WO2016114363A1 - 近赤外線カットフィルタおよび撮像装置 - Google Patents
近赤外線カットフィルタおよび撮像装置 Download PDFInfo
- Publication number
- WO2016114363A1 WO2016114363A1 PCT/JP2016/051021 JP2016051021W WO2016114363A1 WO 2016114363 A1 WO2016114363 A1 WO 2016114363A1 JP 2016051021 W JP2016051021 W JP 2016051021W WO 2016114363 A1 WO2016114363 A1 WO 2016114363A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- wavelength
- transmittance
- group
- light
- carbon atoms
- Prior art date
Links
- 238000003384 imaging method Methods 0.000 title claims description 35
- 238000002834 transmittance Methods 0.000 claims abstract description 159
- 230000003595 spectral effect Effects 0.000 claims abstract description 89
- 238000010521 absorption reaction Methods 0.000 claims description 129
- 125000004432 carbon atom Chemical group C* 0.000 claims description 127
- 150000001875 compounds Chemical class 0.000 claims description 85
- 125000000217 alkyl group Chemical group 0.000 claims description 84
- 229920005989 resin Polymers 0.000 claims description 83
- 239000011347 resin Substances 0.000 claims description 83
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 60
- 239000000758 substrate Substances 0.000 claims description 38
- 239000011521 glass Substances 0.000 claims description 35
- -1 cyanine compound Chemical class 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 238000000862 absorption spectrum Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- 230000035945 sensitivity Effects 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 230000000007 visual effect Effects 0.000 claims description 9
- 239000011358 absorbing material Substances 0.000 claims description 7
- 102100041023 Coronin-2A Human genes 0.000 claims description 6
- 101000748858 Homo sapiens Coronin-2A Proteins 0.000 claims description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 230000014509 gene expression Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 186
- 239000000975 dye Substances 0.000 description 124
- 239000010408 film Substances 0.000 description 55
- 238000000576 coating method Methods 0.000 description 25
- 125000003118 aryl group Chemical group 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 19
- 239000000049 pigment Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 230000003287 optical effect Effects 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 125000003342 alkenyl group Chemical group 0.000 description 14
- 229920001225 polyester resin Polymers 0.000 description 14
- 239000004645 polyester resin Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 125000004423 acyloxy group Chemical group 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- 125000000623 heterocyclic group Chemical group 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 125000000753 cycloalkyl group Chemical group 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 239000009719 polyimide resin Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 229920005668 polycarbonate resin Polymers 0.000 description 7
- 239000004431 polycarbonate resin Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical class [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 125000004663 dialkyl amino group Chemical group 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000005365 phosphate glass Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000005529 alkyleneoxy group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000005303 fluorophosphate glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NDVWOBYBJYUSMF-UHFFFAOYSA-N 2-methylcyclohexan-1-ol Chemical compound CC1CCCCC1O NDVWOBYBJYUSMF-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 102100031650 C-X-C chemokine receptor type 4 Human genes 0.000 description 1
- 0 CCCCC(CC)C(Nc1cc(N(CC)CC)c(C)cc1C(C1=O)=C(*)C1=C(C=C1Cl)C(NC(C(CC)CCCC)=O)=CC1=*(C)CC)=O Chemical compound CCCCC(CC)C(Nc1cc(N(CC)CC)c(C)cc1C(C1=O)=C(*)C1=C(C=C1Cl)C(NC(C(CC)CCCC)=O)=CC1=*(C)CC)=O 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 101000922348 Homo sapiens C-X-C chemokine receptor type 4 Proteins 0.000 description 1
- 241000511976 Hoya Species 0.000 description 1
- 229920004142 LEXAN™ Polymers 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- XVNRSQASUCMHGX-UHFFFAOYSA-N O[Si](O)(O)O.OP(O)(O)=O Chemical compound O[Si](O)(O)O.OP(O)(O)=O XVNRSQASUCMHGX-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical class [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical class C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical class N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 125000005506 phthalide group Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
- G02B5/281—Interference filters designed for the infrared light
- G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection
Definitions
- the present invention relates to a near-infrared cut filter and an imaging device.
- a near-infrared cut filter is generally arranged.
- an absorption layer containing a dye that absorbs near-red light and a dielectric thin film having a different refractive index are laminated to reflect and block near-infrared light by light interference.
- Filters that combine layers are known.
- the dielectric multilayer film constituting the reflective layer has different optical film thickness depending on the incident angle of light, so that the spectral characteristics have an incident angle dependency, and the color reproducibility varies depending on the incident angle. There is a problem of coming.
- Patent Document 1 discloses a filter using near-infrared absorbing glass in which CuO or the like is added to fluorophosphate glass or phosphate glass so as to selectively absorb near infrared light. Yes.
- this filter also has an incident angle dependency, and the problem that the color reproducibility varies depending on the incident angle cannot be solved.
- Patent Document 2 shows a high transmittance exceeding 90% in the visible wavelength region and 5% or less in the infrared wavelength region in a near-infrared cut filter including a reflective layer composed of an absorption layer and a dielectric multilayer film. Those having spectral characteristics exhibiting low transmittance are disclosed. However, this filter has, for example, a wavelength at which the transmittance becomes 50% is around 650 nm, and the transmittance on the long wavelength side is high when the relative visibility curve is used as a reference. There is a problem that cannot be obtained with high accuracy.
- Patent Document 3 similarly discloses a near-infrared cut filter including an absorption layer and a reflective layer made of a dielectric multilayer film.
- This filter has a spectral characteristic close to a relative visibility curve on the long wavelength side as compared with the filter described in Patent Document 2.
- the spectral characteristic of this filter has a large incident angle dependency, and there still remains a problem that the color reproducibility varies depending on the incident angle.
- the present invention shows a near-infrared cut filter that exhibits a spectral characteristic close to a relative visibility curve, particularly on the long wavelength side, and has excellent incident angle dependency and excellent oblique incidence characteristics, and color reproducibility using such a filter.
- An object of the present invention is to provide an imaging device that excels in performance.
- a near-infrared cut filter includes an absorption layer and a reflection layer, and satisfies the following requirements (1) to (3).
- the average transmittance (R) in the wavelength region of 620 to 750 nm is 20% or less
- the average transmittance (G) in the wavelength region of 495 to 570 nm is 90%.
- the ratio (R) / (G) of the average transmittance is 0.20 or less.
- the wavelength ⁇ IR T (80) , 50 at which the transmittance is 80% in the wavelength region of 550 to 750 nm % ⁇ IR T (50) and 20% wavelength ⁇ IR T (20) , and the wavelengths ⁇ IR T (80) , ⁇ IR T (50) and ⁇ IR T (20) are respectively Expressions (a), (b) and (c) are satisfied.
- an imaging apparatus includes the near infrared cut filter.
- the present invention it is possible to obtain a near-infrared cut filter that exhibits a spectral characteristic close to a specific visibility curve on the long wavelength side and that has a low incident angle dependency.
- An imaging device having excellent color reproducibility can be obtained.
- the near-infrared cut filter may be abbreviated as “NIR filter”.
- An NIR filter according to an embodiment of the present invention includes an absorption layer and a reflection layer.
- the absorption layer and the reflection layer may each have one layer in the filter, one may have two or more layers, or both may have two or more layers. When it has two or more layers, each layer may be the same or different.
- one layer is a near-infrared absorbing layer made of a resin containing a near-infrared absorbing dye as described later, and the other layer is an ultraviolet absorbing dye as described later. It is good also as an ultraviolet absorption layer which consists of resin containing.
- this filter may further have a transparent substrate.
- the absorption layer and the reflection layer may be provided on the same main surface of the transparent substrate, or may be provided on different main surfaces.
- the stacking order is not particularly limited.
- This filter may further have other functional layers such as an antireflection layer.
- FIG. 1A is a configuration example including an absorption layer 11 and a reflection layer 12.
- FIG. 1B is a configuration example in which the absorption layer 11 is provided on one main surface of the transparent base material 13 and the reflection layer 12 is provided on the other main surface of the transparent base material 13.
- “equipped with other layers such as the absorption layer 11 and the reflective layer 12 on one main surface of the transparent base material 13” is not limited to the case where the transparent base material 13 is provided with another layer, Including the case where another functional layer is provided between the transparent substrate 13 and another layer, the following configurations are also the same.
- the absorption layer 11 may include two layers, a near infrared absorption layer and an ultraviolet absorption layer.
- a structure having a near-infrared absorbing layer on the reflective layer 12 and an ultraviolet absorbing layer on the near-infrared absorbing layer may be used, or an ultraviolet absorbing layer may be provided on the reflecting layer 12 and close to the ultraviolet absorbing layer.
- the structure which has an infrared rays absorption layer may be sufficient.
- the transparent substrate 13 may have a near infrared absorbing layer, and the near infrared absorbing layer may have an ultraviolet absorbing layer.
- the transparent substrate 13 may have an ultraviolet absorbing layer,
- the structure which has a near-infrared absorption layer on an absorption layer may be sufficient.
- FIG. 1C is a configuration example in which an absorption layer 11 is provided on one main surface of the transparent substrate 13 and reflection layers 12 a and 12 b are provided on the other main surface and the main surface of the absorption layer 11.
- FIG. 1D is a configuration example in which the absorption layers 11a and 11b are provided on both main surfaces of the transparent substrate 11, and the reflection layers 12a and 12b are provided on the main surfaces of the absorption layers 11a and 11b.
- the two reflecting layers 12a and 12b to be combined may be the same or different.
- the reflective layers 12a and 12b have characteristics of reflecting the ultraviolet wavelength region and the near infrared wavelength region and transmitting the visible wavelength region, and the reflective layer 12a includes the ultraviolet wavelength region and the first near infrared wavelength region.
- the reflection layer 12b may reflect the ultraviolet wavelength region and the second near-infrared wavelength region. In the near-infrared wavelength region, the first near-infrared wavelength region is located on the shorter wavelength side than the second near-infrared wavelength region.
- the two absorption layers 11a and 11b may be the same or different.
- the absorption layer 11a may be a near infrared absorption layer
- the absorption layer 11b may be an ultraviolet absorption layer
- the absorption layer 11a may be an ultraviolet absorption layer
- the absorption layer 11b may be a near infrared absorption layer.
- FIG. 1E is a configuration example in which an antireflection layer 14 is provided on the main surface of the absorption layer 11 of the filter shown in FIG. 1B.
- an antireflection layer may be provided on the absorption layer.
- the structure which covers not only the outermost surface of an absorption layer but the whole side surface of an absorption layer may be sufficient as an antireflection layer. In that case, the moisture-proof effect of the absorption layer can be enhanced.
- This filter satisfies the following requirements (1) to (3).
- the average transmittance (R) of light having a wavelength of 620 to 750 nm is 20% or less
- the average transmittance (G) of light having a wavelength of 495 to 570 nm is 90%.
- the ratio (R) / (G) of the average transmittance is 0.2 or less.
- a spectral transmittance curve with an incident angle of 0 ° normalized by the maximum transmittance of light with a wavelength of 450 to 650 nm (hereinafter also referred to as “normalized spectral transmittance curve with an incident angle of 0 °”)
- the wavelength of 550 to in 750 nm the wavelength RamudaIR T which transmittance is 80% (80)
- the wavelength ⁇ IR T (50), which is 50%, and 20% become wavelength RamudaIR T has a (20)
- each wavelength RamudaIR T ( 80) , ⁇ IR T (50), and ⁇ IR T (20) satisfy the following expressions (a), (b), and (c), respectively.
- spectral transmittance curve with an incident angle of 0 ° means a spectral transmittance curve of light incident perpendicularly to the main surface of the optical filter
- spectral transmittance curve with an incident angle of 30 ° means an optical filter. The spectral transmittance curve of light incident at an angle of 30 ° with respect to the direction perpendicular to the main surface of
- This filter may have an average transmittance (R) of light having a wavelength of 620 to 750 nm of 20% or less, preferably 19% or less, more preferably 17% or less, in a spectral transmittance curve with an incident angle of 0 °. 14% or less is more preferable.
- R average transmittance
- the average transmittance (G) of light having a wavelength of 495 to 570 nm may be 90% or more, preferably 93% or more, and more preferably 95% or more. 97% or more is more preferable.
- This filter has an average transmittance ratio (R) / (G) of 0.20 or less, preferably 0.18 or less, and more preferably 0.15 or less.
- R average transmittance ratio
- G average transmittance ratio
- T 0 (600-725) ⁇ T 30 (600-725) may be 3% ⁇ nm or less, preferably 2% ⁇ nm or less, and more preferably 1% ⁇ nm or less.
- is an index indicating the incident angle dependence of light of this filter at a wavelength of 600 to 725 nm. The smaller this value, the lower the incident angle dependency.
- This filter only needs to have a wavelength ⁇ IR T (80) , a wavelength ⁇ IR T (50) , and a wavelength ⁇ IR T (20) in the wavelength range of 550 to 750 nm in the normalized spectral transmittance curve at an incident angle of 0 °. If it is in 580-720 nm, it is preferable, and if it is in wavelength 600-700 nm, it is more preferable.
- ⁇ IR T (80) , ⁇ IR T (50) , and ⁇ IR T (20) are at wavelengths of 550 to 750 nm, a spectral transmittance curve close to a specific luminous efficiency curve can be obtained.
- This filter, ⁇ IR T (80), ⁇ IR T (50) and ⁇ IR T (20) are each formula (a), satisfies the (b) and (c), it is more preferable to satisfy the respective following equations.
- ⁇ IR T (50) ⁇ T (50) and ⁇ IR T (20) ⁇ T (20) all have smaller values (however, 0 or more) It is possible to provide spectral characteristics closer to human visibility on the long wavelength side, and to improve the accuracy of color reproducibility on the long wavelength side.
- ⁇ IR T (80) ⁇ T (80) , ⁇ IRT (50) ⁇ T (50) and ⁇ IRT (20) ⁇ T (20) are each less than 0, that is, the spectral transmittance of the NIR filter is When entering the inside of the visibility curve (on the shorter wavelength side than the specific visibility curve), the red color is cut off and good color reproducibility cannot be obtained. Therefore, this filter can realize a standardized spectral transmittance curve that is close to the specific visibility curve so that it does not enter the shorter wavelength side than the specific visibility curve.
- the ⁇ IR T (80) - ⁇ T ( 80), ⁇ IR T (50) - ⁇ T (50) and ⁇ IR T (20) - ⁇ T ( 20) the sum is 0 ⁇ 102 nm. From the viewpoint of bringing the spectral characteristics closer to human visibility, the total is preferably 0 to 92 nm, and more preferably 0 to 80 nm.
- This filter preferably further satisfies the following requirement (9).
- the average transmittance of light having a wavelength of 750 to 850 nm is 0.2% or less. If the average transmittance in the wavelength region is 0.2% or less, the human eye has no sensitivity, but the solid-state imaging device can largely block sensitive near-infrared light, so that a high-contrast image can be obtained. Cheap. Further, the average transmittance of light having a wavelength of 750 to 850 nm is preferably 0.15% or less, and more preferably 0.1% or less.
- the shape of the transparent substrate is not particularly limited, and may be a block shape, a plate shape, or a film shape.
- the thickness of the transparent substrate depends on the constituent materials, but is preferably 0.03 to 5 mm, and more preferably 0.05 to 1 mm from the viewpoint of thinning.
- the transparent base material is not particularly limited as long as it transmits visible light.
- examples thereof include inorganic materials such as glass and crystals, and organic materials such as resins.
- inorganic materials such as glass and crystals
- organic materials such as resins.
- an inorganic material it is preferable from the viewpoint of shape stability related to long-term reliability such as optical characteristics and mechanical characteristics as an optical filter, and handling characteristics at the time of manufacturing the filter. From the viewpoint of property, glass is preferable.
- an organic material as a transparent base material, it is preferable from points, such as thickness reduction.
- Resins that can be used for transparent substrates include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, acrylic resins such as norbornene resin, polyacrylate, and polymethyl methacrylate, urethane Examples include resins, vinyl chloride resins, fluororesins, polycarbonate resins, polyvinyl butyral resins, polyvinyl alcohol resins, polyimide resins, and the like.
- Examples of the glass that can be used for the transparent substrate include absorption glass obtained by adding CuO or the like to fluorophosphate glass or phosphate glass, soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and the like.
- the “phosphate glass” includes silicic acid phosphate glass in which a part of the glass skeleton is composed of SiO 2 .
- Examples of the crystal material that can be used for the transparent substrate include birefringent crystals such as quartz, lithium niobate, and sapphire. The specific composition example of the glass containing CuO used for a transparent base material is described.
- Examples of commercially available products include, for example, (1) glass such as NF-50E, NF-50EX, NF-50T, NF-50TX (product name) manufactured by Asahi Glass Co., Ltd. , BG-60, BG-61 (above, manufactured by Schott, trade name), etc.
- Examples of the glass of (5) include CD5000 (made by HOYA, trade name).
- the above-described CuO-containing glass may further contain a metal oxide.
- the metal oxide contains, for example, one or more of Fe 2 O 3 , MoO 3 , WO 3 , CeO 2 , Sb 2 O 3 , V 2 O 5, etc.
- the CuO-containing glass has ultraviolet absorption characteristics. Have.
- the content of these metal oxides relative to the CuO-containing glass 100 parts by weight, the Fe 2 O 3, MoO 3, WO 3 and at least one selected from the group consisting of CeO 2, Fe 2 O 3 0.6-5 parts by mass, MoO 3 0.5-5 parts by mass, WO 3 1-6 parts by mass, CeO 2 2.5-6 parts by mass, or two kinds of Fe 2 O 3 and Sb 2 O 3 Fe 2 O 3 0.6 to 5 parts by mass + Sb 2 O 3 0.1 to 5 parts by mass, or V 2 O 5 and CeO 2 in the form of V 2 O 5 0.01 to 0.5 parts by mass + CeO 2
- the amount is preferably 1 to 6 parts by mass.
- the optical characteristics of the transparent substrate may satisfy the optical characteristics of the present invention when an NIR filter obtained by laminating an absorption layer, a reflection layer, and the like is used.
- the transparent base material may be subjected to a surface treatment with a silane coupling agent when the following absorption layer is laminated on the main surface.
- a silane coupling agent As a silane coupling agent, the same thing as used with the following absorption layers can be used, for example.
- the absorption layer is a layer containing a near-infrared absorbing material (A) and a transparent resin (B), and typically the near-infrared absorbing material (A) is uniformly dispersed in the transparent resin (B). Is a layer. It is preferable that the absorption layer further contains an ultraviolet absorber (U).
- the absorption layer may be provided with a plurality of absorption layers, with a layer containing the near infrared absorbing material (A) and a layer containing the ultraviolet absorbing material (U) as separate layers.
- the thickness of the absorbing layer is preferably 0.1 to 100 ⁇ m.
- the total thickness of each absorption layer is preferably 0.1 to 100 ⁇ m.
- the thickness of the absorption layer is determined according to the application. If the thickness is less than 0.1 ⁇ m, the desired optical properties may not be sufficiently exhibited. On the other hand, if the thickness exceeds 100 ⁇ m, the flatness is lowered, and there is a possibility that in-plane variation occurs in the absorption rate.
- the thickness of the absorption layer is more preferably 0.3 to 50 ⁇ m. If the thickness is 0.3 to 50 ⁇ m, both sufficient optical properties and layer flatness can be achieved.
- a near-infrared absorbing dye is used as the near-infrared absorbing material (A), and an ultraviolet absorbing dye is used as the ultraviolet absorbing material (U), but is not particularly limited thereto.
- typically used near-infrared absorbing dyes and ultraviolet absorbing dyes will be described in detail.
- Near-infrared absorbing dye (A) Near-infrared absorbing dye (A) (hereinafter also referred to as dye (A)) has the ability to transmit light in the visible wavelength region (450 to 600 nm) and absorb light in the near-infrared wavelength region (700 to 1100 nm). If there is, it is not particularly limited.
- the dye may be a pigment, that is, a state in which molecules are aggregated.
- the near-infrared absorbing dye is referred to as “NIR absorbing dye” as necessary.
- the dye (A) has a wavelength of 650 to 900 nm in an absorption spectrum of light having a wavelength of 400 to 900 nm measured using a resin film obtained by dispersing the dye (A) in the transparent resin (B). Those that exhibit an absorption maximum wavelength are preferable, and those that exhibit an absorption maximum wavelength within a wavelength of 650 to 750 nm are more preferable.
- the near-infrared absorbing dye having this absorption characteristic is referred to as a dye (A1).
- the absorption maximum wavelength in this absorption spectrum is referred to as ⁇ max of the dye (A1).
- the absorption spectrum of the dye (A1) has an absorption peak having an absorption peak at the wavelength ⁇ max (hereinafter referred to as “ ⁇ max absorption peak”).
- the absorption spectrum of the dye (A1) preferably has ⁇ max within a wavelength of 650 to 900 nm, has little visible light absorption, and has a steep slope on the visible light side as seen from the absorption peak of ⁇ max. . Furthermore, it is preferable that the absorption peak of ⁇ max has a gentle slope on the long wavelength side (on the side opposite to the visible light side as viewed from the absorption peak).
- Examples of the dye (A1) include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, dithiol metal complex compounds, diimonium compounds, polymethine compounds, phthalide compounds, naphthoquinone compounds, anthraquinone compounds, indophenol compounds, Examples include squarylium compounds.
- the dye (A1) composed of a squarylium compound has little absorption of visible light in the above absorption spectrum, the absorption peak of ⁇ max has a steep slope on the visible light side, and has high storage stability and light stability. Therefore, it is preferable.
- the dye (A1) composed of a cyanine compound is preferable because the absorption spectrum has little visible light absorption and has a high light absorption rate on the long wavelength side in the vicinity of ⁇ max . In addition, long-term stability of the cyanine compound can be ensured by forming a salt.
- a dye (A1) made of a phthalocyanine compound is preferable because of excellent heat resistance and weather resistance.
- the dye (A1) that is a squarylium compound include at least one selected from squarylium compounds represented by the following formula (F1).
- the compound represented by the formula (F1) is also referred to as a compound (F1). The same applies to other compounds.
- Compound (F1) is a squarylium compound having a structure in which a benzene ring is bonded to the left and right sides of the squarylium skeleton, and a nitrogen atom is bonded to the 4-position of the benzene ring and a saturated heterocyclic ring containing the nitrogen atom is formed. And a compound having a light-absorbing property as the dye (A1).
- other required characteristics such as increasing the solubility in the solvent (hereinafter sometimes referred to as “host solvent”) used for forming the near-infrared absorbing layer and the transparent resin (B). Accordingly, the substituent of the benzene ring can be appropriately adjusted within the following range.
- R 4 and R 6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl or alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —NR 7 R 8 (R 7 And R 8 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or —C ( ⁇ O) —R 9 (R 9 is a hydrogen atom or an optionally substituted carbon atom).
- At least one of R 1 and R 2 , R 2 and R 5 , and R 1 and R 3 is connected to each other to form a heterocyclic ring A, B, and C each having 5 or 6 members together with a nitrogen atom To do.
- R 1 and R 2 are a divalent group -Q- to which they are bonded, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, An alkylene group which may be substituted with an acyloxy group having 1 to 10 carbon atoms which may have a substituent, or an alkyleneoxy group.
- R 2 and R 5 when the heterocyclic ring B is formed, and R 1 and R 3 when the heterocyclic ring C is formed are each a divalent group —X 1 —Y 1 — and — X 2 —Y 2 — (X 1 and X 2 on the side bonded to nitrogen), X 1 and X 2 are each a group represented by the following formula (1x) or (2x), and Y 1 and Y 2 are each It is a group represented by any one selected from the following formulas (1y) to (5y). When X 1 and X 2 are groups represented by the following formula (2x), Y 1 and Y 2 may each be a single bond.
- Z's are each independently a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, or -NR 28 R 29 (R 28 and R 29 are each independently Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
- R 21 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 27 is an alkyl group having 1 to 6 carbon atoms or an alkyl group having 6 to 10 carbon atoms.
- An aryl group is shown.
- R 7 , R 8 , R 9 , R 4 , R 6 , R 21 to R 27 , R 1 to R 3 when not forming a heterocyclic ring, and R 5 are It may combine to form a 5-membered ring or a 6-membered ring.
- R 21 and R 26 , R 21 and R 27 may be directly bonded.
- R 1 and R 2 are each independently a hydrogen atom, an optionally substituted alkyl group or allyl group having 1 to 6 carbon atoms, or 6 carbon atoms. Represents an aryl group or an araryl group of ⁇ 11.
- R 3 and R 5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having 1 to 6 carbon atoms.
- the heterocycle A may be simply referred to as ring A. The same applies to the heterocyclic rings B and C.
- R 4 and R 6 each independently represent the above atom or group.
- the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
- the alkyl group may be linear, branched or cyclic.
- R 4 and R 6 are preferably a combination in which either one is a hydrogen atom and the other is —NR 7 R 8 .
- —NR 7 R 8 is either R 4 or R 6 May be introduced.
- —NR 7 R 8 is preferably introduced into R 4 .
- each of —NR 7 R 8 is preferably introduced into R 6 .
- R 9 is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 10 carbon atoms, or an optionally substituted group.
- an araryl group having 7 to 18 carbon atoms which may have an oxygen atom between carbon atoms is preferable.
- Substituents include halogen atoms such as fluorine atoms, hydroxyl groups, carboxy groups, sulfo groups, cyano groups, alkyl groups having 1 to 6 carbon atoms, fluoroalkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms. And an acyloxy group having 1 to 6 carbon atoms.
- R 9 is a linear, branched or cyclic alkyl group having 1 to 17 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms and / or a carbon number which may be substituted with a fluorine atom.
- a group selected from an alkyl group which may be substituted and / or an aryl group having a phenyl group which may be substituted with an alkoxy group having 1 to 6 carbon atoms is preferred.
- one or more hydrogen atoms may be independently substituted with a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, or a cyano group, and an unsaturated bond, oxygen atom, saturated or A group which is a hydrocarbon group having 5 to 25 carbon atoms and having at least one branch which may contain an unsaturated ring structure is also preferably used.
- R 9 include groups represented by the following formulas (1a), (1b), (2a) to (2e), and (3a) to (3e).
- R 1 and R 2 , R 2 and R 5 , and R 1 and R 3 are connected to each other to form 5 or 6 members of ring A, ring B, and ring C, At least any one of these may be formed, and two or three may be formed.
- R 1 and R 2 are each independently a hydrogen atom, an optionally substituted alkyl group or allyl group having 1 to 6 carbon atoms, or 6 to 6 carbon atoms.
- 11 aryl groups or araryl groups are shown.
- the alkyl group may be linear, branched or cyclic. Examples of the substituent include a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, and an acyloxy group having 1 to 3 carbon atoms.
- R 3 and R 5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having 1 to 6 carbon atoms.
- R 1 , R 2 , R 3 , and R 5 an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of solubility in a host solvent or a transparent resin (B), and a methyl group, an ethyl group, or the like.
- a 2-propyl group is particularly preferred.
- the groups R 1 to R 6 of the benzene ring bonded to the left and right of the squarylium skeleton may be different on the left and right, but are preferably the same on the left and right.
- the compound (F1) includes the compound (F1-1) represented by the formula (F1-1) having a resonance structure having the structure represented by the general formula (F1).
- compound (F1) a compound represented by formula (F11) having only ring B as a ring structure, a compound represented by formula (F12) having only ring A as a ring structure, ring B and ring And a compound represented by the formula (F13) having two C atoms as a ring structure.
- the compound represented by the formula (F11) is the same compound as the compound (F1) in which only the ring C is included as a ring structure and R 6 is —NR 7 R 8 .
- the compound represented by the formula (F11) and the compound represented by the formula (F13) are compounds described in US Pat. No. 5,543,086.
- X 1 is preferably an ethylene group in which the hydrogen atom represented by (2x) may be substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
- the substituent is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
- X 1 specifically, — (CH 2 ) 2 —, —CH 2 —C (CH 3 ) 2 —, —CH (CH 3 ) —C (CH 3 ) 2 —, —C (CH 3 ) 2 -C (CH 3 ) 2- and the like.
- Examples of the compound (F11) include compounds represented by formulas (F11-1) to (F11-7). Among these, the compounds (F11-2) to (F11-7) are more preferable because of their high solubility in the host solvent and the transparent resin (B).
- Q is substituted with a hydrogen atom by an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyloxy group having 1 to 10 carbon atoms which may have a substituent. And an alkylene group having 4 or 5 carbon atoms and an alkyleneoxy group having 3 or 4 carbon atoms.
- the oxygen position is preferably other than next to N.
- Q is preferably a butylene group which may be substituted with an alkyl group having 1 to 3 carbon atoms, particularly a methyl group.
- —NR 7 R 8 is —NH—C ( ⁇ O) — (CH 2 ) m —CH 3 (m is 0 to 19), —NH—C ( ⁇ O) —Ph— R 10 (-Ph- represents a phenylene group, R 10 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms in which the hydrogen atom may be substituted with a fluorine atom, or an alkoxy group having 1 to 3 carbon atoms, respectively. And the like are preferred.
- Compound (F12) since its lambda max is in the relatively long wavelength side among the above-mentioned wavelength region is spread a transmission area of the visible light by using the compound (F12).
- Examples of the compound (F12) include compounds represented by the formulas (F12-1) to (F12-3).
- X 1 and X 2 are each independently an ethylene in which a hydrogen atom represented by (2x) may be substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms Groups are preferred.
- the substituent is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
- X 1 and X 2 specifically, — (CH 2 ) 2 —, —CH 2 —C (CH 3 ) 2 —, —CH (CH 3 ) —C (CH 3 ) 2 —, —C ( CH 3 ) 2 —C (CH 3 ) 2 — and the like.
- Y 1 and Y 2 are independently —CH 2 —, —C (CH 3 ) 2 —, —CH (C 6 H 5 ) —, —CH ((CH 2 ) m CH 3 ) — (m is 0-5) and the like.
- —NR 7 R 8 is —NH—C ( ⁇ O) —C m H 2m + 1 (m is 1 to 20, and C m H 2m + 1 is linear, branched, or cyclic.
- Examples of the compound (F13) include compounds represented by the formula (F13-1) and the formula (F13-2).
- Formula (F6) represents a compound in which none of ring A to ring C is formed in formula (F1) (wherein R 1 to R 6 are as follows).
- R 1 and R 2 each independently represents a hydrogen atom, an optionally substituted alkyl group or allyl group having 1 to 12 carbon atoms, or an aryl group or aryl group having 6 to 11 carbon atoms.
- R 3 and R 5 each independently represents a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 6 carbon atoms.
- R 4 and R 6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl or alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —NR 7 R 8 (R 7 And R 8 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or —C ( ⁇ O) —R 9 (R 9 is a hydrogen atom or an optionally substituted carbon atom).
- Examples of the compound (F6) include compounds represented by the formula (F6-1) and the formula (F6-2).
- a squarylium compound represented by the formula (F7) can also be used as the dye (A1).
- Compound (F1) such as compound (F11), compound (F12), and compound (F13), compound (F6), and compound (F7) can be produced by a conventionally known method.
- Compound (F11) such as compound (F11-1) can be produced, for example, by the method described in US Pat. No. 5,543,086.
- the compound (F12) is, for example, J.I. Org. Chem. 2005, 70 (13), 5164-5173.
- a commercially available product may be used as the dye (A1) which is a squarylium compound.
- Examples of commercially available products include S2098, S2084 (trade names, manufactured by FEW Chemicals) and the like.
- Specific examples of the dye (A1) that is a cyanine compound include at least one selected from cyanine compounds represented by the formula (F5).
- R 11 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an alkylsulfone group, or an anionic species thereof.
- R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- Z represents PF 6 , ClO 4 , R f —SO 2 , (R f —SO 2 ) 2 —N (R f represents an alkyl group having 1 to 8 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. shown.), or an BF 4.
- R 14 , R 15 , R 16 and R 17 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms.
- n represents an integer of 1 to 6.
- R 11 in the compound (F5) is preferably an alkyl group having 1 to 20 carbon atoms
- R 12 and R 13 are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R 14 , R 15 , R 16 and R 17 are each independently preferably a hydrogen atom, and the number of n is preferably 1 to 4.
- the left and right structures sandwiching n repeating units may be different, but the same structure is preferred.
- Examples of the compound (F5) include a compound represented by the formula (F51) and a compound represented by the formula (F52).
- Z - is an anion represented by Z in the compound (F5) - is the same as.
- a commercially available product may be used as the dye (A1) which is a cyanine compound.
- Examples of commercially available products include ADS680HO (trade name, manufactured by American dye), S0830 (trade name, manufactured by FEW Chemicals), S2137 (trade name, manufactured by FEW Chemicals), and the like.
- phthalocyanine compounds that can be used as the dye (A1) include FB22 (trade name, manufactured by Yamada Chemical Co., Ltd.), TXEX720 (trade name, manufactured by Nippon Shokubai Co., Ltd.), and PC142c (trade name, Yamada Chemical). Commercial products such as Kogyo Co., Ltd.).
- Table 1 shows ⁇ max of each compound used as the pigment (A1) exemplified above together with the type of the transparent resin (B) used at the time of measurement.
- B-OKP2 and Byron (registered trademark) 103 used as the transparent resin (B) in the above are polyester resin, SP3810 is polycarbonate resin, and EA-F5003 is acrylic resin, and details will be described later.
- one type selected from a plurality of compounds having the light absorption characteristics of the dye (A1) may be used alone, or two or more types may be used in combination.
- the dye (A) preferably contains one or more of the dyes (A1).
- dye (A) may contain another NIR absorption pigment
- the content of the pigment (A) in the absorption layer is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and more preferably 1 to 20% by mass with respect to the mass of the transparent resin (B). Is more preferable. By setting it as 0.1 mass% or more, desired near-infrared absorptivity is obtained, and by setting it as 30 mass% or less, the fall of a near-infrared absorptivity, a raise of a haze value, etc. are suppressed.
- dye (A) may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- the ultraviolet absorbing dye (U) (hereinafter also referred to as dye (U)) is a compound that absorbs light having a wavelength of 430 nm or less.
- the dye (U) is preferably a compound that satisfies the following requirements (iv-1) and (iv-2).
- (Iv-1) In a light absorption spectrum having a wavelength of 350 to 800 nm measured by dissolving in dichloromethane, it has at least one absorption maximum wavelength at a wavelength of 415 nm or less, and has the longest wavelength among the absorption maximums at a wavelength of 415 nm or less.
- the absorption maximum wavelength ⁇ max (UV) on the side is at a wavelength of 360 to 415 nm.
- the absorption maximum wavelength of the dye (U) that satisfies the requirement (iv-1) does not change significantly even in the transparent resin. That is, in the dye (U) satisfying (iv-1), even when the dye (U) is dissolved or dispersed in a transparent resin, the absorption maximum wavelength ⁇ max ⁇ P (UV) in the absorption spectrum in the resin is approximately the wavelength. Since it exists within 360-415 nm, it is preferable.
- the dye (U) satisfying the requirement of (iv-2) exhibits excellent steepness even when contained in a transparent resin. That is, the dye (U) satisfying (iv-2) has a transmittance of 50% at a wavelength longer than the absorption maximum wavelength ⁇ max (UV) even when the dye (U) is dissolved or dispersed in a transparent resin.
- the difference ( ⁇ P90 ⁇ P50 ) between the wavelength ⁇ P50 to be 90% and the wavelength ⁇ P90 to have a transmittance of 90% is approximately 14 nm or less, which is preferable because it shows the steepness equivalent to that in dichloromethane.
- ⁇ P90 - ⁇ P50 is more preferably 13 nm or less, and even more preferably 12 nm or less.
- the transparent resin is dissolved or dispersed and embodiments of the NIR wavelength filter lambda 0 which is obtained as a near infrared absorbing layer and (UV) wavelengths lambda 30 (UV) can be present in a wavelength region shorter than a wavelength of 450 nm, preferably in a wavelength range of 400 to 425 nm.
- the dye (U) satisfying the requirement (iv-2) is used, in the NIR filter of the embodiment obtained as a near-infrared absorbing layer by dissolving or dispersing in the transparent resin, the absorption maximum wavelength of the dye (U) The difference between the wavelength at which the transmittance on the long wavelength side is 50% and the wavelength at which the transmittance is 90% can be reduced. That is, the change in the spectral transmittance curve can be made steep in the wavelength region.
- a wavelength ⁇ 0 (UV) and a wavelength in a region shorter than a wavelength of 450 nm, preferably a wavelength of 400 to 425 nm ⁇ 30 (UV) is likely to exist, and a steep change in the spectral transmittance curve in a region shorter than a wavelength of 450 nm is easily obtained.
- an absorption spectrum of light having a wavelength of 350 to 800 nm measured by dissolving the dye (U) in dichloromethane is also referred to as “absorption spectrum of the dye (U)”.
- Maximum absorption wavelength in the absorption spectrum of the dye (U) ⁇ max the (UV) referred to as " ⁇ max of the dye (U) (UV)”.
- a spectral transmittance curve measured by dissolving the dye (U) in dichloromethane is referred to as a “spectral transmittance curve of the dye (U)”.
- the dye (U) In the spectral transmittance curve of the dye (U), when the dye (U) is contained in such an amount that the transmittance at ⁇ max (UV) is 10%, it has a longer wavelength than the ⁇ max (UV) of the dye (U). a wavelength at which the transmittance is 90% is referred to as " ⁇ L90", the wavelength ⁇ max to (UV) transmittance than the long wavelength of the dye (U) is the 50% of " ⁇ L50".
- the absorption spectrum of light having a wavelength of 350 to 800 nm measured in an absorption layer prepared by dissolving the dye (U) in the transparent resin (B) is expressed as “in the resin of the dye (U). Also called “absorption spectrum”.
- Dye absorption maximum wavelength in the resin in the absorption spectrum of the (U) ⁇ max ⁇ P a (UV) referred to as "dye (U) of the ⁇ max ⁇ P (UV)”.
- a spectral transmittance curve measured for an absorption layer prepared by dissolving the dye (U) in a transparent resin is referred to as “in-resin spectral transmittance curve of the dye (U)”.
- the ⁇ max ⁇ P The wavelength at which the transmittance is 90% at a wavelength longer than UV
- ⁇ P50 the wavelength at which the transmittance is 50% longer than ⁇ max ⁇ P (UV) of the dye (U)
- the wavelength ⁇ max (UV) of the dye (U) is preferably in the wavelength range of 365 to 415 nm, and more preferably in the wavelength range of 370 to 410 nm.
- the difference ( ⁇ L90 ⁇ L50 ) between ⁇ L90 and ⁇ L50 of the dye (U) is preferably 12 nm or less, more preferably 11 nm or less, and even more preferably 9 nm or less. Since ⁇ L90 - ⁇ L50 is in this wavelength region, the above-described effect can be easily obtained.
- Specific examples of the dye (U1) satisfying the above requirements (iv-1) and (iv-2) include oxazole, merocyanine, cyanine, naphthalimide, oxadiazole, oxazine, oxazolidine, naphthalate Examples include acid-based, styryl-based, anthracene-based, cyclic carbonyl-based, and triazole-based dyes.
- Examples of the dye (U1) include dyes represented by the following general formula (N).
- N a dye represented by the formula (N)
- dyes of other formulas are also described in the same manner.
- group represented by Formula (1n) is described as group (1n), and groups of other formulas are also described in the same manner.
- each R 18 independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a saturated or unsaturated ring structure and may have a branch. Specific examples include linear or branched alkyl groups, alkenyl groups, saturated cyclic hydrocarbon groups, aryl groups, and araryl groups.
- R 19 each independently represents a cyano group or a group represented by the following formula (n).
- -COOR 30 (n) In the formula (n), R 30 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a saturated or unsaturated ring structure and may have a branch. Specific examples include linear or branched alkyl groups, alkenyl groups, saturated cyclic hydrocarbon groups, aryl groups, and araryl groups.
- R 18 in the dye (N) is particularly preferably a group represented by the formulas (1n) to (4n).
- R 19 in the dye (N) is preferably a group represented by the following formula (5n).
- dyes (N) include dyes (N-1) to (N-4) having the constitution shown in Table 2.
- the specific structures of R 18 and R 19 in Table 2 correspond to formulas (1n) to (5n).
- Table 2 also shows the corresponding dye abbreviations.
- dyes (N-1) to (N-4) two R 18 s are the same, and R 19 is the same.
- oxazole-based and merocyanine-based dyes are preferable, and examples of commercially available products include Uvitex (registered trademark) OB and Hakkol (registered trademark) RF-K, S0511.
- a merocyanine dye represented by the following general formula (M) is particularly preferable.
- Y represents a methylene group or an oxygen atom substituted with Q 6 and Q 7 .
- Q 6 and Q 7 each independently represent a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 10 carbon atoms.
- Q 6 and Q 7 are each independently preferably a hydrogen atom, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and both are hydrogen atoms, or at least one is a hydrogen atom and the other is 1 to More preferred are 4 alkyl groups. Particularly preferably, Q 6 and Q 7 are both hydrogen atoms.
- Q 1 represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
- the monovalent hydrocarbon group having no substituent include an alkyl group having 1 to 12 carbon atoms in which a part of hydrogen atoms may be substituted with an aliphatic ring, an aromatic ring or an alkenyl group, and one hydrogen atom.
- Part of the cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an aromatic ring, an alkyl group or an alkenyl group, and a part of hydrogen atoms may be substituted with an aliphatic ring, an alkyl group or an alkenyl group
- a good aryl group having 6 to 12 carbon atoms is preferred.
- the alkyl group may be linear or branched, and the carbon number thereof is more preferably 1-6.
- the alkyl group having 1 to 12 carbon atoms in which part of the hydrogen atoms is substituted with an aliphatic ring, an aromatic ring or an alkenyl group is an alkyl group having 1 to 4 carbon atoms having a cycloalkyl group having 3 to 6 carbon atoms.
- An alkyl group having 1 to 4 carbon atoms substituted with a phenyl group is more preferred, and an alkyl group having 1 or 2 carbon atoms substituted with a phenyl group is particularly preferred.
- the alkyl group substituted with an alkenyl group means an alkenyl group as a whole but having no unsaturated bond between the 1- and 2-positions, such as an allyl group or a 3-butenyl group.
- the hydrocarbon group having a substituent is preferably an alkoxy group, an acyl group, an acyloxy group, a cyano group, a dialkylamino group, or a hydrocarbon group having at least one chlorine atom.
- the alkoxy group, acyl group, acyloxy group and dialkylamino group preferably have 1 to 6 carbon atoms.
- Preferred Q 1 is an alkyl group having 1 to 6 carbon atoms in which part of hydrogen atoms may be substituted with a cycloalkyl group or a phenyl group.
- Particularly preferred Q 1 is an alkyl group having 1 to 6 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group.
- Q 2 to Q 5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having 1 to 10 carbon atoms.
- the alkyl group and alkoxy group preferably have 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
- At least one of Q 2 and Q 3 is preferably an alkyl group, and more preferably an alkyl group. If Q 2 or Q 3 is not an alkyl group, more preferably a hydrogen atom.
- Q 2 and Q 3 are both particularly preferably alkyl groups having 1 to 6 carbon atoms.
- At least one of Q 4 and Q 5 is preferably a hydrogen atom, and more preferably a hydrogen atom. When Q 4 or Q 5 is not a hydrogen atom, an alkyl group having 1 to 6 carbon atoms is preferable.
- Z represents any of divalent groups represented by formulas (Z1) to (Z5).
- Q 8 and Q 9 each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
- Q 8 and Q 9 may be different groups, but are preferably the same group.
- Examples of the monovalent hydrocarbon group having no substituent include an alkyl group having 1 to 12 carbon atoms in which a part of hydrogen atoms may be substituted with an aliphatic ring, an aromatic ring or an alkenyl group, and one hydrogen atom.
- Part of the cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an aromatic ring, an alkyl group or an alkenyl group, and a part of hydrogen atoms are substituted with an aliphatic ring, an alkyl group or an alkenyl group
- Preferred is an aryl group having 6 to 12 carbon atoms.
- the alkyl groups may be linear or branched, and the number of carbon atoms is more preferably 1-6.
- the alkyl group having 1 to 12 carbon atoms in which part of the hydrogen atoms is substituted with an aliphatic ring, an aromatic ring or an alkenyl group is an alkyl group having 1 to 4 carbon atoms having a cycloalkyl group having 3 to 6 carbon atoms.
- An alkyl group having 1 to 4 carbon atoms substituted with a phenyl group is more preferred, and an alkyl group having 1 or 2 carbon atoms substituted with a phenyl group is particularly preferred.
- the alkyl group substituted with an alkenyl group means an alkenyl group as a whole but having no unsaturated bond between the 1- and 2-positions, such as an allyl group or a 3-butenyl group.
- the monovalent hydrocarbon group having a substituent is preferably an alkoxy group, an acyl group, an acyloxy group, a cyano group, a dialkylamino group, or a hydrocarbon group having at least one chlorine atom.
- the alkoxy group, acyl group, acyloxy group and dialkylamino group preferably have 1 to 6 carbon atoms.
- Preferable Q 8 and Q 9 are both an alkyl group having 1 to 6 carbon atoms in which a part of hydrogen atoms may be substituted with a cycloalkyl group or a phenyl group.
- Particularly preferred Q 8 and Q 9 are all alkyl groups having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group and the like. Is mentioned.
- Q 10 to Q 19 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
- the monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is the same hydrocarbon group as Q 8 and Q 9 .
- the monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is preferably an alkyl group having 1 to 6 carbon atoms which does not have a substituent.
- Both Q 10 and Q 11 are more preferably an alkyl group having 1 to 6 carbon atoms, and the same alkyl group is particularly preferable.
- Q 12 and Q 15 are each preferably a hydrogen atom or a C 1-6 alkyl group having no substituent.
- the two groups (Q 13 and Q 14 , Q 16 and Q 17 , Q 18 and Q 19 ) bonded to the same carbon atom are both hydrogen atoms, or both are preferably alkyl groups having 1 to 6 carbon atoms. .
- the compound represented by the formula (M) is a compound in which Y is an oxygen atom, Z is a group (Z1) or a group (Z2), and a methylene group in which Y is substituted with Q 6 and Q 7
- a compound in which Z is a group (Z1) or a group (Z5) is preferable.
- Q 1 is an alkyl group having 1 to 6 carbon atoms
- Q 2 and Q 3 are both alkyl groups having 1 to 6 carbon atoms
- Q 4 and Q 5 are both hydrogen atoms
- a group (Z1) or a group ( Z2) is preferred.
- Q 1 is an alkyl group having 1 to 6 carbon atoms
- Q 2 and Q 3 Are each a hydrogen atom, preferably an alkyl group having 1 to 6 carbon atoms, Q 4 to Q 7 are all hydrogen atoms, and a group (Z1) or group (Z5) is preferable, and Q 1 is a carbon atom having 1 to 6 carbon atoms.
- the group (Z1) or the group (Z5) in which the alkyl group 6 and Q 2 to Q 7 are all hydrogen atoms are more preferable.
- the compound represented by the formula (M) is preferably a compound in which Y is an oxygen atom, Z is a group (Z1) or a group (Z2), Y is an oxygen atom, and Z is a group (Z1). Certain compounds are particularly preferred.
- dye (M) examples include compounds represented by the formulas (M-1) to (M-11).
- the dye (U1) one kind selected from a plurality of compounds having light absorption characteristics as the dye (U1) may be used alone, or two or more kinds may be used in combination.
- the pigment (U) preferably contains one or more pigments (U1).
- dye (U) may contain another ultraviolet-absorbing pigment
- the content of the dye (U) in the absorption layer is preferably determined so as to have a wavelength at which the transmittance is 50% at a wavelength of 400 to 425 nm of the spectral transmittance curve of the filter having an incident angle of 0 °.
- the dye (U) is preferably contained in the absorbing layer in an amount of 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and more preferably 0.1 to 20% by mass with respect to the mass of the transparent resin. % Is even more preferred.
- the transparent resin (B) preferably has a refractive index of 1.45 or more.
- the refractive index is more preferably 1.5 or more, and particularly preferably 1.6 or more.
- the upper limit of the refractive index of the transparent resin (B) is not particularly limited, but is preferably about 1.72 from the viewpoint of availability.
- the refractive index means a refractive index at a wavelength of 589 nm at 20 ° C. unless otherwise specified.
- the transparent resin (B) is specifically acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyarylene ether.
- Examples include phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, and polyester resins.
- Transparent resin (B) may be used individually by 1 type from these resin, and may mix and use 2 or more types.
- the transparent resin is an acrylic resin, a polyester resin, a polycarbonate resin, an ene / thiol resin, an epoxy resin, a polyimide resin, And at least one selected from cyclic olefin resins.
- the transparent resin is more preferably at least one selected from acrylic resins, polyester resins, polycarbonate resins, polyimide resins, and cyclic olefin resins.
- the polyester resin polyethylene terephthalate resin, polyethylene naphthalate resin and the like are preferable.
- the refractive index of the transparent resin (B) can be adjusted to the above range, for example, by adjusting the molecular structure of the raw material component so that the polymer main chain and side chain have a specific structure.
- Examples of the structure in the polymer for adjusting the refractive index within the above range include fluorene skeletons represented by the following formulas (B1) and (B2).
- a commercially available product may be used as the transparent resin (B).
- acrylic resins include resins obtained by curing OGSOL (registered trademark) EA-F5003 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index: 1.59).
- acrylic resin that can be purchased as a polymer include polymethyl methacrylate (refractive index: 1.49) and polyisobutyl methacrylate (refractive index: 1.48) manufactured by Tokyo Chemical Industry Co., Ltd.
- the glass transition temperature (Tg) of the transparent resin is preferably 0 to 380 ° C., more preferably 40 to 370 ° C., further preferably 100 to 360 ° C., and still more preferably 200 to 360 ° C.
- Tg of the transparent resin is within the above range, deterioration and deformation due to heat can be suppressed.
- a resin having a high Tg can suppress the thermal movement of the pigment and further suppress the thermal expansion of the resin itself. Therefore, when a dielectric multilayer film is provided on the resin (absorption layer), the appearance due to the occurrence of cracks and the like Defects can be reduced. Examples of the resin having a Tg of 100 to 360 ° C.
- polyester resin into which the fluorene skeleton is introduced.
- resin having a Tg of 200 to 360 ° C. include a polyimide resin, a polyether sulfone resin, and a polyallyl ether resin.
- polyester resins examples include OKPH4HT (refractive index: 1.64), OKPH4 (refractive index: 1.61), B-OKP2 (refractive index: 1.63) manufactured by Osaka Gas Chemical Co., Ltd.
- OKP850 reffractive index: 1.64
- Byron registered trademark
- ML9103 manufactured by sabic, refractive index 1.59.
- polymer alloy examples include Panlite (registered trademark) AM-8 series (manufactured by Teijin Chemicals Ltd.) and xylex (registered trademark) 7507 (manufactured by sabic), which are alloys of polycarbonate and polyester.
- polyimide resins examples include C3630 (refractive index: 1.59) and C3450 (refractive index: 1.62) manufactured by Mitsubishi Gas Chemical Company, Inc.
- the absorbing layer may further contain various optional components that are normally contained in this type of absorbing layer as long as the effects of the present invention are not impaired.
- the optional component include a color tone correction dye, a leveling agent, an antistatic agent, a heat stabilizer, a light stabilizer, an antioxidant, a dispersant, a flame retardant, a lubricant, and a plasticizer.
- the absorption layer dissolves the dye (A), the dye (U), the raw material component of the transparent resin (B) or the transparent resin (B), and each component blended as necessary, in a solvent. It can be formed by preparing a coating liquid by dispersing, coating the transparent substrate, drying, and further curing as necessary.
- the solvent for dissolving or dispersing the dye (A), the dye (U), the transparent resin (B), etc. is a dispersion medium or solution that can stably disperse these raw material components and each component that is blended as necessary. If possible, it is not particularly limited.
- the term “solvent” is used in a concept including both a dispersion medium and a solvent.
- the solvent include alcohols such as diacetone alcohol, ethyl cellosolve, methyl cellosolve, tridecyl alcohol, cyclohexyl alcohol, 2-methylcyclohexyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene alcohol, glycerin.
- Glycols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, diacetone alcohol, etc., 1-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide
- Amides such as sulfoxides, ethers, esters, chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, trichlore
- Aliphatic halogenated hydrocarbons such as alkylene, aromatic, aliphatic hydrocarbons, fluorine-based solvents and the like. These solvents can be used alone or in combination of two or more.
- the concentration when the transparent resin (B) or the raw material component of the transparent resin (B) is dissolved in the solvent is preferably 2 to 50% by mass, more preferably 5 to 40% by mass with respect to the total amount of the coating liquid.
- the coating liquid can contain a surfactant.
- the inclusion of the surfactant can improve the appearance, in particular, voids due to fine bubbles, dents due to adhesion of foreign matters, and repelling in the drying process.
- the surfactant is not particularly limited, and a cationic, anionic, nonionic or the like can be arbitrarily used.
- the solid content concentration of the transparent resin (B), the pigment (A), the pigment (U), etc. in the coating solution is generally 10 to 60% by mass. If the solid content concentration is too low, uneven coating tends to occur. Conversely, if the solid content concentration is too high, the coating appearance tends to be poor.
- dip coating, cast coating, spray coating, spinner coating, bead coating, wire bar coating, blade coating, roller coating, curtain coating, slit coating, Coating methods such as a coating method, a gravure coater method, a slit reverse coater method, a micro gravure method, an ink jet method, or a comma coater method can be used.
- a bar coater method, a screen printing method, a flexographic printing method, etc. can also be used.
- an absorption layer is formed by drying.
- drying heat drying, hot air drying, or the like can be used.
- a curing treatment is further performed.
- the reaction is thermal curing, drying and curing can be performed simultaneously.
- a curing step is provided separately from the drying.
- the absorption layer formed by coating the coating liquid on a peelable support substrate different from the transparent substrate may be peeled off from the support substrate and pasted on the transparent substrate.
- the releasable support substrate is not particularly limited in its shape and material as long as it has releasability.
- glass plates and release-treated plastic films for example, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, polyacrylate, polymethyl methacrylate
- polyester resins such as polyethylene terephthalate and polybutylene terephthalate
- polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer
- polyacrylate polymethyl methacrylate
- acrylic resin such as urethane resin, vinyl chloride resin, fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, etc., stainless steel plate and the like are used.
- the absorbing layer can be manufactured into a film by extrusion depending on the type of transparent resin, and a plurality of manufactured films may be laminated and integrated by thermocompression bonding or the like. These are then stuck on a transparent substrate.
- a transparent substrate (or a peelable substrate) can be pretreated.
- Pretreatment agents include aminosilanes, epoxysilanes, vinylsilanes, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, (3-ureidopropyl) trimethoxysilane Etc. can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
- the absorbent layer preferably satisfies the following requirements (4), (5), and (6). It is more preferable to satisfy the following requirements (4), (5) ′, and (6).
- the absorption spectrum in the wavelength region of 500 to 900 nm has an absorption maximum wavelength at a wavelength of 650 to 900 nm. It is more preferable to have an absorption maximum wavelength at a wavelength of 650 to 750 nm, and it is further preferable to have an absorption maximum wavelength at a wavelength of 680 to 720 nm.
- the spectral transmittance curve at an incident angle of 0 ° at least two wavelengths at a wavelength of 600 to 800 nm and a wavelength at which the transmittance is 10%, the longest wavelength among the wavelengths at which the transmittance is 10%
- the difference between the wavelength IR10 (L) on the side and the wavelength IR10 (S) on the shortest wavelength side, IR10 (L) -IR10 (S), is 30 to 70 nm. This difference is preferably 35 to 70 nm, more preferably 35 to 65 nm.
- the difference is less than 30 nm, a change in the spectral transmittance curve due to the incident angle may occur in the filter due to a change in the spectral transmittance curve due to the incident angle caused by the reflective layer.
- the difference is more than 70 nm, the absorption spectrum becomes broad, and the spectral transmittance curve of this filter deviates more than the specific luminous efficiency curve, so that reddish color reproducibility can be obtained with high accuracy. There is a risk of disappearing.
- the wavelength is at least two at wavelengths of 600 to 800 nm and the transmittance is 1%, and the longest wavelength among the wavelengths at which the transmittance is 1%.
- the difference between the wavelength IR1 (L) on the wavelength side and the wavelength IR1 (S) on the shortest wavelength side, IR1 (L) ⁇ IR1 (S), is 25 to 50 nm. This difference is preferably 30 to 45 nm, more preferably 33 to 40 nm.
- the difference is less than 25 nm, a change in the spectral transmittance curve due to the incident angle may occur in this filter due to a change in the spectral transmittance curve due to the incident angle caused by the reflective layer.
- the difference is more than 50 nm, the absorption spectrum becomes broad and the spectral transmittance curve of this filter deviates greatly from the specific luminous efficiency curve, so that reddish color reproducibility can be obtained with high accuracy. There is a risk of disappearing.
- the ratio of the spectral transmittance curve of the incident angle 0 °, and the average transmittance of light having a wavelength of 620 ⁇ 700nm T (620-700), the average transmittance of light having a wavelength of 495 ⁇ 570nm T (495-570) T (620-700) / T (495-570) is 0.35 or less.
- the ratio T (620-700) / T (495-570) is preferably 0.30 or less, more preferably 0.28 or less. If the absorption layer satisfies the requirements (4), (5), and (6), the filter can easily obtain spectral characteristics that satisfy the requirements (1) to (3).
- the absorption layer when the absorption layer satisfies the requirements of (4), (5), and (6), the absorption layer is provided on the absorption glass containing CuO, so that it is high in the near infrared wavelength region as an optical filter. Light absorption is obtained. It is more preferable that the optical filter using the absorption type glass includes an absorption layer that satisfies the requirements of (4), (5) ′, and (6).
- the reflective layer is often composed of a dielectric multilayer film in which a low refractive index dielectric film (low dielectric film) and a high refractive index dielectric film (high dielectric film) are alternately laminated.
- the low refractive index and the high refractive index mean having a low refractive index and a high refractive index with respect to the refractive index of the adjacent layer.
- the high dielectric film preferably has a refractive index of 1.6 or more, more preferably 2.2 to 2.5.
- the high dielectric film material include Ta 2 O 5 , TiO 2 , and Nb 2 O 5 . Of these, TiO 2 is preferable from the viewpoint of film formability, reproducibility in refractive index, and stability.
- the low dielectric film preferably has a refractive index of less than 1.6, more preferably 1.45 or more and less than 1.55, and even more preferably 1.45 to 1.47.
- the low dielectric film material include SiO 2 and SiO x N y . From the viewpoint of reproducibility, stability, economical efficiency, etc. in film formability, SiO 2 is preferable.
- the reflection layer expresses a function of controlling the transmission and shielding of light in a specific wavelength region by utilizing the interference of light, and the transmission / shielding characteristics depend on the incident angle.
- the wavelength of light shielded by reflection is shorter for light incident obliquely than for light incident vertically (incidence angle 0 °).
- the dielectric multilayer film constituting the reflective layer preferably satisfies the following requirement (7).
- the average transmittance of light with a wavelength of 420 to 695 nm is 90% or more, and the average transmittance of light with a wavelength of 750 to 1100 nm is 10% or less.
- the average transmittance of light having a wavelength of 420 to 695 nm is preferably 93% or more, more preferably 95% or more, and still more preferably 97% or more.
- the average transmittance of light having a wavelength of 750 to 1100 nm is preferably 7% or less, more preferably 5% or less, and further preferably 3% or less. If the reflective layer satisfies the requirement (7), the filter can easily obtain spectral characteristics that satisfy the requirements (1) to (3).
- the reflective layer preferably further satisfies the requirement (8).
- the average transmittance of light having a wavelength of 350 to 400 nm is 10% or less.
- the average transmittance of light having a wavelength of 350 to 400 nm is preferably 7% or less, more preferably 5% or less, and further preferably 3% or less.
- the reflection layer has a sharp change in transmittance in the boundary wavelength region between the transmitted light wavelength and the light shielding wavelength.
- the dielectric multilayer film constituting the reflective layer is preferably 15 layers or more, more preferably 25 layers or more, and further preferably 30 layers or more as the total number of laminated low refractive index films and high refractive index films. .
- the dielectric multilayer film is preferably 100 layers or less, more preferably 75 layers or less, and even more preferably 60 layers or less.
- the thinner one is preferable from the viewpoint of reducing the thickness of the optical filter after satisfying the preferable number of stacked layers.
- the film thickness of such a dielectric multilayer film is preferably 2 to 10 ⁇ m, depending on the selective wavelength shielding characteristics.
- a vacuum film forming process such as a CVD method, a sputtering method, or a vacuum deposition method, or a wet film forming process such as a spray method or a dip method can be used.
- the reflective layer may be a single layer (a group of dielectric multilayer films) having predetermined reflection characteristics, or a plurality of layers may have predetermined reflection characteristics.
- a plurality of layers may have predetermined reflection characteristics.
- it may be provided on one side of the transparent substrate, or may be provided on both sides of the transparent substrate.
- the transmittance in a specific wavelength region that the transmittance is, for example, 90% or more means that the transmittance is not less than 90% in the entire wavelength region, and similarly, the transmittance is, for example, 2 % Or less means that the transmittance does not exceed 2% in the entire wavelength region.
- the antireflection layer examples include a dielectric multilayer film, an intermediate refractive index medium, and a moth-eye structure in which the refractive index gradually changes.
- a dielectric multilayer film is preferable from the viewpoints of optical efficiency and productivity.
- the dielectric multilayer film used for the antireflection layer is obtained by alternately laminating a low refractive index film and a high refractive index film in the same manner as the dielectric multilayer film used for the reflection layer.
- the configuration of the present filter is not particularly limited except that it has an absorption layer and a reflection layer, and other components can be added.
- other components include inorganic fine particles that control the transmission and absorption of light in a specific wavelength region.
- Specific examples of the inorganic fine particles include ITO (Indium Tin Oxides), ATO (Antimony-doped Tin Oxides), cesium tungstate, lanthanum boride and the like.
- ITO fine particles and cesium tungstate fine particles have high visible light transmittance and a wide range of light absorptivity including an infrared wavelength region exceeding 1200 nm. Therefore, when such infrared light shielding properties are required. preferable.
- this filter can be used even if it sticks directly to the solid-state image sensor, imaging lens, etc. of an imaging device through an adhesive layer.
- the NIR filter of the present invention is suitably used in a solid-state imaging device such as a digital still camera, and is disposed, for example, between an imaging lens and a solid-state imaging device.
- the imaging device 20 of the present embodiment includes a solid-state imaging device 21, a near-infrared cut filter 22 of the present invention, an imaging lens 23, and a casing 24 that houses these.
- the imaging lens 23 is fixed by a lens unit 25 further provided inside the housing 24.
- the solid-state imaging device 21 and the imaging lens 23 are disposed along the optical axis x.
- the imaging lens 23 is an electronic component that converts the light that has passed through the imaging lens 23 into an electrical signal. Specifically, a CCD, a CMOS, or the like is used.
- the near-infrared cut filter shown to FIG. 1E is used as the near-infrared cut filter 22, and the reflective layer 12 side is arrange
- the light incident through the imaging lens 23 is received by the solid-state imaging device 21 through the near-infrared cut filter 22, and the received light is electrically converted by the solid-state imaging device 21. It is converted into a signal and output as an image signal.
- the near-infrared cut line filter 22 an optical filter that has excellent oblique incidence characteristics and exhibits spectral characteristics that are very close to the specific visibility curve, particularly on the long wavelength side, is used. A remarkably excellent high quality photographed image can be obtained.
- the near-infrared cut filter 22 is disposed between the imaging lens 23 and the solid-state image sensor 21, but the arrangement position is particularly limited as long as it is the front surface of the solid-state image sensor 21.
- the imaging lens 23 is composed of only one lens, but a combination of a plurality of lenses may be used.
- Examples 1 to 5 and 9 are examples of the present invention, and examples 6 to 8 are comparative examples.
- Example 1 A TiO 2 film, which is a high refractive index film, and an SiO 2 film, which is a low refractive index film, are alternately deposited on a 0.3 mm thick glass (non-alkali glass; manufactured by Asahi Glass Co., Ltd., product name: AN100) by vapor deposition.
- a reflective layer composed of 52 dielectric multilayer films was formed. The configuration of the reflective layer is simulated by using the number of dielectric multilayer films, the thickness of the TiO 2 film, and the thickness of the SiO 2 film as parameters. In the spectral transmittance curve at an incident angle of 0 °, light having a wavelength of 350 to 400 nm is simulated.
- the transmittance of light having a wavelength of 420 to 695 nm is determined to be 90% or more, and the transmittance of light having a wavelength of 750 to 1100 nm is determined to be 10% or less.
- FIG. 3 shows spectral transmittance curves (incidence angles of 0 ° and 30 °) of the reflective layer produced based on the above design. Further, 1- [3- (trimethoxysilyl) propyl] urea as a silane coupling agent was added to an 18% by mass cyclohexanone solution of a polyester resin (trade name: OKP850; refractive index: 1.64, manufactured by Osaka Gas Chemical Co., Ltd.).
- an NIR absorbing dye (compound F11-7) is added to this resin solution at a ratio of 9% by mass with respect to the mass of the polyester resin, and dissolved to prepare a coating solution for forming an absorption layer. did.
- This coating solution is applied to the surface opposite to the reflective layer forming surface of the glass substrate on which the reflective layer is formed, by spin coating, and at atmospheric pressure at 90 ° C. for 5 minutes and then at 150 ° C. for 1 hour. By heating, an absorption layer having a thickness of 1 ⁇ m was formed.
- an antireflection layer was formed by alternately laminating TiO 2 films and SiO 2 films on the surface of the absorption layer by vapor deposition as in the case of the reflection layer to obtain a near-infrared cut filter. Also construction of the antireflection layer stack number of the dielectric multilayer film, the thickness of the TiO 2 film having a film thickness and a SiO 2 film as the parameter was determined by simulating to have desired optical characteristics.
- Example 2 The type and / or addition amount of the NIR absorbing dye added to the coating liquid for forming the absorbing layer is changed as shown in Table 3. Further, for Examples 5 and 6, in addition to the NIR absorbing dye, the UV absorbing dye A NIR filter was produced in the same manner as in Example 1 except that was added in the ratio shown in Table 3.
- the glass substrate is a fluorophosphate glass (Asahi Glass Co., Ltd., trade name: NF-50T, 0.25 mm thickness) substrate, transparent resin, NIR absorbing dye, and UV absorption used for the coating liquid for forming the absorption layer
- a NIR filter was produced in the same manner as in Example 1 except that the type and / or addition amount of the dye were as shown in Table 3.
- the coating liquid for forming the absorption layer prepared in each of the above examples was applied onto a glass substrate by a spin coating method, and the atmospheric pressure was 90 ° C. for 5 minutes, and then 150 ° C. An absorption layer having a thickness of 1 ⁇ m was formed by heating for 1 hour.
- Spectral transmittance curves of each of the formed absorption layers were measured using an ultraviolet-visible spectrophotometer (manufactured by Hitachi High-Technologies Corporation, model name: U-4100) with the atmosphere as the background. Spectral characteristics were calculated. The results are also shown in Table 3.
- the spectral transmittance curves (incidence angles 0 ° and 30 °) of the NIR filters obtained in Examples 1 to 9 were measured using the above-described ultraviolet-visible spectrophotometer.
- the obtained spectral transmittance curve was normalized with the maximum transmittance at a wavelength of 450 to 650 nm, and each spectral characteristic was calculated. The results are shown in Table 4.
- the normalized spectral transmittance curve of Example 4 is shown in FIG.
- the near-infrared cut filters of Examples 1 to 5 and 9 have improved incident angle dependency, and the transmittance in the long wavelength region of the visible wavelength region is very high in the relative luminous efficiency curve. It ’s close. Therefore, the spectral sensitivity of the solid-state imaging device using this near-infrared cut line filter is very close to the normal human visual sensitivity, and good color reproducibility can be obtained.
- the oblique incidence characteristics are good, but the red (R) transmittance is high with respect to the green (G) transmittance, and the deviation from the specific luminous efficiency curve is large and good. Reproducibility cannot be obtained.
- Example 8 the oblique incidence characteristic is good and the transmittance (R) / (G) of red for green is suppressed, but the wavelength ⁇ IR T (80) indicating the transmittance of 80% and 20% are obtained.
- wavelength ⁇ IR T (20) is the spectral luminous efficiency curve (respectively wavelength lambda T (80) and the wavelength lambda T (20)) shown located on the shorter wavelength side than can not be obtained good color reproducibility.
- the glass substrate with an absorption layer provided with an absorption layer containing a squarylium compound in a polyester resin or polyimide resin has a high dye residual rate even after heating at 160 ° C. for 3 hours. Therefore, the NIR filter of the above embodiment can maintain the initial spectral transmittance even after the heating process, that is, the effect of suppressing the change of the spectral transmittance can be obtained.
- the near-infrared cut filter of the present invention has a spectral characteristic that is very close to normal human visibility and has a low incident angle dependency, and is useful for an imaging device that requires high color reproducibility. It is.
- SYMBOLS 11 Absorbing layer, 12 ... Reflective layer, 13 ... Transparent base material, 14 ... Antireflection layer, 20 ... Solid-state imaging device, 21 ... Solid-state image sensor, 22 ... NIR filter, 23 ... Imaging lens, 24 ... Housing.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Optical Filters (AREA)
- Solid State Image Pick-Up Elements (AREA)
- Laminated Bodies (AREA)
Abstract
Description
しかしながら、このフィルタにおいて、反射層を構成する誘電体多層膜は、光の入射角によって各膜の光学膜厚が異なるため、分光特性に入射角依存性があり、入射角によって色再現性が異なってくるという問題がある。
したがって、本発明は、特に長波長側で比視感度曲線に近い分光特性を示し、かつ入射角依存性が少なく斜入射特性に優れる近赤外線カットフィルタ、およびそのようなフィルタを用いた色再現性に優れる撮像装置の提供を目的とする。
(1)入射角0°の分光透過率曲線において、620~750nmの波長領域の平均透過率(R)が20%以下であり、495~570nmの波長領域の平均透過率(G)が90%以上であり、かつ前記平均透過率の比(R)/(G)が0.20以下である。
(2)入射角0°の分光透過率曲線における600~725nmの波長領域の透過率の積分値T0(600-725)と、入射角30°の分光透過率曲線における600~725nmの波長領域の透過率の積分値T30(600-725)の差|T0(600-725)-T30(600-725)|が3%・nm以下である。
(3)450~650nmの波長領域の最大透過率で規格化した入射角0°の分光透過率曲線において、550~750nmの波長領域に透過率が80%となる波長λIRT(80)、50%となる波長λIRT(50)、および20%となる波長λIRT(20)を有し、かつ前記各波長λIRT(80)、λIRT(50)およびλIRT(20)が、それぞれ次式(a)、(b)および(c)を満たしている。
0≦λIRT(80)-λT(80)≦30nm …(a)
0≦λIRT(50)-λT(50)≦35nm …(b)
0≦λIRT(20)-λT(20)≦37nm …(c)
(式中、λT(80)、λT(50)およびλT(20)は比視感度曲線において比視感度がそれぞれ0.8、0.5および0.2を示す長波長側の波長である)。
また、本発明の他の態様に係る撮像装置は、上記近赤外線カットフィルタを備えたことを特徴とする。
本発明の一実施形態のNIRフィルタ(以下、「本フィルタ」という)は、吸収層と反射層を有する。
吸収層と反射層は本フィルタの中にそれぞれ1層有してもよく、一方を2層以上有してもよく、両方を2層以上有してもよい。2層以上有する場合、各層は同じ構成でも異なってもよい。一例を挙げれば、吸収層を2層有する場合、一方の層を、後述するような近赤外線吸収色素を含む樹脂からなる近赤外線吸収層とし、もう一方の層を、後述するような紫外線吸収色素を含む樹脂からなる紫外線吸収層としてもよい。
また、本フィルタは、透明基材をさらに有してもよい。この場合、吸収層と反射層は、透明基材の同一主面上に有してもよく、異なる主面上に有してもよい。吸収層と反射層を同一主面上に有する場合、これらの積層順は特に限定されない。
本フィルタは、さらに反射防止層等の他の機能層を有してもよい。
図1Bは、透明基材13の一方の主面に吸収層11を備え、透明基材13の他方の主面上に反射層12を備える構成例である。
なお、「透明基材13の一方の主面に、吸収層11、反射層12等の他の層を備える」とは、透明基材13に接触して他の層が備わる場合に限らず、透明基材13と他の層との間に、別の機能層が備わっている場合も含み、以下の構成も同様である。
同様に、図1Bにおいて、透明基材13上に近赤外線吸収層を有し、近赤外線吸収層上に紫外線吸収層を有する構成でもよく、透明基材13上に紫外線吸収層を有し、紫外線吸収層上に近赤外線吸収層を有する構成でもよい。
図1Dは、透明基材11の両主面に吸収層11aおよび11bを備え、さらに吸収層11aおよび11bの主面上に、反射層12aおよび12bを備えた構成例である。
(1)入射角0°の分光透過率曲線において、波長620~750nmの光の平均透過率(R)が20%以下であり、波長495~570nmの光の平均透過率(G)が90%以上であり、かつ前記平均透過率の比(R)/(G)が0.2以下である。
(2)入射角0°の分光透過率曲線における波長600~725nmの光の透過率の積分値T0(600-725)と、入射角30°の分光透過率曲線における波長600~725nmの光の透過率の積分値T30(600-725)の差|T0(600-725)-T30(600-725)|が3%・nm以下である。
(3)波長450~650nmの光の最大透過率で規格化した入射角0°の分光透過率曲線(以下、「入射角0°の規格化分光透過率曲線」ともいう)において、波長550~750nmで、透過率が80%となる波長λIRT(80)、50%となる波長λIRT(50)、および20%となる波長λIRT(20)を有し、かつ前記各波長λIRT(80)、λIRT(50)およびλIRT(20)が、それぞれ次式(a)、(b)および(c)を満たしている。
0≦λIRT(80)-λT(80)≦30nm …(a)
0≦λIRT(50)-λT(50)≦35nm …(b)
0≦λIRT(20)-λT(20)≦37nm …(c)
(式中、λT(80)、λT(50)およびλT(20)は比視感度曲線において比視感度がそれぞれ0.8、0.5および0.2を示す長波長側の波長である)
要件(2)を満たすことで、波長600~725nmの光の入射角依存性を低くできる。その結果、入射角による色再現性の異なりを抑制できる。
0≦λIRT(80)-λT(80)≦25nm
0≦λIRT(50)-λT(50)≦32nm
0≦λIRT(20)-λT(20)≦35nm
λIRT(80)-λT(80)、λIRT(50)-λT(50)およびλIRT(20)-λT(20)は、いずれもその値が小さいほど(ただし、0以上)、長波長側で人の視感度により近い分光特性を備えることができ、長波長側の色再現性の精度を高めることができる。
λIRT(80)-λT(80)、λIRT(50)-λT(50)およびλIRT(20)-λT(20)がそれぞれ0未満、すなわち、NIRフィルタの分光透過率が比視感度曲線の内側(比視感度曲線よりも短波長側)に入る場合、赤色が削られる形となり良好な色再現性が得られない。そのため、本フィルタは、比視感度曲線よりも短波長側に入らない程度に、比視感度曲線に近づけた規格化分光透過率曲線を実現できる。
上記λIRT(80)-λT(80)、λIRT(50)-λT(50)およびλIRT(20)-λT(20)は、その総和が、0~102nmである。なお、分光特性を人の視感度により近づける観点から、該総和は、0~92nmが好ましく、0~80nmがより好ましい。また、(λIRT(80)-λT(80))/(λIRT(50)-λT(50))≦1.5、(λIRT(20)-λT(20))/(λIRT(50)-λT(50))≦2.0であると、分光特性を人の視感度により一層近づけることができ、さらに好ましい。
(9)入射角0°の分光透過率曲線において、波長750~850nmの光の平均透過率が0.2%以下である。
該波長領域の平均透過率が0.2%以下であれば、人間の目では感度が無いものの、固体撮像素子では感度を有する近赤外光を大きく遮断できるので、コントラストの高い画像が得られやすい。また、波長750~850nmの光の平均透過率は、0.15%以下が好ましく、0.1%以下がより好ましい。
[透明基材]
透明基材の形状は特に限定されず、ブロック状、板状、フィルム状いずれでもよい。透明基材の厚さは、構成する材料にも依存するが、0.03~5mmが好ましく、薄型化の点から、0.05~1mmがより好ましい。
また、透明基材に使用できる結晶材料は、水晶、ニオブ酸リチウム、サファイヤ等の複屈折性結晶が挙げられる。
透明基材に使用されるCuOを含有するガラスの具体的な組成例を記載する。
吸収層は、近赤外線吸収材(A)と、透明樹脂(B)とを含有する層であり、典型的には、透明樹脂(B)中に近赤外線吸収材(A)が均一に分散した層である。吸収層は、さらに紫外線吸収材(U)を含有することが好ましい。
吸収層は、例えば、近赤外線吸収材(A)を含む層と、紫外線吸収材(U)を含む層を別の層として複数の吸収層を設けるようにしてもよい。
(近赤外線吸収色素(A))
近赤外線吸収色素(A)(以下、色素(A)ともいう)は、可視波長領域(450~600nm)の光を透過し、近赤外波長領域(700~1100nm)の光を吸収する能力を有すれば特に制限されない。色素は顔料、すなわち分子が凝集した状態でもよい。以下、近赤外線吸収色素を必要に応じて「NIR吸収色素」という。
R4およびR6は、それぞれ独立して、水素原子、ハロゲン原子、水酸基、炭素数1~6のアルキル基もしくはアルコキシ基、炭素数1~10のアシルオキシ基、または-NR7R8(R7およびR8は、それぞれ独立して、水素原子、炭素数1~20のアルキル基、または-C(=O)-R9(R9は、水素原子、置換基を有していてもよい炭素数1~20のアルキル基もしくは炭素数6~11のアリール基または、置換基を有していてもよく、炭素原子間に酸素原子を有していてもよい炭素数7~18のアルアリール基))を示す。
以下、複素環Aを単に環Aということもある。複素環B、Cについても同様である。
なお、化合物(F1)は、上記一般式(F1)で示される構造の共鳴構造を有する式(F1-1)で示される化合物(F1-1)を含む。
化合物(F13)として、式(F13-1)、式(F13-2)でそれぞれ示される化合物等が挙げられる。
R1およびR2は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数1~12のアルキル基もしくはアリル基、または炭素数6~11のアリール基もしくはアルアリール基を示す。R3およびR5は、それぞれ独立して、水素原子、ハロゲン原子、または、炭素数1~6のアルキル基もしくはアルコキシ基を示す。R4およびR6は、それぞれ独立して、水素原子、ハロゲン原子、水酸基、炭素数1~6のアルキル基もしくはアルコキシ基、炭素数1~10のアシルオキシ基、または-NR7R8(R7およびR8は、それぞれ独立して、水素原子、炭素数1~20のアルキル基、または-C(=O)-R9(R9は、水素原子、置換基を有していてもよい炭素数1~20のアルキル基もしくは炭素数6~11のアリール基または、置換基を有していてもよく、炭素原子間に酸素原子を有していてもよい炭素数7~18のアルアリール基))を示す。
化合物(F6)として、式(F6-1)、式(F6-2)で示される化合物等が挙げられる。
色素(A)は、好ましくは色素(A1)の1種または2種以上を含有する。なお、色素(A)は、色素(A1)以外に、必要に応じてその他のNIR吸収色素を含有してもよい。色素(A)として複数のNIR吸収色素を用いる場合も、これらを透明樹脂(B)に分散して作製した樹脂膜に対して測定される波長400~900nmの光の吸収スペクトルにおいて、波長650~900nm内に吸収極大波長を発現するようにNIR吸収色素を組合せて用いることが好ましく、波長650~750nm内に吸収極大波長を発現するよう用いることがより好ましい。さらには、該吸収スペクトルにおいて、可視光の吸収が少なく、λmaxの吸収ピークからみて可視光側の傾きが急峻であり、長波長側(吸収ピークからみて可視光側とは反対側)では傾きは緩やかとなるように、NIR吸収色素を組合せて用いることが好ましい。
紫外線吸収色素(U)(以下、色素(U)ともいう。)は、波長430nm以下の光を吸収する化合物である。色素(U)としては、下記(iv-1)および(iv-2)の要件を満たす化合物が好ましい。
(iv-2)ジクロロメタンに溶解して測定される分光透過率曲線において、前記吸収極大波長λmax(UV)における透過率を10%としたとき、前記吸収極大波長λmax(UV)より長波長で透過率が90%となる波長λL90と、前記吸収極大波長λmax(UV)より長波長で透過率が50%となる波長λL50との差λL90-λL50が13nm以下である。
(iv-2)の要件を満たす色素(U)を使用すれば、透明樹脂中に溶解または分散して近赤外線吸収層として得られる実施形態のNIRフィルタにおいて、色素(U)による吸収極大波長の長波長側での透過率が50%となる波長と透過率が90%となる波長の差を小さくできる。すなわち、該波長領域において、分光透過率曲線の変化を急峻にできる。
色素(U)の吸収スペクトルにおける吸収極大波長λmax(UV)を「色素(U)のλmax(UV)」という。
色素(U)を、ジクロロメタンに溶解して測定される分光透過率曲線を「色素(U)の分光透過率曲線」という。
色素(U)の分光透過率曲線において、色素(U)のλmax(UV)における透過率が10%となる量で含有したときに、色素(U)のλmax(UV)より長波長で透過率が90%となる波長を「λL90」といい、色素(U)のλmax(UV)より長波長で透過率が50%となる波長を「λL50」という。
色素(U)の樹脂中吸収スペクトルにおける吸収極大波長λmax・P(UV)を「色素(U)のλmax・P(UV)」という。
色素(U)を、透明樹脂に溶解して作製される吸収層の測定される分光透過率曲線を「色素(U)の樹脂中分光透過率曲線」という。
色素(U)の樹脂中分光透過率曲線において、色素(U)のλmax・P(UV)における透過率が10%となる量で含有したときに、色素(U)のλmax・P(UV)より長波長で透過率が90%となる波長を「λP90」といい、色素(U)のλmax・P(UV)より長波長で透過率が50%となる波長を「λP50」という。
また、色素(U)のλL90とλL50の差(λL90-λL50)は、12nm以下が好ましく、11nm以下がより好ましく、9nm以下がより一層好ましい。λL90-λL50がこの波長領域にあることで上述した効果が得られやすい。
-COOR30 …(n)
式(n)中、R30は、飽和もしくは不飽和の環構造を含んでもよく、分岐を有してもよい炭素数1~20の炭化水素基を示す。具体的には、直鎖状または分枝鎖状のアルキル基、アルケニル基、飽和環状炭化水素基、アリール基、アルアリール基等が挙げられる。
色素(U1)としては、特に、下記一般式(M)で示されるメロシアニン系色素が好ましい。
Q1が無置換のアルキル基である場合、そのアルキル基は直鎖状でも、分岐状でもよく、その炭素数は1~6がより好ましい。
Q2およびQ3は、少なくとも一方が、アルキル基が好ましく、いずれもアルキル基がより好ましい。Q2またはQ3がアルキル基でない場合は、水素原子がより好ましい。Q2およびQ3は、いずれも炭素数1~6のアルキル基が特に好ましい。
Q4およびQ5は、少なくとも一方が、水素原子が好ましく、いずれも水素原子がより好ましい。Q4またはQ5が水素原子でない場合、炭素数1~6のアルキル基が好ましい。
透明樹脂(B)は、屈折率が、1.45以上が好ましい。屈折率は1.5以上がより好ましく、1.6以上が特に好ましい。透明樹脂(B)の屈折率の上限は特にないが、入手のしやすさ等から1.72程度が好ましい。本明細書において屈折率とは、特に断らない限り、20℃において波長589nmにおける屈折率をいう。
吸収層には、上述の色素(A)および色素(U)の他にさらに、本発明の効果を損なわない範囲で、この種の吸収層が通常含有する各種任意成分を含有してもよい。任意成分としては、例えば、色調補正色素、レベリング剤、帯電防止剤、熱安定剤、光安定剤、酸化防止剤、分散剤、難燃剤、滑剤、可塑剤等が挙げられる。
(吸収層)
吸収層は、例えば、色素(A)と、色素(U)と、透明樹脂(B)または透明樹脂(B)の原料成分と、必要に応じて配合される各成分とを、溶媒に溶解または分散させて塗工液を調製し、これを透明基材に塗工し乾燥させ、さらに必要に応じて硬化させることにより形成できる。
(4)500~900nmの波長領域の吸収スペクトルにおいて、波長650~900nmに吸収極大波長を有する。また、波長650~750nmに吸収極大波長を有することがより好ましく、波長680~720nmに吸収極大波長を有することがさらに好ましい。
(5)入射角0°の分光透過率曲線において、波長600~800nmに少なくとも2つ、透過率が10%となる波長を有し、該透過率が10%となる波長のうち、最も長波長側の波長IR10(L)と最も短波長側の波長IR10(S)の差、IR10(L)-IR10(S)が30~70nmである。この差は、好ましくは35~70nmであり、より好ましくは35~65nmである。
上記差が30nm未満であれば、反射層による入射角による分光透過率曲線の変化により、本フィルタにおいても入射角による分光透過率曲線の変化が発生するおそれがある。一方、上記差が70nm超であれば、吸収スペクトルがブロードになり、本フィルタの分光透過率曲線が、比視感度曲線よりも大きくずれてしまい、赤味の色再現性が高い精度で得られなくなるおそれがある。
(5)´入射角0°の分光透過率曲線において、波長600~800nmに少なくとも2つ、透過率が1%となる波長を有し、前記透過率が1%となる波長のうち、最も長波長側の波長IR1(L)と最も短波長側の波長IR1(S)の差、IR1(L)-IR1(S)が25~50nmである。この差は、好ましくは30~45nmであり、より好ましくは33~40nmである。
上記差が25nm未満であれば、反射層による入射角による分光透過率曲線の変化により、本フィルタにおいても入射角による分光透過率曲線の変化が発生するおそれがある。一方、上記差が50nm超であれば、吸収スペクトルがブロードになり、本フィルタの分光透過率曲線が、比視感度曲線よりも大きくずれてしまい、赤味の色再現性が高い精度で得られなくなるおそれがある。
(6)入射角0°の分光透過率曲線において、波長620~700nmの光の平均透過率T(620-700)と、波長495~570nmの光の平均透過率T(495-570)の比T(620-700)/T(495-570)が0.35以下である。比T(620-700)/T(495-570)は、好ましくは0.30以下であり、より好ましくは0.28以下である。
吸収層が上記(4)、(5)、(6)の要件を満たせば、本フィルタは、(1)~(3)の要件を満たす分光特性が容易に得られる。
反射層は、低屈折率の誘電体膜(低誘電体膜)と高屈折率の誘電体膜(高誘電体膜)とを交互に積層した誘電体多層膜から構成される場合が多い。ここで、低屈折率と高屈折率とは、隣接する層の屈折率に対して低い屈折率と高い屈折率を有することを意味する。高誘電体膜は、好ましくは、屈折率が1.6以上であり、より好ましくは2.2~2.5である。高誘電体膜材料としては、例えばTa2O5、TiO2、Nb2O5が挙げられる。このうち、成膜性、屈折率等における再現性、安定性等の点から、TiO2が好ましい。一方、低誘電体膜は、好ましくは、屈折率1.6未満であり、より好ましくは1.45以上1.55未満であり、より一層好ましくは1.45~1.47である。低誘電体膜材料としては、例えばSiO2、SiOxNy等が挙げられる。成膜性における再現性、安定性、経済性等の点から、SiO2が好ましい。
(7)入射角0°の分光透過率曲線において、波長420~695nmの光の平均透過率が90%以上であり、かつ波長750~1100nmの光の平均透過率が10%以下である。波長420~695nmの光の平均透過率は、93%以上が好ましく、95%以上がより好ましく、97%以上がさらに好ましい。また、波長750~1100nmの光の平均透過率は、7%以下が好ましく、5%以下がより好ましく、3%以下がさらに好ましい。
反射層が(7)の要件を満たせば、本フィルタは、(1)~(3)の要件を満たす分光特性が容易に得られる。
(8)入射角0°の分光透過率曲線において、波長350~400nmの光の平均透過率が10%以下である。波長350~400nmの光の平均透過率は、7%以下が好ましく、5%以下がより好ましく、3%以下がさらに好ましい。
反射層が、(8)の要件を満たすことで、紫外波長領域の光に対してもカット性を備えたフィルタが得られる。また、本フィルタは、要件(7)を満たすと、要件(9)も満たされる。
反射防止層としては、誘電体多層膜や中間屈折率媒体、屈折率が漸次的に変化するモスアイ構造などが挙げられる。なかでも光学的効率、生産性の観点から誘電体多層膜の使用が好ましい。反射防止層に用いられる誘電体多層膜は、反射層に使用される誘電体多層膜と同様に低屈折率膜と高屈折率膜を交互に積層して得られる。
また、本フィルタは、撮像装置の固体撮像素子、撮像レンズ等に粘着剤層を介して直接貼着しても使用できる。
以下に図2を参照しながら、本発明の固体撮像装置20の一例を説明する。
本実施形態の撮像装置20は固体撮像素子21と、本発明の近赤外線カットフィルタ22と、撮像レンズ23と、これらを収容する筺体24とを有する。撮像レンズ23は、筐体24の内側にさらに設けられたレンズユニット25により固定されている。固体撮像素子21と、撮像レンズ23は、光軸xに沿って配置されている。撮像レンズ23は、固体撮像素子21は、撮像レンズ23を通過した光を電気信号に変換する電子部品であり、具体的にはCCDやCMOS等が使用される。
そして、図面の例では、近赤外線カットフィルタ22として、図1Eに示す近赤外線カットフィルタが使用され、その反射層12側を固体撮像素子21側に向けて配置されている。
厚さ0.3mmのガラス(無アルカリガラス;旭硝子(株)製、商品名:AN100)基板に蒸着法により、高屈折率膜であるTiO2膜と低屈折率膜であるSiO2膜を交互に積層して、誘電体多層膜52層からなる反射層を形成した。反射層の構成は、誘電体多層膜の積層数、TiO2膜の膜厚およびSiO2膜の膜厚をパラメータとしてシミュレーションし、入射角0°の分光透過率曲線において、波長350~400nmの光の透過率が10%以下、波長420~695nmの光の透過率が90%以上、波長750~1100nmの光の透過率が10%以下となるように求めたものである。図3に、上記設計をもとに作製した反射層の分光透過率曲線(入射角0°および30°)を示す。
また、ポリエステル樹脂(大阪ガスケミカル(株)製 商品名:OKP850;屈折率1.64)の18質量%シクロヘキサノン溶液に、シランカップリング剤として1-[3-(トリメトキシシリル)プロピル]ウレアをポリエステル樹脂の質量に対して3質量%となる割合で添加し溶解させた。さらに、この樹脂溶液に、NIR吸収色素(化合物F11-7)を、ポリエステル樹脂の質量に対して9質量%となる割合で添加し溶解させて、吸収層を形成するための塗工液を調製した。
この塗工液を、反射層を形成した上記ガラス基板の反射層形成面とは反対側の面に、スピンコート法により塗布し、大気圧下、90℃で5分間、次いで150℃で1時間加熱して、厚さ1μmの吸収層を形成した。
この後、吸収層の表面に、反射層と同様、蒸着法により、TiO2膜とSiO2膜を交互に積層して反射防止層を形成し、近赤外線カットフィルタを得た。
なお、反射防止層の構成もまた、誘電体多層膜の積層数、TiO2膜の膜厚およびSiO2膜の膜厚をパラメータとして、所望の光学特性を有するようにシミュレーションして決定した。
吸収層を形成するための塗工液に添加するNIR吸収色素の種類および/または添加量を表3に示すように変え、さらに例5、例6については、NIR吸収色素に加え、UV吸収色素を表3に示す割合で添加した以外は例1と同様にして、NIRフィルタを製造した。
ガラス基板をフツリン酸ガラス(旭硝子(株)製、商品名:NF-50T、0.25mm厚)基板とし、吸収層を形成するための塗工液に使用する透明樹脂、NIR吸収色素およびUV吸収色素の種類および/または添加量を、表3に示すようにした以外は例1と同様にして、NIRフィルタを製造した。
上記NIRフィルタの製造とは別に、ガラス基板上に、上記各例で調製した吸収層形成用の塗工液をスピンコート法により塗布し、大気圧下、90℃で5分間、次いで150℃で1時間加熱して、厚さ1μmの吸収層を形成した。
形成された各吸収層の分光透過率曲線を、紫外可視分光光度計((株)日立ハイテクノロジーズ製、型名:U-4100)を用いて大気をバックグラウンドとして測定し、その測定結果から各分光特性を算出した。結果を表3に併せ示す。
例1~9で得られたNIRフィルタの分光透過率曲線(入射角0°および30°)を、上記の紫外可視分光光度計を用いて測定した。得られた分光透過率曲線を波長450~650nmにおける最大透過率で規格化し、各分光特性を算出した。結果を表4に示す。また、例4の規格化分光透過率曲線を図4に示す。
一方、例6、7は、斜入射特性は良好であるが、緑色(G)の透過率に対して赤色(R)の透過率が高く、また比視感度曲線との乖離が大きく良好な色再現性が得られない。例8では、斜入射特性は良好で、かつ、緑色に対する赤色の透過率(R)/(G)は抑えられているものの、透過率が80%を示す波長λIRT(80)と20%を示す波長λIRT(20)が比視感度曲線(それぞれ、波長λT(80)と波長λT(20))よりも短波長側にあり、良好な色再現性が得られない。
耐熱性を評価するため、ガラス基板(AN100)上に、式(F11-7)、(F11-5)および(F11-2)で示されるスクアリリウム系化合物を、ポリエステル樹脂(OKP850)およびポリイミド樹脂(C3630)に含有した吸収層を備えた、吸収層付ガラス基板を準備した。該吸収層付ガラス基板を160℃で3時間加熱し、含有する色素の最大吸収波長における吸光係数を測定し、次式より色素残存率(%)を算出した。結果を表5に示す。
色素残存率(%)=(加熱後の最大吸収波長における吸光係数)/(初期の最大吸収波長における吸光係数)×100
Claims (13)
- 吸収層と、反射層とを備え、下記(1)~(3)の要件を満たすことを特徴とする近赤外線カットフィルタ。
(1)入射角0°の分光透過率曲線において、波長620~750nmの光の平均透過率(R)が20%以下であり、波長495~570nmの光の平均透過率(G)が90%以上であり、かつ前記平均透過率の比(R)/(G)が0.20以下である。
(2)入射角0°の分光透過率曲線における波長600~725nmの光の透過率の積分値T0(600-725)と、入射角30°の分光透過率曲線における波長600~725nmの光の透過率の積分値T30(600-725)の差|T0(600-725)-T30(600-725)|が3%・nm以下である。
(3)波長450~650nmの光の最大透過率で規格化した入射角0°の分光透過率曲線において、波長550~750nmに透過率が80%となる波長λIRT(80)、50%となる波長λIRT(50)、および20%となる波長λIRT(20)を有し、かつ前記各波長λIRT(80)、λIRT(50)およびλIRT(20)が、それぞれ次式(a)、(b)および(c)を満たしている。
0≦λIRT(80)-λT(80)≦30nm …(a)
0≦λIRT(50)-λT(50)≦35nm …(b)
0≦λIRT(20)-λT(20)≦37nm …(c)
(式中、λT(80)、λT(50)およびλT(20)は比視感度曲線において比視感度がそれぞれ0.8、0.5および0.2を示す長波長側の波長である) - 前記吸収層は下記(4)~(6)の要件を満たす請求項1に記載の近赤外線カットフィルタ。
(4)波長500~900nmの光の吸収スペクトルにおいて、波長650~900nmに吸収極大波長を有する。
(5)入射角0°の分光透過率曲線において、波長600~800nmに少なくとも2つの透過率が10%となる波長を有し、前記透過率が10%となる波長のうち、最も長波長側の波長IR10(L)と最も短波長側の波長IR10(S)の差IR10(L)-IR10(S)が30~70nmである。
(6)入射角0°の分光透過率曲線において、波長620~700nmの光の平均透過率T(620-700)と、495~570nmの波長領域の平均透過率T(495-570)の比T(620-700)/T(495-570)が0.35以下である。 - 前記吸収層は下記(5)´の要件をさらに満たす請求項2に記載の近赤外線カットフィルタ。
(5)´入射角0°の分光透過率曲線において、波長600~800nmに少なくとも2つの透過率が1%となる波長を有し、前記透過率が1%となる波長のうち、最も長波長側の波長IR1(L)と最も短波長側の波長IR1(S)の差IR1(L)-IR1(S)が25~50nmである。 - 前記反射層は下記(7)の要件を満たす請求項1~3のいずれか1項に記載の近赤外線カットフィルタ。
(7)入射角0°の分光透過率曲線において、波長420~695nmの光の平均透過率が90%以上であり、かつ波長750~1100nmの光の平均透過率が10%以下である。 - 前記反射層は下記(8)の要件をさらに満たす請求項1~4のいずれか1項に記載の近赤外線カットフィルタ。
(8)入射角0°の分光透過率曲線において、波長350~400nmの光の平均透過率が10%以下である。 - 下記(9)の要件をさらに満たす請求項1~5のいずれか1項に記載の近赤外線カットフィルタ。
(9)入射角0°のの分光透過率曲線において、波長750~850nmの光の平均透過率が0.2%以下である。 - 透明基材と、該透明基材の主表面側に前記吸収層および前記反射層を備える請求項1~6のいずれか1項に記載の近赤外線カットフィルタ。
- 前記透明基材は、樹脂またはガラスを含む請求項1~7いずれか1項に記載の近赤外線カットフィルタ。
- 前記透明基材は、吸収型のガラスを含む請求項8に記載の近赤外線カットフィルタ。
- 前記吸収層は、シアニン系化合物、フタロシアニン系化合物、およびスクアリリウム系化合物から選ばれる少なくとも1種の近赤外線吸収材を含む請求項1~9のいずれか1項に記載の近赤外線カットフィルタ。
- 前記吸収層は、紫外線吸収材を含む請求項1~10のいずれか1項に記載の近赤外線カットフィルタ。
- 前記紫外線吸収材は、下記式(M)で表される化合物を含む請求項11に記載の近赤外線カットフィルタ。
Yは、Q6およびQ7で置換されたメチレン基または酸素原子(ここで、Q6およびQ7は、それぞれ独立に、水素原子、ハロゲン原子、または炭素数1~10のアルキル基もしくはアルコキシ基)を示し、
Q1は、置換基を有していてもよい炭素数1~12の1価の炭化水素基を示し、
Q2~Q5は、それぞれ独立に、水素原子、ハロゲン原子、または、炭素数1~10のアルキル基もしくはアルコキシ基を示し、
Zは、下記式(Z1)~(Z5)で表される2価の基を示す。
- 請求項1~12のいずれか1項に記載の近赤外線カットフィルタを備えたことを特徴とする撮像装置。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016545370A JP6119920B2 (ja) | 2015-01-14 | 2016-01-14 | 近赤外線カットフィルタおよび撮像装置 |
CN201680000786.4A CN106062592B (zh) | 2015-01-14 | 2016-01-14 | 近红外线截止滤波器和摄像装置 |
KR1020167020553A KR101913482B1 (ko) | 2015-01-14 | 2016-01-14 | 근적외선 커트 필터 및 촬상 장치 |
US15/279,700 US10365417B2 (en) | 2015-01-14 | 2016-09-29 | Near-infrared cut filter and imaging device |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015005383 | 2015-01-14 | ||
JP2015-005383 | 2015-01-14 | ||
JP2015-163264 | 2015-08-20 | ||
JP2015163264 | 2015-08-20 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/279,700 Continuation US10365417B2 (en) | 2015-01-14 | 2016-09-29 | Near-infrared cut filter and imaging device |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016114363A1 true WO2016114363A1 (ja) | 2016-07-21 |
Family
ID=56405903
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/051021 WO2016114363A1 (ja) | 2015-01-14 | 2016-01-14 | 近赤外線カットフィルタおよび撮像装置 |
Country Status (5)
Country | Link |
---|---|
US (1) | US10365417B2 (ja) |
JP (2) | JP6119920B2 (ja) |
KR (1) | KR101913482B1 (ja) |
CN (1) | CN106062592B (ja) |
WO (1) | WO2016114363A1 (ja) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170318758A1 (en) * | 2016-05-09 | 2017-11-09 | Kevin Beauregard | Ultraviolet Radiation Blocking Sheet |
JP2018120097A (ja) * | 2017-01-25 | 2018-08-02 | Jsr株式会社 | 光学フィルターおよびその用途 |
JP6435033B1 (ja) * | 2017-10-20 | 2018-12-05 | 日本板硝子株式会社 | 光学フィルタ |
WO2019069689A1 (ja) * | 2017-10-03 | 2019-04-11 | 日本板硝子株式会社 | 光学フィルタ及び撮像装置 |
WO2019150908A1 (ja) * | 2018-02-01 | 2019-08-08 | 富士フイルム株式会社 | 硬化性組成物、近赤外線吸収剤、膜、近赤外線カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ |
JP2019151708A (ja) * | 2018-03-01 | 2019-09-12 | 株式会社日本触媒 | 樹脂組成物および光学フィルター |
JP2020024450A (ja) * | 2019-10-24 | 2020-02-13 | 日本板硝子株式会社 | 光学フィルタ、カメラモジュール、及び情報端末 |
JP2020073983A (ja) * | 2019-10-24 | 2020-05-14 | 日本板硝子株式会社 | 光学フィルタ、カメラモジュール、及び情報端末 |
US11059977B2 (en) | 2016-02-02 | 2021-07-13 | AGC Inc. | Near-infrared-absorbing dye, optical filter, and imaging device |
JP2021140177A (ja) * | 2017-06-29 | 2021-09-16 | Agc株式会社 | 光学フィルタおよび撮像装置 |
WO2022154017A1 (ja) * | 2021-01-13 | 2022-07-21 | Hoya株式会社 | 近赤外線カットフィルタ及びそれを備える撮像装置 |
WO2023008291A1 (ja) * | 2021-07-30 | 2023-02-02 | Agc株式会社 | 光学フィルタ |
US11586108B2 (en) | 2017-09-19 | 2023-02-21 | Fujifilm Corporation | Pattern-forming composition, film, infrared cut filter, infrared transmitting filter, solid image pickup element, infrared sensor, and camera module |
US11640021B2 (en) | 2017-10-03 | 2023-05-02 | Nippon Sheet Glass Company, Limited | Optical filter and imaging apparatus |
WO2023157403A1 (ja) * | 2022-02-21 | 2023-08-24 | パナソニックIpマネジメント株式会社 | 光学フィルターおよび撮像装置 |
JP7415815B2 (ja) | 2020-06-22 | 2024-01-17 | Agc株式会社 | 光学フィルタ |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017094858A1 (ja) * | 2015-12-01 | 2017-06-08 | 旭硝子株式会社 | 光学フィルタおよび撮像装置 |
CN106169481B (zh) * | 2016-07-20 | 2019-04-05 | 武汉华星光电技术有限公司 | 柔性阵列基板及其制备方法、柔性显示装置 |
JP6959794B2 (ja) * | 2017-08-09 | 2021-11-05 | 株式会社日本触媒 | スクアリリウム化合物 |
JP7070555B2 (ja) * | 2017-09-11 | 2022-05-18 | Agc株式会社 | 光学フィルタおよび撮像装置 |
KR101931731B1 (ko) | 2017-09-28 | 2018-12-24 | 주식회사 엘엠에스 | 광학 물품 및 이를 포함하는 광학 필터 |
KR101892941B1 (ko) | 2017-09-28 | 2018-08-30 | (주)유티아이 | 광학 필터 및 그 제조방법 |
JP6273063B1 (ja) * | 2017-10-03 | 2018-01-31 | 日本板硝子株式会社 | 光学フィルタ及び撮像装置 |
US11531149B2 (en) * | 2017-12-07 | 2022-12-20 | Nippon Sheet Glass Company, Limited | Optical filter and imaging apparatus |
WO2019151348A1 (ja) * | 2018-02-05 | 2019-08-08 | Agc株式会社 | 光学フィルタおよび撮像装置 |
JP7279718B2 (ja) * | 2018-06-28 | 2023-05-23 | Agc株式会社 | 光学フィルタおよび情報取得装置 |
CN112689780A (zh) * | 2018-09-12 | 2021-04-20 | Agc株式会社 | 光学滤波器和摄像装置 |
JP7342944B2 (ja) * | 2019-04-03 | 2023-09-12 | Agc株式会社 | 光学フィルタおよび撮像装置 |
JP2021089357A (ja) | 2019-12-03 | 2021-06-10 | Hoya株式会社 | 近赤外線カットフィルタ及びそれを備える撮像装置 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000137172A (ja) * | 1998-10-29 | 2000-05-16 | Olympus Optical Co Ltd | 撮像装置 |
JP2001042230A (ja) * | 1999-07-27 | 2001-02-16 | Olympus Optical Co Ltd | 撮像光学系 |
WO2011158635A1 (ja) * | 2010-06-18 | 2011-12-22 | 株式会社大真空 | 赤外線カットフィルタ |
JP2012159658A (ja) * | 2011-01-31 | 2012-08-23 | Daishinku Corp | 光学フィルタモジュール、および光学フィルタシステム |
WO2014030628A1 (ja) * | 2012-08-23 | 2014-02-27 | 旭硝子株式会社 | 近赤外線カットフィルタおよび固体撮像装置 |
Family Cites Families (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5013022A (ja) | 1973-06-05 | 1975-02-10 | ||
US4333983A (en) * | 1980-04-25 | 1982-06-08 | Optical Coating Laboratory, Inc. | Optical article and method |
US5282084A (en) * | 1989-05-19 | 1994-01-25 | Minolta Camera Kabushiki Kaisha | Multi-layered coating for optical part comprising YF3 layer |
DE10057141A1 (de) | 2000-11-17 | 2002-05-23 | Few Chemicals Gmbh | UV- und blaulichtempfindliche Photosensibilitoren für die Photopolymerisation |
JP4169545B2 (ja) | 2002-07-05 | 2008-10-22 | Hoya株式会社 | 近赤外光吸収ガラス、近赤外光吸収素子、近赤外光吸収フィルターおよび近赤外光吸収ガラス成形体の製造方法 |
JP2004079608A (ja) * | 2002-08-12 | 2004-03-11 | Sanyo Electric Co Ltd | 固体撮像装置および固体撮像装置の製造方法 |
JP4595383B2 (ja) * | 2003-05-19 | 2010-12-08 | 住友化学株式会社 | 微粒αアルミナの製造法 |
JP2006106570A (ja) | 2004-10-08 | 2006-04-20 | Adl:Kk | 光吸収フィルター |
JP2006195373A (ja) * | 2005-01-17 | 2006-07-27 | Matsushita Electric Ind Co Ltd | 視感度補正近赤外カットフィルタ、並びに、それを用いた光学ローパスフィルタ及び視感度補正素子 |
DE602006011448D1 (de) * | 2005-03-28 | 2010-02-11 | Mitsubishi Eng Plastics Corp | Polycarbonatharzzusammensetzung und formprodukt zum schutz gegen heisse strahlung |
JP2006301489A (ja) | 2005-04-25 | 2006-11-02 | Nidec Copal Corp | 近赤外線カットフィルタ |
JP2008051985A (ja) | 2006-08-24 | 2008-03-06 | Nidec Copal Corp | 近赤外線吸収フィルタ |
JP5168917B2 (ja) | 2007-01-26 | 2013-03-27 | Jsr株式会社 | 近赤外線カットフィルターおよびその製造方法 |
JP4598102B2 (ja) * | 2008-05-28 | 2010-12-15 | 富士フイルム株式会社 | 撮像装置 |
JP5489669B2 (ja) | 2008-11-28 | 2014-05-14 | Jsr株式会社 | 近赤外線カットフィルターおよび近赤外線カットフィルターを用いた装置 |
KR101474351B1 (ko) | 2008-11-28 | 2014-12-18 | 제이에스알 가부시끼가이샤 | 근적외선 컷 필터 및, 이를 구비하는 고체 촬상 장치 및 카메라 모듈 |
JP5769918B2 (ja) | 2009-08-26 | 2015-08-26 | ソニー株式会社 | 光学素子、撮像光学系及び撮像装置 |
WO2011071052A1 (ja) * | 2009-12-07 | 2011-06-16 | 旭硝子株式会社 | 光学部材、近赤外線カットフィルタ、固体撮像素子、撮像装置用レンズ、およびそれらを用いた撮像・表示装置 |
JP5936299B2 (ja) | 2010-11-08 | 2016-06-22 | Jsr株式会社 | 近赤外線カットフィルター、およびそれを備える固体撮像素子ならびに固体撮像装置 |
JP5741283B2 (ja) * | 2010-12-10 | 2015-07-01 | 旭硝子株式会社 | 赤外光透過フィルタ及びこれを用いた撮像装置 |
JP5823119B2 (ja) | 2010-12-27 | 2015-11-25 | キヤノン電子株式会社 | 紫外赤外線カット用光学フィルタ |
JP5789373B2 (ja) | 2010-12-27 | 2015-10-07 | キヤノン電子株式会社 | 光学フィルタ |
JP2012137651A (ja) | 2010-12-27 | 2012-07-19 | Canon Electronics Inc | 光学フィルタ |
JP5819063B2 (ja) | 2010-12-27 | 2015-11-18 | キヤノン電子株式会社 | 光学フィルタ |
JP5759717B2 (ja) | 2010-12-27 | 2015-08-05 | キヤノン電子株式会社 | 監視カメラ用撮像光学系 |
JP2012137649A (ja) | 2010-12-27 | 2012-07-19 | Canon Electronics Inc | 光学フィルタ |
JP5693949B2 (ja) | 2010-12-27 | 2015-04-01 | キヤノン電子株式会社 | 光学フィルタ |
CN103608705B (zh) | 2011-06-06 | 2016-10-12 | 旭硝子株式会社 | 滤光片、固体摄像元件、摄像装置用透镜和摄像装置 |
JP6127974B2 (ja) * | 2011-09-15 | 2017-05-17 | Jsr株式会社 | 近赤外線カットフィルターおよび近赤外線カットフィルターを用いた装置 |
JP5741347B2 (ja) | 2011-09-21 | 2015-07-01 | 旭硝子株式会社 | 光学フィルタ及びこれを用いた撮像装置 |
CN105754367A (zh) | 2011-10-14 | 2016-07-13 | Jsr株式会社 | 固体摄影装置用滤光器及使用该滤光器的固体摄影装置及照相机模块 |
JP6017805B2 (ja) | 2012-03-13 | 2016-11-02 | 株式会社日本触媒 | 光選択透過フィルター、紫光吸収シート及び固体撮像素子 |
JP6256335B2 (ja) | 2012-06-25 | 2018-01-10 | Jsr株式会社 | 固体撮像素子用光学フィルターおよびその用途 |
JP6183041B2 (ja) | 2012-08-23 | 2017-08-23 | 旭硝子株式会社 | 近赤外線カットフィルタ |
JP6183048B2 (ja) | 2012-08-27 | 2017-08-23 | 旭硝子株式会社 | 光学フィルタおよび固体撮像装置 |
JP6317875B2 (ja) | 2012-09-06 | 2018-04-25 | 日本板硝子株式会社 | 赤外線カットフィルタ、撮像装置および赤外線カットフィルタの製造方法 |
JP6024339B2 (ja) | 2012-09-26 | 2016-11-16 | 旭硝子株式会社 | 撮像レンズおよび撮像装置 |
CN104838294B (zh) | 2012-12-06 | 2017-03-08 | 旭硝子株式会社 | 近红外线截止滤波器 |
JP2014126642A (ja) | 2012-12-26 | 2014-07-07 | Adeka Corp | 波長カットフィルタ |
JP2014191346A (ja) | 2013-03-28 | 2014-10-06 | Konica Minolta Inc | Irカットフィルターおよびそれを備えた撮像装置 |
KR101527821B1 (ko) | 2013-04-04 | 2015-06-16 | 주식회사 엘엠에스 | 근적외선 커트 필터 및 이를 포함하는 고체 촬상 장치 |
JP2014203044A (ja) * | 2013-04-09 | 2014-10-27 | 日本板硝子株式会社 | 赤外線カットフィルタおよび撮像装置 |
WO2014168189A1 (ja) | 2013-04-10 | 2014-10-16 | 旭硝子株式会社 | 赤外線遮蔽フィルタ |
WO2014192715A1 (ja) | 2013-05-29 | 2014-12-04 | Jsr株式会社 | 光学フィルターおよび前記フィルターを用いた装置 |
JP6380390B2 (ja) | 2013-05-29 | 2018-08-29 | Jsr株式会社 | 光学フィルターおよび前記フィルターを用いた装置 |
WO2015022892A1 (ja) | 2013-08-13 | 2015-02-19 | Jsr株式会社 | 光学フィルターおよび前記フィルターを用いた装置 |
WO2015034211A1 (ko) | 2013-09-06 | 2015-03-12 | 주식회사 엘엠에스 | 광학 필터 및 이를 포함하는 촬상 장치 |
WO2015034217A1 (ko) | 2013-09-06 | 2015-03-12 | 주식회사 엘엠에스 | 광학 필터 및 이를 포함하는 촬상 장치 |
KR101611807B1 (ko) | 2013-12-26 | 2016-04-11 | 아사히 가라스 가부시키가이샤 | 광학 필터 |
KR101453469B1 (ko) | 2014-02-12 | 2014-10-22 | 나우주 | 광학 필터 및 이를 포함하는 촬상 장치 |
-
2016
- 2016-01-14 WO PCT/JP2016/051021 patent/WO2016114363A1/ja active Application Filing
- 2016-01-14 CN CN201680000786.4A patent/CN106062592B/zh active Active
- 2016-01-14 JP JP2016545370A patent/JP6119920B2/ja active Active
- 2016-01-14 KR KR1020167020553A patent/KR101913482B1/ko active IP Right Grant
- 2016-09-29 US US15/279,700 patent/US10365417B2/en active Active
-
2017
- 2017-03-17 JP JP2017053386A patent/JP6168252B2/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000137172A (ja) * | 1998-10-29 | 2000-05-16 | Olympus Optical Co Ltd | 撮像装置 |
JP2001042230A (ja) * | 1999-07-27 | 2001-02-16 | Olympus Optical Co Ltd | 撮像光学系 |
WO2011158635A1 (ja) * | 2010-06-18 | 2011-12-22 | 株式会社大真空 | 赤外線カットフィルタ |
JP2012159658A (ja) * | 2011-01-31 | 2012-08-23 | Daishinku Corp | 光学フィルタモジュール、および光学フィルタシステム |
WO2014030628A1 (ja) * | 2012-08-23 | 2014-02-27 | 旭硝子株式会社 | 近赤外線カットフィルタおよび固体撮像装置 |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11059977B2 (en) | 2016-02-02 | 2021-07-13 | AGC Inc. | Near-infrared-absorbing dye, optical filter, and imaging device |
US20170318758A1 (en) * | 2016-05-09 | 2017-11-09 | Kevin Beauregard | Ultraviolet Radiation Blocking Sheet |
JP2018120097A (ja) * | 2017-01-25 | 2018-08-02 | Jsr株式会社 | 光学フィルターおよびその用途 |
JP2021140177A (ja) * | 2017-06-29 | 2021-09-16 | Agc株式会社 | 光学フィルタおよび撮像装置 |
US11586108B2 (en) | 2017-09-19 | 2023-02-21 | Fujifilm Corporation | Pattern-forming composition, film, infrared cut filter, infrared transmitting filter, solid image pickup element, infrared sensor, and camera module |
WO2019069689A1 (ja) * | 2017-10-03 | 2019-04-11 | 日本板硝子株式会社 | 光学フィルタ及び撮像装置 |
US11640021B2 (en) | 2017-10-03 | 2023-05-02 | Nippon Sheet Glass Company, Limited | Optical filter and imaging apparatus |
US11630252B2 (en) | 2017-10-03 | 2023-04-18 | Nippon Sheet Glass Company, Limited | Optical filter and imaging apparatus |
JP6435033B1 (ja) * | 2017-10-20 | 2018-12-05 | 日本板硝子株式会社 | 光学フィルタ |
JP2019028420A (ja) * | 2017-10-20 | 2019-02-21 | 日本板硝子株式会社 | 光学フィルタ |
JPWO2019150908A1 (ja) * | 2018-02-01 | 2021-02-04 | 富士フイルム株式会社 | 硬化性組成物、近赤外線吸収剤、膜、近赤外線カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ |
WO2019150908A1 (ja) * | 2018-02-01 | 2019-08-08 | 富士フイルム株式会社 | 硬化性組成物、近赤外線吸収剤、膜、近赤外線カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ |
US11886112B2 (en) | 2018-02-01 | 2024-01-30 | Fujifilm Corporation | Curable composition, near infrared absorber, film, near infrared cut filter, solid-state imaging element, image display device, and infrared sensor |
JP7128633B2 (ja) | 2018-03-01 | 2022-08-31 | 株式会社日本触媒 | 樹脂組成物および光学フィルター |
JP2019151708A (ja) * | 2018-03-01 | 2019-09-12 | 株式会社日本触媒 | 樹脂組成物および光学フィルター |
JP2020073983A (ja) * | 2019-10-24 | 2020-05-14 | 日本板硝子株式会社 | 光学フィルタ、カメラモジュール、及び情報端末 |
JP2020024450A (ja) * | 2019-10-24 | 2020-02-13 | 日本板硝子株式会社 | 光学フィルタ、カメラモジュール、及び情報端末 |
JP7415815B2 (ja) | 2020-06-22 | 2024-01-17 | Agc株式会社 | 光学フィルタ |
WO2022154017A1 (ja) * | 2021-01-13 | 2022-07-21 | Hoya株式会社 | 近赤外線カットフィルタ及びそれを備える撮像装置 |
WO2023008291A1 (ja) * | 2021-07-30 | 2023-02-02 | Agc株式会社 | 光学フィルタ |
WO2023157403A1 (ja) * | 2022-02-21 | 2023-08-24 | パナソニックIpマネジメント株式会社 | 光学フィルターおよび撮像装置 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2016114363A1 (ja) | 2017-04-27 |
US20170017024A1 (en) | 2017-01-19 |
CN106062592A (zh) | 2016-10-26 |
JP2017122934A (ja) | 2017-07-13 |
JP6119920B2 (ja) | 2017-04-26 |
KR20170054322A (ko) | 2017-05-17 |
JP6168252B2 (ja) | 2017-07-26 |
KR101913482B1 (ko) | 2018-10-30 |
CN106062592B (zh) | 2018-11-23 |
US10365417B2 (en) | 2019-07-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6168252B2 (ja) | 近赤外線カットフィルタおよび撮像装置 | |
US11693163B2 (en) | Optical filter and imaging device | |
US10310150B2 (en) | Near-infrared cut filter and solid-state imaging device | |
KR101832114B1 (ko) | 광학 필터 및 촬상 장치 | |
JP7468568B2 (ja) | 光学フィルタおよび撮像装置 | |
JP7222361B2 (ja) | 光学フィルタおよび撮像装置 | |
WO2023008291A1 (ja) | 光学フィルタ | |
JP2022000704A (ja) | 紫外線透過フィルタ | |
JP2024069437A (ja) | 光学フィルタおよび撮像装置 | |
WO2024048513A1 (ja) | 光学フィルタ | |
JP7415815B2 (ja) | 光学フィルタ | |
WO2024048512A1 (ja) | 光学フィルタ | |
JP7342958B2 (ja) | 光学フィルタおよび撮像装置 | |
WO2023022118A1 (ja) | 光学フィルタ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2016545370 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20167020553 Country of ref document: KR Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16737434 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16737434 Country of ref document: EP Kind code of ref document: A1 |