 8.53, 6.57 (q, 1H); 5.86 (d = 18 Hz, 1H); 5.38 (d = 10.8 Hz, 1H); 1.59 (d = 7) .2Hz, 3H)
実施例5
5-(I): 2,4-ビス(2-ナフチルチオ)アセトフェノンの合成
2,4-ジフルオロアセトフェノン12.2g(0.078mol)、2-ナフタレンチオール25.0g(0.156mol)、炭酸カリウム21.6g(0.156mol)をDMF250mlに溶解させ、130℃で8時間攪拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(200ml)、酢酸エチル(200ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、33.9gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 5
5- (I): Synthesis of 2,4-bis (2-naphthylthio) acetophenone 12.4-g (0.078 mol) 2,4-difluoroacetophenone, 25.0 g (0.156 mol) 2-naphthalenethiol, potassium carbonate 21 0.6 g (0.156 mol) was dissolved in 250 ml of DMF and stirred at 130 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (200 ml) and ethyl acetate (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 33.9 g of a crude product. The obtained crude product was used in the next reaction without further purification.
5-(I): 2,4-ビス(2-ナフチルチオ)アセトフェノンの合成
2,4-ジフルオロアセトフェノン12.2g(0.078mol)、2-ナフタレンチオール25.0g(0.156mol)、炭酸カリウム21.6g(0.156mol)をDMF250mlに溶解させ、130℃で8時間攪拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(200ml)、酢酸エチル(200ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、33.9gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 5
5- (I): Synthesis of 2,4-bis (2-naphthylthio) acetophenone 12.4-g (0.078 mol) 2,4-difluoroacetophenone, 25.0 g (0.156 mol) 2-naphthalenethiol, potassium carbonate 21 0.6 g (0.156 mol) was dissolved in 250 ml of DMF and stirred at 130 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (200 ml) and ethyl acetate (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 33.9 g of a crude product. The obtained crude product was used in the next reaction without further purification.
5-(II): 1-(1-ヒドロキシエチル)-2,4-ビス(2-ナフチルチオ)ベンゼンの合成
上記の反応にて得た2,4-ビス(2-ナフチルチオ)アセトフェノン33.9g(0.078mol)をメタノール300mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム4.4g(0.117mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(300ml)を加え、酢酸エチル(200ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物28.0gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 5- (II): Synthesis of 1- (1-hydroxyethyl) -2,4-bis (2-naphthylthio) benzene 33.9 g of 2,4-bis (2-naphthylthio) acetophenone obtained by the above reaction ( 0.078 mol) was dissolved in 300 ml of methanol and cooled to 0 ° C., and 4.4 g (0.117 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower. Stir for hours. After completion of the reaction, water (300 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 28.0 g of a crude product. The obtained crude product was used in the next reaction without further purification.
上記の反応にて得た2,4-ビス(2-ナフチルチオ)アセトフェノン33.9g(0.078mol)をメタノール300mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム4.4g(0.117mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(300ml)を加え、酢酸エチル(200ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物28.0gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 5- (II): Synthesis of 1- (1-hydroxyethyl) -2,4-bis (2-naphthylthio) benzene 33.9 g of 2,4-bis (2-naphthylthio) acetophenone obtained by the above reaction ( 0.078 mol) was dissolved in 300 ml of methanol and cooled to 0 ° C., and 4.4 g (0.117 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower. Stir for hours. After completion of the reaction, water (300 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 28.0 g of a crude product. The obtained crude product was used in the next reaction without further purification.
5-(III): 2,4-ビス(2-ナフチルチオ)スチレンの合成
ディーン・スタークトラップを具えた反応容器に、上記の反応にて得た1-(1-ヒドロキシエチル)-2,4-ビス(2-ナフチルチオ)ベンゼン15.0g(0.034mol)、p-トルエンスルホン酸一水和物0.016g(0.08mmol)、トルエン150mlとを加え、混合物をトルエン還流下で7時間攪拌した。反応終了後、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物11.8gを白色固体(粉末)として得た。この白色固体は60℃の温浴中で無色透明の液体となった。
1H-NMR(CDCl3、600MHz ) δ(ppm):7.20-7.81(m,17H);5.71(d=17.4Hz,1H);4.13(d=7.2Hz,1H) 5- (III): Synthesis of 2,4-bis (2-naphthylthio) styrene
In a reaction vessel equipped with a Dean-Stark trap, 15.0 g (0.034 mol) of 1- (1-hydroxyethyl) -2,4-bis (2-naphthylthio) benzene obtained by the above reaction, p-toluene 0.016 g (0.08 mmol) of sulfonic acid monohydrate and 150 ml of toluene were added, and the mixture was stirred for 7 hours under toluene reflux. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 11.8 g of the target compound as a white solid (powder). This white solid became a colorless and transparent liquid in a hot bath at 60 ° C.
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.20-7.81 (m, 17H); 5.71 (d = 17.4 Hz, 1H); 4.13 (d = 7.2 Hz) , 1H)
1H-NMR(CDCl3、600MHz ) δ(ppm):7.20-7.81(m,17H);5.71(d=17.4Hz,1H);4.13(d=7.2Hz,1H) 5- (III): Synthesis of 2,4-bis (2-naphthylthio) styrene
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.20-7.81 (m, 17H); 5.71 (d = 17.4 Hz, 1H); 4.13 (d = 7.2 Hz) , 1H)
実施例6
6-(I): 2,4-ビス[4-(メチルチオ)フェニルチオ]アセトフェノンの合成
2,4-ジフルオロアセトフェノン7.1g(0.45mol)、4-(メチルチオ)ベンゼンチオール10g(0.091mol)、炭酸カリウム12.5g(0.091mol)をDMF150mlに溶解させ、130℃で8時間攪拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(200ml)、酢酸エチル(200ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、16.5gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 6
6- (I): Synthesis of 2,4-bis [4- (methylthio) phenylthio]acetophenone 2,4-difluoroacetophenone 7.1 g (0.45 mol), 4- (methylthio) benzenethiol 10 g (0.091 mol) 12.5 g (0.091 mol) of potassium carbonate was dissolved in 150 ml of DMF and stirred at 130 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (200 ml) and ethyl acetate (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 16.5 g of a crude product. The obtained crude product was used in the next reaction without further purification.
6-(I): 2,4-ビス[4-(メチルチオ)フェニルチオ]アセトフェノンの合成
2,4-ジフルオロアセトフェノン7.1g(0.45mol)、4-(メチルチオ)ベンゼンチオール10g(0.091mol)、炭酸カリウム12.5g(0.091mol)をDMF150mlに溶解させ、130℃で8時間攪拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(200ml)、酢酸エチル(200ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、16.5gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 6
6- (I): Synthesis of 2,4-bis [4- (methylthio) phenylthio]
6-(II): 1-(1-ヒドロキシエチル)-2,4-ビス[4-(メチルチオ)フェニルチオ]ベンゼンの合成
上記の反応にて得た2,4-ビス[4-(メチルチオ)フェニルチオ]アセトフェノン16.5g(0.039mol)をメタノール300mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム2.2g(0.058mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(300ml)を加え、酢酸エチル(200ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物15.6gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 6- (II): Synthesis of 1- (1-hydroxyethyl) -2,4-bis [4- (methylthio) phenylthio]benzene 2,4-bis [4- (methylthio) phenylthio obtained by the above reaction A solution of 16.5 g (0.039 mol) of acetophenone in 300 ml of methanol and cooling to 0 ° C. slowly added 2.2 g (0.058 mol) of sodium borohydride so that the liquid temperature was kept at 15 ° C. or lower. And the mixture was stirred for 1 hour. After completion of the reaction, water (300 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 15.6 g of a crude product. The obtained crude product was used in the next reaction without further purification.
上記の反応にて得た2,4-ビス[4-(メチルチオ)フェニルチオ]アセトフェノン16.5g(0.039mol)をメタノール300mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム2.2g(0.058mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(300ml)を加え、酢酸エチル(200ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物15.6gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 6- (II): Synthesis of 1- (1-hydroxyethyl) -2,4-bis [4- (methylthio) phenylthio]
6-(III): 2,4-ビス[4-(メチルチオ)フェニルチオ]スチレンの合成
ディーン・スタークトラップを具えた反応容器に、上記の反応にて得た1-(1-ヒドロキシエチル)-2,4-ビス[4-(メチルチオ)フェニルチオ]ベンゼン13.6g(0.032mol)、p-トルエンスルホン酸一水和物0.014g(0.075mmol)、トルエン150mlとを加え、混合物をトルエン還流下で7時間攪拌した。反応終了後、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物1.0gを無色透明の液体として得た(収率7%)。
1H-NMR(CDCl3、600MHz) δ(ppm):6.84-7.45(m,10H);5.77(d=18.0Hz,1H);5.67(d=18.0Hz,1H)。 6- (III): Synthesis of 2,4-bis [4- (methylthio) phenylthio] styrene
In a reaction vessel equipped with a Dean-Stark trap, 13.6 g (0.032 mol) of 1- (1-hydroxyethyl) -2,4-bis [4- (methylthio) phenylthio] benzene obtained in the above reaction, 0.014 g (0.075 mmol) of p-toluenesulfonic acid monohydrate and 150 ml of toluene were added, and the mixture was stirred under toluene reflux for 7 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 1.0 g of the objective compound as a colorless transparent liquid (yield 7%).
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 6.84-7.45 (m, 10H); 5.77 (d = 18.0 Hz, 1H); 5.67 (d = 18.0 Hz) , 1H).
1H-NMR(CDCl3、600MHz) δ(ppm):6.84-7.45(m,10H);5.77(d=18.0Hz,1H);5.67(d=18.0Hz,1H)。 6- (III): Synthesis of 2,4-bis [4- (methylthio) phenylthio] styrene
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 6.84-7.45 (m, 10H); 5.77 (d = 18.0 Hz, 1H); 5.67 (d = 18.0 Hz) , 1H).
実施例7
7-(I): 2,4,6-トリス(フェニルチオ)アセトフェノンの合成
2,4,6-トリフルオロアセトフェノン25g(0.144mol)、チオフェノール47.5g(0.430mol)、炭酸カリウム59.5g(0.430mol)をDMF500mlに溶解させ、130℃で8時間攪拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(400ml)、酢酸エチル(400ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、68.7gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 7
7- (I): Synthesis of 2,4,6-tris (phenylthio) acetophenone 25,4,6-trifluoroacetophenone 25. 4 (0.144 mol), 47.5 g thiophenol (0.430 mol), potassium carbonate 59. 5 g (0.430 mol) was dissolved in 500 ml of DMF and stirred at 130 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (400 ml) and ethyl acetate (400 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 68.7 g of a crude product. The obtained crude product was used in the next reaction without further purification.
7-(I): 2,4,6-トリス(フェニルチオ)アセトフェノンの合成
2,4,6-トリフルオロアセトフェノン25g(0.144mol)、チオフェノール47.5g(0.430mol)、炭酸カリウム59.5g(0.430mol)をDMF500mlに溶解させ、130℃で8時間攪拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(400ml)、酢酸エチル(400ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、68.7gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 7
7- (I): Synthesis of 2,4,6-tris (phenylthio)
7-(II): 1-(1-ヒドロキシエチル)-2,4,6-トリス(フェニルチオ)ベンゼンの合成
上記の反応にて得た2,4,6-トリス(フェニルチオ)アセトフェノン66.0g(0.148mol)をメタノール500mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム16.8g(0.445mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(500ml)を加え、酢酸エチル(200ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物56.7gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 7- (II): Synthesis of 1- (1-hydroxyethyl) -2,4,6-tris (phenylthio) benzene 66.0 g of 2,4,6-tris (phenylthio) acetophenone obtained by the above reaction ( 0.148 mol) was dissolved in 500 ml of methanol and cooled to 0 ° C., and 16.8 g (0.445 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower. Stir for hours. After completion of the reaction, water (500 ml) was added to the mixture and extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 56.7 g of a crude product. The obtained crude product was used in the next reaction without further purification.
上記の反応にて得た2,4,6-トリス(フェニルチオ)アセトフェノン66.0g(0.148mol)をメタノール500mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム16.8g(0.445mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(500ml)を加え、酢酸エチル(200ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物56.7gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 7- (II): Synthesis of 1- (1-hydroxyethyl) -2,4,6-tris (phenylthio) benzene 66.0 g of 2,4,6-tris (phenylthio) acetophenone obtained by the above reaction ( 0.148 mol) was dissolved in 500 ml of methanol and cooled to 0 ° C., and 16.8 g (0.445 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower. Stir for hours. After completion of the reaction, water (500 ml) was added to the mixture and extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 56.7 g of a crude product. The obtained crude product was used in the next reaction without further purification.
7-(III): 2,4,6-トリス(フェニルチオ)スチレンの合成
ディーン・スタークトラップを具えた反応容器に、上記の反応にて得た1-(1-ヒドロキシエチル)-2,4,6-トリス(フェニルチオ)ベンゼン20.0g(0.448mol)、p-トルエンスルホン酸一水和物0.204g(0.107mmol)、トルエン300mlとを加え、混合物をトルエン還流下で7時間攪拌した。反応終了後、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物14.5gを無色透明の粘稠液体として得た(収率78%)。
1H-NMR(CDCl3、600MHz) δ(ppm):7.10-7.41(m,17H);5.71(d=18.0Hz,1H);5.32(d=10.8Hz,1H)。 7- (III): Synthesis of 2,4,6-tris (phenylthio) styrene
In a reaction vessel equipped with a Dean-Stark trap, 20.0 g (0.448 mol) of 1- (1-hydroxyethyl) -2,4,6-tris (phenylthio) benzene obtained by the above reaction, p-toluene 0.204 g (0.107 mmol) of sulfonic acid monohydrate and 300 ml of toluene were added, and the mixture was stirred for 7 hours under toluene reflux. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 14.5 g of the objective compound as a colorless transparent viscous liquid (yield 78%).
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.10-7.41 (m, 17H); 5.71 (d = 18.0 Hz, 1H); 5.32 (d = 10.8 Hz) , 1H).
1H-NMR(CDCl3、600MHz) δ(ppm):7.10-7.41(m,17H);5.71(d=18.0Hz,1H);5.32(d=10.8Hz,1H)。 7- (III): Synthesis of 2,4,6-tris (phenylthio) styrene
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.10-7.41 (m, 17H); 5.71 (d = 18.0 Hz, 1H); 5.32 (d = 10.8 Hz) , 1H).
実施例8
8-(I): 4,4’-ビス(フェニルチオ)ベンゾフェノンの合成
4,4’-ジフルオロベンゾフェノン50.0g(0.229mol)、チオフェノール53.0g(0.481mol)、炭酸カリウム66.5g(0.481mol)をジメチルホルムアミド(DMF)250mlに溶解させ、130℃で3時間攪拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(500ml)、酢酸エチル(300ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、101.1gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 8
8- (I): Synthesis of 4,4′-bis (phenylthio) benzophenone 4,4′-difluorobenzophenone 50.0 g (0.229 mol), thiophenol 53.0 g (0.481 mol), potassium carbonate 66.5 g (0.481 mol) was dissolved in 250 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (300 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 101.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.
8-(I): 4,4’-ビス(フェニルチオ)ベンゾフェノンの合成
4,4’-ジフルオロベンゾフェノン50.0g(0.229mol)、チオフェノール53.0g(0.481mol)、炭酸カリウム66.5g(0.481mol)をジメチルホルムアミド(DMF)250mlに溶解させ、130℃で3時間攪拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(500ml)、酢酸エチル(300ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、101.1gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 8
8- (I): Synthesis of 4,4′-bis (phenylthio)
8-(II): 4,4’-ビス(フェニルチオ)ベンズヒドロールの合成
上記の反応にて得た4,4’-ビス(フェニルチオ)ベンゾフェノン80.0g(0.200mol)をメタノール500mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム9.2g(0.241mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(1000ml)を加え、酢酸エチル(300ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物77.1gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 8- (II): Synthesis of 4,4′-bis (phenylthio) benzhydrol 80.0 g (0.200 mol) of 4,4′-bis (phenylthio) benzophenone obtained by the above reaction was dissolved in 500 ml of methanol. Then, 9.2 g (0.241 mol) of sodium borohydride was slowly added to the solution cooled to 0 ° C. so that the liquid temperature was kept at 15 ° C. or lower, and the mixture was stirred for 1 hour. After completion of the reaction, water (1000 ml) was added to the mixture and extracted with ethyl acetate (300 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 77.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.
上記の反応にて得た4,4’-ビス(フェニルチオ)ベンゾフェノン80.0g(0.200mol)をメタノール500mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム9.2g(0.241mol)を液温が15℃以下に保たれるようゆっくりと加え、混合物を1時間撹拌した。反応終了後、混合物に水(1000ml)を加え、酢酸エチル(300ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物77.1gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 8- (II): Synthesis of 4,4′-bis (phenylthio) benzhydrol 80.0 g (0.200 mol) of 4,4′-bis (phenylthio) benzophenone obtained by the above reaction was dissolved in 500 ml of methanol. Then, 9.2 g (0.241 mol) of sodium borohydride was slowly added to the solution cooled to 0 ° C. so that the liquid temperature was kept at 15 ° C. or lower, and the mixture was stirred for 1 hour. After completion of the reaction, water (1000 ml) was added to the mixture and extracted with ethyl acetate (300 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 77.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.
8-(III): 4,4’-ビス(フェニルチオ)フェニルメチルアクリレートの合成
8- (III): Synthesis of 4,4'-bis (phenylthio) phenylmethyl acrylate
上記、8-(II)の反応で得た4,4’-ビス(フェニルチオ)ベンズヒドロール46.5g(0.116mol)とトリエチルアミン24.7g(0.232mol)をジクロロメタン300mlに溶解させ0℃に冷却したものに、アクリロイルクロリドを滴下し、混合物を30分間攪拌後、室温に昇温してさらに1時間攪拌した。反応終了後、水(300ml)を加えジクロロメタン(200ml)で抽出した。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物38.8gを無色透明の液体として得た(収率74%)。
1H-NMR(CDCl3、600MHz ) δ(ppm):7.25-7.38(m,18H);6.87(s,1H);6.48(d=16.2Hz,1H);6.21(dd=8.4Hz&10.8Hz,1H);5.82(dd=16.2Hz&1.2Hz,1H) 46.5 g (0.116 mol) of 4,4′-bis (phenylthio) benzhydrol obtained by the above 8- (II) reaction and 24.7 g (0.232 mol) of triethylamine were dissolved in 300 ml of dichloromethane, and 0 ° C. To the cooled product, acryloyl chloride was added dropwise, and the mixture was stirred for 30 minutes, then warmed to room temperature and further stirred for 1 hour. After completion of the reaction, water (300 ml) was added and extracted with dichloromethane (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 38.8 g of the target compound as a colorless transparent liquid (yield 74%).
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.25-7.38 (m, 18H); 6.87 (s, 1H); 6.48 (d = 16.2 Hz, 1H); 6.21 (dd = 8.4 Hz & 10.8 Hz, 1 H); 5.82 (dd = 16.2 Hz & 1.2 Hz, 1 H)
1H-NMR(CDCl3、600MHz ) δ(ppm):7.25-7.38(m,18H);6.87(s,1H);6.48(d=16.2Hz,1H);6.21(dd=8.4Hz&10.8Hz,1H);5.82(dd=16.2Hz&1.2Hz,1H) 46.5 g (0.116 mol) of 4,4′-bis (phenylthio) benzhydrol obtained by the above 8- (II) reaction and 24.7 g (0.232 mol) of triethylamine were dissolved in 300 ml of dichloromethane, and 0 ° C. To the cooled product, acryloyl chloride was added dropwise, and the mixture was stirred for 30 minutes, then warmed to room temperature and further stirred for 1 hour. After completion of the reaction, water (300 ml) was added and extracted with dichloromethane (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 38.8 g of the target compound as a colorless transparent liquid (yield 74%).
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.25-7.38 (m, 18H); 6.87 (s, 1H); 6.48 (d = 16.2 Hz, 1H); 6.21 (dd = 8.4 Hz & 10.8 Hz, 1 H); 5.82 (dd = 16.2 Hz & 1.2 Hz, 1 H)
実施例9
9-(I): 4-(2-ナフチルチオ)-2-フェニルチオアセトフェノンの合成
2,4-ジフルオロアセトフェノン24.4g(0.156mol)、2-ナフタレンチオール25g(0.156mol)、炭酸カリウム43.13g(0.312mol)をジメチルホルムアミド(DMF)300mlに溶解させ、130℃で1時間攪拌を行った。次いで、チオフェノール17.2g(0.156mol)を少しずつ加えた後、更に130℃で1時間撹拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(500ml)、酢酸エチル(500ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、20.1gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 9
9- (I): Synthesis of 4- (2-naphthylthio) -2-phenylthioacetophenone 2,4-difluoroacetophenone 24.4 g (0.156 mol), 2-naphthalenethiol 25 g (0.156 mol), potassium carbonate 43 .13 g (0.312 mol) was dissolved in 300 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 1 hour. Subsequently, after 17.2 g (0.156 mol) of thiophenol was added little by little, the mixture was further stirred at 130 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (500 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 20.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.
9-(I): 4-(2-ナフチルチオ)-2-フェニルチオアセトフェノンの合成
2,4-ジフルオロアセトフェノン24.4g(0.156mol)、2-ナフタレンチオール25g(0.156mol)、炭酸カリウム43.13g(0.312mol)をジメチルホルムアミド(DMF)300mlに溶解させ、130℃で1時間攪拌を行った。次いで、チオフェノール17.2g(0.156mol)を少しずつ加えた後、更に130℃で1時間撹拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(500ml)、酢酸エチル(500ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、20.1gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 9
9- (I): Synthesis of 4- (2-naphthylthio) -2-
9-(II): 1-(1-ヒドロキシエチル)-4-(2-ナフチルチオ)-2-フェニルチオベンゼンの合成
上記の反応にて得た4-(2-ナフチルチオ)-2-フェニルチオアセトフェノン20.0g(0.052mol)をTHF200mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム3.91g(0.104mol)を加え、液温が15℃以下に保たれるようにゆっくりとメタノール50mlを加え、混合物を1時間撹拌した。反応終了後、混合物に水(250ml)を加え、酢酸エチル(125ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物21.3gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 9- (II): Synthesis of 1- (1-hydroxyethyl) -4- (2-naphthylthio) -2-phenylthiobenzene 4- (2-naphthylthio) -2-phenylthioacetophenone obtained by the above reaction To 20.0 g (0.052 mol) dissolved in 200 ml of THF and cooled to 0 ° C., 3.91 g (0.104 mol) of sodium borohydride was added and slowly added so that the liquid temperature was kept at 15 ° C. or lower. And 50 ml of methanol were added and the mixture was stirred for 1 hour. After completion of the reaction, water (250 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (125 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 21.3 g of a crude product. The obtained crude product was used in the next reaction without further purification.
上記の反応にて得た4-(2-ナフチルチオ)-2-フェニルチオアセトフェノン20.0g(0.052mol)をTHF200mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム3.91g(0.104mol)を加え、液温が15℃以下に保たれるようにゆっくりとメタノール50mlを加え、混合物を1時間撹拌した。反応終了後、混合物に水(250ml)を加え、酢酸エチル(125ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物21.3gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 9- (II): Synthesis of 1- (1-hydroxyethyl) -4- (2-naphthylthio) -2-phenylthiobenzene 4- (2-naphthylthio) -2-phenylthioacetophenone obtained by the above reaction To 20.0 g (0.052 mol) dissolved in 200 ml of THF and cooled to 0 ° C., 3.91 g (0.104 mol) of sodium borohydride was added and slowly added so that the liquid temperature was kept at 15 ° C. or lower. And 50 ml of methanol were added and the mixture was stirred for 1 hour. After completion of the reaction, water (250 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (125 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 21.3 g of a crude product. The obtained crude product was used in the next reaction without further purification.
9-(III): 4-(2-ナフチルチオ)-2-フェニルチオスチレンの合成
9- (III): Synthesis of 4- (2-naphthylthio) -2-phenylthiostyrene
ディーン・スタークトラップを具えた反応容器に、上記の反応にて得た1-(1-ヒドロキシエチル)-4-(2-ナフチルチオ)-2-フェニルチオベンゼン20.0g(0.052mol)、p-トルエンスルホン酸一水和物0.079g(0.41mmol)、トルエン200mlとを加え、混合物をトルエン還流下で4時間攪拌した。反応終了後、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物4.2gを得た。
1H-NMR(CDCl3、600MHz) δ(ppm):7.80-7.82(m,2H);7.71-7.73(m,2H);7.48-7.51(m,3H);7.35(d=8.7Hz,1H);7.04-7.21(m,7H);5.69(d=16.9Hz,1H);5.30(d=11.4Hz,1H)。 In a reaction vessel equipped with a Dean-Stark trap, 20.0 g (0.052 mol) of 1- (1-hydroxyethyl) -4- (2-naphthylthio) -2-phenylthiobenzene obtained in the above reaction, p -Toluenesulfonic acid monohydrate 0.079 g (0.41 mmol) andtoluene 200 ml were added and the mixture was stirred for 4 hours under toluene reflux. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 4.2 g of the desired compound.
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.80-7.82 (m, 2H); 7.71-7.73 (m, 2H); 7.48-7.51 (m , 3H); 7.35 (d = 8.7 Hz, 1H); 7.04-7.21 (m, 7H); 5.69 (d = 16.9 Hz, 1H); 5.30 (d = 11) .4Hz, 1H).
1H-NMR(CDCl3、600MHz) δ(ppm):7.80-7.82(m,2H);7.71-7.73(m,2H);7.48-7.51(m,3H);7.35(d=8.7Hz,1H);7.04-7.21(m,7H);5.69(d=16.9Hz,1H);5.30(d=11.4Hz,1H)。 In a reaction vessel equipped with a Dean-Stark trap, 20.0 g (0.052 mol) of 1- (1-hydroxyethyl) -4- (2-naphthylthio) -2-phenylthiobenzene obtained in the above reaction, p -Toluenesulfonic acid monohydrate 0.079 g (0.41 mmol) and
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.80-7.82 (m, 2H); 7.71-7.73 (m, 2H); 7.48-7.51 (m , 3H); 7.35 (d = 8.7 Hz, 1H); 7.04-7.21 (m, 7H); 5.69 (d = 16.9 Hz, 1H); 5.30 (d = 11) .4Hz, 1H).
実施例10
10-(I): 2-(2-ナフチルチオ)-4-フェニルチオアセトフェノンの合成
2,4-ジフルオロアセトフェノン24.4g(0.156mol)、チオフェノール17.2g(0.156mol)、炭酸カリウム43.13g(0.312mol)をジメチルホルムアミド(DMF)300mlに溶解させ、130℃で1時間攪拌を行った。次いで、2-ナフタレンチオール25g(0.156mol)を少しずつ加えた後、更に130℃で1時間撹拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(500ml)、酢酸エチル(500ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、48.1gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 10
10- (I): Synthesis of 2- (2-naphthylthio) -4-phenylthioacetophenone 2,4-difluoroacetophenone 24.4 g (0.156 mol), thiophenol 17.2 g (0.156 mol), potassium carbonate 43 .13 g (0.312 mol) was dissolved in 300 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 1 hour. Next, 25 g (0.156 mol) of 2-naphthalenethiol was added little by little, and the mixture was further stirred at 130 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (500 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 48.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.
10-(I): 2-(2-ナフチルチオ)-4-フェニルチオアセトフェノンの合成
2,4-ジフルオロアセトフェノン24.4g(0.156mol)、チオフェノール17.2g(0.156mol)、炭酸カリウム43.13g(0.312mol)をジメチルホルムアミド(DMF)300mlに溶解させ、130℃で1時間攪拌を行った。次いで、2-ナフタレンチオール25g(0.156mol)を少しずつ加えた後、更に130℃で1時間撹拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(500ml)、酢酸エチル(500ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、48.1gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 10
10- (I): Synthesis of 2- (2-naphthylthio) -4-
10-(II): 1-(1-ヒドロキシエチル)-2-(2-ナフチルチオ)-4-フェニルチオベンゼンの合成
上記の反応にて得た2-(2-ナフチルチオ)-4-フェニルチオアセトフェノン48.1g(0.124mol)をTHF400mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム14.2g(0.375mol)を加え、液温が15℃以下に保たれるようにゆっくりとメタノール200mlを加え、混合物を1時間撹拌した。反応終了後、混合物に水(400ml)を加え、酢酸エチル(125ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物50.8gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 10- (II): Synthesis of 1- (1-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene 2- (2-naphthylthio) -4-phenylthioacetophenone obtained by the above reaction 48.1 g (0.124 mol) was dissolved in 400 ml of THF, and cooled to 0 ° C., 14.2 g (0.375 mol) of sodium borohydride was added, and the solution temperature was slowly kept so as to be kept at 15 ° C. or lower. And 200 ml of methanol were added and the mixture was stirred for 1 hour. After completion of the reaction, water (400 ml) was added to the mixture and extracted with ethyl acetate (125 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 50.8 g of a crude product. The obtained crude product was used in the next reaction without further purification.
上記の反応にて得た2-(2-ナフチルチオ)-4-フェニルチオアセトフェノン48.1g(0.124mol)をTHF400mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム14.2g(0.375mol)を加え、液温が15℃以下に保たれるようにゆっくりとメタノール200mlを加え、混合物を1時間撹拌した。反応終了後、混合物に水(400ml)を加え、酢酸エチル(125ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物50.8gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 10- (II): Synthesis of 1- (1-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene 2- (2-naphthylthio) -4-phenylthioacetophenone obtained by the above reaction 48.1 g (0.124 mol) was dissolved in 400 ml of THF, and cooled to 0 ° C., 14.2 g (0.375 mol) of sodium borohydride was added, and the solution temperature was slowly kept so as to be kept at 15 ° C. or lower. And 200 ml of methanol were added and the mixture was stirred for 1 hour. After completion of the reaction, water (400 ml) was added to the mixture and extracted with ethyl acetate (125 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 50.8 g of a crude product. The obtained crude product was used in the next reaction without further purification.
10-(III): 2-(2-ナフチルチオ)-4-フェニルチオスチレンの合成
10- (III): Synthesis of 2- (2-naphthylthio) -4-phenylthiostyrene
ディーン・スタークトラップを具えた反応容器に、上記の反応にて得た1-(1-ヒドロキシエチル)-2-(2-ナフチルチオ)-4-フェニルチオベンゼン40.0g(0.052mol)、p-トルエンスルホン酸一水和物0.157g(0.82mmol)、トルエン400mlとを加え、混合物をトルエン還流下で4時間攪拌した。反応終了後、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物6.3gを得た。
1H-NMR(CDCl3、600MHz) δ(ppm):7.78-7.80(m,1H);7.67-7.73(m,3H);7.46-7.52(m,3H);7.04-7.28(m,8H);5.70(d=16.2Hz,1H);5.30(d=11.4Hz,1H)。 In a reaction vessel equipped with a Dean-Stark trap, 40.0 g (0.052 mol) of 1- (1-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene obtained in the above reaction, p -Toluenesulfonic acid monohydrate (0.157 g, 0.82 mmol) and toluene (400 ml) were added, and the mixture was stirred under toluene reflux for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 6.3 g of the desired compound.
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.78-7.80 (m, 1H); 7.67-7.73 (m, 3H); 7.46-7.52 (m 7.04-7.28 (m, 8H); 5.70 (d = 16.2 Hz, 1H); 5.30 (d = 11.4 Hz, 1H).
1H-NMR(CDCl3、600MHz) δ(ppm):7.78-7.80(m,1H);7.67-7.73(m,3H);7.46-7.52(m,3H);7.04-7.28(m,8H);5.70(d=16.2Hz,1H);5.30(d=11.4Hz,1H)。 In a reaction vessel equipped with a Dean-Stark trap, 40.0 g (0.052 mol) of 1- (1-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene obtained in the above reaction, p -Toluenesulfonic acid monohydrate (0.157 g, 0.82 mmol) and toluene (400 ml) were added, and the mixture was stirred under toluene reflux for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 6.3 g of the desired compound.
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 7.78-7.80 (m, 1H); 7.67-7.73 (m, 3H); 7.46-7.52 (m 7.04-7.28 (m, 8H); 5.70 (d = 16.2 Hz, 1H); 5.30 (d = 11.4 Hz, 1H).
実施例11
11-(I): 2-(2-ナフチルチオ)-4-フェニルチオベンゾフェノンの合成
2,4-ジフルオロベンゾフェノン48.7g(0.312mol)、チオフェノール34.4g(0.312mol)、炭酸カリウム43.13g(0.614mol)をジメチルホルムアミド(DMF)500mlに溶解させ、130℃で1時間攪拌を行った。次いで、2-ナフタレンチオール50g(0.312mol)を少しずつ加えた後、更に130℃で1時間撹拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(500ml)、酢酸エチル(500ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、94.1gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 11
11- (I): Synthesis of 2- (2-naphthylthio) -4-phenylthiobenzophenone 4,4-difluorobenzophenone 48.7 g (0.312 mol), thiophenol 34.4 g (0.312 mol), potassium carbonate 43 .13 g (0.614 mol) was dissolved in 500 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 1 hour. Next, 50 g (0.312 mol) of 2-naphthalenethiol was added little by little, and the mixture was further stirred at 130 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (500 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 94.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.
11-(I): 2-(2-ナフチルチオ)-4-フェニルチオベンゾフェノンの合成
2,4-ジフルオロベンゾフェノン48.7g(0.312mol)、チオフェノール34.4g(0.312mol)、炭酸カリウム43.13g(0.614mol)をジメチルホルムアミド(DMF)500mlに溶解させ、130℃で1時間攪拌を行った。次いで、2-ナフタレンチオール50g(0.312mol)を少しずつ加えた後、更に130℃で1時間撹拌を行った。反応終了後、混合物を室温に冷却し、飽和塩化アンモニウム水溶液(500ml)、酢酸エチル(500ml)を加え抽出を行った。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去し、94.1gの粗生成物を得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 Example 11
11- (I): Synthesis of 2- (2-naphthylthio) -4-
11-(II): 1-(2-ヒドロキシエチル)-2-(2-ナフチルチオ)-4-フェニルチオベンゼンの合成
上記の反応にて得た2-(2-ナフチルチオ)-4-フェニルチオベンゾフェノン94.1g(0.243mol)をTHF400mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム27.6g(0.73mol)を加え、液温が15℃以下に保たれるようにゆっくりとメタノール200mlを加え、混合物を1時間撹拌した。反応終了後、混合物に水(400ml)を加え、酢酸エチル(125ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物101.2gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 11- (II): Synthesis of 1- (2-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene 2- (2-naphthylthio) -4-phenylthiobenzophenone obtained by the above reaction To 94.1 g (0.243 mol) dissolved in 400 ml of THF and cooled to 0 ° C., 27.6 g (0.73 mol) of sodium borohydride is added and slowly added so that the liquid temperature is kept at 15 ° C. or lower. And 200 ml of methanol were added and the mixture was stirred for 1 hour. After completion of the reaction, water (400 ml) was added to the mixture and extracted with ethyl acetate (125 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 101.2 g of a crude product. The obtained crude product was used in the next reaction without further purification.
上記の反応にて得た2-(2-ナフチルチオ)-4-フェニルチオベンゾフェノン94.1g(0.243mol)をTHF400mlに溶解させ、0℃に冷却したものに、水素化ホウ素ナトリウム27.6g(0.73mol)を加え、液温が15℃以下に保たれるようにゆっくりとメタノール200mlを加え、混合物を1時間撹拌した。反応終了後、混合物に水(400ml)を加え、酢酸エチル(125ml)で抽出した。有機層を無水硫酸ナトリウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物101.2gを得た。得られた粗生成物は更なる精製を行わず次の反応に使用した。 11- (II): Synthesis of 1- (2-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene 2- (2-naphthylthio) -4-phenylthiobenzophenone obtained by the above reaction To 94.1 g (0.243 mol) dissolved in 400 ml of THF and cooled to 0 ° C., 27.6 g (0.73 mol) of sodium borohydride is added and slowly added so that the liquid temperature is kept at 15 ° C. or lower. And 200 ml of methanol were added and the mixture was stirred for 1 hour. After completion of the reaction, water (400 ml) was added to the mixture and extracted with ethyl acetate (125 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 101.2 g of a crude product. The obtained crude product was used in the next reaction without further purification.
11-(III):2-[2-(2-ナフチルチオ)-4-フェニルチオフェニル]エチル アクリレートの合成
上記、2-(II)の反応で得た1-(2-ヒドロキシエチル)-2-(2-ナフチルチオ)-4-フェニルチオベンゼン100.0g(0.267mol)とトリエチルアミン108.1g(1.07mol)をジクロロメタン500mlに溶解させ0℃に冷却したものに、アクリロイルクロリド81.2ml(1.07mmol)を滴下し、混合物を30分間攪拌後、室温に昇温してさらに1時間攪拌した。反応終了後、水(500ml)を加えジクロロメタン(500ml)で抽出した。有機層を無水硫酸マグネシウムで乾燥し、乾燥剤を濾別して、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物をカラムクロマトグラフィで精製することで目的の化合物25.4gを得た。
1H-NMR(CDCl3、600MHz ) δ(ppm):6.90-7.52(m,15H);6.37-6.45(m,1H);6.13(dd=18.6Hz&10.2Hz,1H);5.82(dd=10.2Hz&1.2Hz,1H);5.20(s,2H) 11- (III): Synthesis of 2- [2- (2-naphthylthio) -4-phenylthiophenyl] ethyl acrylate
100.0 g (0.267 mol) of 1- (2-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene obtained by the reaction of 2- (II) and 108.1 g (1. (07 mol) was dissolved in 500 ml of dichloromethane and cooled to 0 ° C., 81.2 ml (1.07 mmol) of acryloyl chloride was added dropwise, and the mixture was stirred for 30 minutes, then warmed to room temperature and further stirred for 1 hour. After completion of the reaction, water (500 ml) was added and extracted with dichloromethane (500 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 25.4 g of the target compound.
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 6.90-7.52 (m, 15H); 6.37-6.45 (m, 1H); 6.13 (dd = 18.6 Hz & 10 .2 Hz, 1 H); 5.82 (dd = 10.2 Hz & 1.2 Hz, 1 H); 5.20 (s, 2 H)
1H-NMR(CDCl3、600MHz ) δ(ppm):6.90-7.52(m,15H);6.37-6.45(m,1H);6.13(dd=18.6Hz&10.2Hz,1H);5.82(dd=10.2Hz&1.2Hz,1H);5.20(s,2H) 11- (III): Synthesis of 2- [2- (2-naphthylthio) -4-phenylthiophenyl] ethyl acrylate
1 H-NMR (CDCl 3 , 600 MHz) δ (ppm): 6.90-7.52 (m, 15H); 6.37-6.45 (m, 1H); 6.13 (dd = 18.6 Hz & 10 .2 Hz, 1 H); 5.82 (dd = 10.2 Hz & 1.2 Hz, 1 H); 5.20 (s, 2 H)
実施例1~11で得られた化合物について、各々以下の手順に従って屈折率を求めた。測定にはアタゴ社製アッベ屈折率計DR-M2を使用し、波長589nmで25℃に温調して測定した。実施例4で得られた化合物は固体であったことから、屈折率が既知の溶媒に溶解させたものの屈折率を上記の装置を使用して測定し、基質100%に外挿した値を当該化合物の屈折率とした。この場合は溶媒としてN-メチルピロリドンを使用し、基質濃度は10質量%、20質量%、30質量%とした。屈折率測定の結果を表1に示す。
The refractive index of each of the compounds obtained in Examples 1 to 11 was determined according to the following procedure. For measurement, an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. was used, and the temperature was adjusted to 25 ° C. at a wavelength of 589 nm. Since the compound obtained in Example 4 was a solid, the refractive index of a compound dissolved in a solvent having a known refractive index was measured using the above apparatus, and the value extrapolated to 100% of the substrate The refractive index of the compound was used. In this case, N-methylpyrrolidone was used as a solvent, and the substrate concentrations were 10% by mass, 20% by mass, and 30% by mass. The results of refractive index measurement are shown in Table 1.
実施例1~11で得られた化合物について、各々以下の手順に従って紫外・可視吸収スペクトルを測定した。上記化合物をアセトニトリルに溶解し、0.001重量%溶液とし、日本分光製紫外可視分光光度計V-650を使用し、波長500~200nmの領域で吸収スペクトルを測定した。図1は実施例1~3、9、11で得られた化合物の紫外・可視吸収スペクトルである。いずれのサンプルにおいても400nm以上の可視領域に吸収がなく、透明性が高いことが確認された。
For the compounds obtained in Examples 1 to 11, ultraviolet / visible absorption spectra were measured according to the following procedures. The above compound was dissolved in acetonitrile to make a 0.001% by weight solution, and an absorption spectrum was measured in a wavelength region of 500 to 200 nm using an ultraviolet-visible spectrophotometer V-650 manufactured by JASCO Corporation. FIG. 1 is an ultraviolet / visible absorption spectrum of the compounds obtained in Examples 1 to 3, 9, and 11. In any sample, it was confirmed that there was no absorption in the visible region of 400 nm or more, and the transparency was high.
実施例1~11で得られた化合物について、パーキンエルマー製赤外分光光度計Frontierを使用し、波数500~4000cm-1の領域で吸収スペクトルを測定した。図2は実施例1~3で得られた化合物の赤外吸収スペクトルである。図2中の挿入図は、波数500~1000cm-1の領域を拡大したものである。
The compounds obtained in Examples 1 to 11 were measured for absorption spectra in the region of wave numbers of 500 to 4000 cm −1 using a Perkin Elmer infrared spectrophotometer Frontier. FIG. 2 is an infrared absorption spectrum of the compounds obtained in Examples 1 to 3. The inset in FIG. 2 is an enlarged view of the wave number range of 500 to 1000 cm −1 .
実施例12
重合性化合物として実施例2で得られた2,4-ビス(フェニルチオ)スチレン99.5重量部、熱ラジカル重合開始剤としてアゾビスイソブチロニトリル0.5重量部を40℃で攪拌、混合し、樹脂組成物を得た。更に、この樹脂組成物を、剥離剤を塗布したガラス基板(50mm×50mm)2枚をシリコンフィルムスペーサ(厚み1.0mm)を介して貼り合わせた空隙に導入した。60℃で15時間加熱処理を施した後、ガラス基板を剥がすことにより、無色透明なシート状の樹脂硬化物を得た。 Example 12
99.5 parts by weight of 2,4-bis (phenylthio) styrene obtained in Example 2 as a polymerizable compound and 0.5 parts by weight of azobisisobutyronitrile as a thermal radical polymerization initiator are stirred and mixed at 40 ° C. Thus, a resin composition was obtained. Furthermore, this resin composition was introduced into a gap formed by bonding two glass substrates (50 mm × 50 mm) coated with a release agent through silicon film spacers (thickness 1.0 mm). After heat treatment at 60 ° C. for 15 hours, the glass substrate was peeled off to obtain a colorless and transparent sheet-like resin cured product.
重合性化合物として実施例2で得られた2,4-ビス(フェニルチオ)スチレン99.5重量部、熱ラジカル重合開始剤としてアゾビスイソブチロニトリル0.5重量部を40℃で攪拌、混合し、樹脂組成物を得た。更に、この樹脂組成物を、剥離剤を塗布したガラス基板(50mm×50mm)2枚をシリコンフィルムスペーサ(厚み1.0mm)を介して貼り合わせた空隙に導入した。60℃で15時間加熱処理を施した後、ガラス基板を剥がすことにより、無色透明なシート状の樹脂硬化物を得た。 Example 12
99.5 parts by weight of 2,4-bis (phenylthio) styrene obtained in Example 2 as a polymerizable compound and 0.5 parts by weight of azobisisobutyronitrile as a thermal radical polymerization initiator are stirred and mixed at 40 ° C. Thus, a resin composition was obtained. Furthermore, this resin composition was introduced into a gap formed by bonding two glass substrates (50 mm × 50 mm) coated with a release agent through silicon film spacers (thickness 1.0 mm). After heat treatment at 60 ° C. for 15 hours, the glass substrate was peeled off to obtain a colorless and transparent sheet-like resin cured product.
実施例13
重合性化合物として実施例3で得られた1-[2,4-ビス(フェニルチオ)フェニル]エチルアクリレートを用いた以外は実施例12と同様にして、無色透明なシート状の樹脂硬化物を得た。 Example 13
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 1- [2,4-bis (phenylthio) phenyl] ethyl acrylate obtained in Example 3 was used as the polymerizable compound. It was.
重合性化合物として実施例3で得られた1-[2,4-ビス(フェニルチオ)フェニル]エチルアクリレートを用いた以外は実施例12と同様にして、無色透明なシート状の樹脂硬化物を得た。 Example 13
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 1- [2,4-bis (phenylthio) phenyl] ethyl acrylate obtained in Example 3 was used as the polymerizable compound. It was.
実施例14
重合性化合物として実施例8で得られた4,4’-ビス(フェニルチオ)フェニルメチルアクリレートを用いた以外は実施例12と同様にして、無色透明なシート状の樹脂硬化物を得た。 Example 14
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 4,4′-bis (phenylthio) phenylmethyl acrylate obtained in Example 8 was used as the polymerizable compound.
重合性化合物として実施例8で得られた4,4’-ビス(フェニルチオ)フェニルメチルアクリレートを用いた以外は実施例12と同様にして、無色透明なシート状の樹脂硬化物を得た。 Example 14
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 4,4′-bis (phenylthio) phenylmethyl acrylate obtained in Example 8 was used as the polymerizable compound.
実施例15
重合性化合物として実施例10で得られた2-(2-ナフチルチオ)-4-フェニルチオスチレンを用いた以外は実施例12と同様にして、無色透明なシート状の樹脂硬化物を得た。 Example 15
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12, except that 2- (2-naphthylthio) -4-phenylthiostyrene obtained in Example 10 was used as the polymerizable compound.
重合性化合物として実施例10で得られた2-(2-ナフチルチオ)-4-フェニルチオスチレンを用いた以外は実施例12と同様にして、無色透明なシート状の樹脂硬化物を得た。 Example 15
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12, except that 2- (2-naphthylthio) -4-phenylthiostyrene obtained in Example 10 was used as the polymerizable compound.
実施例16
重合性化合物として実施例11で得られた2-(2-ナフチルチオ)-4-フェニルチオベンゾフェノンを用いた以外は実施例12と同様にして、無色透明なシート状の樹脂硬化物を得た。 Example 16
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 2- (2-naphthylthio) -4-phenylthiobenzophenone obtained in Example 11 was used as the polymerizable compound.
重合性化合物として実施例11で得られた2-(2-ナフチルチオ)-4-フェニルチオベンゾフェノンを用いた以外は実施例12と同様にして、無色透明なシート状の樹脂硬化物を得た。 Example 16
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 2- (2-naphthylthio) -4-phenylthiobenzophenone obtained in Example 11 was used as the polymerizable compound.
比較例1
重合性化合物としてフェニルチオエチルアクリレート(BIMAX社製、BX-PTEA)を用いた以外は実施例9と同様にして、淡黄色透明なシート状の樹脂硬化物を得た。 Comparative Example 1
A pale yellow transparent sheet-like cured resin was obtained in the same manner as in Example 9 except that phenylthioethyl acrylate (manufactured by BIMAX, BX-PTEA) was used as the polymerizable compound.
重合性化合物としてフェニルチオエチルアクリレート(BIMAX社製、BX-PTEA)を用いた以外は実施例9と同様にして、淡黄色透明なシート状の樹脂硬化物を得た。 Comparative Example 1
A pale yellow transparent sheet-like cured resin was obtained in the same manner as in Example 9 except that phenylthioethyl acrylate (manufactured by BIMAX, BX-PTEA) was used as the polymerizable compound.
比較例2
重合性化合物としてベンジルメタクリレート(共栄社化学(株)製、ライトエステルBZ)を用いた以外は実施例9と同様にして、無色透明なシート状の樹脂硬化物を得た。 Comparative Example 2
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 9, except that benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester BZ) was used as the polymerizable compound.
重合性化合物としてベンジルメタクリレート(共栄社化学(株)製、ライトエステルBZ)を用いた以外は実施例9と同様にして、無色透明なシート状の樹脂硬化物を得た。 Comparative Example 2
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 9, except that benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester BZ) was used as the polymerizable compound.
比較例3
重合性化合物としてエトキシ化o-フェニルフェノールアクリレート(MIWON社製、Miramer M1142)を用いた以外は実施例9と同様にして、淡黄色透明なシート状の樹脂硬化物を得た。 Comparative Example 3
A light yellow transparent sheet-like resin cured product was obtained in the same manner as in Example 9 except that ethoxylated o-phenylphenol acrylate (Miramer M1142 manufactured by MIWON) was used as the polymerizable compound.
重合性化合物としてエトキシ化o-フェニルフェノールアクリレート(MIWON社製、Miramer M1142)を用いた以外は実施例9と同様にして、淡黄色透明なシート状の樹脂硬化物を得た。 Comparative Example 3
A light yellow transparent sheet-like resin cured product was obtained in the same manner as in Example 9 except that ethoxylated o-phenylphenol acrylate (Miramer M1142 manufactured by MIWON) was used as the polymerizable compound.
実施例12~16、および比較例1~3で得られたシート状の樹脂硬化物から、長さ20mm、幅5mm、厚さ1.0mmの試料を切り出し、屈折率の測定を行った。結果を表2に示す。測定にはアタゴ社製アッベ屈折率計DR-M2を使用し、波長589nmで25℃に温調して測定した。
Samples having a length of 20 mm, a width of 5 mm, and a thickness of 1.0 mm were cut out from the sheet-like resin cured products obtained in Examples 12 to 16 and Comparative Examples 1 to 3, and the refractive index was measured. The results are shown in Table 2. For measurement, an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. was used, and the temperature was adjusted to 25 ° C. at a wavelength of 589 nm.
上記のように、本発明の重合性化合物、それを用いた樹脂組成物およびその硬化物は高屈折率性に優れるとともに、透明性に優れており、レンズ用途等のガラス代替材料、液晶ディスプレイ用カラーフィルタの保護膜材料、光学製品の保護用コーティング材料、電子ペーパーや液晶ディスプレイ等のスペーサ用微粒子、光ディスクや光ファイバー等用の接着剤、ホログラム記録媒体用の光記録材料等の各種光学材料に好適に使用される。
As described above, the polymerizable compound of the present invention, the resin composition using the same, and the cured product thereof are excellent in high refractive index and excellent in transparency, and are used for glass substitute materials for lens applications, liquid crystal displays, and the like. Suitable for various optical materials such as protective film materials for color filters, coating materials for protecting optical products, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, optical recording materials for hologram recording media, etc. Used for.
以下ホログラフィック記録用材料についての実施例を示す。ホログラフィック記録用材料の調製例における略号等の説明は以下のとおりである。
HMDI:ヘキサメチレンジイソシアネート(東京化成工業(株)製、屈折率nD=1.453)
G-400:ポリエーテルトリオール((株)ADEKA製、G-400、平均分子量430、屈折率nD=1.469)
OFHDO:2,2,3,3,4,4,5,5-オクタフルオロ-1,6-ヘキサンジオール(東京化成工業(株)製、屈折率nD=1.342)
マトリックス樹脂形成触媒:ジブチルスズジラウレート(東京化成工業(株)製)
光重合開始剤:1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-2-(O-アセチルオキシム)-3-シクロペンチル-1,2-プロパンジオン
可塑剤:O-アセチルクエン酸トリブチル(東京化成工業(株)製、屈折率nD=1.443) Examples of holographic recording materials are shown below. The abbreviations and the like in the preparation examples of the holographic recording material are as follows.
HMDI: Hexamethylene diisocyanate (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.453)
G-400: Polyether triol (manufactured by ADEKA, G-400, average molecular weight 430, refractive index nD = 1.469)
OFHDO: 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.342)
Matrix resin forming catalyst: Dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Photopolymerization initiator: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -2- (O-acetyloxime) -3-cyclopentyl-1,2-propanedione plastic Agent: O-acetyl tributyl citrate (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.443)
HMDI:ヘキサメチレンジイソシアネート(東京化成工業(株)製、屈折率nD=1.453)
G-400:ポリエーテルトリオール((株)ADEKA製、G-400、平均分子量430、屈折率nD=1.469)
OFHDO:2,2,3,3,4,4,5,5-オクタフルオロ-1,6-ヘキサンジオール(東京化成工業(株)製、屈折率nD=1.342)
マトリックス樹脂形成触媒:ジブチルスズジラウレート(東京化成工業(株)製)
光重合開始剤:1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-2-(O-アセチルオキシム)-3-シクロペンチル-1,2-プロパンジオン
可塑剤:O-アセチルクエン酸トリブチル(東京化成工業(株)製、屈折率nD=1.443) Examples of holographic recording materials are shown below. The abbreviations and the like in the preparation examples of the holographic recording material are as follows.
HMDI: Hexamethylene diisocyanate (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.453)
G-400: Polyether triol (manufactured by ADEKA, G-400, average molecular weight 430, refractive index nD = 1.469)
OFHDO: 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.342)
Matrix resin forming catalyst: Dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Photopolymerization initiator: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -2- (O-acetyloxime) -3-cyclopentyl-1,2-propanedione plastic Agent: O-acetyl tributyl citrate (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.443)
実施例17
マトリックス樹脂形成成分として、HMDI 34.2部(質量部)、G-400 45.8部、OFHDO 10.0部、及びマトリックス樹脂形成触媒 0.06部を配合し、重合性反応基を有する化合物として9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルの3-ブテン酸付加物(新日鉄住金化学(株)製)1.0質量部、重合性化合物として実施例2で得られた2,4-ビス(フェニルチオ)スチレン3.0質量部、光重合開始剤 0.05部、及び可塑剤 6.0部を配合して、ホログラフィック記録用材料を調製した。 Example 17
Compound having a polymerizable reactive group containing 34.2 parts (parts by mass) of HMDI, 45.8 parts of G-400, 10.0 parts of OFHDO, and 0.06 parts of matrix resin-forming catalyst as matrix resin-formingcomponents 9 parts of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether 3-butenoic acid adduct (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 2 parts obtained as a polymerizable compound in Example 2 , 4-bis (phenylthio) styrene (3.0 parts by mass), photopolymerization initiator (0.05 parts), and plasticizer (6.0 parts) were blended to prepare a holographic recording material.
マトリックス樹脂形成成分として、HMDI 34.2部(質量部)、G-400 45.8部、OFHDO 10.0部、及びマトリックス樹脂形成触媒 0.06部を配合し、重合性反応基を有する化合物として9,9-ビス(4-ヒドロキシフェニル)フルオレンジグリシジルエーテルの3-ブテン酸付加物(新日鉄住金化学(株)製)1.0質量部、重合性化合物として実施例2で得られた2,4-ビス(フェニルチオ)スチレン3.0質量部、光重合開始剤 0.05部、及び可塑剤 6.0部を配合して、ホログラフィック記録用材料を調製した。 Example 17
Compound having a polymerizable reactive group containing 34.2 parts (parts by mass) of HMDI, 45.8 parts of G-400, 10.0 parts of OFHDO, and 0.06 parts of matrix resin-forming catalyst as matrix resin-forming
このホログラフィック記録用材料を、シリコンフィルムスペーサー(厚み0.5mm)を介して貼り合わせた2枚のガラス基板(30mm×30mm)の空隙に導入した。窒素雰囲気下、60℃で2時間加熱処理を施しマトリックス樹脂を形成させ、2枚のガラス基板の間にホログラフィック記録用材料からなる記録層が厚さ0.5mmで形成されたホログラフィック記録媒体を得た。
This holographic recording material was introduced into the gap between two glass substrates (30 mm × 30 mm) bonded together via a silicon film spacer (thickness 0.5 mm). Holographic recording medium in which a matrix resin is formed by heat treatment at 60 ° C. for 2 hours in a nitrogen atmosphere, and a recording layer made of a holographic recording material is formed between two glass substrates to a thickness of 0.5 mm Got.
実施例18
マトリックス樹脂形成成分として、HMDI 33.7部、G-400 44.9部、及び重合性化合物として実施例4で得られた1-[2,4-ビス(フェニルチオ)フェニル]エチル 4-ビニルベンゾエート4.4部を用いた以外は実施例17と同様にしてホログラフィック記録媒体を得た。 Example 18
As a matrix resin forming component, 33.7 parts of HMDI, 44.9 parts of G-400, and 1- [2,4-bis (phenylthio) phenyl] ethyl 4-vinylbenzoate obtained in Example 4 as a polymerizable compound A holographic recording medium was obtained in the same manner as in Example 17 except that 4.4 parts were used.
マトリックス樹脂形成成分として、HMDI 33.7部、G-400 44.9部、及び重合性化合物として実施例4で得られた1-[2,4-ビス(フェニルチオ)フェニル]エチル 4-ビニルベンゾエート4.4部を用いた以外は実施例17と同様にしてホログラフィック記録媒体を得た。 Example 18
As a matrix resin forming component, 33.7 parts of HMDI, 44.9 parts of G-400, and 1- [2,4-bis (phenylthio) phenyl] ethyl 4-vinylbenzoate obtained in Example 4 as a polymerizable compound A holographic recording medium was obtained in the same manner as in Example 17 except that 4.4 parts were used.
実施例19
マトリックス樹脂形成成分として、HMDI 33.9部、G-400 45.2部、及び重合性化合物として実施例5で得られた2,4-ビス(2-ナフチルチオ)スチレン4.0部を用いた以外は実施例17と同様にしてホログラフィック記録媒体を得た。 Example 19
As the matrix resin forming component, 33.9 parts of HMDI, 45.2 parts of G-400, and 4.0 parts of 2,4-bis (2-naphthylthio) styrene obtained in Example 5 as a polymerizable compound were used. A holographic recording medium was obtained in the same manner as Example 17 except for the above.
マトリックス樹脂形成成分として、HMDI 33.9部、G-400 45.2部、及び重合性化合物として実施例5で得られた2,4-ビス(2-ナフチルチオ)スチレン4.0部を用いた以外は実施例17と同様にしてホログラフィック記録媒体を得た。 Example 19
As the matrix resin forming component, 33.9 parts of HMDI, 45.2 parts of G-400, and 4.0 parts of 2,4-bis (2-naphthylthio) styrene obtained in Example 5 as a polymerizable compound were used. A holographic recording medium was obtained in the same manner as Example 17 except for the above.
実施例20
マトリックス樹脂形成成分として、HMDI 33.8部、G-400 45.5部、及び重合性化合物として実施例9で得られた4-(2-ナフチルチオ)-2-フェニルチオスチレン3.5部を用いた以外は実施例17と同様にしてホログラフィック記録媒体を得た。 Example 20
As a matrix resin forming component, 33.8 parts of HMDI, 45.5 parts of G-400, and 3.5 parts of 4- (2-naphthylthio) -2-phenylthiostyrene obtained in Example 9 as a polymerizable compound were used. A holographic recording medium was obtained in the same manner as in Example 17 except that it was used.
マトリックス樹脂形成成分として、HMDI 33.8部、G-400 45.5部、及び重合性化合物として実施例9で得られた4-(2-ナフチルチオ)-2-フェニルチオスチレン3.5部を用いた以外は実施例17と同様にしてホログラフィック記録媒体を得た。 Example 20
As a matrix resin forming component, 33.8 parts of HMDI, 45.5 parts of G-400, and 3.5 parts of 4- (2-naphthylthio) -2-phenylthiostyrene obtained in Example 9 as a polymerizable compound were used. A holographic recording medium was obtained in the same manner as in Example 17 except that it was used.
比較例4
マトリックス樹脂形成成分として、HMDI 34.8部、G-400 46.7部、及び重合性化合物として酢酸4-ビニルフェニル(東京化成工業(株)製、屈折率nD=1.538)1.5部を用いた以外は実施例17と同様にしてホログラフィック記録媒体を得た。 Comparative Example 4
As a matrix resin forming component, 34.8 parts of HMDI, 46.7 parts of G-400, and 4-vinylphenyl acetate as a polymerizable compound (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.538) 1.5 A holographic recording medium was obtained in the same manner as in Example 17 except that the part was used.
マトリックス樹脂形成成分として、HMDI 34.8部、G-400 46.7部、及び重合性化合物として酢酸4-ビニルフェニル(東京化成工業(株)製、屈折率nD=1.538)1.5部を用いた以外は実施例17と同様にしてホログラフィック記録媒体を得た。 Comparative Example 4
As a matrix resin forming component, 34.8 parts of HMDI, 46.7 parts of G-400, and 4-vinylphenyl acetate as a polymerizable compound (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.538) 1.5 A holographic recording medium was obtained in the same manner as in Example 17 except that the part was used.
比較例5
マトリックス樹脂形成成分として、HMDI 34.7部、G-400 46.6質量部、及び重合性化合物として4-ブロモスチレン(東京化成工業(株)製、屈折率nD=1.594)1.7部を用いた以外は実施例17と同様にしてホログラフィック記録媒体を得た。 Comparative Example 5
As a matrix resin forming component, 34.7 parts of HMDI, 46.6 parts by mass of G-400, and 4-bromostyrene (refractive index nD = 1.594, manufactured by Tokyo Chemical Industry Co., Ltd.) 1.7 as a polymerizable compound. A holographic recording medium was obtained in the same manner as in Example 17 except that the part was used.
マトリックス樹脂形成成分として、HMDI 34.7部、G-400 46.6質量部、及び重合性化合物として4-ブロモスチレン(東京化成工業(株)製、屈折率nD=1.594)1.7部を用いた以外は実施例17と同様にしてホログラフィック記録媒体を得た。 Comparative Example 5
As a matrix resin forming component, 34.7 parts of HMDI, 46.6 parts by mass of G-400, and 4-bromostyrene (refractive index nD = 1.594, manufactured by Tokyo Chemical Industry Co., Ltd.) 1.7 as a polymerizable compound. A holographic recording medium was obtained in the same manner as in Example 17 except that the part was used.
実施例17~20、比較例4、5のホログラフィック記録用材料前駆体の組成を表3に示す。表3中の配合量の数字は質量部である。
Table 3 shows the compositions of the holographic recording material precursors of Examples 17 to 20 and Comparative Examples 4 and 5. The number of the compounding amount in Table 3 is part by mass.
ホログラフィック記録再生評価は、二光束干渉法に基づくホログラフィック記録再生評価機を用いて行なった。多重記録は、角度多重を用いて行った。
Holographic recording / reproduction evaluation was performed using a holographic recording / reproduction evaluation machine based on the two-beam interference method. Multiple recording was performed using angle multiplexing.
(平面波記録再生方法)
M#及び記録感度の評価には、図3、図4に示す記録・再生の光学系を用いて行った。尚、記録・再生には波長405nmの連続発振(CW)半導体レーザを用いた。記録光の記録媒体上での光強度(二光束の合計)を18mW/cm2とし、角度多重記録(101多重)を総露光エネルギーが600mJ/cm2となるようにして行った。記録されたホログラムの回折効率は、再生時の回折光及び透過光それぞれの強度を光パワーメーターで読み取った値を用いて、次式により算出した。
回折効率(η)=〔回折光強度/(透過光強度+回折光強度)〕×100 (%)
この回折効率の値を用い、ホログラム記録媒体の多重記録性の指標として、M#(エムナンバー)の値を前述の式(I)によって計算した。
また、得られた回折効率の値を用い、記録感度を式(III)によって計算し、その最大値を最大感度とした。
ここで
ηは回折効率
Eは露光エネルギー [mJ/cm2]
Lは媒体厚み [cm]
を表わす。 (Plane wave recording and playback method)
Evaluation of M # and recording sensitivity was performed using the recording / reproducing optical system shown in FIGS. For recording and reproduction, a continuous wave (CW) semiconductor laser having a wavelength of 405 nm was used. The light intensity of the recording light on the recording medium (total of the two light beams) was 18 mW / cm 2, and angle multiplex recording (101 multiplex) was performed so that the total exposure energy was 600 mJ / cm 2 . The diffraction efficiency of the recorded hologram was calculated by the following equation using values obtained by reading the intensity of each of the diffracted light and transmitted light during reproduction with an optical power meter.
Diffraction efficiency (η) = [diffracted light intensity / (transmitted light intensity + diffracted light intensity)] × 100 (%)
Using this diffraction efficiency value, the value of M # (M number) was calculated by the above-mentioned formula (I) as an index of the multiple recording property of the hologram recording medium.
Further, using the obtained diffraction efficiency value, the recording sensitivity was calculated by the formula (III), and the maximum value was defined as the maximum sensitivity.
Where η is diffraction efficiency E is exposure energy [mJ / cm 2 ]
L is the media thickness [cm]
Represents.
M#及び記録感度の評価には、図3、図4に示す記録・再生の光学系を用いて行った。尚、記録・再生には波長405nmの連続発振(CW)半導体レーザを用いた。記録光の記録媒体上での光強度(二光束の合計)を18mW/cm2とし、角度多重記録(101多重)を総露光エネルギーが600mJ/cm2となるようにして行った。記録されたホログラムの回折効率は、再生時の回折光及び透過光それぞれの強度を光パワーメーターで読み取った値を用いて、次式により算出した。
回折効率(η)=〔回折光強度/(透過光強度+回折光強度)〕×100 (%)
この回折効率の値を用い、ホログラム記録媒体の多重記録性の指標として、M#(エムナンバー)の値を前述の式(I)によって計算した。
また、得られた回折効率の値を用い、記録感度を式(III)によって計算し、その最大値を最大感度とした。
ηは回折効率
Eは露光エネルギー [mJ/cm2]
Lは媒体厚み [cm]
を表わす。 (Plane wave recording and playback method)
Evaluation of M # and recording sensitivity was performed using the recording / reproducing optical system shown in FIGS. For recording and reproduction, a continuous wave (CW) semiconductor laser having a wavelength of 405 nm was used. The light intensity of the recording light on the recording medium (total of the two light beams) was 18 mW / cm 2, and angle multiplex recording (101 multiplex) was performed so that the total exposure energy was 600 mJ / cm 2 . The diffraction efficiency of the recorded hologram was calculated by the following equation using values obtained by reading the intensity of each of the diffracted light and transmitted light during reproduction with an optical power meter.
Diffraction efficiency (η) = [diffracted light intensity / (transmitted light intensity + diffracted light intensity)] × 100 (%)
Using this diffraction efficiency value, the value of M # (M number) was calculated by the above-mentioned formula (I) as an index of the multiple recording property of the hologram recording medium.
Further, using the obtained diffraction efficiency value, the recording sensitivity was calculated by the formula (III), and the maximum value was defined as the maximum sensitivity.
L is the media thickness [cm]
Represents.
(平面波記録条件)
記録前露光:無し
記録スケジューリング:無し
多重度:100多重
角度方向:100多重(-29.7~+29.7°、ステップ 0.6°)
記録光強度:18mW/cm2
記録総露光エネルギー:600mJ/cm2
記録後露光エネルギー:LEDにて、90J/cm2 (Plane wave recording conditions)
Exposure before recording: None Recording scheduling: None Multiplicity: 100 multiplexing Angular direction: 100 multiplexing (−29.7 to + 29.7 °, step 0.6 °)
Recording light intensity: 18 mW / cm 2
Total exposure energy for recording: 600 mJ / cm 2
Exposure energy after recording: 90 J / cm 2 with LED
記録前露光:無し
記録スケジューリング:無し
多重度:100多重
角度方向:100多重(-29.7~+29.7°、ステップ 0.6°)
記録光強度:18mW/cm2
記録総露光エネルギー:600mJ/cm2
記録後露光エネルギー:LEDにて、90J/cm2 (Plane wave recording conditions)
Exposure before recording: None Recording scheduling: None Multiplicity: 100 multiplexing Angular direction: 100 multiplexing (−29.7 to + 29.7 °, step 0.6 °)
Recording light intensity: 18 mW / cm 2
Total exposure energy for recording: 600 mJ / cm 2
Exposure energy after recording: 90 J / cm 2 with LED
<評価結果>
(平面波記録特性)
図5は、記録露光エネルギーに対するM#の積算値である。実施例17~20による媒体はいずれも比較例4、5による媒体に比べてM#が高く、多重記録性に優れたものであることが分かる。
図6は、記録露光エネルギーに対する感度を示したものである。実施例17~20による媒体はいずれも比較例4、5による媒体に比べて感度が高く、高いデータ転送レートが実現可能である。 <Evaluation results>
(Plane wave recording characteristics)
FIG. 5 is an integrated value of M # with respect to the recording exposure energy. It can be seen that the media according to Examples 17 to 20 all have a higher M # than the media according to Comparative Examples 4 and 5 and are excellent in multiplex recording properties.
FIG. 6 shows the sensitivity to the recording exposure energy. All the media according to Examples 17 to 20 have higher sensitivity than the media according to Comparative Examples 4 and 5, and a high data transfer rate can be realized.
(平面波記録特性)
図5は、記録露光エネルギーに対するM#の積算値である。実施例17~20による媒体はいずれも比較例4、5による媒体に比べてM#が高く、多重記録性に優れたものであることが分かる。
図6は、記録露光エネルギーに対する感度を示したものである。実施例17~20による媒体はいずれも比較例4、5による媒体に比べて感度が高く、高いデータ転送レートが実現可能である。 <Evaluation results>
(Plane wave recording characteristics)
FIG. 5 is an integrated value of M # with respect to the recording exposure energy. It can be seen that the media according to Examples 17 to 20 all have a higher M # than the media according to Comparative Examples 4 and 5 and are excellent in multiplex recording properties.
FIG. 6 shows the sensitivity to the recording exposure energy. All the media according to Examples 17 to 20 have higher sensitivity than the media according to Comparative Examples 4 and 5, and a high data transfer rate can be realized.
平面波測定によって得られたM#、最大感度、重合性化合物の屈折率、及び材料1gあたりの分子数を数値で比較した結果を表4に示す。
Table 4 shows the results of numerical comparison of M # obtained by plane wave measurement, maximum sensitivity, refractive index of polymerizable compound, and number of molecules per gram of material.
ここで、重合性化合物はホログラフィック記録が行なわれる際の屈折率変調構造を形成する担い手であるので、含有量を増加させればM#と感度は向上するが、反面重合収縮を起しやすくなる。一般的にビニルモノマーの重合収縮率は分子量の逆数と比例することが知られており、材料に含まれる重合性化合物の分子数を揃えることで、記録媒体の収縮率を揃えた状態で重合性化合物間の性能を比較することができる。
表4より収縮率を同程度に揃えた場合は、明らかにいずれも実施例による媒体の方が比較例による媒体に比べてM#、感度が高く好ましいことがわかる。 Here, since the polymerizable compound is responsible for forming a refractive index modulation structure when holographic recording is performed, increasing the content improves M # and sensitivity, but on the other hand, it tends to cause polymerization shrinkage. Become. Generally, it is known that the polymerization shrinkage of vinyl monomers is proportional to the inverse of the molecular weight. By aligning the number of molecules of the polymerizable compound contained in the material, it is possible to polymerize with the same shrinkage of the recording medium. The performance between compounds can be compared.
It can be seen from Table 4 that when the shrinkage ratios are set to the same level, the medium according to the example clearly has higher M # and sensitivity than the medium according to the comparative example.
表4より収縮率を同程度に揃えた場合は、明らかにいずれも実施例による媒体の方が比較例による媒体に比べてM#、感度が高く好ましいことがわかる。 Here, since the polymerizable compound is responsible for forming a refractive index modulation structure when holographic recording is performed, increasing the content improves M # and sensitivity, but on the other hand, it tends to cause polymerization shrinkage. Become. Generally, it is known that the polymerization shrinkage of vinyl monomers is proportional to the inverse of the molecular weight. By aligning the number of molecules of the polymerizable compound contained in the material, it is possible to polymerize with the same shrinkage of the recording medium. The performance between compounds can be compared.
It can be seen from Table 4 that when the shrinkage ratios are set to the same level, the medium according to the example clearly has higher M # and sensitivity than the medium according to the comparative example.
1:レーザ発生装置
2、11、13:ミラー
3、8:1/2波長板(HWP)
4、9:偏光ビームスプリッタ(PBS)
5:ビームエキスパンダ
6、10:シャッタ
7、15:絞り
12:1/4波長板(QWP)
14:回転ステージ
16、17:光パワーメータ
Ls:記録信号光
Lw:記録参照光
Lr:再生参照光
S:ホログラフィック記録媒体 1: Laser generator 2, 11, 13: Mirror 3, 8: 1/2 wavelength plate (HWP)
4, 9: Polarization beam splitter (PBS)
5:Beam expander 6, 10: Shutter 7, 15: Aperture 12: 1/4 wavelength plate (QWP)
14:Rotation stage 16, 17: Optical power meter Ls: Recording signal light Lw: Recording reference light Lr: Reproduction reference light S: Holographic recording medium
2、11、13:ミラー
3、8:1/2波長板(HWP)
4、9:偏光ビームスプリッタ(PBS)
5:ビームエキスパンダ
6、10:シャッタ
7、15:絞り
12:1/4波長板(QWP)
14:回転ステージ
16、17:光パワーメータ
Ls:記録信号光
Lw:記録参照光
Lr:再生参照光
S:ホログラフィック記録媒体 1:
4, 9: Polarization beam splitter (PBS)
5:
14:
Claims (11)
- 下記一般式(1)で表される重合性化合物。
X1は直接結合、酸素原子、硫黄原子、炭素数1~4のアルキレン基、炭素数1~4のオキシアルキレン基、炭素数1~4のチオアルキレン基、炭素数1~4のアルキレンオキシ基または炭素数1~4のアルキレンチオ基を表し、ここで、アルキレン基、オキシアルキレン基、チオアルキレン基、アルキレンオキシ基及びアルキレンチオ基は、置換基を有してもよく、置換基を有する場合の置換基は塩素原子、臭素原子、炭素数1~4のアルキルオキシ基、炭素数1~4のアルキルチオ基、炭素数6~10のアリール基、炭素数6~10のアリールオキシ基または炭素数6~10のアリールチオ基である。
R6はグリシジル基、アクリロイル基、メタクリロイル基、ビニル基、置換基を有していてもよいビニルアリール基またはビニルアリーロイル基を表わす。
上記-S-Ar1のAr1は環員数6~14のアリール基または環員数5~14の複素アリール基を表わし、また2つ以上の環が縮合していてもよく、置換基を有していてもよい。置換基を有する場合の置換基は塩素原子、臭素原子、炭素数1~4のアルキル基、炭素数1~4のアルキルオキシ基または炭素数1~4のアルキルチオ基、フェニルオキシ基またはフェニルチオ基であり、これらがフェニルオキシ基またはフェニルチオ基である場合は更に該置換基と同様な置換基を有してもよい。 The polymeric compound represented by following General formula (1).
X 1 is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms, wherein the alkylene group, oxyalkylene group, thioalkylene group, alkyleneoxy group and alkylenethio group may have a substituent, The substituent of is a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a carbon number 6 to 10 arylthio groups.
R 6 represents a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, a vinyl aryl group which may have a substituent, or a vinyl aryloyl group.
The -S-Ar Ar 1 of 1 represents an aryl group or ring members 5-14 heterocyclic aryl group ring members 6-14, also may have combined two or more rings are condensed, substituted It may be. In the case of having a substituent, the substituent is chlorine atom, bromine atom, alkyl group having 1 to 4 carbon atoms, alkyloxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, phenyloxy group or phenylthio group. In the case where these are a phenyloxy group or a phenylthio group, they may further have a substituent similar to the substituent. - R1~R5の1つが、-S-Ar1である請求項1に記載の重合性化合物。 The polymerizable compound according to claim 1 , wherein one of R 1 to R 5 is -S-Ar 1 .
- R1~R5の2つ又は3つが、-S-Ar1である請求項1に記載の重合性化合物。 The polymerizable compound according to claim 1 , wherein two or three of R 1 to R 5 are -S-Ar 1 .
- 請求項1~3のいずれかに記載の重合性化合物含むことを特徴とする樹脂組成物。 A resin composition comprising the polymerizable compound according to any one of claims 1 to 3.
- 請求項4に記載の樹脂組成物を硬化させてなることを特徴とする樹脂硬化物。 A cured resin obtained by curing the resin composition according to claim 4.
- 請求項4に記載の樹脂組成物またはこれを硬化させてなる樹脂硬化物を含むことを特徴とする光学材料。 5. An optical material comprising the resin composition according to claim 4 or a cured resin obtained by curing the resin composition.
- 請求項1に記載の重合性化合物を配合したことを特徴とするホログラフィック記録用材料。 A holographic recording material comprising the polymerizable compound according to claim 1.
- A)重合性化合物、B)マトリックス樹脂又はマトリックス樹脂形成成分及びC)光重合開始剤を含むホログラフィック記録用材料であって、前記重合性化合物が、請求項1に記載の重合性化合物であることを特徴とするホログラフィック記録用材料。 A holographic recording material comprising A) a polymerizable compound, B) a matrix resin or a matrix resin forming component, and C) a photopolymerization initiator, wherein the polymerizable compound is the polymerizable compound according to claim 1. A holographic recording material characterized by the above.
- 前記重合性化合物の25℃における屈折率nDが、1.60以上である請求項7に記載のホログラフィック記録用材料。 The holographic recording material according to claim 7, wherein the polymerizable compound has a refractive index n D at 25 ° C. of 1.60 or more.
- 前記マトリックス樹脂がイソシアネート-ヒドロキシル重付加物である請求項8に記載のホログラフィック記録用材料。 The holographic recording material according to claim 8, wherein the matrix resin is an isocyanate-hydroxyl polyadduct.
- 請求項7に記載のホログラフィック記録用材料を含有する記録層を備えることを特徴とするホログラフィック記録媒体。 A holographic recording medium comprising a recording layer containing the holographic recording material according to claim 7.
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Also Published As
Publication number | Publication date |
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JP6869636B2 (en) | 2021-05-12 |
JP2020037693A (en) | 2020-03-12 |
JPWO2015068839A1 (en) | 2017-03-09 |
JP6870054B2 (en) | 2021-05-12 |
TW201533068A (en) | 2015-09-01 |
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