KR20230016355A - Pyridone based compound, resin composition for near-infrared ray absorption containing the same, and near-infrared ray blocking filter manufactured by using this - Google Patents
Pyridone based compound, resin composition for near-infrared ray absorption containing the same, and near-infrared ray blocking filter manufactured by using this Download PDFInfo
- Publication number
- KR20230016355A KR20230016355A KR1020210097740A KR20210097740A KR20230016355A KR 20230016355 A KR20230016355 A KR 20230016355A KR 1020210097740 A KR1020210097740 A KR 1020210097740A KR 20210097740 A KR20210097740 A KR 20210097740A KR 20230016355 A KR20230016355 A KR 20230016355A
- Authority
- KR
- South Korea
- Prior art keywords
- branched
- alkyl
- straight
- chain
- infrared
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 62
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 38
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011342 resin composition Substances 0.000 title claims abstract description 30
- 230000000903 blocking effect Effects 0.000 title abstract description 15
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- 125000000217 alkyl group Chemical group 0.000 claims description 44
- -1 (Z)-1-butyl-5-((2Z,4E)-5-(5,6-dimethoxyindolin-1-yl)-2-hydroxypenta-2,4-diene- 1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile Chemical compound 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 150000002431 hydrogen Chemical class 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 8
- 125000003282 alkyl amino group Chemical group 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 238000003384 imaging method Methods 0.000 claims description 5
- 125000006648 (C1-C8) haloalkyl group Chemical group 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 4
- 229920002312 polyamide-imide Polymers 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims 1
- 230000008033 biological extinction Effects 0.000 abstract description 5
- 239000011358 absorbing material Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000010410 layer Substances 0.000 description 24
- 238000002834 transmittance Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MDKCUUBEHNEEFG-UHFFFAOYSA-N 1-butyl-4-methyl-2,6-dioxo-3h-pyridine-5-carbonitrile Chemical compound CCCCN1C(=O)CC(C)=C(C#N)C1=O MDKCUUBEHNEEFG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 150000002475 indoles Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LHJDRSSYPZYQIL-UHFFFAOYSA-N 1-cyclohexyl-2,3-dihydroindol-6-amine Chemical compound C12=CC(N)=CC=C2CCN1C1CCCCC1 LHJDRSSYPZYQIL-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- PUPGGSNXXPJGII-UHFFFAOYSA-N 1-methyl-2,6-dioxo-3H-pyridine-5-carbonitrile Chemical compound CN1C(=O)CC=C(C1=O)C#N PUPGGSNXXPJGII-UHFFFAOYSA-N 0.000 description 1
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 description 1
- MKZAAOOSZBRZEP-UHFFFAOYSA-N 5-methoxy-2-methyl-2,3-dihydro-1h-indole Chemical compound COC1=CC=C2NC(C)CC2=C1 MKZAAOOSZBRZEP-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 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
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000004531 indol-5-yl group Chemical group [H]N1C([H])=C([H])C2=C([H])C(*)=C([H])C([H])=C12 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940060942 methylin Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MGZNARROBKPUST-UHFFFAOYSA-N n-butyl-2-cyanoacetamide Chemical compound CCCCNC(=O)CC#N MGZNARROBKPUST-UHFFFAOYSA-N 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound 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
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound 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 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
- C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
- H04N23/50—Constructional details
- H04N23/54—Mounting of pick-up tubes, electronic image sensors, deviation or focusing coils
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N25/00—Circuitry of solid-state image sensors [SSIS]; Control thereof
- H04N25/10—Circuitry of solid-state image sensors [SSIS]; Control thereof for transforming different wavelengths into image signals
- H04N25/11—Arrangement of colour filter arrays [CFA]; Filter mosaics
- H04N25/13—Arrangement of colour filter arrays [CFA]; Filter mosaics characterised by the spectral characteristics of the filter elements
- H04N25/131—Arrangement of colour filter arrays [CFA]; Filter mosaics characterised by the spectral characteristics of the filter elements including elements passing infrared wavelengths
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Multimedia (AREA)
- Signal Processing (AREA)
- Toxicology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
본 발명은 광학 필터용 근적외선 색소 화합물로 사용되는 피리돈계 화합물, 이를 포함하는 근적외선 흡수용 수지 조성물 및 이를 이용하여 제조된 근적외선 차단필터에 관한 것이다.The present invention relates to a pyridone-based compound used as a near-infrared dye compound for an optical filter, a near-infrared absorbing resin composition containing the same, and a near-infrared cut-off filter manufactured using the same.
스마트폰, 디지털 카메라 등 스마트 기기에 들어가는 카메라 렌즈 및 다양한 용도에 가시 파장 영역의 광은 충분히 투과하지만 근적외 영역의 광은 차폐하는 광학필터가 사용되고 있다. 촬상 장치용 광학필터로는 근적외 영역의 광을 선택적으로 흡수하도록 불소인산염계 유리나 인산염계 유리에 CuO 등을 첨가한 유리 필터가 알려져 있으나, 광 흡수형의 유리 필터는 고가이며 박형화가 어려워 최근 촬상 장치의 소형화 및 박형화 요구에 어려움이 있다.Optical filters that sufficiently transmit light in the visible wavelength region but shield light in the near-infrared region are used for camera lenses and various applications for smart devices such as smart phones and digital cameras. As an optical filter for an imaging device, a fluorophosphate-based glass or a glass filter in which CuO or the like is added to phosphate-based glass is known to selectively absorb light in the near-infrared region, but light-absorbing glass filters are expensive and difficult to thin. There is a difficulty in miniaturization and thinning of the device.
이러한 문제점을 해결하기 위하여 투명 수지에 근적외선 파장 영역의 광을 흡수하는 색소를 함유하는 필름 등의 개발이 주목 받고 있으며, 근적외선 차폐 특성이 우수한 근적외선 흡수 색소를 사용하여 소형화, 박막화 및 저비용화가 가능한 광학필터의 개발이 계속 요구되고 있다.In order to solve these problems, the development of a film containing a pigment that absorbs light in the near-infrared wavelength region in a transparent resin is attracting attention, and an optical filter that can be miniaturized, thinned, and reduced in cost by using a near-infrared absorbing pigment with excellent near-infrared shielding properties. development is still in demand.
근적외선 색소로는 시아닌(Cyanine)계, 아조(Azo)계, 아조-금속 착체(Azo-Metal complex)계, 인돌(Indole)계, 포피린(Porphyrin)계, 프탈로시아닌(Phthalocyanine)계, 나프탈로시아닌(Naphthalocyanine)계, 스쿠아릴륨(Squarylium)계, 디이모늄(Diimmonium)계, 이미다졸(Imidazole)계, 로다민(Rhodamine)계, 아크리딘(Acridine)계, 니켈금속착체(Nickel-Metal complex)계 디시아노비닐페닐(Dicyanovinylphenyl)계, 안트라퀴논(Anthraquinone)계, 쿠마린(Coumarin)계, 나프토퀴논(Naphthoquinone)계 및 인도페놀(Indophenol)계 등의 화합물이 사용되고 있다.Near-infrared pigments include Cyanine, Azo, Azo-Metal complex, Indole, Porphyrin, Phthalocyanine, and Naphthalocyanine. ), Squarylium, Diimmonium, Imidazole, Rhodamine, Acridine, Nickel-Metal complex Compounds such as dicyanovinylphenyl, anthraquinone, coumarin, naphthoquinone, and indophenol are used.
근적외선 색소는 광학 필터, 광학기록 시스템, 레이저 프린터, 레이저 여과(laser filter)시스템, 농업용 필름(보온, 식물육성조절용), 반도체 감광재료, 레이저용 색소, 액정표시를 위한 이색성 색소, 적외선 전자사진, 군사용 위장재료, 분석용, 의료진단 및 치료용, 에너지 저감을 위한 적외선 차단 필름 등의 폭넓은 응용이 가능하다.Near-infrared pigments include optical filters, optical recording systems, laser printers, laser filter systems, agricultural films (for warmth and plant growth control), photosensitive materials for semiconductors, pigments for lasers, dichroic pigments for liquid crystal displays, and infrared electrophotography. , military camouflage materials, analysis, medical diagnosis and treatment, and infrared blocking films for energy reduction.
광학 필터용 근적외선 색소는 최대흡수파장이 630 ~ 750 nm이고, 몰흡광계수가 높고, 제조가 용이하며, 수지와의 상용성이 우수하고, 열안정성 및 저장안정성이 높아 취급이 용이하며, 사용 용제에 대한 만족할 만한 용해도 등 산업 현장의 요구를 충족시킬 수 있는 다양한 용도에 적합한 새로운 근적외선 색소가 지속적으로 요구되고 있다. Near-infrared dyes for optical filters have a maximum absorption wavelength of 630 ~ 750 nm, have a high molar extinction coefficient, are easy to manufacture, have excellent compatibility with resins, have high thermal and storage stability, are easy to handle, and use solvents There is a continuous demand for new near-infrared dyes suitable for various uses that can meet industrial requirements, such as satisfactory solubility.
본 발명의 일 목적은 피리돈계 화합물, 이를 포함한 근적외선 흡수용 수지 조성물, 및 이를 이용한 근적외선 차단필터를 제공하는 것이다.One object of the present invention is to provide a pyridone-based compound, a resin composition for absorbing near-infrared rays including the same, and a near-infrared cut-off filter using the same.
본 발명의 다른 일 목적은 본 발명의 피리돈계 화합물을 포함하는 근적외선 흡수용 수지 조성물을 근적외선 차단필터에 사용함으로써, 최대흡수파장이 630 nm 내지 750 nm이고, 몰흡광계수가 높으며, 용해성이 우수한 광학 필터용 근적외선 흡수 소재를 제공하는 것이다.Another object of the present invention is to use the near-infrared absorption resin composition containing the pyridone-based compound of the present invention in a near-infrared cut filter, so that the maximum absorption wavelength is 630 nm to 750 nm, the molar extinction coefficient is high, and the solubility is excellent. It is to provide a near-infrared ray absorbing material for a filter.
상기 목적을 달성하기 위하여,In order to achieve the above purpose,
본 발명의 일 측면은 하기 화학식 1로 표시되는 피리돈계 화합물, 이의 입체 이성질체, 또는 이의 수화물을 제공한다.One aspect of the present invention provides a pyridone-based compound represented by Formula 1 below, a stereoisomer thereof, or a hydrate thereof.
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
상기 R1 내지 R4는 각각 독립적으로 수소, 할로겐, 직쇄 또는 분지쇄의 C1-10알킬, 직쇄 또는 분지쇄의 C1-10알콕시, 직쇄 또는 분지쇄의 C1-10할로알킬, 직쇄 또는 분지쇄의 C1-10할로알콕시, C6-10아릴C1-10알킬, 또는 직쇄 또는 분지쇄의 C1-10알킬아미노이고;Wherein R 1 to R 4 are each independently hydrogen, halogen, straight-chain or branched C 1-10 alkyl, straight-chain or branched-chain C 1-10 alkoxy, straight-chain or branched-chain C 1-10 haloalkyl, straight-chain or branched C 1-10 haloalkoxy, C 6-10 arylC 1-10 alkyl, or straight or branched C 1-10 alkylamino;
상기 R5 및 R6은 각각 독립적으로 수소, 또는 직쇄 또는 분지쇄의 C1-10알킬이고;R 5 and R 6 are each independently hydrogen or linear or branched C 1-10 alkyl;
상기 R7은 수소, 할로겐, 또는 직쇄 또는 분지쇄의 C1-5알킬이고;R 7 is hydrogen, halogen, or straight or branched C 1-5 alkyl;
상기 R8는 수소, 직쇄 또는 분지쇄의 C1-10알킬, 또는 C6-10아릴C1-10알킬이고; 및 R 8 is hydrogen, straight-chain or branched-chain C 1-10 alkyl, or C 6-10 arylC 1-10 alkyl; and
상기 n은 0 내지 5의 정수이다.Said n is an integer from 0 to 5.
본 발명의 다른 일 측면은 상기 화학식 1로 표시되는 피리돈계 화합물, 이의 입체 이성질체 또는 이의 수화물, 및 수지를 포함하는 근적외선 흡수용 수지 조성물을 제공한다.Another aspect of the present invention provides a resin composition for near infrared ray absorption comprising the pyridone-based compound represented by Formula 1, a stereoisomer thereof or a hydrate thereof, and a resin.
본 발명의 또 다른 일 측면은 상기 근적외선 흡수용 수지 조성물을 포함하는 근적외선 흡수층을 포함하는, 근적외선 차단필터를 제공한다.Another aspect of the present invention provides a near-infrared cut filter comprising a near-infrared absorbing layer containing the resin composition for absorbing near-infrared rays.
본 발명의 다른 일 측면은 상기 근적외선 차단필터를 포함하는 전자 장치, 고체 촬상 장치, 또는 카메라 모듈을 제공한다.Another aspect of the present invention provides an electronic device, a solid-state imaging device, or a camera module including the near-infrared cut filter.
본 발명은 상기 화학식 1로 표시되는 피리돈계 화합물, 이를 포함한 근적외선 흡수용 수지 조성물, 및 이를 이용한 근적외선 차단필터에 관한 것으로, 본 발명의 일 측면에서 제공하는 근적외선 흡수용 수지 조성물은, 상기 화학식 1로 표시되는 피리돈계 화합물을 포함함으로써, 기존의 발명보다 합성 과정이 매우 짧을 뿐만 아니라 수율이 좋은 장점이 있다. The present invention relates to a pyridone-based compound represented by Formula 1, a near-infrared ray absorbing resin composition including the same, and a near-infrared ray blocking filter using the same. In one aspect of the present invention, the near-infrared ray absorbing resin composition is By including the indicated pyridone-based compound, there is an advantage in that the synthesis process is very short and the yield is good compared to the existing invention.
또한, 본 발명의 일 측면에서 제공하는 근적외선 흡수용 수지 조성물은, 몰흡광계수가 높아 소량을 사용하여도 근적외선 차단 효과가 월등히 우수하고 가시광선 영역에서 투과율이 우수한 장점이 있다.In addition, the resin composition for near-infrared absorption provided in one aspect of the present invention has a high molar absorption coefficient, so even when a small amount is used, the near-infrared ray blocking effect is far superior and the transmittance in the visible ray region is excellent.
또한, 본 발명의 일 측면에서 제공하는 근적외선 흡수용 수지 조성물은 열안정성, 내화학성, 사용 용매에 대한 용해도 등이 우수하여 성능 및 효율성이 향상된 근적외선 차단필터를 제조할 수 있는 장점이 있다.In addition, the resin composition for near-infrared absorption provided in one aspect of the present invention has excellent thermal stability, chemical resistance, solubility in solvents used, etc., and thus has the advantage of being able to manufacture a near-infrared cut-off filter with improved performance and efficiency.
도 1은 본 발명의 근적외선 차단필터를 나타낸 모식도이다.
도 2는 본 발명의 실시예 11 및 실시예 12에서 제조된 근적외선 흡수층에 대한 광 투과율 결과를 나타낸 도면이다.
도 3은 본 발명의 실시예 13, 실시예 14, 및 비교예 2에서 제조된 근적외선 흡수층에 대한 광 투과율 결과를 나타낸 도면이다.1 is a schematic diagram showing a near-infrared cut filter of the present invention.
2 is a view showing the light transmittance results of the near-infrared absorbing layers prepared in Examples 11 and 12 of the present invention.
3 is a view showing the light transmittance results for the near-infrared absorbing layers prepared in Examples 13, 14, and Comparative Example 2 of the present invention.
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
한편, 본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시형태로 한정되는 것은 아니다. 또한 본 발명의 실시 형태는 당해 기술분야에서 평균적인 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위해서 제공되는 것이다. 또한 명세서 및 첨부된 특허청구범위에서 사용되는 단수 형태는 문맥에서 특별한 지시가 없는 한 복수 형태도 포함하는 것으로 의도할 수 있다. 나아가, 명세서 전체에서 어떤 구성요소를 "포함"한다는 것은 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있다는 것을 의미한다.On the other hand, the embodiments of the present invention can be modified in many different forms, and the scope of the present invention is not limited to the embodiments described below. In addition, embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art. Also, the singular forms used in the specification and appended claims may be intended to include the plural forms as well, unless the context dictates otherwise. Furthermore, "include" a certain component throughout the specification means that other components may be further included without excluding other components unless otherwise stated.
본 발명의 일 측면은 하기 화학식 1로 표시되는 피리돈계 화합물, 이의 입체 이성질체, 또는 이의 수화물을 제공한다.One aspect of the present invention provides a pyridone-based compound represented by Formula 1 below, a stereoisomer thereof, or a hydrate thereof.
[화학식 1] [Formula 1]
상기 화학식 1에서,In Formula 1,
상기 R1 내지 R4는 각각 독립적으로 수소, 할로겐, 직쇄 또는 분지쇄의 C1-10알킬, 직쇄 또는 분지쇄의 C1-10알콕시, 직쇄 또는 분지쇄의 C1-10할로알킬, 직쇄 또는 분지쇄의 C1-10할로알콕시, C6-10아릴C1-10알킬, 또는 직쇄 또는 분지쇄의 C1-10알킬아미노이고;Wherein R 1 to R 4 are each independently hydrogen, halogen, straight-chain or branched C 1-10 alkyl, straight-chain or branched-chain C 1-10 alkoxy, straight-chain or branched-chain C 1-10 haloalkyl, straight-chain or branched C 1-10 haloalkoxy, C 6-10 arylC 1-10 alkyl, or straight or branched C 1-10 alkylamino;
상기 R5 및 R6은 각각 독립적으로 수소, 또는 직쇄 또는 분지쇄의 C1-10알킬이고;R 5 and R 6 are each independently hydrogen or linear or branched C 1-10 alkyl;
상기 R7은 수소, 할로겐, 또는 직쇄 또는 분지쇄의 C1-5알킬이고;R 7 is hydrogen, halogen, or straight or branched C 1-5 alkyl;
상기 R8는 수소, 직쇄 또는 분지쇄의 C1-10알킬, 또는 C6-10아릴C1-10알킬이고; 및 R 8 is hydrogen, straight-chain or branched-chain C 1-10 alkyl, or C 6-10 arylC 1-10 alkyl; and
상기 n은 0 내지 5의 정수이다.Said n is an integer from 0 to 5.
상기 화학식 1로 표시되는 피리돈계 화합물은 상용화된 용매에 대한 용해도가 우수하고, 몰흡광계수가 높아 소량을 사용하여도 근적외선 차단 효과가 월등히 높으며, 열안정성 및 내화학성이 우수하여 이를 근적외선 흡수층으로 포함하는 근적외선 차단 필터는 성능이 향상된 특성을 가진다.The pyridone-based compound represented by Formula 1 has excellent solubility in commercially available solvents and a high molar absorption coefficient, so even when used in a small amount, the near-infrared ray blocking effect is significantly high, and it has excellent thermal stability and chemical resistance, so it is included as a near-infrared absorbing layer The near-infrared ray cut filter to have improved performance.
다른 측면에서,On the other side,
상기 R1 내지 R4는 각각 독립적으로 수소, 할로겐, 직쇄 또는 분지쇄의 C1-8알킬, 직쇄 또는 분지쇄의 C1-8알콕시, 직쇄 또는 분지쇄의 C1-8할로알킬, 직쇄 또는 분지쇄의 C1-8할로알콕시, C6-10아릴C1-8알킬, 또는 직쇄 또는 분지쇄의 C1-8알킬아미노이고;R 1 to R 4 are each independently hydrogen, halogen, linear or branched C 1-8 alkyl, linear or branched C 1-8 alkoxy, linear or branched C 1-8 haloalkyl, linear or branched C 1-8 haloalkyl, branched C 1-8 haloalkoxy, C 6-10 arylC 1-8 alkyl, or straight or branched C 1-8 alkylamino;
상기 R5 및 R6은 각각 독립적으로 수소, 또는 직쇄 또는 분지쇄의 C1-8알킬이고;R 5 and R 6 are each independently hydrogen or straight or branched C 1-8 alkyl;
상기 R7은 수소, 또는 직쇄 또는 분지쇄의 C1-5알킬이고;R 7 is hydrogen or straight or branched C 1-5 alkyl;
상기 R8는 수소, 직쇄 또는 분지쇄의 C1-8알킬, 또는 C6-10아릴C1-8알킬이고; 및R 8 is hydrogen, straight-chain or branched-chain C 1-8 alkyl, or C 6-10 arylC 1-8 alkyl; and
상기 n은 0 내지 3의 정수일 수 있다..The n may be an integer from 0 to 3.
또 다른 측면에서,On another aspect,
상기 R1 내지 R4는 각각 독립적으로 수소, 직쇄 또는 분지쇄의 C1-5알킬, 직쇄 또는 분지쇄의 C1-5알콕시, 직쇄 또는 분지쇄의 C1-5할로알킬, 또는 직쇄 또는 분지쇄의 C1-5할로알콕시이고;R 1 to R 4 are each independently hydrogen, linear or branched C 1-5 alkyl, linear or branched C 1-5 alkoxy, linear or branched C 1-5 haloalkyl, or linear or branched chain C 1-5 alkoxy. chain C 1-5 haloalkoxy;
상기 R5 및 R6은 각각 독립적으로 수소, 또는 직쇄 또는 분지쇄의 C1-5알킬이고;R 5 and R 6 are each independently hydrogen or straight or branched C 1-5 alkyl;
상기 R7은 수소, 또는 직쇄 또는 분지쇄의 C1-3알킬이고;R 7 is hydrogen or straight or branched C 1-3 alkyl;
상기 R8는 수소, 또는 직쇄 또는 분지쇄의 C1-5알킬이고; 및R 8 is hydrogen or straight or branched C 1-5 alkyl; and
상기 n은 0 내지 2의 정수 또는 1 내지 2의 정수일 수 있다.The n may be an integer of 0 to 2 or an integer of 1 to 2.
다른 측면에서,On the other side,
상기 R1 내지 R4는 각각 독립적으로 수소 또는 -OCH3이고;The R 1 to R 4 are each independently hydrogen or -OCH 3 ;
상기 R5 및 R6은 각각 독립적으로 수소 또는 -CH3이고;Wherein R 5 and R 6 are each independently hydrogen or -CH 3 ;
상기 R7은 -CH3이고;R 7 is -CH 3 ;
상기 R8는 -CH2CH2CH2CH3이고; 및R 8 is -CH 2 CH 2 CH 2 CH 3 ; and
상기 n은 1일 수 있다.The n may be 1.
또 다른 측면에서,On another aspect,
상기 화학식 1로 표시되는 피리돈계 화합물은 하기 화합물 군으로부터 선택되는 어느 하나의 화합물일 수 있으나, 하기 화합물이 본 발명을 한정하는 것은 아니다. The pyridone-based compound represented by Formula 1 may be any one compound selected from the group of compounds below, but the compounds below do not limit the present invention.
(1) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(5-메톡시-2-메틸인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴((Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5-methoxy-2-methylindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile);(1) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5-methoxy-2-methylindolin-1-yl)penta-2,4-di En-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile ((Z)-1-butyl-5-((2Z, 4E)-2-hydroxy-5-(5-methoxy-2-methylindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5 ,6-tetrahydropyridine-3-carbonitrile);
(2) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(5-메톡시인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴((Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5-methoxyindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile);(2) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5-methoxyindolin-1-yl)penta-2,4-dien-1-yl Den)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile ((Z)-1-butyl-5-((2Z,4E)-2- hydroxy-5-(5-methoxyindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile) ;
(3) (Z)-1-뷰틸-5-((2Z,4E)-5-(5,6-다이메톡시인돌린-1-일)-2-하이드록시펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴((Z)-1-butyl-5-((2Z,4E)-5-(5,6-dimethoxyindolin-1-yl)-2-hydroxypenta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile);(3) (Z)-1-butyl-5-((2Z,4E)-5-(5,6-dimethoxyindolin-1-yl)-2-hydroxypenta-2,4-diene- 1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile ((Z)-1-butyl-5-((2Z,4E) -5-(5,6-dimethoxyindolin-1-yl)-2-hydroxypenta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine- 3-carbonitrile);
(4) (Z)-1-뷰틸-5-((2Z,4E)-5-(5,6-다이메톡시-2-메틸인돌린-1-일)-2-하이드록시펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴((Z)-1-butyl-5-((2Z,4E)-5-(5,6-dimethoxy-2-methylindolin-1-yl)-2-hydroxypenta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile);(4) (Z)-1-butyl-5-((2Z,4E)-5-(5,6-dimethoxy-2-methylindolin-1-yl)-2-hydroxypenta-2; 4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile ((Z)-1-butyl-5-( (2Z,4E)-5-(5,6-dimethoxy-2-methylindolin-1-yl)-2-hydroxypenta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1 ,2,5,6-tetrahydropyridine-3-carbonitrile);
(5) (Z)-1-뷰틸-5-((2Z,4E)-5-(5,6-다이메톡시-3-메틸인돌린-1-일)-2-하이드록시펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴((Z)-1-butyl-5-((2Z,4E)-5-(5,6-dimethoxy-3-methylindolin-1-yl)-2-hydroxypenta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile);(5) (Z)-1-butyl-5-((2Z,4E)-5-(5,6-dimethoxy-3-methylindolin-1-yl)-2-hydroxypenta-2; 4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile ((Z)-1-butyl-5-( (2Z,4E)-5-(5,6-dimethoxy-3-methylindolin-1-yl)-2-hydroxypenta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1 ,2,5,6-tetrahydropyridine-3-carbonitrile);
(6) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(5,6,7-트라이메톡시인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴((Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5,6,7-trimethoxyindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile);(6) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5,6,7-trimethoxyindolin-1-yl)penta-2,4-di En-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile ((Z)-1-butyl-5-((2Z, 4E)-2-hydroxy-5-(5,6,7-trimethoxyindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5 ,6-tetrahydropyridine-3-carbonitrile);
(7) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(4,5,6,7-테트라메톡시인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴((Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(4,5,6,7-tetramethoxyindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile);(7) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(4,5,6,7-tetramethoxyindolin-1-yl)penta-2,4 -Dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile ((Z)-1-butyl-5-(( 2Z,4E)-2-hydroxy-5-(4,5,6,7-tetramethoxyindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1 ,2,5,6-tetrahydropyridine-3-carbonitrile);
(8) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴((Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(indolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile);(8) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(indolin-1-yl)penta-2,4-dien-1-ylidene)- 4-Methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile ((Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5 -(indolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile);
(9) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(2-메틸인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴((Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(2-methylindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile); 및(9) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(2-methylindolin-1-yl)penta-2,4-dien-1-yl Den)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile ((Z)-1-butyl-5-((2Z,4E)-2- hydroxy-5-(2-methylindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile) ; and
(10) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(3-메틸인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴((Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(3-methylindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile).(10) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(3-methylindolin-1-yl)penta-2,4-dien-1-yl Den)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile ((Z)-1-butyl-5-((2Z,4E)-2- hydroxy-5-(3-methylindolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile) .
나아가, 본 발명은 상기 화학식 1로 표시되는 피리돈계 화합물, 이로부터 제조될 수 있는 용매화물, 광학 이성질체, 수화물 등을 모두 포함한다.Furthermore, the present invention includes all of the pyridone-based compound represented by Formula 1 and solvates, optical isomers, and hydrates that can be prepared therefrom.
본 발명에 따른 상기 화학식 1로 표시되는 피리돈계 화합물은 하기 반응식 1에 나타난 바와 같이 제조될 수 있으나, 당업자가 인식할 수 있는 범위 내에서의 유기합성분야에서 가능한 방법이라면 모두 가능하다.The pyridone-based compound represented by Chemical Formula 1 according to the present invention may be prepared as shown in Reaction Scheme 1 below, but any method available in the field of organic synthesis within the scope recognized by those skilled in the art is possible.
[반응식 1][Scheme 1]
상기 반응식 1에서, R1 내지 R8 및 n은 상기 화학식 1에서의 정의와 동일하다.In Reaction Scheme 1, R 1 to R 8 and n are the same as defined in Formula 1 above.
본 발명의 다른 측면은 상기 화학식 1로 표시되는 피리돈계 화합물, 이의 입체 이성질체 또는 이의 수화물, 및 수지를 포함하는 근적외선 흡수용 수지 조성물을 제공한다.Another aspect of the present invention provides a resin composition for near-infrared absorption comprising the pyridone-based compound represented by Formula 1, a stereoisomer thereof or a hydrate thereof, and a resin.
상기 근적외선 흡수용 수지 조성물은 근적외선 색소로 반드시 본 발명의 상기 화학식 1로 표시되는 피리돈계 화합물을 적어도 1종 이상을 포함한다.The resin composition for absorbing near-infrared rays necessarily includes at least one pyridone-based compound represented by Formula 1 of the present invention as a near-infrared dye.
상기 근적외선 흡수용 수지 조성물은 상기 화학식 1로 표시되는 피리돈계 화합물을 유기용제에 용해한 용액과 수지를 혼합하여 제조하며, 투명 유리기판 또는 투명 수지제 기판의 일면 또는 양면에 코팅하여 용제를 건조시키는 방법, 또는 경화 및 건조시키는 방법으로 근적외선 흡수층을 형성할 수 있다.The resin composition for absorbing near-infrared rays is prepared by mixing a solution in which the pyridone-based compound represented by Formula 1 is dissolved in an organic solvent and a resin, and coated on one or both sides of a transparent glass substrate or a transparent resin substrate to dry the solvent Alternatively, a near infrared ray absorbing layer may be formed by curing and drying.
근적외선 차단필터를 제조하기 위한 근적외선 흡수용 수지 조성물에 포함되는 본 발명의 일 측면에 따른 피리돈계 화합물의 용해도는, 0.1% 내지 20%, 0.2% 내지 10%, 또는 2% 내지 7%일 수 있다.The solubility of the pyridone-based compound according to one aspect of the present invention included in the near-infrared absorption resin composition for preparing the near-infrared cut filter may be 0.1% to 20%, 0.2% to 10%, or 2% to 7%. .
상기 근적외선 흡수용 수지 조성물에 포함되는 수지는 투명수지일 수 있으며, 본 발명의 효과를 손상시키지 않는 것인 한 특별히 제한되지 않지만, 열안정성 및 유기용제에 대한 용해성을 확보하고, 고온 증착에 의해 유전체 다층막을 형성할 수 있는 근적외선 흡수층을 형성하기 위해, 유리전이온도(Tg)가, 바람직하게는 100 ℃ 내지 350 ℃, 보다 바람직하게는 110 ℃ 내지 300 ℃, 더욱 바람직하게는 120 ℃ 내지 250 ℃인 투명수지일 수 있다.The resin included in the near-infrared absorbing resin composition may be a transparent resin, and is not particularly limited as long as the effect of the present invention is not impaired, but thermal stability and solubility in organic solvents are secured, and the dielectric material is obtained by high-temperature deposition. In order to form a near-infrared absorption layer capable of forming a multilayer film, the glass transition temperature (Tg) is preferably 100 ° C to 350 ° C, more preferably 110 ° C to 300 ° C, still more preferably 120 ° C to 250 ° C It may be a transparent resin.
예를 들어, 상기 수지는 환상 올레핀계 수지, (변성)아크릴계 수지, 방향족 폴리에테르계 수지, 폴리이미드계 수지, 플루오렌폴리카보네이트계 수지, 플루오렌폴리에스테르계 수지, 폴리카보네이트계 수지, 폴리아미드계 수지, 폴리아릴레이트계 수지, 폴리술폰계 수지, 폴리에테르술폰계 수지, 폴리파라페닐렌계 수지, 폴리아미드이미드계 수지, 폴리에틸렌나트탈레이트계 수지, 불소화 방향족 폴리머계 수지, 우레탄 수지 및 에폭시계 수지로 이루어지는 군으로부터 선택되는 어느 하나 이상일 수 있으며, 바람직하게 환상 올레핀계 수지, (변성)아크릴계 수지 및 우레탄 수지에서 선택되는 하나 이상일 수 있다.For example, the resin is a cyclic olefin-based resin, (modified) acrylic resin, aromatic polyether-based resin, polyimide-based resin, fluorene polycarbonate-based resin, fluorene polyester-based resin, polycarbonate-based resin, polyamide based resins, polyarylate based resins, polysulfone based resins, polyethersulfone based resins, polyparaphenylene based resins, polyamideimide based resins, polyethylene naphthalate based resins, fluorinated aromatic polymer based resins, urethane resins and epoxy based resins It may be any one or more selected from the group consisting of, and preferably may be one or more selected from cyclic olefin-based resins, (modified) acrylic resins, and urethane resins.
상기 근적외선 흡수용 수지 조성물은 산화 방지제, 난연제, 대전 방지제, 무기 미립자 등의 추가 첨가제가 더 포함될 수 있다.The resin composition for absorbing near-infrared rays may further include additional additives such as antioxidants, flame retardants, antistatic agents, and inorganic particles.
상기 근적외선 흡수용 수지 조성물에 사용되는 유기용매는 이에 제한되는 것은 아니나, 벤젠, 톨루엔, 자일렌 등의 방향족 탄화수소류; 아세트산 에틸, 아세트산 부틸, 락트산 에틸, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트 등의 에스테르류; 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 사이클로헥사온 등의 케톤류; 염화 메틸렌, 클로로포름, 4염화 탄소 등의 할로겐화 탄화수소류; 에틸렌글리콜노모메틸에테르, 디에틸렌글리콜모노부틸에테르 등의 에테르류; 디메틸 포름아미드, 디메틸아세트아미드, N-메틸피롤리돈 등의 아미드류일 수 있다. 또한, 이들 유기용매는 1종 단독으로 또는 2종 이상을 병용하여 사용될 수 있다.The organic solvent used in the resin composition for absorbing near-infrared rays is not limited thereto, but aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexaone; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; ethers such as ethylene glycol nomomethyl ether and diethylene glycol monobutyl ether; amides such as dimethyl formamide, dimethylacetamide, and N-methylpyrrolidone. In addition, these organic solvents may be used singly or in combination of two or more.
상기 근적외선 흡수용 수지 조성물을 투명 유리기판 또는 투명 수지제 기판의 일면 또는 양면에 코팅하여 용제를 건조시키는 방법, 또는 경화 및 건조시키는 방법으로 근적외선 흡수층을 형성할 수 있다.The near-infrared absorption layer may be formed by coating the resin composition for absorbing near-infrared rays on one side or both sides of a transparent glass substrate or a transparent resin substrate and drying the solvent, or by curing and drying the composition.
상기 투명 수지제 기판은 환상 올레핀계 수지, 폴리카보네이트 수지(PC), 폴리술폰 수지(PSF), 폴리에테르술폰 수지(PES), 폴리아릴레이트 수지(PAR), 폴리파라페닐렌 수지(PPP), 폴리아릴렌에테르포스핀옥사이드 수지(PEPO), 폴리이미드 수지(PI), 폴리에테르이미드 수지(PEI), 폴리아미드이미드 수지(PAI), (변성)아크릴 수지, 폴리에틸렌 나프탈레이트 수지(PEN), 유기-무기 나노 하이브리드 재료 등일 수 있다.The transparent resin substrate is a cyclic olefin resin, polycarbonate resin (PC), polysulfone resin (PSF), polyethersulfone resin (PES), polyarylate resin (PAR), polyparaphenylene resin (PPP), Polyarylene ether phosphine oxide resin (PEPO), polyimide resin (PI), polyetherimide resin (PEI), polyamideimide resin (PAI), (modified) acrylic resin, polyethylene naphthalate resin (PEN), organic -It may be an inorganic nano-hybrid material or the like.
본 발명의 또 다른 측면은 상기 근적외선 흡수용 수지 조성물을 포함하는 근적외선 흡수층을 포함하는 근적외선 차단필터를 제공한다.Another aspect of the present invention provides a near-infrared cut filter including a near-infrared absorbing layer containing the resin composition for absorbing near-infrared rays.
상기 근적외선 차단필터는 상기 화학식 1로 표시되는 피리돈계 화합물을 근적외선 색소로 사용하여 몰흡광계수가 높아 소량을 사용하여도 근적외선 차단 효과가 우수하고 가시광선 영역에서 투과율이 우수하며, 열안정성, 내화학성, 용해도가 우수하여 높은 성능 및 효율성을 가진다. The near-infrared cut filter uses the pyridone-based compound represented by Formula 1 as a near-infrared dye and has a high molar absorption coefficient, so even when a small amount is used, the near-infrared cutoff effect is excellent, the transmittance in the visible ray region is excellent, and thermal stability and chemical resistance are excellent. , it has excellent solubility and high performance and efficiency.
상기 근적외선 흡수층은 투명 유리기판 또는 투명 수지제 기판의 일면 또는 양면에 형성될 수 있으며, 그 두께가 바람직하게는 0.1 ㎛ 내지 30 ㎛, 더욱 바람직하게는 0.3 ㎛ 내지 20 ㎛, 특히 바람직하게는 0.5 ㎛ 내지 10 ㎛이며, 상기 화학식 1로 표시되는 피리돈계 화합물의 몰흡광계수 및 용해도가 높을수록 근적외선 흡수층의 두께를 최소화 할 수 있다.The near-infrared absorption layer may be formed on one side or both sides of a transparent glass substrate or a transparent resin substrate, and has a thickness of preferably 0.1 μm to 30 μm, more preferably 0.3 μm to 20 μm, and particularly preferably 0.5 μm. to 10 μm, and the higher the molar absorption coefficient and solubility of the pyridone-based compound represented by Formula 1, the smaller the thickness of the near-infrared absorption layer.
상기 근적외선 차단필터는, 상기 근적외선 흡수층의 일면 또는 양면에 근적외선 반사막을 가질 수 있으며, 상기 근적외선 반사막은 굴절률이 1.7 이상인 고굴절률 재료와 굴절률이 1.6 이하인 저굴절률 재료를 교대로 적층한 유전체 다층막으로 형성될 수 있다.The near-infrared cut filter may have a near-infrared reflective film on one side or both sides of the near-infrared absorbing layer, and the near-infrared reflective film may be formed of a dielectric multilayer film in which a high refractive index material having a refractive index of 1.7 or more and a low refractive index material having a refractive index of 1.6 or less are alternately laminated. can
또한 본 발명의 다른 측면은 상기 근적외선 차단필터를 포함하는 전자 장치, 예를 들면, 상기 근적외선 차단필터를 포함하는 고체 촬상 장치 또는 카메라 모듈을 제공한다.Another aspect of the present invention provides an electronic device including the near-infrared cut-off filter, for example, a solid-state imaging device or camera module including the near-infrared cut-off filter.
상기 근적외선 차단필터를 포함하는 전자 장치, 고체 촬상 장치 또는 카메라 모듈은 근적외선 차단 효과가 우수하여 성능 및 효율성이 매우 향상된다.An electronic device, a solid-state imaging device, or a camera module including the near-infrared cut-off filter has an excellent near-infrared cut-off effect, so that performance and efficiency are greatly improved.
상기 전자 장치는 디지털 카메라, 디지털 카메라, 캠코더, CCTV와 같은 감시용 카메라, 자동차용 카메라, 의료기기용 카메라, 카메라가 내장 또는 외장된 휴대전화, 카메라가 내장 또는 외장된 컴퓨터, 카메라가 내장 또는 외장된 랩탑 컴퓨터, 등일 수 있으나, 이에 한정되는 것은 아니다.The electronic device includes a digital camera, a digital camera, a camcorder, a surveillance camera such as a CCTV, a camera for a vehicle, a camera for medical devices, a mobile phone with a built-in or external camera, a computer with a built-in or external camera, and a camera with a built-in or external camera. It may be a laptop computer, etc., but is not limited thereto.
이하에서, 본 발명의 상세한 이해를 위하여 본 발명의 대표 화합물을 실시예 및 비교예를 들어 상세하게 설명하겠는바, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되어서는 안 된다. 본 발명의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.Hereinafter, representative compounds of the present invention will be described in detail with Examples and Comparative Examples for a detailed understanding of the present invention. should not be construed as being limited to the embodiments detailed below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
<실시예 1> (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(5-메톡시-2-메틸인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴의 제조<Example 1> (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5-methoxy-2-methylindolin-1-yl)penta-2,4 Preparation of -dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile
단계 1: 1-뷰틸-4-메틸-2,6-다이옥소-1,2,5,6-테트라하드로피리딘-3-카보나이트릴의 제조Step 1: Preparation of 1-butyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile
N-부틸-2-사이아노아세트아마이드 10 g (0.071 mol)을 250 mL 둥근바닥플라스크에 넣고 에틸 아세토아세테이트 18.56 g (0.142 mol)을 파이퍼리딘 100 mL에 녹여 넣어 준 후 100 ℃에서 14시간 반응하였다. 반응물을 실온으로 냉각하고 1M 염산을 천천히 넣어주면서 pH를 조절하여 침전시키고 여과하여 연한 노란색 고체인 1-뷰틸-4-메틸-2,6-다이옥소-1,2,5,6-테트라 하드로피리딘-3-카보나이트릴 13 g (88%)를 얻었다.10 g (0.071 mol) of N-butyl-2-cyanoacetamide was placed in a 250 mL round bottom flask, and 18.56 g (0.142 mol) of ethyl acetoacetate was dissolved in 100 mL of piperidine, followed by reaction at 100 ° C for 14 hours. . The reactant was cooled to room temperature, and pH was adjusted while 1M hydrochloric acid was slowly added to precipitate and filtered to obtain 1-butyl-4-methyl-2,6-dioxo-1,2,5,6-tetra hard as a pale yellow solid. This gave 13 g (88%) of pyridine-3-carbonitrile.
1H NMR (δ ppm; CDCl3): 4.97 (1H, s), 4.00 (2H, t), 2.98 (1H, s), 1.87 (3H, s), 1.55-1.49 (2H, m), 1.41-1.28 (2H, m), 0.88 (3H, t) 1 H NMR (δ ppm; CDCl 3 ): 4.97 (1H, s), 4.00 (2H, t), 2.98 (1H, s), 1.87 (3H, s), 1.55-1.49 (2H, m), 1.41- 1.28 (2H, m), 0.88 (3H, t)
단계 2: 1-뷰틸-5-(퓨란-2-일메틸)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하드로피리딘-3-카보나이트릴의 제조Step 2: Preparation of 1-butyl-5-(furan-2-ylmethyl)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile
상기 실시예 1의 단계 1에서 얻어진 화합물 1-뷰틸-4-메틸-2,6-다이옥소-1,2,5,6-테트라 하드로피리딘-3-카보나이트릴 1 g (5 mmol)에 상온에서 THF 10 mL와 푸르푸랄 2 mL을 넣은 후 30분 동안 교반시킨다. 짙은 노란색이 증가함을 확인 후 10분 내지 20분 더 교반 후 75 중량% MeOH 수용액 20 mL을 넣어 침전시키고 여과하여 짙은 노란색 고체인 1-뷰틸-5-(퓨란-2-일메틸)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하드로피리딘-3-카보나이트릴 1.05 g (76.6%)을 얻었다.Add 1 g (5 mmol) of the compound 1-butyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile obtained in step 1 of Example 1 at room temperature. After adding 10 mL of THF and 2 mL of furfural, the mixture was stirred for 30 minutes. After confirming the increase in dark yellow color, after stirring for 10 to 20 minutes, 20 mL of 75 wt% MeOH aqueous solution was added to precipitate and filtered to obtain 1-butyl-5-(furan-2-ylmethyl)-4- as a dark yellow solid. 1.05 g (76.6%) of methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile was obtained.
1H NMR (δ ppm; CDCl3): 8.71 (1H, d), 7.88 (1H, d), 7.70 (1H, s), 6.81 (1H, d), 4.00 (2H, t), 2.64 (3H, s), 1.55-1.49 (2H, m), 1.41-1.28 (2H, m), 0.88 (3H, t) 1 H NMR (δ ppm; CDCl 3 ): 8.71 (1H, d), 7.88 (1H, d), 7.70 (1H, s), 6.81 (1H, d), 4.00 (2H, t), 2.64 (3H, s), 1.55-1.49 (2H, m), 1.41-1.28 (2H, m), 0.88 (3H, t)
단계 3:(Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(5-메톡시-2-메틸인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴의 제조Step 3: (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5-methoxy-2-methylindolin-1-yl)penta-2,4-di Preparation of en-1-ylidene) -4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile
상기 실시예 1의 단계 2에서 얻어진 화합물 1-뷰틸-5-(퓨란-2-일메틸)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하드로피리딘-3-카보나이트릴 200 mg (0.7 mmol)을 THF 4 mL에 녹이고 5-메톡시-2-메틸 인돌린 140 mg (0.84 mmol)을 넣고 상온에서 15분 동안 교반시킨다. TLC로 반응 확인 후 에터 15 mL을 넣어주어 침전시킨 후 여과하여 (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(5-메톡시-2-메틸인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴 280 mg (89%)를 얻었다.Compound 1-butyl-5-(furan-2-ylmethyl)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3 obtained in step 2 of Example 1 Dissolve 200 mg (0.7 mmol) of carbonitrile in 4 mL of THF, add 140 mg (0.84 mmol) of 5-methoxy-2-methyl indoline, and stir at room temperature for 15 minutes. After confirming the reaction by TLC, 15 mL of ether was added to precipitate, and filtered to obtain (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5-methoxy-2-methylin) Dolin-1-yl)penta-2,4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile 280 mg (89%) was obtained.
1H NMR (δ ppm; CDCl3): 13.20 (1H, s), 7.97 (1H, d), 7.28 (1H, d), 6.94 (1H, d), 6.89 - 6.76 (2H, m), 6.47 (1H, t), 6.22 (1H, s), 4.84 (1H, q), 3.95 (2H, td), 3.83 (3H, s,), 3.60 (1H, dd), 2.82 (1H, d), 2.36 (3H, s), 1.56 (2H, q), 1.47 (3H, d), 1.33 (2H, q), 0.90 (3H, t) 1 H NMR (δ ppm; CDCl 3 ): 13.20 (1H, s), 7.97 (1H, d), 7.28 (1H, d), 6.94 (1H, d), 6.89 - 6.76 (2H, m), 6.47 ( 1H, t), 6.22 (1H, s), 4.84 (1H, q), 3.95 (2H, td), 3.83 (3H, s,), 3.60 (1H, dd), 2.82 (1H, d), 2.36 ( 3H, s), 1.56 (2H, q), 1.47 (3H, d), 1.33 (2H, q), 0.90 (3H, t)
<실시예 2 내지 실시예 10> <Examples 2 to 10>
상기 실시예 1과 동일한 방법으로 제조하되, 상기 실시예 1의 단계 3에서 첨가된 반응물인 인돌 유도체를 달리 사용하여 실시예 2 내지 실시예 10의 피리돈계 화합물을 얻었다. 이를 표 1에 정리하였다.The pyridone-based compounds of Examples 2 to 10 were obtained in the same manner as in Example 1, except that the indole derivative added in step 3 of Example 1 was used differently. These are summarized in Table 1.
<비교예 1>1,3-비스-[6-(아세틸아미노)-2,3-디하이드로-1-사이클로헥실-1H-인돌-5-일]-스쿠아릴륨의 제조<Comparative Example 1> Preparation of 1,3-bis-[6-(acetylamino)-2,3-dihydro-1-cyclohexyl-1H-indol-5-yl]-squalylium
단계 1: N-(2,3-디하이드로-1-사이클로헥실-1H-인돌-6-일)-아세트아마이드의 제조Step 1: Preparation of N-(2,3-dihydro-1-cyclohexyl-1H-indol-6-yl)-acetamide
6-아미노-2,3-디하이드로-1-사이클로헥실-1H-인돌 1.08 g (5.0 mmol)을 디클로로메탄 15 mL에 용해시키고 반응물을 -5 ℃로 유지한 다음, 트리에틸아민 0.7 mL (5.0 mmol)을 가해주고 반응용액을 10분 동안 교반하였다. 그 후, 염화아세틸 0.39 g (5.0 mmol)을 천천히 가해주고 반응물이 승온되지 않도록 주의하면서 1시간 동안 교반하였다. 그런 다음, 증류수 50 mL를 반응물에 천천히 가해주고 30분 동안 교반 후 유기층을 분리하고 증류수로 여러 번 씻어준 다음, 회수한 유기층을 감압 증류하여 고체 생성물을 얻었다. 얻어진 고체 생성물을 메탄올 20 mL에 분산시키고 실온에서 30분 동안 교반 후 여과하고 건조하여 흰색의 N-(2,3-디하이드로-1-사이클로헥실-1H-인돌-6-일)-아세트아마이드 0.92 g (71.3%)을 얻었다.Dissolve 1.08 g (5.0 mmol) of 6-amino-2,3-dihydro-1-cyclohexyl-1H-indole in 15 mL of dichloromethane, keep the reaction at -5 ° C, and then add 0.7 mL (5.0 mmol) of triethylamine. mmol) was added and the reaction solution was stirred for 10 minutes. Thereafter, 0.39 g (5.0 mmol) of acetyl chloride was slowly added thereto, and the reaction mixture was stirred for 1 hour while being careful not to raise the temperature. Then, 50 mL of distilled water was slowly added to the reactant, stirred for 30 minutes, the organic layer was separated, washed several times with distilled water, and the recovered organic layer was distilled under reduced pressure to obtain a solid product. The obtained solid product was dispersed in 20 mL of methanol, stirred at room temperature for 30 minutes, filtered, and dried to obtain white N-(2,3-dihydro-1-cyclohexyl-1H-indol-6-yl)-acetamide 0.92 g (71.3%) was obtained.
단계 2: 1,3-비스-[6-(아세틸아미노)-2,3-디하이드로-1-사이클로헥실- 1H-인돌-5-일]-스쿠아릴륨 제조Step 2: Preparation of 1,3-bis-[6-(acetylamino)-2,3-dihydro-1-cyclohexyl-1H-indol-5-yl]-squallium
상기 비교예 1의 단계 1에서 얻어진 N-[2,3-디하이드로-1-사이클로헥실-1H-인돌-6-일]-아세트아마이드(5) 0.88 g (3.4 mmol)을 무수 에탄올 30 mL에 분산시키고 실온에서 30분 동안 교반한 다음, 스쿠아릭산 0.19 g (1.7 mmol)과 오르토포름산트리에틸 1.9 mL (11.4 mmol)을 차례로 가해주고 반응물을 서서히 승온하여 4시간 동안 환류반응하였다. 반응물을 실온으로 냉각 후 얻어진 고체 생성물을 여과하고 메탄올로 여러 번 씻어준 후 건조하여 진한 초록색의 1,3-비스-[6-(아세틸아미노)-2,3-디하이드로-1-사이클로헥실-1H-인돌-5-일)]-스쿠아릴륨 0.54 g (53.5%)을 얻었다.0.88 g (3.4 mmol) of N-[2,3-dihydro-1-cyclohexyl-1H-indol-6-yl]-acetamide (5) obtained in step 1 of Comparative Example 1 was added to 30 mL of absolute ethanol. After dispersing and stirring at room temperature for 30 minutes, 0.19 g (1.7 mmol) of squaric acid and 1.9 mL (11.4 mmol) of triethyl orthoformate were sequentially added thereto, and the reaction mixture was slowly raised to reflux for 4 hours. After cooling the reactant to room temperature, the obtained solid product was filtered, washed several times with methanol, and dried to obtain dark green 1,3-bis-[6-(acetylamino)-2,3-dihydro-1-cyclohexyl- This gave 0.54 g (53.5%) of 1H-indol-5-yl)]-squallium.
하기 표 2에는 상기 실시예 1 내지 실시예 10 및 비교예 1에서 제조한 화합물의 최대 흡수파장(λmax), 430 nm 내지 560 nm 파장영역에서의 투과율, UV-VIS-NIR 스펙트럼의 몰 흡광계수(ε), 및 용해도 측정과 TGA 분석 자료를 기재하였다.Table 2 below shows the maximum absorption wavelength (λ max ), transmittance in the wavelength range of 430 nm to 560 nm, and molar extinction coefficient of the UV-VIS-NIR spectrum of the compounds prepared in Examples 1 to 10 and Comparative Example 1. (ε), and solubility measurement and TGA analysis data are described.
용매로서 사용되는 모든 유기용매를 사용할 수 있으며, 본 실시예에서는 환상 올레핀계 수지, (변성)아크릴계 수지, 우레탄 수지 및 에폭시계 수지 등 투명수지에 혼합이 가능한 톨루엔에 본 발명의 피리돈계 화합물을 용해하여 용해도를 측정하였다.All organic solvents used as solvents can be used, and in this embodiment, the pyridone-based compound of the present invention is dissolved in toluene that can be mixed with transparent resins such as cyclic olefin-based resins, (modified) acrylic-based resins, urethane resins, and epoxy-based resins. Solubility was measured.
(%)TGA *3
(%)
(nm)maximum absorption wavelength
(nm)
(430~560 nm, %)transmittance
(430~560 nm, %)
(×104)molar extinction coefficient
(×10 4 )
* 1: UV solvent; Toluene 사용* 1: UV solvent; Use of toluene
* 2: 용해도: 일정 온도에서 용매 100 g에 녹일 수 있는 용질의 g수* 2: Solubility: the number of grams of solute that can be dissolved in 100 g of solvent at a certain temperature
* 3: 230 ℃ 분해정도* 3: Degree of decomposition at 230 ℃
그 결과, 실시예 1 내지 실시예 10에 따른 피리돈계 화합물은 몰흡광계수가 높고 열안정성이 높은 것으로 나타났다.As a result, it was found that the pyridone-based compounds according to Examples 1 to 10 had high molar absorption coefficients and high thermal stability.
또한, 실시예 1 내지 실시예 10에 따른 피리돈계 화합물은 비교예 1의 화합물과 대비하여 용해도가 높은 것으로 나타났다.In addition, the pyridone-based compounds according to Examples 1 to 10 showed higher solubility compared to the compound of Comparative Example 1.
본 발명의 피리돈계 화합물 중 실시예 8, 9 화합물의 용해도가 0.7%이상으로 가장 우수하였으며, 실시예 4 및 10의 화합물은 만족할 만한 용해도를 나타내었으며, 비교예 1의 화합물은 용해도가 0.01% 이하로 낮아 근적외선 흡수용 수지 조성물에 포함하기 부적합하였다.Among the pyridone-based compounds of the present invention, the solubility of the compounds of Examples 8 and 9 was the most excellent at 0.7% or more, the compounds of Examples 4 and 10 showed satisfactory solubility, and the compound of Comparative Example 1 had a solubility of 0.01% or less was unsuitable for inclusion in the resin composition for absorbing near-infrared rays.
하기에서는, 본 발명의 피리돈계 화합물의 근적외선 흡수 기능을 비교하기 위하여, 피리돈계 화합물을 이용하여 제조한 근적외선 차단필터의 광 투과도 실험을 수행하였다. 구체적으로, 피리돈계 화합물을 톨루엔에 용해한 용해액과 환상 올레핀계 수지로 근적외선 흡수용 수지 조성물을 제조하였고, 상기 수지 조성물을 유리기판에 도포하여 근적외선 흡수층을 제조하였다.In the following, in order to compare the near-infrared absorption function of the pyridone-based compound of the present invention, a light transmittance test of a near-infrared cut-off filter prepared using a pyridone-based compound was performed. Specifically, a near-infrared absorbing resin composition was prepared using a solution in which a pyridone-based compound was dissolved in toluene and a cyclic olefin-based resin, and the resin composition was coated on a glass substrate to prepare a near-infrared absorbing layer.
<실시예 11><Example 11>
용해도가 우수한 실시예 4 화합물을 톨루엔에 0.6% 농도가 되도록 용해한 용해액 1.25 g과 환상 올레핀계 투명수지 ZEONEX 480R(Zeon사) 1.0 g과 톨루엔 7.75 g으로 근적외선 흡수용 수지 조성물을 제조하였다.A resin composition for near-infrared absorption was prepared from 1.25 g of a solution in which the compound of Example 4 having excellent solubility was dissolved in toluene at a concentration of 0.6%, 1.0 g of cyclic olefin-based transparent resin ZEONEX 480R (Zeon), and 7.75 g of toluene.
이후 제조된 근적외선 흡수용 수지 조성물을 도 1과 같이 투명 유리기판상에 스핀코팅법으로 도포한 후 140 ℃에서 10분 동안 건조한 다음 두께 3.0 ㎛의 근적외선 흡수층을 제조하여 광 투과도 실험을 수행하였으며, 그 결과를 도 2 및 표 3에 나타내었다.Thereafter, the prepared near-infrared absorbing resin composition was applied on a transparent glass substrate by spin coating as shown in FIG. 1, dried at 140 ° C. for 10 minutes, and then a near-infrared absorbing layer having a thickness of 3.0 μm was prepared to conduct light transmittance experiments. As a result, It is shown in Figure 2 and Table 3.
<실시예 12 내지 실시예 14>.<Example 12 to Example 14>.
상기 실시예 11과 동일한 방법으로 근적외선 흡수층을 제조하되, 제조에 사용되는 실시예 화합물 및 톨루엔에 용해한 정도를 달리하여 실시예 12 내지 실시예 14의 근적외선 흡수층을 제조하였다. 이를 표 3에 정리하였다. 또한, 실시예 12 내지 실시예 14에 따른 광 투과도 실험 결과를 도 2, 도 3, 및 표 3에 나타내었다.The near-infrared absorbing layer was prepared in the same manner as in Example 11, but the near-infrared absorbing layer of Examples 12 to 14 was prepared by varying the degree of dissolution in the example compound and toluene used in the preparation. These are summarized in Table 3. In addition, the light transmittance test results according to Examples 12 to 14 are shown in FIGS. 2, 3, and Table 3.
<비교예 2><Comparative Example 2>
상기 실시예 11과 동일한 방법으로 근적외선 흡수층을 제조하되, 비교예 1 화합물을 톨루엔에 0.01% 농도가 되도록 용해한 용해액으로 근적외선 흡수용 수지 조성물을 제조하였으며, 그 결과는 도 3 및 표 3에 나타내었다.A near-infrared absorption layer was prepared in the same manner as in Example 11, but a near-infrared absorption resin composition was prepared using a solution in which the compound of Comparative Example 1 was dissolved in toluene at a concentration of 0.01%. The results are shown in FIG. 3 and Table 3. .
(nm)maximum absorption wavelength
(nm)
실험 결과, 비교예 1에 따른 화합물은 톨루엔에서의 용해도가 부족하여 근적외선 흡수층 내 화합물 함량이 낮아 이를 이용하여 제조한 근적외선 흡수층(비교예 2)은 최대흡수파장에서의 투과율이 30% 이상으로 근적외선 차단필터로 이용되기에 부적합하였다. 톨루엔에서의 용해도가 0.6% 이상으로 우수한 실시예 4 및 실시예 10에 따른 화합물은 근적외선 흡수층 내 화합물 함량을 충분히 높일 수 있어 이를 이용하여 제조한 근적외선 흡수층(실시예 11 및 실시예 14)은 최대흡수파장에서의 투과율이 7.5% 이하로 근적외선 차단기능이 우수했다. 또한, 용해도가 0.7% 이상으로 우수한 실시예 8 및 실시예 9에 따른 화합물을 이용하여 제조한 근적외선 흡수층(실시예 12 및 실시예 13)은 최대흡수파장에서의 투과율이 2.1% 이하로 더욱 우수한 근적외선 차단기능을 지녔다.또한, 실시예 4 및 실시예 8 내지 10 화합물은 430 nm 내지 560 nm 파장영역에서 높은 투과율을 가져, 이를 이용하여 제조한 근적외선 흡수층(실시예 11 내지 실시예 14)은 극전외선 차단기능이 우수할 뿐만 아니라, 가시광선 투과율이 높아 뛰어난 성능의 근적외선 차단필터를 제조할 수 있다. 특히 실시예 12를 제조하는 데에 쓰인 실시예 8 화합물은 가장 우수한 근적외선 차단기능과 430 nm 내지 560 nm 파장영역에서 높은 투과율을 가져, 실시예 12에 따른 근적외선 흡수층은 근적외선 차단필터용 색소 화합물로 적합함을 알 수 있었다.As a result of the experiment, the compound according to Comparative Example 1 has a low solubility in toluene, so the compound content in the near-infrared absorption layer is low, and the near-infrared absorption layer (Comparative Example 2) prepared using the same has a transmittance of 30% or more at the maximum absorption wavelength, blocking near-infrared rays. Unsuitable for use as a filter. The compounds according to Examples 4 and 10 having excellent solubility in toluene of 0.6% or more can sufficiently increase the compound content in the near-infrared absorbing layer, so the near-infrared absorbing layers (Examples 11 and 14) prepared using them have maximum absorption The transmittance at the wavelength was less than 7.5%, and the near-infrared ray blocking function was excellent. In addition, the near-infrared ray absorption layers (Examples 12 and 13) prepared using the compounds according to Examples 8 and 9 having excellent solubility of 0.7% or more have transmittance of 2.1% or less at the maximum absorption wavelength, which is more excellent in near-infrared rays. In addition, the compounds of Examples 4 and 8 to 10 have high transmittance in the wavelength range of 430 nm to 560 nm, and the near-infrared absorbing layer (Examples 11 to 14) prepared using them has an extreme ultraviolet ray In addition to excellent blocking function, it is possible to manufacture a near-infrared ray blocking filter with excellent performance due to its high visible light transmittance. In particular, the compound of Example 8 used to prepare Example 12 has the most excellent near-infrared ray blocking function and high transmittance in the 430 nm to 560 nm wavelength range, so the near-infrared absorbing layer according to Example 12 is suitable as a dye compound for a near-infrared ray blocking filter. could know that
10: 투명 유리기판 또는 투명 수지제 기판
20: 근적외선 흡수층10: transparent glass substrate or transparent resin substrate
20: near infrared ray absorption layer
Claims (12)
[화학식 1]
상기 화학식 1에서,
상기 R1 내지 R4는 각각 독립적으로 수소, 할로겐, 직쇄 또는 분지쇄의 C1-10알킬, 직쇄 또는 분지쇄의 C1-10알콕시, 직쇄 또는 분지쇄의 C1-10할로알킬, 직쇄 또는 분지쇄의 C1-10할로알콕시, C6-10아릴C1-10알킬, 또는 직쇄 또는 분지쇄의 C1-10알킬아미노이고;
상기 R5 및 R6은 각각 독립적으로 수소, 또는 직쇄 또는 분지쇄의 C1-10알킬이고;
상기 R7은 수소, 할로겐, 또는 직쇄 또는 분지쇄의 C1-5알킬이고;
상기 R8는 수소, 직쇄 또는 분지쇄의 C1-10알킬, 또는 C6-10아릴C1-10알킬이고; 및
상기 n은 0 내지 5의 정수이다.
A pyridone-based compound represented by Formula 1 below, a stereoisomer thereof, or a hydrate thereof:
[Formula 1]
In Formula 1,
Wherein R 1 to R 4 are each independently hydrogen, halogen, straight-chain or branched C 1-10 alkyl, straight-chain or branched-chain C 1-10 alkoxy, straight-chain or branched-chain C 1-10 haloalkyl, straight-chain or branched C 1-10 haloalkoxy, C 6-10 arylC 1-10 alkyl, or straight or branched C 1-10 alkylamino;
R 5 and R 6 are each independently hydrogen or linear or branched C 1-10 alkyl;
R 7 is hydrogen, halogen, or straight or branched C 1-5 alkyl;
R 8 is hydrogen, straight-chain or branched-chain C 1-10 alkyl, or C 6-10 arylC 1-10 alkyl; and
Said n is an integer from 0 to 5.
상기 R1 내지 R4는 각각 독립적으로 수소, 할로겐, 직쇄 또는 분지쇄의 C1-8알킬, 직쇄 또는 분지쇄의 C1-8알콕시, 직쇄 또는 분지쇄의 C1-8할로알킬, 직쇄 또는 분지쇄의 C1-8할로알콕시, C6-10아릴C1-8알킬, 또는 직쇄 또는 분지쇄의 C1-8알킬아미노이고;
상기 R5 및 R6은 각각 독립적으로 수소, 또는 직쇄 또는 분지쇄의 C1-8알킬이고;
상기 R7은 수소, 또는 직쇄 또는 분지쇄의 C1-5알킬이고;
상기 R8는 수소, 직쇄 또는 분지쇄의 C1-8알킬, 또는 C6-10아릴C1-8알킬이고; 및
상기 n은 0 내지 3의 정수인, 피리돈계 화합물, 이의 입체 이성질체, 또는 이의 수화물.
According to claim 1,
R 1 to R 4 are each independently hydrogen, halogen, linear or branched C 1-8 alkyl, linear or branched C 1-8 alkoxy, linear or branched C 1-8 haloalkyl, linear or branched C 1-8 haloalkyl, branched C 1-8 haloalkoxy, C 6-10 arylC 1-8 alkyl, or straight or branched C 1-8 alkylamino;
R 5 and R 6 are each independently hydrogen or straight or branched C 1-8 alkyl;
R 7 is hydrogen or straight or branched C 1-5 alkyl;
R 8 is hydrogen, straight-chain or branched-chain C 1-8 alkyl, or C 6-10 arylC 1-8 alkyl; and
wherein n is an integer of 0 to 3, a pyridone-based compound, a stereoisomer thereof, or a hydrate thereof.
상기 R1 내지 R4는 각각 독립적으로 수소, 직쇄 또는 분지쇄의 C1-5알킬, 직쇄 또는 분지쇄의 C1-5알콕시, 직쇄 또는 분지쇄의 C1-5할로알킬, 또는 직쇄 또는 분지쇄의 C1-5할로알콕시이고;
상기 R5 및 R6은 각각 독립적으로 수소, 또는 직쇄 또는 분지쇄의 C1-5알킬이고;
상기 R7은 수소, 또는 직쇄 또는 분지쇄의 C1-3알킬이고;
상기 R8는 수소, 또는 직쇄 또는 분지쇄의 C1-5알킬이고; 및
상기 n은 0 내지 2의 정수인, 피리돈계 화합물, 이의 입체 이성질체, 또는 이의 수화물.
According to claim 1,
R 1 to R 4 are each independently hydrogen, linear or branched C 1-5 alkyl, linear or branched C 1-5 alkoxy, linear or branched C 1-5 haloalkyl, or linear or branched chain C 1-5 alkoxy. chain C 1-5 haloalkoxy;
R 5 and R 6 are each independently hydrogen or straight or branched C 1-5 alkyl;
R 7 is hydrogen or straight or branched C 1-3 alkyl;
R 8 is hydrogen or straight or branched C 1-5 alkyl; and
wherein n is an integer of 0 to 2, a pyridone-based compound, a stereoisomer thereof, or a hydrate thereof.
상기 R1 내지 R4는 각각 독립적으로 수소 또는 -OCH3이고;
상기 R5 및 R6은 각각 독립적으로 수소 또는 -CH3이고;
상기 R7은 -CH3이고;
상기 R8는 -CH2CH2CH2CH3이고; 및
상기 n은 1인, 피리돈계 화합물, 이의 입체 이성질체, 또는 이의 수화물.
According to claim 1,
The R 1 to R 4 are each independently hydrogen or -OCH 3 ;
Wherein R 5 and R 6 are each independently hydrogen or -CH 3 ;
R 7 is -CH 3 ;
R 8 is -CH 2 CH 2 CH 2 CH 3 ; and
wherein n is 1, a pyridone-based compound, a stereoisomer thereof, or a hydrate thereof.
상기 화학식 1로 표시되는 화합물은 하기 화합물 군으로부터 선택되는 어느 하나인 것을 특징으로 하는, 피리돈계 화합물, 이의 입체 이성질체, 또는 이의 수화물:
(1) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(5-메톡시-2-메틸인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴;
(2) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(5-메톡시인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴;
(3) (Z)-1-뷰틸-5-((2Z,4E)-5-(5,6-다이메톡시인돌린-1-일)-2-하이드록시펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴;
(4) (Z)-1-뷰틸-5-((2Z,4E)-5-(5,6-다이메톡시-2-메틸인돌린-1-일)-2-하이드록시펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴;
(5) (Z)-1-뷰틸-5-((2Z,4E)-5-(5,6-다이메톡시-3-메틸인돌린-1-일)-2-하이드록시펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴;
(6) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(5,6,7-트라이메톡시인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴;
(7) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(4,5,6,7-테트라메톡시인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴;
(8) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴;
(9) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(2-메틸인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴; 및
(10) (Z)-1-뷰틸-5-((2Z,4E)-2-하이드록시-5-(3-메틸인돌린-1-일)펜타-2,4-다이엔-1-일리덴)-4-메틸-2,6-다이옥소-1,2,5,6-테트라하이드로피리딘-3-카보나이트릴.
According to claim 1,
A pyridone-based compound, a stereoisomer thereof, or a hydrate thereof, characterized in that the compound represented by Formula 1 is any one selected from the group of compounds below:
(1) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5-methoxy-2-methylindolin-1-yl)penta-2,4-di en-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile;
(2) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5-methoxyindolin-1-yl)penta-2,4-dien-1-yl den)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile;
(3) (Z)-1-butyl-5-((2Z,4E)-5-(5,6-dimethoxyindolin-1-yl)-2-hydroxypenta-2,4-diene- 1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile;
(4) (Z)-1-butyl-5-((2Z,4E)-5-(5,6-dimethoxy-2-methylindolin-1-yl)-2-hydroxypenta-2; 4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile;
(5) (Z)-1-butyl-5-((2Z,4E)-5-(5,6-dimethoxy-3-methylindolin-1-yl)-2-hydroxypenta-2; 4-dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile;
(6) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(5,6,7-trimethoxyindolin-1-yl)penta-2,4-di en-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile;
(7) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(4,5,6,7-tetramethoxyindolin-1-yl)penta-2,4 -dien-1-ylidene)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile;
(8) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(indolin-1-yl)penta-2,4-dien-1-ylidene)- 4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile;
(9) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(2-methylindolin-1-yl)penta-2,4-dien-1-yl den)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile; and
(10) (Z)-1-butyl-5-((2Z,4E)-2-hydroxy-5-(3-methylindolin-1-yl)penta-2,4-dien-1-yl den)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile.
[화학식 1]
상기 화학식 1에서,
상기 R1 내지 R4는 각각 독립적으로 수소, 할로겐, 직쇄 또는 분지쇄의 C1-10알킬, 직쇄 또는 분지쇄의 C1-10알콕시, 직쇄 또는 분지쇄의 C1-10할로알킬, 직쇄 또는 분지쇄의 C1-10할로알콕시, C6-10아릴C1-10알킬, 또는 직쇄 또는 분지쇄의 C1-10알킬아미노이고;
상기 R5 및 R6은 각각 독립적으로 수소, 또는 직쇄 또는 분지쇄의 C1-10알킬이고;
상기 R7은 수소, 할로겐, 또는 직쇄 또는 분지쇄의 C1-5알킬이고;
상기 R8는 수소, 직쇄 또는 분지쇄의 C1-10알킬, 또는 C6-10아릴C1-10알킬이고; 및
상기 n은 0 내지 5의 정수이다.
A resin composition for near-infrared absorption comprising a pyridone-based compound represented by Formula 1, a stereoisomer thereof or a hydrate thereof, and a resin:
[Formula 1]
In Formula 1,
Wherein R 1 to R 4 are each independently hydrogen, halogen, straight-chain or branched C 1-10 alkyl, straight-chain or branched-chain C 1-10 alkoxy, straight-chain or branched-chain C 1-10 haloalkyl, straight-chain or branched C 1-10 haloalkoxy, C 6-10 arylC 1-10 alkyl, or straight or branched C 1-10 alkylamino;
R 5 and R 6 are each independently hydrogen or linear or branched C 1-10 alkyl;
R 7 is hydrogen, halogen, or straight or branched C 1-5 alkyl;
R 8 is hydrogen, straight-chain or branched-chain C 1-10 alkyl, or C 6-10 arylC 1-10 alkyl; and
Said n is an integer from 0 to 5.
상기 수지는 환상 올레핀계 수지, (변성)아크릴계 수지, 방향족 폴리에테르계 수지, 폴리이미드계 수지, 플루오렌폴리카보네이트계 수지, 플루오렌폴리에스테르계 수지, 폴리카보네이트계 수지, 폴리아미드계 수지, 폴리아릴레이트계 수지, 폴리술폰계 수지, 폴리에테르술폰계 수지, 폴리파라페닐렌계 수지, 폴리아미드이미드계 수지, 폴리에틸렌나트탈레이트계 수지, 불소화 방향족 폴리머계 수지, 우레탄 수지 및 에폭시계 수지로 이루어지는 군으로부터 선택되는 어느 하나 이상인, 근적외선 흡수용 수지 조성물.
According to claim 6,
The resin is a cyclic olefin-based resin, (modified) acrylic resin, aromatic polyether-based resin, polyimide-based resin, fluorene polycarbonate-based resin, fluorene polyester-based resin, polycarbonate-based resin, polyamide-based resin, polyamide from the group consisting of relate-based resins, polysulfone-based resins, polyethersulfone-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate-based resins, fluorinated aromatic polymer-based resins, urethane resins and epoxy-based resins; Any one or more selected, the resin composition for near-infrared absorption.
A near-infrared cut-off filter comprising a near-infrared absorbing layer comprising the resin composition for absorbing near-infrared rays of claim 6.
상기 근적외선 흡수층은 투명 유리기판 또는 투명 수지제 기판의 일면 또는 양면에 형성된 것인, 근적외선 차단필터.
According to claim 8,
The near infrared ray absorbing layer is formed on one or both sides of a transparent glass substrate or a transparent resin substrate.
An electronic device comprising the near-infrared cut-off filter of claim 8.
A solid-state imaging device comprising the near-infrared cut-off filter of claim 8.
A camera module comprising the near-infrared cut-off filter of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210097740A KR102591097B1 (en) | 2021-07-26 | 2021-07-26 | Pyridone based compound, resin composition for near-infrared ray absorption containing the same, and near-infrared ray blocking filter manufactured by using this |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210097740A KR102591097B1 (en) | 2021-07-26 | 2021-07-26 | Pyridone based compound, resin composition for near-infrared ray absorption containing the same, and near-infrared ray blocking filter manufactured by using this |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20230016355A true KR20230016355A (en) | 2023-02-02 |
| KR102591097B1 KR102591097B1 (en) | 2023-10-19 |
Family
ID=85225659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020210097740A KR102591097B1 (en) | 2021-07-26 | 2021-07-26 | Pyridone based compound, resin composition for near-infrared ray absorption containing the same, and near-infrared ray blocking filter manufactured by using this |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102591097B1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140120690A (en) | 2013-04-04 | 2014-10-14 | 주식회사 엘엠에스 | Near infrared ray cut filter and solid state imaging device comprising the same |
| KR101842495B1 (en) * | 2017-03-13 | 2018-03-27 | 한국화학연구원 | Novel squarylium compounds, resin composition for absorbing near infrared ray including the same and absorbing near infrared ray blocking filter manufactured by using this |
| KR20190060701A (en) * | 2017-11-24 | 2019-06-03 | 란세스 도이치란트 게엠베하 | Novel methine dyes |
| KR102138070B1 (en) * | 2015-05-20 | 2020-07-27 | 후지필름 가부시키가이샤 | Infrared absorbing composition, infrared blocking filter, laminate, pattern forming method, and solid-state imaging device |
-
2021
- 2021-07-26 KR KR1020210097740A patent/KR102591097B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140120690A (en) | 2013-04-04 | 2014-10-14 | 주식회사 엘엠에스 | Near infrared ray cut filter and solid state imaging device comprising the same |
| KR102138070B1 (en) * | 2015-05-20 | 2020-07-27 | 후지필름 가부시키가이샤 | Infrared absorbing composition, infrared blocking filter, laminate, pattern forming method, and solid-state imaging device |
| KR101842495B1 (en) * | 2017-03-13 | 2018-03-27 | 한국화학연구원 | Novel squarylium compounds, resin composition for absorbing near infrared ray including the same and absorbing near infrared ray blocking filter manufactured by using this |
| KR20190060701A (en) * | 2017-11-24 | 2019-06-03 | 란세스 도이치란트 게엠베하 | Novel methine dyes |
Non-Patent Citations (1)
| Title |
|---|
| Controlling Dark Equilibria and Enhancing Donor-Acceptor Stenhouse Adduct Photoswitching Properties through Carbon Acid Design. J. Hemmer et al.. J. Am. Chem. Soc.. 2018, Vol. 140, pp. 10425-10429* * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102591097B1 (en) | 2023-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103323897B (en) | Selectively light-transmitting filter, resin sheet and solid state image sensor | |
| JP7222361B2 (en) | Optical filters and imagers | |
| EP1564260A1 (en) | Coloring matter absorbing near-infrared ray and filter for cutting off near-infrared ray | |
| JP6599194B2 (en) | Mixture of oxocarbon compounds | |
| KR101842495B1 (en) | Novel squarylium compounds, resin composition for absorbing near infrared ray including the same and absorbing near infrared ray blocking filter manufactured by using this | |
| JP6599192B2 (en) | Oxocarbon compounds | |
| EP3546990B1 (en) | Near-infrared absorbing film, optical filter compring the same and electronic device | |
| CN106397300A (en) | Cyanine compound, optical filter, apparatus using optical filter and resin composite | |
| JP2019078816A (en) | Optical filter and imaging apparatus | |
| US11333809B2 (en) | Composition for near-infrared light-absorbing films, near-infrared light-absorbing layers, camera modules, and electronic devices | |
| KR102591097B1 (en) | Pyridone based compound, resin composition for near-infrared ray absorption containing the same, and near-infrared ray blocking filter manufactured by using this | |
| JP2019031637A (en) | Squarylium compound | |
| WO2019230570A1 (en) | Near-infrared absorbing dye, optical filter and imaging device | |
| JP2017082029A (en) | Oxocarbon compound | |
| KR20210042029A (en) | Novel squarylium compounds, and compositions comprising same | |
| JP6811602B2 (en) | Optical selective transmission filter | |
| JP7415788B2 (en) | Squarylium compounds, pigment compositions, films, optical filters, solid-state imaging devices, image display devices, and infrared sensors | |
| KR102377756B1 (en) | Coloring matter absorbing Near-infrared ray and filter for cutting off Near-infrared ray using Thereof | |
| JP2017151176A (en) | Light selective transmission filter | |
| KR102622663B1 (en) | Squarylium compounds, resin composition for absorbing near infrared ray including the same and absorbing near infrared ray blocking filter manufactured by using the same | |
| KR20230064882A (en) | Diimmonium-based compound and near-infrared absorption composition comprising the same | |
| JP6634147B2 (en) | Oxocarbon-based compound, resin composition and ink composition | |
| JP7537309B2 (en) | Dye composition, film, optical filter, image display device, infrared sensor, and fingerprint authentication sensor | |
| KR102492266B1 (en) | Squaraine compound, composition having the same, light absorption layer having the same, and optical filter having the same | |
| JP2021195515A (en) | Croconic acid compound, pigment composition, film, optical filter, solid state imaging device, picture display unit and infrared ray sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right |