JP3710912B2 - Photochromic material - Google Patents
Photochromic material Download PDFInfo
- Publication number
- JP3710912B2 JP3710912B2 JP08487897A JP8487897A JP3710912B2 JP 3710912 B2 JP3710912 B2 JP 3710912B2 JP 08487897 A JP08487897 A JP 08487897A JP 8487897 A JP8487897 A JP 8487897A JP 3710912 B2 JP3710912 B2 JP 3710912B2
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- Prior art keywords
- aminomethyl
- group
- atom
- photochromic material
- solution
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- 239000000463 material Substances 0.000 title claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 claims description 11
- MPBCUCGKHDEUDD-UHFFFAOYSA-N (5-methylpyrazin-2-yl)methanamine Chemical compound CC1=CN=C(CN)C=N1 MPBCUCGKHDEUDD-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- FEWQWMKPPJZYCQ-UHFFFAOYSA-N isoquinolin-1-ylmethanamine Chemical compound C1=CC=C2C(CN)=NC=CC2=C1 FEWQWMKPPJZYCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QNLAYSBIWHHNIT-UHFFFAOYSA-N (3-methylpyridin-2-yl)methanamine Chemical compound CC1=CC=CN=C1CN QNLAYSBIWHHNIT-UHFFFAOYSA-N 0.000 claims description 3
- QVDFBCYBLHPIOI-UHFFFAOYSA-N (4-methylpyridin-2-yl)methanamine Chemical compound CC1=CC=NC(CN)=C1 QVDFBCYBLHPIOI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000005035 acylthio group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- TXMHNJDESIWXIA-UHFFFAOYSA-N isoquinolin-3-ylmethanamine Chemical compound C1=CC=C2C=NC(CN)=CC2=C1 TXMHNJDESIWXIA-UHFFFAOYSA-N 0.000 claims description 3
- QPRZPKGMUJBNPY-UHFFFAOYSA-N (3-chloropyridin-2-yl)methanamine Chemical compound NCC1=NC=CC=C1Cl QPRZPKGMUJBNPY-UHFFFAOYSA-N 0.000 claims description 2
- CCSXJBGBEXZUAD-UHFFFAOYSA-N (3-nitropyridin-2-yl)methanamine Chemical compound NCC1=NC=CC=C1[N+]([O-])=O CCSXJBGBEXZUAD-UHFFFAOYSA-N 0.000 claims description 2
- IRXZAESUDRFBDZ-UHFFFAOYSA-N (4-nitropyridin-2-yl)methanamine Chemical compound NCC1=CC([N+]([O-])=O)=CC=N1 IRXZAESUDRFBDZ-UHFFFAOYSA-N 0.000 claims description 2
- NXTVBKWLOZSCQE-UHFFFAOYSA-N (5-methylpyridin-2-yl)methanamine Chemical compound CC1=CC=C(CN)N=C1 NXTVBKWLOZSCQE-UHFFFAOYSA-N 0.000 claims description 2
- GOZNQVJBZJTDQI-UHFFFAOYSA-N C1=CNN(N=C1)CN Chemical compound C1=CNN(N=C1)CN GOZNQVJBZJTDQI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- ROSKZJGILXBSFM-UHFFFAOYSA-N pyrimidin-2-ylmethanamine Chemical compound NCC1=NC=CC=N1 ROSKZJGILXBSFM-UHFFFAOYSA-N 0.000 claims description 2
- HGHPGHVNTQSTNM-UHFFFAOYSA-N quinolin-2-ylmethanamine Chemical compound C1=CC=CC2=NC(CN)=CC=C21 HGHPGHVNTQSTNM-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- HAMPAYCXCRJMQE-UHFFFAOYSA-N C1=C(N=CC(=N1)[N+](=O)[O-])CN Chemical compound C1=C(N=CC(=N1)[N+](=O)[O-])CN HAMPAYCXCRJMQE-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- -1 n- Alternatively Chemical group 0.000 description 23
- 238000004090 dissolution Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 150000002391 heterocyclic compounds Chemical class 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003606 tin compounds Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- DIVTWACHZOQOBF-UHFFFAOYSA-K diacetyloxy(butyl)stannanylium;acetate Chemical compound CCCC[Sn](OC(C)=O)(OC(C)=O)OC(C)=O DIVTWACHZOQOBF-UHFFFAOYSA-K 0.000 description 3
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- NLDDLJBGRZJASZ-UHFFFAOYSA-N 3,5-dimethylpyridin-2-amine Chemical compound CC1=CN=C(N)C(C)=C1 NLDDLJBGRZJASZ-UHFFFAOYSA-N 0.000 description 1
- RZJPBQGRCNJYBU-UHFFFAOYSA-N 3-chloropyridin-2-amine Chemical compound NC1=NC=CC=C1Cl RZJPBQGRCNJYBU-UHFFFAOYSA-N 0.000 description 1
- YHXMPLXAZQRIAA-UHFFFAOYSA-N 6-(aminomethyl)-3-nitropyridine Chemical compound NCC1=CC=C([N+]([O-])=O)C=N1 YHXMPLXAZQRIAA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ISXUHJXWYNONDI-UHFFFAOYSA-L dichloro(diphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](Cl)(Cl)C1=CC=CC=C1 ISXUHJXWYNONDI-UHFFFAOYSA-L 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- FSXWCUSOFGPQKK-UHFFFAOYSA-N ethanebis(thioic s-acid) Chemical compound SC(=O)C(S)=O FSXWCUSOFGPQKK-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- DUYAAUVXQSMXQP-UHFFFAOYSA-M thioacetate Chemical compound CC([S-])=O DUYAAUVXQSMXQP-UHFFFAOYSA-M 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、有機錫化合物と、オルソ位にアミノメチル基を有する含窒素芳香族複素環化合物とを含有する新規なホトクロミック材料に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
従来、多くのホトクロミック材料が知られているが、一般的に繰返し使用における寿命が短いため、色変換速度が次第に遅くなったり、発色強度が弱まったりするという欠点がある。
【０００３】
そこで本発明者らは、繰返し使用における寿命が長いホトクロミック材料を得るために種々検討を行った結果、特定の有機錫化合物とオルソ位にアミノメチル基を有する含窒素芳香族複素環化合物とが５員環構造の錯体を形成し、光を照射することによって著しい色変化を生じ、暗所に放置することによって元の色に戻り、かつこの色変化の長期保存安定性が良好で、繰返し使用における寿命が長いこと、及び有機錫化合物とオルソ位にアミノメチル基を有する含窒素芳香族複素環化合物とを混合するだけで錯体を形成することができ、両者を含有する材料が上記目的を達成できることを見出し本発明を完成させたものである。
【０００４】
【課題を解決するための手段】
すなわち本発明は、下記一般式［１］、［２］又は［３］で表される有機錫化合物と、配位子である含窒素芳香族複素環を有し且つ芳香環上の窒素原子からオルソ位となる位置にアミノメチル基を有する化合物とを含有するホトクロミック材料を提供するものである。。
【０００５】
（Ｒ）k −Ｓｎ−（Ｘ）(4-k) ［１］
【０００６】
【化４】
【化５】
（上記式［１］、［２］又は［３］中、Ｒは、それぞれ同一又は異なっていてもよい炭素原子数１〜１２の炭化水素基を表し、Ｘは、水素原子、ハロゲン原子、酸素原子、アシルオキシ基、アシルチオ基、アルコキシル基又はアルキルチオ基を表し、Ｘのそれぞれは同一又は異なっていてもよく、Ａは直接結合又は炭素原子数１〜２０の炭化水素基を表し、Ｙは酸素原子又は硫黄原子を表し、各繰返し単位中における各Ｒ、各Ｘ、各Ａ及び各Ｙは同一又は異なっていてもよく、ｋは１〜３の整数、ｊは１又は２の整数、ｍは１〜１００の整数を示し、Ｄは、それぞれ同一又は異なって、水素原子又は下記式［４］で表される基である）
【０００９】
【化６】
（上記式［４］中、Ｒ、Ｘ及びｋは、それぞれ前記と同じ意味を有する）
【００１１】
【発明の実施の形態】
本発明のホトクロミック材料を形成する有機錫化合物において、前記一般式［１］、［２］、［３］及び［４］中のＲによって示される一価の炭素原子数１〜１２の炭化水素基は、アルコキシル基、エステル基又はハロゲン原子が置換していてもよい炭素原子数１〜１２の一価の炭化水素基であり、アルキル基、アルケニル基、シクロアルキル基、シクロアルキルアルキル基、アリール基、アラルキル基などの脂肪族、脂環族又は芳香族炭化水素基を例示できる。これらのうち、フェニル基及びアルキル基が好ましく、アルキル基としては直鎖状及び分岐鎖状のいずれであってもよく、特に炭素原子数１〜８のものが望ましく、例えばメチル、エチル、ｎ−もしくはｉｓｏ−プロピル、ｎ−，ｉｓｏ−，ｓｅｃ−もしくはｔ−ブチル、ペンチル、ヘキシル、オクチル基などが挙げられる。
【００１２】
アルコキシル基置換炭化水素基の好ましい例としては、メトキシメチル、エトキシメチル、エトキシエチル、ｎ−プロポキシエチル、ｎ−ブトキシメチル、ｉｓｏ−ブトキシエチル基などのアルコキシアルキル基などが挙げられる。エステル基置換炭化水素基の好ましい例としては、メトキシカルボニルメチル、プロポキシカルボニルエチル、エトキシカルボニルプロピル、メトキシカルボニルブチルなどのアルコキシカルボニルアルキル基；メトキシカルボニルエチレニル、エトキシカルボニルエチレニル基等が挙げられる。ハロゲン原子置換炭化水素基の好ましい例としては、クロロメチル、ブロモメチル、ヨードメチル、ジクロロメチル、トリクロロメチル、クロロエチル、クロロブチル基等が挙げられる。
【００１３】
前記一般式［１］、［２］、［３］及び［４］中のＸによって示されるハロゲン原子としては、Ｃｌ、Ｂｒ、Ｉ、Ｆ原子を挙げることができる。
【００１４】
また上記Ｘによって示されるアシルオキシ基としては、好適なものとして炭素原子数１〜１８の基、例えば、ホルミルオキシ、アセチルオキシ、プロピオニルオキシ、ブチリルオキシ、イソブチリルオキシ、バレリルオキシ、イソバレリルオキシ、オクタノイルオキシ、デカノイルオキシ、ラウロイルオキシ、ミリストイルオキシ、パルミトイルオキシ、ステアロイルオキシ、ピバロイルオキシ、ベンゾイルオキシ、トルオイルオキシ、アクリロイルオキシ、メタクリロイルオキシ基を挙げることができる。
【００１５】
さらに上記Ｘによって示されるアシルチオ基としては、好適なものとして炭素原子数１〜１８の基、例えば、アセチルチオ、プロピオニルチオ、ブチリルチオ、バレリルチオ、オクタノイルチオ、ラウロイルチオ、ステアロイルチオ基などを挙げることができる。
【００１６】
また上記Ｘによって示されるアルコキシル基としては、好適なものとして炭素原子数１〜１２の基、例えばメトキシ、エトキシ、ｎ−もしくはｉｓｏ−プロポキシ、ｎ−，ｉｓｏ−，ｓｅｃ−もしくはｔ−ブトキシ、ペンチルオキシ、ヘキシルオキシ、オクチルオキシ、ラウリルオキシ基などを挙げることができる。
【００１７】
さらに上記Ｘによって示されるアルキルチオ基としては、好適なものとして炭素原子数１〜１２の基、例えば、メチルチオ、エチルチオ、プロピルチオ、ブチルチオ、ヘキシルチオ、オクチルチオ、ラウリルチオ基などを挙げることができる。
【００１８】
前記一般式［２］及び［３］中のＡによって示される炭素原子数１〜２０の二価の炭化水素基としては、二塩基カルボン酸から２個のカルボキシル基を除去した残基又は二塩基チオカルボン酸から２個のチオカルボキシル基を除去した残基であり、例えば、メチレン、エチレン、プロピレン、テトラメチレン、ヘキサメチレン、エチルエチレン、ペンタメチレン、ヘキサメチレン、オクタメチレン、ドデカンジイル、ヘキサデカンジイル、オクタデカンジイル、ビニレン、プロペニレン、オクタデセンジイル基などを挙げることができる。
【００１９】
前記一般式［１］によって表される有機錫化合物の具体例としては、例えば、ジブチル錫ジアセテート、モノブチル錫トリアセテート、モノブチル錫トリオクチレート、モノブチル錫トリクロライド、ジブチル錫ジクロライド、トリブチル錫モノクロライド、ジブチル錫ジオクチレート、ジブチル錫ジラウレート、ジフェニル錫ジクロライド、トリフェニル錫モノクロライド、ジブチル錫ジオキサイド、ジオクチル錫ジオキサイド、ジブチル錫ジマレエート、ジブチル錫ジ（チオ酢酸エステル）などを挙げることができる。
【００２０】
前記一般式［２］及び［３］中のｍの値は、１〜１００、好ましくは１〜４である。
【００２１】
前記一般式［２］によって表される有機錫化合物の具体例としては、例えば、マレイン酸とジブチル錫ジオキサイドとのエステル化物である、式［２］のＡがビニレン、Ｙが酸素原子、Ｘが酸素原子、Ｒがブチル基、Ｄが水素原子、ｊが２、ｋが２、ｍが２の化合物；コハク酸とジブチル錫ジオキサイドとのエステル化物である、式［２］のＡがエチレン、Ｙが酸素原子、Ｘが酸素原子、Ｒがブチル基、２つのＤがいずれも式［４］で表される基であり、ｊが２、ｋが２、ｍが２の化合物；アジピン酸とジブチル錫ジオキサイドとのエステル化物である、式［２］のＡがテトラメチレン、Ｙが酸素原子、Ｘが酸素原子、Ｄが水素原子、Ｒがブチル基、ｋが２、ｍが１の化合物；エタンビス（チオイックアシッド）とジブチル錫ジオキサイドとのエステル化物である、式［２］のＡがエチレン、Ｙが硫黄原子、Ｘが酸素原子、Ｒがブチル基、ｊが２、ｋが２、ｍが３の化合物などを挙げることができる。
【００２２】
前記一般式［３］によって表される有機錫化合物は、閉環した環状化合物であり、この具体例としては、例えば、マレイン酸とジブチル錫ジオキサイドとのエステル化物である、式［２］のＡがビニレン、Ｙが酸素原子、Ｘが酸素原子、Ｒがブチル基、ｊが２、ｍが２の化合物などを挙げることができる。
【００２３】
本発明のホトクロミック材料を形成する、配位子である含窒素芳香族複素環を有し且つ芳香環上の窒素原子からオルソ位となる位置にアミノメチル基を有する化合物（以下、「アミノメチル基含有複素環化合物」と略称する）としては、窒素原子からオルソ位となる位置にアミノメチル基を有する含窒素芳香族複素環化合物であれば制限なく使用でき、例えば２−アミノメチルピリジン、２−アミノメチル−５−メチルピラジン、２−アミノメチルキノリン、２−アミノメチルピリミジン、２−アミノメチルトリアジン、２−アミノメチル−３−メチルピリジン、２−アミノメチル−４−メチルピリジン、２−アミノメチル−５−メチルピリジン、１−アミノメチルイソキノリン、３−アミノメチルイソキノリン、２−アミノメチル−５−ニトロピラジン、２−アミノメチル−３−ニトロピリジン、２−アミノメチル−４−ニトロピリジン、２−アミノメチル−５−ニトロピリジン及び２−アミノメチル−３−クロロピリジンなどを挙げることができる。
【００２４】
本発明において、有機錫化合物とアミノメチル基含有複素環化合物とが形成する錯体は、有機錫化合物が前記式［１］で表される化合物である場合を例にして示すと、下記のとおりになる。
【００２５】
【化７】
上記式において、アミノメチル基含有複素環化合物を下記式で表す。
【００２７】
【化８】
本発明において、有機錫化合物及びアミノメチル基含有複素環化合物は、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ベンジルアルコール、２−メトキシエタノール、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテルなどのアルコール溶剤；酢酸エチル、酢酸ブチル、エチレングリコールモノエチルエーテルアセテートなどのエステル溶剤；トルエン、キシレンなどの芳香族炭化水素溶剤；ヘキサン、ヘプタン、オクタン、イソオクタン、ドデカンなどの脂肪族炭化水素溶剤などの溶剤の一種または二種以上の混合溶剤に溶解させることができ、この溶液をホトクロミック材料として使用することができる。また上記溶液中に樹脂を混合溶解させてなる溶液、さらにこの樹脂を混合溶解させてなる溶液から形成してなる固体膜もホトクロミック材料として使用することができる。
【００２９】
上記溶液中に混合溶解できる樹脂としては、例えば、アクリル樹脂、ポリエステル樹脂、エポキシ樹脂、ポリウレタン樹脂、アミノ樹脂などを挙げることができる。上記樹脂は、ホトクロミック材料を構成する全成分量に対し７０重量％以下の量配合することができる。
【００３０】
本発明のホトクロミック材料において、前記有機錫化合物とアミノメチル基含有複素環化合物との配合比は、特に限定されるものではないが、通常、有機錫化合物中の錫原子の当量とアミノメチル基含有複素環化合物との当量の比が、前者：後者で１０：１〜１：１００００、好ましくは１：１〜１：１００の範囲にあることが好適である。
【００３１】
本発明のホトクロミック材料において、前記有機錫化合物とアミノメチル基含有複素環化合物との合計量の濃度は、特に限定されるものではないが、通常、ホトクロミック材料を構成する全成分量に対し０．１〜４０重量％、さらには０．５〜３０重量％の範囲にあることが好適である。
【００３２】
アミノメチル基含有複素環化合物と前記有機錫化合物とを含有する溶液は溶解直後に、赤色、紫色又は緑色などに発色する。この発色した溶液に可視光線又は紫外線を照射すると消色する。続いて、この消色した溶液を暗所に放置すると元の色に発色する。
【００３３】
本発明のホトクロミック材料である溶液は、発色−消色の繰り返し使用によっても劣化せず、繰り返し使用における良好な安定性を示す。なかには繰り返し使用によって、暗所での放置による発色に要する時間が徐々に短くなり、且つ可視光線又は紫外線の照射による消色に要する時間が徐々に短くなって、応答がより良くなるものもある。
【００３４】
【実施例】
以下、実施例により本発明をさらに具体的に説明する。
【００３５】
実施例１
２−アミノメチルピリジン１．０８部、ジブチル錫ジアセテート１．７５５部及びベンジルアルコール１００部（２−アミノメチルピリジン／ジブチル錫ジアセテート中の錫原子のモル比は２／１）を混合溶解させ、ホトクロミック材料である溶液Ａを得た。溶解直後の溶液Ａは赤色であり、波長５７２ｎｍに最大吸収を有しており、波長４１２ｎｍに第２番目に大きい吸収を有していた。この溶液Ａの溶解直後の吸収スペクトルを図１に示す。次に溶液Ａについて、光照射及び暗所放置を繰返した際の、波長５７２ｎｍにおける吸光度の変化を図２に示す。図２から明らかなように、溶液Ａは光照射及び暗所放置を繰返すことにより、消色及び発色に要する時間が徐々に短くなった。また、消色及び発色を１０００サイクル繰り返しても色変換速度が遅くなったり、発色強度が弱まったりすることがなく良好な繰り返し使用安定性を示した。
【００３６】
実施例２〜１２
実施例１において、ジブチル錫ジアセテートのかわりに下記表１に示す有機錫化合物を使用し、２−アミノメチルピリジン／有機錫化合物中の錫原子のモル比が４／１となるように有機錫化合物の量を変更する以外は、実施例１と同様に行いホトクロミック材料である各種溶液を得た。下記表１に有機錫化合物の種類及び溶解直後の溶液の最大吸収波長を示す。
【００３７】
【表１】
実施例１３
２−アミノメチル−５−メチルピラジン３．６９部、ジブチル錫ジオキサイド７．９５部及びｎ−ブタノール１００部（２−アミノメチル−５−メチルピラジン／ジブチル錫ジオキサイド中の錫原子のモル比は１／１）を混合溶解させ、ホトクロミック材料である溶液を得た。溶解直後のこの溶液は緑色であり、波長６５０ｎｍに最大吸収を有していた。この溶液の溶解直後の吸収スペクトルを図３に示す。
【００３９】
実施例１４
２−アミノメチル−５−メチルピラジン７．３８部、ジブチル錫マレエート１０．３５部及びトルエン１００部（２−アミノメチル−５−メチルピラジン／ジブチル錫マレエート中の錫原子のモル比は２／１）を混合溶解させ、ホトクロミック材料である溶液を得た。溶解直後の溶液は緑色であり、波長６５０ｎｍに最大吸収を有していた。
【００４０】
実施例１５
２−アミノメチルピリジン６．４８部、ジブチル錫ジアセテート１０．５３部及びｎ−ブタノール１００部（２−アミノメチルピリジン／ジブチル錫ジアセテートのモル比は２／１）を混合溶解させ、ホトクロミック材料である溶液を得た。溶解直後の溶液は赤色であり、波長５７０ｎｍに最大吸収を有していた。
【００４１】
実施例１６
２−アミノメチル−３−メチルピリジン１０部、ジブチル錫ジアセテート１部及び２−メトキシエタノール１０００部を混合溶解させ、ホトクロミック材料である溶液を得た。溶解直後の溶液は黄緑色であり、波長６０５ｎｍに最大吸収を有していた。
【００４２】
実施例１７
２−アミノメチル−４−メチルピリジン１０部、ジブチル錫ジアセテート１部及びブタノール１０００部を混合溶解させ、ホトクロミック材料である溶液を得た。溶解直後の溶液は緑色であり、波長６３２ｎｍに最大吸収を有していた。
【００４３】
実施例１８
２−アミノメチル−５−メチルピリジン１０部、ジブチル錫ジアセテート１部及びブタノール１０００部を混合溶解させホトクロミック材料である溶液を得た。溶解直後の溶液は緑青色であり、波長６４０ｎｍに最大吸収を有していた。
【００４４】
実施例１９
３−アミノメチルイソキノリン５部、ジブチル錫ジアセテート１部及びトルエン１０００部を混合溶解させ、ホトクロミック材料である溶液を得た。溶解直後の溶液は青緑色であり、波長６４８ｎｍに最大吸収を有していた。
【００４５】
実施例２０
１−アミノメチルイソキノリン１００部、ジブチル錫ジアセテート１部及びトルエン１０００部を混合溶解させ、ホトクロミック材料である溶液を得た。溶解直後の溶液は緑青色であり、波長６４０ｎｍに最大吸収を有していた。
【００４６】
実施例２１
１−アミノメチルイソキノリン１００部、モノブチル錫トリアセテート１部及びトルエン１０００部を混合し、５０℃で２時間加熱して溶解させ、ホトクロミック材料である溶液を得た。溶解直後の溶液は青色であり、波長６５５ｎｍに最大吸収を有していた。
【００４７】
実施例２２
２−アミノメチル−３−クロロピリジン２００部、モノブチル錫トリアセテート１部及びトルエン１０００部を混合し、５０℃で２時間加熱して溶解させ、ホトクロミック材料である溶液を得た。溶解直後の溶液は橙色であり、波長５３０ｎｍに最大吸収を有していた。
【００４８】
実施例２３
２−アミノメチル−５−メチルピラジン１２．３部、ジオクチル錫ジオキサイド３７．７部、ｎ−ブタノール１００部及び重量平均分子量約２０，０００の共重合体樹脂（モノマー組成はメチルメタクリレート／２−ヒドロキシエチルの重量比が８０／２０）（２−アミノメチル−５−メチルピラジン／ジオクチル錫ジオキサイドのモル比は１／１）を混合溶解させ、ホトクロミック材料である溶液を得た。溶解直後のこの溶液は緑色であり、波長６５０ｎｍに最大吸収を有していた。得られた溶液を乾燥膜厚５μｍとなるようようにスピンコータにて塗布して被膜を得た。次にスパッタリング法により１００ｎｍの窒化ケイ素遮断膜を上記被膜上に形成した。
【００４９】
実施例２〜２２で得た溶液及び実施例２３で得た総合被膜は、実施例１と同様に消色及び発色を１０００サイクル繰り返しても色変換速度が遅くなったり、発色強度が弱まったりすることがなく良好な繰り返し使用安定性を示した。
【００５０】
比較例１
２−アミノメチルピリジン１．０８部、塩化第１錫０．９５部及びベンジルアルコール１００部（２−アミノメチルピリジン／塩化第１錫中の錫原子のモル比は２／１）を混合溶解させた。得られた溶液は、発色が認められなかった。
【００５１】
比較例２
２−アミノメチルピリジン１．０８部、錫ジオクテート２．０４部及びベンジルアルコール１００部（２−アミノメチルピリジン／錫ジオクテート中の錫原子のモル比は２／１）を混合溶解させた。得られた溶液は、発色が認められなかった。
【００５２】
【発明の効果】
本発明によって、繰返し使用における寿命が長いホトクロミック材料を得ることができる。本発明によって得られるホトクロミック材料は、光照射によって消色し、光照射をしないと着色するので、光センサー、光メモリー、また感光性樹脂に対する光反応開始剤などの用途に使用することができる。
【図面の簡単な説明】
【図１】本発明の実施例１における、溶解直後の溶液Ａの吸収スペクトルを示す図である。
【図２】本発明の実施例１における、溶解直後の溶液Ａに光照射及び暗所放置を繰返した際の、波長５７２ｎｍにおける吸光度の変化を示す図である。
【図３】本発明の実施例１３における、溶解直後の溶液の吸収スペクトルを示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel photochromic material containing an organotin compound and a nitrogen-containing aromatic heterocyclic compound having an aminomethyl group at the ortho position.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, many photochromic materials are known, but generally have shortcomings in that the color conversion speed is gradually decreased and the color intensity is weakened due to the short life in repeated use.
[0003]
Therefore, as a result of various studies to obtain a photochromic material having a long life in repeated use, the present inventors have found that a specific organotin compound and a nitrogen-containing aromatic heterocyclic compound having an aminomethyl group at the ortho position are obtained. Forming a complex with a 5-membered ring structure, causing a significant color change when irradiated with light, returning to the original color when left in a dark place, and good long-term storage stability of this color change, repeated use A complex can be formed by simply mixing an organotin compound and a nitrogen-containing aromatic heterocyclic compound having an aminomethyl group at the ortho position, and a material containing both achieves the above purpose. The present invention has been found out and completed.
[0004]
[Means for Solving the Problems]
That is, the present invention includes an organotin compound represented by the following general formula [1], [2] or [3], a nitrogen-containing aromatic heterocyclic ring as a ligand, and a nitrogen atom on the aromatic ring. The present invention provides a photochromic material containing a compound having an aminomethyl group at a position to be an ortho position. .
[0005]
(R) k -Sn- (X) (4-k) [1]
[0006]
[Formula 4]
[Chemical formula 5]
(In the above formula [1], [2] or [3], R represents a hydrocarbon group having 1 to 12 carbon atoms which may be the same or different, and X represents a hydrogen atom, a halogen atom or an oxygen atom. Represents an atom, an acyloxy group, an acylthio group, an alkoxyl group or an alkylthio group, each of X may be the same or different; A represents a direct bond or a hydrocarbon group having 1 to 20 carbon atoms; Y represents an oxygen atom Or a sulfur atom, each R, each X, each A and each Y in each repeating unit may be the same or different, k is an integer of 1 to 3, j is an integer of 1 or 2, and m is 1 Represents an integer of ˜100, and D is the same or different and each represents a hydrogen atom or a group represented by the following formula [4])
[0009]
[Chemical 6]
(In the above formula [4], R, X and k each have the same meaning as above)
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the organotin compound forming the photochromic material of the present invention, a monovalent hydrocarbon having 1 to 12 carbon atoms represented by R in the general formulas [1], [2], [3] and [4] The group is an alkoxyl group, an ester group, or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl Examples thereof include aliphatic, alicyclic or aromatic hydrocarbon groups such as a group and an aralkyl group. Among these, a phenyl group and an alkyl group are preferable, and the alkyl group may be either a straight chain or a branched chain, and those having 1 to 8 carbon atoms are particularly desirable. For example, methyl, ethyl, n- Alternatively, iso-propyl, n-, iso-, sec- or t-butyl, pentyl, hexyl, octyl group and the like can be mentioned.
[0012]
Preferable examples of the alkoxyl group-substituted hydrocarbon group include alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, ethoxyethyl, n-propoxyethyl, n-butoxymethyl, and iso-butoxyethyl groups. Preferable examples of the ester group-substituted hydrocarbon group include alkoxycarbonylalkyl groups such as methoxycarbonylmethyl, propoxycarbonylethyl, ethoxycarbonylpropyl and methoxycarbonylbutyl; methoxycarbonylethylenyl, ethoxycarbonylethylenyl groups and the like. Preferable examples of the halogen atom-substituted hydrocarbon group include chloromethyl, bromomethyl, iodomethyl, dichloromethyl, trichloromethyl, chloroethyl, chlorobutyl groups and the like.
[0013]
Examples of the halogen atom represented by X in the general formulas [1], [2], [3] and [4] include Cl, Br, I and F atoms.
[0014]
The acyloxy group represented by X is preferably a group having 1 to 18 carbon atoms such as formyloxy, acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, valeryloxy, isovaleryloxy, octa Examples include noyloxy, decanoyloxy, lauroyloxy, myristoyloxy, palmitoyloxy, stearoyloxy, pivaloyloxy, benzoyloxy, toluoyloxy, acryloyloxy and methacryloyloxy groups.
[0015]
Furthermore, preferable examples of the acylthio group represented by X include groups having 1 to 18 carbon atoms such as acetylthio, propionylthio, butyrylthio, valerylthio, octanoylthio, lauroylthio, stearoylthio groups and the like.
[0016]
The alkoxyl group represented by X is preferably a group having 1 to 12 carbon atoms such as methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- or t-butoxy, pentyl. An oxy, hexyloxy, octyloxy, lauryloxy group, etc. can be mentioned.
[0017]
Furthermore, preferable examples of the alkylthio group represented by X include groups having 1 to 12 carbon atoms, such as methylthio, ethylthio, propylthio, butylthio, hexylthio, octylthio, and laurylthio groups.
[0018]
In the general formulas [2] and [3], the divalent hydrocarbon group having 1 to 20 carbon atoms represented by A is a residue or dibasic acid in which two carboxyl groups are removed from a dibasic carboxylic acid. A residue obtained by removing two thiocarboxyl groups from thiocarboxylic acid, such as methylene, ethylene, propylene, tetramethylene, hexamethylene, ethylethylene, pentamethylene, hexamethylene, octamethylene, dodecanediyl, hexadecanediyl, octadecanediyl , Vinylene, propenylene, octadecenediyl group and the like.
[0019]
Specific examples of the organic tin compound represented by the general formula [1] include, for example, dibutyltin diacetate, monobutyltin triacetate, monobutyltin trioctylate, monobutyltin trichloride, dibutyltin dichloride, tributyltin monochloride, Examples thereof include dibutyltin dioctylate, dibutyltin dilaurate, diphenyltin dichloride, triphenyltin monochloride, dibutyltin dioxide, dioctyltin dioxide, dibutyltin dimaleate, and dibutyltin di (thioacetate).
[0020]
The value of m in the general formulas [2] and [3] is 1 to 100, preferably 1 to 4.
[0021]
Specific examples of the organic tin compound represented by the general formula [2] include, for example, an esterified product of maleic acid and dibutyltin dioxide, A in the formula [2] is vinylene, Y is an oxygen atom, X Is an oxygen atom, R is a butyl group, D is a hydrogen atom, j is 2, k is 2, m is 2; an esterified product of succinic acid and dibutyltin dioxide, A in formula [2] is ethylene Y is an oxygen atom, X is an oxygen atom, R is a butyl group, two D are groups represented by the formula [4], j is 2, k is 2, m is 2; adipic acid In the formula [2] is tetramethylene, Y is an oxygen atom, X is an oxygen atom, D is a hydrogen atom, R is a butyl group, k is 2, m is 1. Compound; ethanebis (thioic acid) and dibutyltin dioxide Is a ester, A of formula [2] is ethylene, Y is a sulfur atom, X is an oxygen atom, R is a butyl group, j is 2, k is 2, m can be cited such as three compounds.
[0022]
The organotin compound represented by the general formula [3] is a ring-closed cyclic compound. Specific examples thereof include, for example, an esterified product of maleic acid and dibutyltin dioxide, A of formula [2] And vinylene, Y is an oxygen atom, X is an oxygen atom, R is a butyl group, j is 2, and m is 2.
[0023]
A compound having a nitrogen-containing aromatic heterocyclic ring as a ligand and having an aminomethyl group at a position ortho to the nitrogen atom on the aromatic ring, which forms the photochromic material of the present invention (hereinafter referred to as “aminomethyl”). As the “group-containing heterocyclic compound”, any nitrogen-containing aromatic heterocyclic compound having an aminomethyl group at a position ortho to the nitrogen atom can be used without limitation. For example, 2-aminomethylpyridine, 2 -Aminomethyl-5-methylpyrazine, 2-aminomethylquinoline, 2-aminomethylpyrimidine, 2-aminomethyltriazine, 2-aminomethyl-3-methylpyridine, 2-aminomethyl-4-methylpyridine, 2-amino Methyl-5-methylpyridine, 1-aminomethylisoquinoline, 3-aminomethylisoquinoline, 2-aminomethyl-5-ni Ropirajin, 2-aminomethyl-3-nitropyridine, 2-aminomethyl-4-nitropyridine, and the like of 2-aminomethyl-5-nitropyridine and 2-amino-3-chloropyridine.
[0024]
In the present invention, the complex formed by the organotin compound and the aminomethyl group-containing heterocyclic compound is as follows when the organotin compound is a compound represented by the formula [1]. Become.
[0025]
[Chemical 7]
In the above formula, the aminomethyl group-containing heterocyclic compound is represented by the following formula.
[0027]
[Chemical 8]
In the present invention, the organotin compound and the aminomethyl group-containing heterocyclic compound are ethanol, n-propanol, isopropanol, n-butanol, isobutanol, benzyl alcohol, 2-methoxyethanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether. , Alcohol solvents such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; ester solvents such as ethyl acetate, butyl acetate and ethylene glycol monoethyl ether acetate; aromatic hydrocarbon solvents such as toluene and xylene; hexane, heptane, octane, isooctane, It can be dissolved in one or more solvents such as aliphatic hydrocarbon solvent such as dodecane, and this solution can be dissolved in photochromic material It can be used as. Further, a solution obtained by mixing and dissolving a resin in the above solution, and a solid film formed from a solution obtained by mixing and dissolving this resin can also be used as the photochromic material.
[0029]
Examples of the resin that can be mixed and dissolved in the solution include an acrylic resin, a polyester resin, an epoxy resin, a polyurethane resin, and an amino resin. The resin can be blended in an amount of 70% by weight or less based on the total amount of components constituting the photochromic material.
[0030]
In the photochromic material of the present invention, the compounding ratio of the organotin compound and the aminomethyl group-containing heterocyclic compound is not particularly limited, but usually the equivalent of tin atoms in the organotin compound and the aminomethyl group It is suitable that the ratio of the equivalent to the containing heterocyclic compound is in the range of 10: 1 to 1: 10000, preferably 1: 1 to 1: 100 in the former: latter.
[0031]
In the photochromic material of the present invention, the concentration of the total amount of the organotin compound and the aminomethyl group-containing heterocyclic compound is not particularly limited, but is usually based on the total amount of components constituting the photochromic material. It is preferable to be in the range of 0.1 to 40% by weight, more preferably 0.5 to 30% by weight.
[0032]
A solution containing the aminomethyl group-containing heterocyclic compound and the organotin compound develops red, purple or green color immediately after dissolution. When the colored solution is irradiated with visible light or ultraviolet light, the color is lost. Subsequently, when the decolored solution is left in a dark place, the original color is developed.
[0033]
The solution which is the photochromic material of the present invention does not deteriorate even after repeated use of coloring and decoloring, and exhibits good stability in repeated use. In some cases, repeated use gradually shortens the time required for color development when left in a dark place, and gradually shortens the time required for decoloration by irradiation with visible light or ultraviolet light, thereby improving the response.
[0034]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
[0035]
Example 1
Mix and dissolve 1.08 parts 2-aminomethylpyridine, 1.755 parts dibutyltin diacetate and 100 parts benzyl alcohol (molar ratio of tin atom in 2-aminomethylpyridine / dibutyltin diacetate is 2/1). Solution A which is a photochromic material was obtained. Solution A immediately after dissolution was red and had a maximum absorption at a wavelength of 572 nm and a second largest absorption at a wavelength of 412 nm. An absorption spectrum immediately after dissolution of the solution A is shown in FIG. Next, with respect to the solution A, the change in absorbance at a wavelength of 572 nm when light irradiation and standing in the dark are repeated is shown in FIG. As is clear from FIG. 2, the time required for decoloring and color development of the solution A was gradually shortened by repeating the light irradiation and leaving in the dark. Further, even when the decoloring and color development were repeated 1000 cycles, the color conversion speed was not slowed, and the color development intensity was not weakened.
[0036]
Examples 2-12
In Example 1, instead of dibutyltin diacetate, an organic tin compound shown in Table 1 below was used, and the organic tin was adjusted so that the molar ratio of 2-aminomethylpyridine / tin atom in the organic tin compound was 4/1. Except changing the quantity of the compound, it carried out similarly to Example 1 and obtained various solutions which are photochromic materials. Table 1 below shows the types of organotin compounds and the maximum absorption wavelength of the solution immediately after dissolution.
[0037]
[Table 1]
Example 13
2.69 parts 2-aminomethyl-5-methylpyrazine, 7.95 parts dibutyltin dioxide and 100 parts n-butanol (molar ratio of tin atoms in 2-aminomethyl-5-methylpyrazine / dibutyltin dioxide) 1/1) was mixed and dissolved to obtain a photochromic material solution. This solution immediately after dissolution was green and had a maximum absorption at a wavelength of 650 nm. The absorption spectrum immediately after dissolution of this solution is shown in FIG.
[0039]
Example 14
7.38 parts of 2-aminomethyl-5-methylpyrazine, 10.35 parts of dibutyltin maleate and 100 parts of toluene (the molar ratio of tin atoms in 2-aminomethyl-5-methylpyrazine / dibutyltin maleate was 2/1 ) Were mixed and dissolved to obtain a solution that was a photochromic material. The solution immediately after dissolution was green and had a maximum absorption at a wavelength of 650 nm.
[0040]
Example 15
6.48 parts of 2-aminomethylpyridine, 10.53 parts of dibutyltin diacetate and 100 parts of n-butanol (2-aminomethylpyridine / dibutyltin diacetate molar ratio is 2/1) are mixed and dissolved to produce a photochromic mixture. A material solution was obtained. The solution immediately after dissolution was red and had maximum absorption at a wavelength of 570 nm.
[0041]
Example 16
10 parts of 2-aminomethyl-3-methylpyridine, 1 part of dibutyltin diacetate and 1000 parts of 2-methoxyethanol were mixed and dissolved to obtain a solution as a photochromic material. The solution immediately after dissolution was yellowish green and had maximum absorption at a wavelength of 605 nm.
[0042]
Example 17
10 parts of 2-aminomethyl-4-methylpyridine, 1 part of dibutyltin diacetate and 1000 parts of butanol were mixed and dissolved to obtain a solution as a photochromic material. The solution immediately after dissolution was green and had maximum absorption at a wavelength of 632 nm.
[0043]
Example 18
10 parts of 2-aminomethyl-5-methylpyridine, 1 part of dibutyltin diacetate and 1000 parts of butanol were mixed and dissolved to obtain a solution as a photochromic material. The solution immediately after dissolution was greenish blue and had maximum absorption at a wavelength of 640 nm.
[0044]
Example 19
5 parts of 3-aminomethylisoquinoline, 1 part of dibutyltin diacetate and 1000 parts of toluene were mixed and dissolved to obtain a solution as a photochromic material. The solution immediately after dissolution was blue-green and had maximum absorption at a wavelength of 648 nm.
[0045]
Example 20
100 parts of 1-aminomethylisoquinoline, 1 part of dibutyltin diacetate and 1000 parts of toluene were mixed and dissolved to obtain a solution as a photochromic material. The solution immediately after dissolution was greenish blue and had maximum absorption at a wavelength of 640 nm.
[0046]
Example 21
100 parts of 1-aminomethylisoquinoline, 1 part of monobutyltin triacetate and 1000 parts of toluene were mixed and heated to dissolve at 50 ° C. for 2 hours to obtain a solution as a photochromic material. The solution immediately after dissolution was blue and had maximum absorption at a wavelength of 655 nm.
[0047]
Example 22
200 parts of 2-aminomethyl-3-chloropyridine, 1 part of monobutyltin triacetate, and 1000 parts of toluene were mixed and dissolved by heating at 50 ° C. for 2 hours to obtain a solution as a photochromic material. The solution immediately after dissolution was orange and had maximum absorption at a wavelength of 530 nm.
[0048]
Example 23
2-aminomethyl-5-methylpyrazine 12.3 parts, dioctyltin dioxide 37.7 parts, n-butanol 100 parts and a weight average molecular weight of about 20,000 copolymer resin (monomer composition is methyl methacrylate / 2- The weight ratio of hydroxyethyl was 80/20) (the molar ratio of 2-aminomethyl-5-methylpyrazine / dioctyltin dioxide was 1/1) was mixed and dissolved to obtain a photochromic material solution. This solution immediately after dissolution was green and had a maximum absorption at a wavelength of 650 nm. The obtained solution was applied with a spin coater so as to have a dry film thickness of 5 μm to obtain a film. Next, a 100 nm silicon nitride blocking film was formed on the coating by sputtering.
[0049]
The solutions obtained in Examples 2 to 22 and the integrated film obtained in Example 23 are slow in color conversion or weakened in color intensity even after 1000 cycles of decoloring and color development as in Example 1. It showed good stability for repeated use.
[0050]
Comparative Example 1
1.08 parts of 2-aminomethylpyridine, 0.95 parts of stannous chloride and 100 parts of benzyl alcohol (the molar ratio of tin atom in 2-aminomethylpyridine / stannous chloride is 2/1) are mixed and dissolved. It was. The resulting solution did not show color development.
[0051]
Comparative Example 2
1.08 parts of 2-aminomethylpyridine, 2.04 parts of tin dioctate and 100 parts of benzyl alcohol (molar ratio of tin atom in 2-aminomethylpyridine / tin dioctate was 2/1) were mixed and dissolved. The resulting solution did not show color development.
[0052]
【The invention's effect】
According to the present invention, a photochromic material having a long life in repeated use can be obtained. The photochromic material obtained by the present invention can be used for applications such as photosensors, optical memories, and photoinitiators for photosensitive resins because it is decolored by light irradiation and colored without light irradiation. .
[Brief description of the drawings]
FIG. 1 is a graph showing an absorption spectrum of a solution A immediately after dissolution in Example 1 of the present invention.
FIG. 2 is a graph showing changes in absorbance at a wavelength of 572 nm when light irradiation and standing in a dark place are repeated in solution A immediately after dissolution in Example 1 of the present invention.
FIG. 3 is a graph showing an absorption spectrum of a solution immediately after dissolution in Example 13 of the present invention.
Claims (3)
（Ｒ）k −Ｓｎ−（Ｘ）4-k ［１］
(R) k -Sn- (X) 4-k [1]
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