CN101402594A - Substituted benzene dithiol metal complex and photoabsorption pigment composition containing the same - Google Patents
Substituted benzene dithiol metal complex and photoabsorption pigment composition containing the same Download PDFInfo
- Publication number
- CN101402594A CN101402594A CNA2008101669192A CN200810166919A CN101402594A CN 101402594 A CN101402594 A CN 101402594A CN A2008101669192 A CNA2008101669192 A CN A2008101669192A CN 200810166919 A CN200810166919 A CN 200810166919A CN 101402594 A CN101402594 A CN 101402594A
- Authority
- CN
- China
- Prior art keywords
- photoabsorption
- substituted benzene
- pigment
- metal complex
- benzene dithiol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 89
- -1 benzene dithiol metal complex Chemical class 0.000 title claims abstract description 86
- 230000010748 Photoabsorption Effects 0.000 title claims description 66
- 239000000203 mixture Substances 0.000 title claims description 46
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical group C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 58
- 229910052759 nickel Chemical group 0.000 claims description 27
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 230000003287 optical effect Effects 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 12
- 150000003624 transition metals Chemical group 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 8
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical class SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 claims description 6
- 125000004193 piperazinyl group Chemical group 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Chemical group 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 abstract description 9
- 239000003381 stabilizer Substances 0.000 abstract description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 5
- 125000001424 substituent group Chemical group 0.000 abstract 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 abstract 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 abstract 1
- 230000001052 transient effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 12
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003086 colorant Substances 0.000 description 6
- 150000004699 copper complex Chemical class 0.000 description 6
- 150000002815 nickel Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 150000001879 copper Chemical class 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 150000004687 hexahydrates Chemical class 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 150000004698 iron complex Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- QOZOFODNIBQPGN-UHFFFAOYSA-N 2,4-dimethylpiperidine Chemical compound CC1CCNC(C)C1 QOZOFODNIBQPGN-UHFFFAOYSA-N 0.000 description 1
- ICBFNPPCXPMCBP-UHFFFAOYSA-N 2,5-dimethylpiperidine Chemical compound CC1CCC(C)NC1 ICBFNPPCXPMCBP-UHFFFAOYSA-N 0.000 description 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- RGNFMQJLAOONTP-UHFFFAOYSA-N 2-ethylmorpholine Chemical compound CCC1CNCCO1 RGNFMQJLAOONTP-UHFFFAOYSA-N 0.000 description 1
- QBBKKFZGCDJDQK-UHFFFAOYSA-N 2-ethylpiperidine Chemical compound CCC1CCCCN1 QBBKKFZGCDJDQK-UHFFFAOYSA-N 0.000 description 1
- LQMMFVPUIVBYII-UHFFFAOYSA-N 2-methylmorpholine Chemical compound CC1CNCCO1 LQMMFVPUIVBYII-UHFFFAOYSA-N 0.000 description 1
- MHHCLPHGZOISFK-UHFFFAOYSA-N 2-methylthiomorpholine Chemical compound CC1CNCCS1 MHHCLPHGZOISFK-UHFFFAOYSA-N 0.000 description 1
- GKEDZBGZXKTTDZ-UHFFFAOYSA-N 2-piperazin-2-ylpyrimidine Chemical compound C1NCCNC1C1=NC=CC=N1 GKEDZBGZXKTTDZ-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- QWCOYLHSPLONNI-UHFFFAOYSA-N 3-butylthiomorpholine Chemical compound CCCCC1CSCCN1 QWCOYLHSPLONNI-UHFFFAOYSA-N 0.000 description 1
- SFWWGMKXCYLZEG-UHFFFAOYSA-N 3-methylmorpholine Chemical compound CC1COCCN1 SFWWGMKXCYLZEG-UHFFFAOYSA-N 0.000 description 1
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 description 1
- KZZPRWYOUNLBQK-UHFFFAOYSA-N 3-methylthiomorpholine Chemical compound CC1CSCCN1 KZZPRWYOUNLBQK-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UZOFELREXGAFOI-UHFFFAOYSA-N 4-methylpiperidine Chemical compound CC1CCNCC1 UZOFELREXGAFOI-UHFFFAOYSA-N 0.000 description 1
- KDTVWEHAAISPNW-UHFFFAOYSA-N 4-methylthiomorpholine Chemical compound CN1CCSCC1 KDTVWEHAAISPNW-UHFFFAOYSA-N 0.000 description 1
- FHQRDEDZJIFJAL-UHFFFAOYSA-N 4-phenylmorpholine Chemical compound C1COCCN1C1=CC=CC=C1 FHQRDEDZJIFJAL-UHFFFAOYSA-N 0.000 description 1
- UTBULQCHEUWJNV-UHFFFAOYSA-N 4-phenylpiperidine Chemical compound C1CNCCC1C1=CC=CC=C1 UTBULQCHEUWJNV-UHFFFAOYSA-N 0.000 description 1
- DPXANBQAIVUQDO-UHFFFAOYSA-N 4-phenylthiomorpholine Chemical compound C1CSCCN1C1=CC=CC=C1 DPXANBQAIVUQDO-UHFFFAOYSA-N 0.000 description 1
- MGCDHLCYJZAAKL-UHFFFAOYSA-N 4-propylthiomorpholine Chemical compound CCCN1CCSCC1 MGCDHLCYJZAAKL-UHFFFAOYSA-N 0.000 description 1
- CQAOCWVRDYSQRD-UHFFFAOYSA-N 5-azabicyclo[3.1.0]hexa-1,3-diene Chemical compound C1=CN2CC2=C1 CQAOCWVRDYSQRD-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 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
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- ASIPLGLDOUQLOQ-UHFFFAOYSA-N benzo[c]chromen-1-one Chemical compound C1=CC=CC2=C3C(=O)C=CC=C3OC=C21 ASIPLGLDOUQLOQ-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000004820 halides Chemical class 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229920003987 resole Polymers 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
- 150000003839 salts Chemical class 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
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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Abstract
The present invention provides a neutral substituted benzene dithioglycol metal complex having a function as a pigment stabilizer. The neutral substituted benzene dithioglycol metal complex is showed by the general formula (1), where, R1 and R2 denote independently alkyl with 1-6 carbon atomic number, alkyl amidocyanogen with 1-8 carbon atomic number, piperidine subbase with or without substituent, morpholines substituent with or without substituent, pyrrolidinyl with or without substituent, thiomorpholine substituent with or without substituent, ethylene imine with or without substituent, or phenyl with or without substituent; M denotes transient metal atom.
Description
Technical field
The present invention relates to substituted benzene dithiol metal complex, contain the photoabsorption pigment composition of this metal complexes and optical absorption pigment, and use said composition and the photoabsorption part that obtains.
Background technology
In recent years, the photoabsorption part that contains the composition of the light that absorbs various wavelength regions is used to various fields.For example, as plasma display panel (PDP) near infrared ray barrier films, has the spectral filter that the semiconductor light-receiving device of absorption-reduction near infrared ray function is used, be used for the energy-conservation near-infrared absorption film that covers invisible heat, near-infrared absorbing plate, for the agricultural near-infrared absorption film of selective use sunlight, utilize the photosensitive lithographic plate of laser etc. and utilize the near infrared recording medium that absorbs heat etc. to be widely used.These photoabsorption parts for example can be coated by the photoabsorption pigment composition that will contain optical absorption pigment on the substrate such as film and obtain, and with the various films with other functions, use tackiness agent to fit on the parts etc. of regulation and use.
It is that pigment, Diimonium salt are that pigment and cyanines are optical absorption pigments such as pigment that these photoabsorption parts generally can use phthalocyanine.In addition, the known various method that is used to improve these optical absorption pigment characteristics.For example, though in order to improve cheap the solubleness in solvent insufficient or be considered in time through and the cyanines of the trend that receptivity declines to a great extent are the characteristic of pigment, proposed to use the specific substituted benzene dithiol metal complex negatively charged ion that plays a role as colorant stabilizer and the photoabsorption part (with reference to patent documentation 1) of the cationic counterion combination of pigment.
These counterion combinations are applicable to forming cationic optical absorption pigment.Yet,, can't form same counterion combination for the neutral optical absorption pigment of positively charged, negative electricity not.
On the other hand, as being used to prevent that the characteristics that optical absorption pigment had such as neutral optical absorption pigment from passing through and the colorant stabilizer of deterioration in time, specific substituted benzene dithiol metal complex salt (with reference to patent documentation 2) has been proposed.
As the substituted benzene dithiol metal complex salt of record in this patent documentation 2, by have form as positively charged ions such as the substituted benzene dithiol metal complex negatively charged ion of cancellation singlet oxygen (Singlet-oxygen Quencher) function and quaternary ammonium Huo quaternary phosphines, as the substituted benzene dithiol metal complex salt of colorant stabilizer, sometimes the reactions such as tackiness agent used with being used to fit on the predetermined member of this positively charged ion cause various unfavorable conditions.
For example, use is with neutral optical absorption pigment, above-mentioned substituted benzene dithiol metal complex salt and tackiness agent mix and the photoabsorption pigment composition that obtains, it is coated on the substrate such as film and form the photoabsorption part, when the parts etc. that the photoabsorption part that so forms fitted in regulation with tackiness agent are gone up, perhaps use neutral optical absorption pigment, above-mentioned substituted benzene dithiol metal complex salt and tackiness agent mix and the photoabsorption pigment composition that obtains, it is coated on the substrate such as film and form the photoabsorption part, when the parts etc. that the photoabsorption part that so forms directly fitted in regulation are gone up, according to (methyl) acrylate copolymer, the kind of tackiness agents such as polyester, can promote the curing of this bonding coat out of anticipation ground, perhaps form to solidify badly etc., can't obtain the molding as imagining sometimes.As one of its reason, think to constitute the positively charged ion and the adhesive reaction of substituted benzene dithiol metal complex salt.
Patent documentation 1: the spy opens the 2006-291183 communique
Patent documentation 2: the spy opens the 2000-226377 communique
Summary of the invention
Problem of the present invention is to suppress unfavorable condition as described above, though provide a kind of himself as colorant stabilizer play a role with various tackiness agents use can not cause yet unnecessary reaction, the neutral substituted benzene dithiol metal complex.In addition, problem of the present invention is to provide a kind of and contains the photoabsorption pigment composition of this metal complexes and optical absorption pigment and use said composition and the photoabsorption part that obtains.
The invention provides substituted benzene dithiol metal complex as follows, photoabsorption pigment composition and photoabsorption part.
The 1st. a kind of substituted benzene dithiol metal complex, with general formula (1) expression.
(in the formula, R
1And R
2Independent separately, the expression carbonatoms is 1～6 alkyl, carbonatoms is 1～8 alkylamino, morpholino base with substituting group or unsubstituted, piperidino-(1-position only) with substituting group or unsubstituted, pyrrolidyl with substituting group or unsubstituted, the thiomorpholine with substituting group or unsubstituted have the piperazinyl of substituting group or unsubstituted or have substituting group or the phenyl of unsubstituted for base.M represents transition metal atoms.)
The 2nd. as the 1st described substituted benzene dithiol metal complex, wherein, the represented transition metal atoms of M is copper, cobalt or nickel in the general formula (1).
The 3rd. a kind of photoabsorption pigment composition, contain the 1st or the 2nd described substituted benzene dithiol metal complex and optical absorption pigment and form.
The 4th. a kind of photoabsorption part, the 3rd described photoabsorption pigment composition coated on the substrate and obtained.
Substituted benzene dithiol metal complex of the present invention owing to himself be neutral, therefore can not have positively charged ions such as quaternary ammonium or quaternary phosphine as the substituted benzene dithiol metal complex salt of record in the above-mentioned patent documentation 2.Therefore, for the photoabsorption pigment composition that uses this metal complexes, use said composition and the photoabsorption part that obtains, do not worry to produce the various unfavorable conditions that tackiness agent or other additive reactions because of above-mentioned positively charged ion and coexistence cause.
Substituted benzene dithiol metal complex of the present invention, its structure and above-mentioned substituted benzene dithiol metal complex salt are approximate, but are not used in positively charged ion such as the salifiable quaternary ammonium of shape.Therefore, the photoabsorption pigment composition that contains substituted benzene dithiol metal complex of the present invention, can regard as: compare the material that is improved as the performance of the per unit weight of colorant stabilizer with the photoabsorption pigment composition of the substituted benzene dithiol metal complex salt that has used above-mentioned patent documentation 2.The various molding of the photoabsorption part of colorant stabilizer have been used in application, realized all the time in order to realize the various improvement of performance raising, the raising of manufacturing efficient etc., from this viewpoint, substituted benzene dithiol metal complex of the present invention can be described as is of value to the material that improves these molding.
Below, describe the present invention in detail.
Substituted benzene dithiol metal complex of the present invention is the represented new compound of following general formula (1).
In the general formula (1), R
1And R
2Independent separately, the expression carbonatoms is 1～6 alkyl, carbonatoms is 1～8 alkylamino, morpholino base with substituting group or unsubstituted, piperidino-(1-position only) with substituting group or unsubstituted, pyrrolidyl with substituting group or unsubstituted, the thiomorpholine with substituting group or unsubstituted have the piperazinyl of substituting group or unsubstituted or have substituting group or the phenyl of unsubstituted for base.M represents transition metal atoms.
As carbonatoms is 1～6 alkyl, can enumerate for example methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl and isohexyl etc.
It as carbonatoms 1～8 alkylamino, can enumerate for example N-methylamino, the N-ethylamino, N-sec.-propyl amino, N-n-propyl amino, N-normal-butyl amino, N, the N-dimethylamino, N, N-methylethyl amino, N, the N-diethylamino, N, N-ethyl sec.-propyl amino, N, N-ethyl isohexyl amino, N, N-ethyl n-hexyl amino, N, the different heptyl amino of N-methyl, N, N-methyl n-heptyl amino, N, the N-diisopropylaminoethyl, N, N-di amino, N, N-di-n-butyl amino, N, N-diisobutyl amino, N, N-two sec-butyl amino and N, N-di-t-butyl amino etc.
As morpholino base with substituting group or unsubstituted, for example can enumerate morpholino base, 2-methylmorpholine for base, 3-methylmorpholine for base, 4-methylmorpholine for base, 2-ethyl morpholine for base, 4-n-propyl morpholino base, 3-normal-butyl morpholino base, 2, the 4-thebaine is for base, 2, and the 6-thebaine is for base and 4-phenylmorpholine Dai Ji etc.
As piperidino-(1-position only) with substituting group or unsubstituted, can enumerate for example piperidino-(1-position only), pipecoline subbase, 3-methyl piperidine subbase, 4-methyl piperidine subbase, 2-ethyl piperidine subbase, 4-n-propyl piperidino-(1-position only), 3-normal-butyl piperidino-(1-position only), 2,4-lupetidine subbase, 2,5-lupetidine subbase and 4-Phenylpiperidine subbase etc.
As pyrrolidyl with substituting group or unsubstituted, can enumerate for example pyrrolidyl, 2-methylpyrrole alkyl, 3-methylpyrrole alkyl, 4-methylpyrrole alkyl, 2-N-ethyl pyrrole N-alkyl, 4-n-propyl pyrrolidyl, 3-n-butylpyrrolioine base, 2,4-alkyl dimethyl pyrrole, 2,5-alkyl dimethyl pyrrole and 4-phenylpyrrole alkyl etc.
As thiomorpholine with substituting group or unsubstituted for base, for example can enumerate thiomorpholine for base, 2-methyl thiomorpholine for base, 3-methyl thiomorpholine for base, 4-methyl thiomorpholine for base, 2-ethylenebis dithiocarbamate morpholino base, 4-n-propyl thiomorpholine for base, 3-normal-butyl thiomorpholine for basic, 2, the 4-dimethyl sulphide is for morpholino base, 2, and the 6-dimethyl sulphide is for morpholino base and 4-phenyl thiomorpholine Dai Ji etc.
As piperazinyl with substituting group or unsubstituted, can enumerate for example piperazinyl, 2-methylpiperazine base, 3-methylpiperazine base, 4-methylpiperazine base, 2-ethyl piperazidine base, 4-n-propyl piperazinyl, 3-normal-butyl piperazinyl, 2,4-lupetazin base, 2,6-lupetazin base, 4-Phenylpiperazinyl and 2-pyrimidylpiperazine base etc.
As phenyl with substituting group or unsubstituted; can enumerate for example phenyl; the 2-aminomethyl phenyl; the 3-aminomethyl phenyl; the 4-aminomethyl phenyl; 2; the 6-3,5-dimethylphenyl; the 4-ethylphenyl; 2-n-propyl phenyl; the 4-n-butylphenyl; the 2-chloro-phenyl-; the 4-chloro-phenyl-; 2; the 4-dichlorophenyl; the 2-bromophenyl; the 4-bromophenyl; 2-chloro-4-bromophenyl; the 4-aminophenyl; 2; the 4-diamino-phenyl; 2, the 4-dinitrophenyl; the 2-acetylphenyl; the 4-acetylphenyl; the 2-hydroxy phenyl; the 4-hydroxy phenyl; the 2-p-methoxy-phenyl; the 4-p-methoxy-phenyl; 2-methyl thio-phenyl and 4-methyl thio-phenyl etc.
In above-mentioned general formula (1), from the viewpoint of the solvability excellence all kinds of SOLVENTS, preferred R
1And R
2Independent separately, be N, N-diethylamino, N, N-diisobutyl amino, morpholino base, pyrrolidyl, piperidino-(1-position only), piperazinyl or phenyl.
As the concrete example of the represented transition metal atoms of M, can enumerate copper, cobalt, nickel etc.
The represented substituted benzene dithiol metal complex of general formula (1) can followingly be made: for example, in solvent, the substituted benzene dithiol metal complex salt oxidation of using oxygenant to be formed by positively charged ions such as suitable substituted benzene dithiol metal complex negatively charged ion and quaternary ammoniums is made thus.
This substituted benzene dithiol metal complex salt can be with opening the same method of disclosed method in the flat 10-45767 communique and synthesize with for example special flat 9-309886 communique, spy opened.That is, at first, in the presence of sulphur and iron powder, in polar organic solvent, make reaction such as the sulfhydrate that replaces halogeno-benzene and sodium sulfhydrate, form the iron complex of substituted benzene dithiol.Make the iron complex of substituted benzene dithiol of gained and the halide reaction of transition metal, after forming the transition metal complex of substituted benzene dithiol, make reactions such as this transition metal complex and ammonium salt, can obtain above-mentioned substituted benzene dithiol metal complex salt thus.
As the solvent of above-mentioned oxidizing reaction,, can preferably use for example acetonitrile or acetone isopolarity solvent so long as this reaction just is not particularly limited for the inert solvent.
The usage quantity of solvent is 100～100000 weight parts with respect to substituted benzene dithiol metal complex salt 100 weight parts preferably, more preferably 100～50000 weight parts.
As oxygenant, be not particularly limited, can enumerate for example iodine, ferrocene salt compound etc.
The usage ratio of oxygenant is not particularly limited, and from the viewpoint of raising yield and the viewpoint of economy, with respect to 1 mole of substituted benzene dithiol metal complex salt, is preferably 1～5 mole ratio, more preferably 1～3 mole ratio.
The temperature of reaction of oxidation, preferred 15～40 ℃, more preferably 25～35 ℃.Reaction times is preferably 1～24 hour according to the difference of temperature of reaction and different.
In addition, other manufacture method as the substituted benzene dithiol metal complex shown in the general formula (1), can be set forth in the process of making above-mentioned substituted benzene dithiol metal complex salt, after forming the transition metal complex of substituted benzene dithiol, do not make reactions such as itself and ammonium salt, but make itself and above-mentioned oxidant reaction, with the method for the transition metal complex oxidation of substituted benzene dithiol.At this moment, the usage ratio of oxygenant, temperature of reaction and reaction times are identical with above-mentioned oxidizing reaction.According to this method, can more easily make substituted benzene dithiol metal complex of the present invention.
The substituted benzene dithiol metal complex that so obtains can easily separate by filtering to wait.
Photoabsorption pigment composition of the present invention is to contain optical absorption pigments such as substituted benzene dithiol metal complex shown in the above-mentioned general formula (1) and neutral optical absorption pigment to form.
As optical absorption pigment, be not particularly limited, for example can enumerate the sour cyanines in side (squarylium) and be pigment, anthraquinone and be pigment, phthalocyanine and be pigment, methyne and be pigment, azomethine and be pigment, oxazine and be pigment, azo and be pigment, vinylbenzene base system pigment, coumarin series pigment, porphyrin is that pigment, dibenzopyrone are that pigment, diketopyrrolopyrrolecocrystals are that pigment, rhodamine are that pigment, xanthene are that pigment, methylene pyrrole are commercially available organic pigments such as pigment.These optical absorption pigments can be used alone, and perhaps can will be used in combination more than 2 kinds.
The usage ratio of optical absorption pigment is not particularly limited, and preferably is 0.1～10 mole ratio, more preferably 0.8～1.2 mole ratio with respect to 1 mole of substituted benzene dithiol metal complex.
Photoabsorption pigment composition of the present invention except above-mentioned substituted benzene dithiol metal complex and optical absorption pigment, can also further contain tackiness agent, tackiness agent and other additive.
As tackiness agent, be not particularly limited, for example can enumerate (methyl) acrylic copolymer, polyvinyl chloride, Resins, epoxy, urethane, vinyl acetate copolymer, vinylbenzene-(methyl) acrylic copolymer, polyester, polymeric amide, polyolefine, styrene-butadiene copolymer is rubber, isoprene-isobutylene rubber and silicone resin etc.As tackiness agent, be not particularly limited, can enumerate for example resins such as polycarbonate resin, rhodia, (methyl) acrylic resin and resol.As other additive, can enumerate for example solidifying agent, curing catalysts, linking agent, tone revisal pigment, flow agent, antistatic agent, thermo-stabilizer, antioxidant, dispersion agent, fire retardant, lubricant, softening agent and UV light absorber etc.
As the method for making photoabsorption pigment composition of the present invention, be not particularly limited, carry out the blended method after can enumerating the tackiness agent that for example adds the substituted benzene dithiol metal complex shown in the above-mentioned general formula (1), optical absorption pigment and specified amount as required, tackiness agent, other additive etc.
Photoabsorption part of the present invention can followingly be made: the photoabsorption pigment composition that uses solvent so to obtain is as required made pigment solution, coats on the substrate of glass or resin system etc. and makes its drying.
The solvent that uses as being used to obtain pigment solution can be enumerated for example hydro carbons such as toluene, dimethylbenzene, pentane, hexane, heptane, hexanaphthene; Halogenated hydrocarbon such as methylene dichloride, chloroform; Methyl alcohol, ethanol, Virahol, 2,2,3, alcohols such as 3-C3-Fluoroalcohol; Cellosolve such as methylcyclohexane, ethyl cellosolve class; Ester classes such as ethyl acetate, propyl acetate, butylacetate; Ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, pimelinketone.Wherein, preferably use ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, pimelinketone.These solvents can be used alone or mix more than 2 kinds and use.
The usage quantity of the solvent when using solvent is below 5000 weight parts with respect to above-mentioned photoabsorption pigment composition 100 weight parts preferably, more preferably below 3000 weight parts.
As aforesaid substrate, can use the transparent component of glass, resin etc.As resin, the high resins of the transparency such as preference such as pet resin, plexiglass, polycarbonate resin, poly-ethylidene resin, polysulfone resin, polyethersulfone resin, polyamide resin, polyvinyl chloride (PVC) RESINS, polyacrylate resin.Substrate can be a flexible substrate, also can be hard substrate.
As with the method for photoabsorption pigment composition, can adopt for example excellent common coating processes such as method, spin-coating method that are coated with to base plate coating.
Even substituted benzene dithiol metal complex of the present invention when using with various tackiness agents, can not cause unnecessary reaction yet.Therefore, contain the photoabsorption part that photoabsorption pigment composition that this metal complexes and optical absorption pigment form and coating said composition obtain, can make stable molding by use.
Embodiment
Below, enumerate embodiment, further specify the present invention, but the present invention is not subjected to any qualification of these embodiment.
Production Example 1
In 1-(3,4-dichlorobenzene alkylsulfonyl) morpholine 14.8g (0.05 mole), add N, dinethylformamide 46g and 70% sodium sulfhydrate 8.4g (0.105 mole) were 70 ℃ of reactions 3 hours.In this solution, add iron powder 1.5g (0.026 mole) and sulphur powder 1.7g (0.052 mole), 100～110 ℃ of reactions 5 hours.The temperature of reaction solution is returned to after the room temperature, add methyl alcohol 34g and nickelous chloride (II) hexahydrate 6.2g (0.026 mole), at room temperature reacted 1 hour, and then add Tetrabutyl amonium bromide 8.5g (0.025 mole), ventilating air.
Concentrate the reaction solution of gained, after making with extra care by silica gel chromatography, enriched fraction obtains deep green solid tetra-n-butyl ammonium=two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel 17.6g thus.The tetra-n-butyl ammonium of gained=two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel is 80% with respect to the yield of 1-(3,4-dichlorobenzene alkylsulfonyl) morpholine.
Production Example 2
In Production Example 1; use cupric chloride (II) the dihydrate 4.4g (0.026 mole) except replacing nickelous chloride (II) hexahydrate 6.2g (0.026 mole); similarly operate with Production Example 1; obtain deep green solid tetra-n-butyl ammonium=two [4-morpholino base alkylsulfonyls-1; 2-diphenyl disulfide alkoxide-S, S '] copper 17.5g.The tetra-n-butyl ammonium of gained=two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper is 79% with respect to the yield of 1-(3,4-dichlorobenzene alkylsulfonyl) morpholine.
Embodiment 1
In tetra-n-butyl ammonium=two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel 2.64g (0.003 mole) that Production Example 1 obtains, add acetone 170g and dissolve.In this solution, drip the solution that iodine 1.52g (0.006 mole) is dissolved in 50g acetone and obtains, at room temperature stir 15 hours after, filter; washing, drying obtains two [the 4-morpholino base alkylsulfonyls-1 of deep green solid thus; 2-diphenyl disulfide alkoxide-S, S '] nickel complex 0.92g.Two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel complexes of gained are 48.1% with respect to the yield of tetra-n-butyl ammonium=two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel.
Two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, the S '] nickel complexes that it should be noted that gained can be identified owing to have following rerum natura.
In addition, for two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel complexes of gained, behind the use ion-chromatographic determination, do not check out positively charged ion.
1H-NMR (solvent: CDCl
3) δ (ppm): 2.86 (8H, t), 3.65 (8H, t), 7.60～7.84 (6H, m)
Ultimate analysis: C 37.68; H 3.48; N 4.39; S 30.18; Ni 9.21 (calculated value C 37.5; H 3.4; N 4.4; S 30.1; Ni 9.2).
Embodiment 2
In embodiment 1; the tetra-n-butyl ammonium that replacement obtains in Production Example 1=two [4-morpholino base alkylsulfonyl-1; 2-phenylene dimercaptan-S; S '] nickel 2.64g (0.003 mole); and tetra-n-butyl ammonium=two [4-morpholino base alkylsulfonyls-1 that use obtains in Production Example 2; 2-diphenyl disulfide alkoxide-S; S '] copper 2.65g (0.003 mole); in addition operation similarly to Example 1; obtain two [4-morpholino base alkylsulfonyls-1 of white-yellowish solid; 2-diphenyl disulfide alkoxide-S, S '] copper complex 1.04g.Two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper complexes of gained are 54.1% with respect to the yield of tetra-n-butyl ammonium=two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper.
Two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, the S '] copper complexes that it should be noted that gained can be identified owing to have following rerum natura.
In addition, for two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper complexes of gained, behind the use ion-chromatographic determination, do not check out positively charged ion.
Ultimate analysis: C 37.40; H 3.45; N 4.36; S 29.95; Cu 9.89 (calculated value C 37.2; H 3.4; N 4.4; S 29.8; Cu 9.8).
Embodiment 3
In 1-(3,4-dichlorobenzene alkylsulfonyl) piperidinyl-1 4.7g (0.05 mole), add N, dinethylformamide 46g and 70% sodium sulfhydrate 8.4g (0.105 mole) were 70 ℃ of reactions 3 hours.In this solution, add iron powder 1.5g (0.026 mole) and sulphur powder 1.7g (0.052 mole), 100～110 ℃ of reactions 5 hours.The temperature of reaction solution is returned to after the room temperature, add methyl alcohol 34g and nickelous chloride (II) hexahydrate 6.2g (0.026 mole), at room temperature reacted 1 hour.In this solution, drip the solution that iodine 12.69g (0.05 mole) is dissolved in 150g acetone and obtains; after at room temperature stirring 15 hours; it is concentrated; after making with extra care by silica gel chromatography; cut is concentrated; obtain two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] the nickel complex 5.88g of deep green solid thus.Two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel complexes of gained are 37.1% with respect to the yield of 1-(3,4-dichlorobenzene alkylsulfonyl) piperidines.
Two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, the S '] nickel complexes that it should be noted that gained can be identified owing to have following rerum natura.
In addition, for two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel complexes of gained, behind the use ion-chromatographic determination, do not check out positively charged ion.
1H-NMR (solvent: CDCl
3) δ (ppm): 1.42 (4H, m), 1.63 (8H, m), 7.58～7.92 (6H, m)
Ultimate analysis: C 41.71; H 4.14; N 4.42; S 30.37; Ni 9.26 (calculated value C 41.5; H 4.1; N 4.4; S 30.3; Ni 9.2).
Embodiment 4
In embodiment 3; replace nickelous chloride (II) hexahydrate 6.2g (0.026 mole) and use cupric chloride (II) dihydrate 4.5g (0.026 mole); replace iodine 12.69g (0.05 mole) and use ferrocene salt hexafluorophosphate 10.3g (0.031 mole); in addition; operation similarly to Example 3; obtain two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper complex 6.73g of yellow solid.Two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper complexes of gained are 41.9% with respect to the yield of 1-(3,4-dichlorobenzene alkylsulfonyl) piperidines.
Two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, the S '] copper complexes that it should be noted that gained can be identified owing to have following rerum natura.
In addition, for two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper compounds of gained, behind the use ion-chromatographic determination, do not check out positively charged ion.
Ultimate analysis: C 41.39; H 4.11; N 4.39; S 30.14; Cu 9.95 (calculated value C 41.3; H 4.1; N 4.3; S 30.1; Cu 9.9).
Embodiment 5
Two [4-morpholino base alkylsulfonyls-1 that will in embodiment 1, obtain; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 120mg (0.188 micromole); side sour cyanines pigment (FEW company; trade(brand)name " Rn638 ") 50mg (0.186 micromole); tackiness agent (NIPPON CARBIDEINDUSTRIES company; trade(brand)name " SZ6232 ") 6g; solidifying agent (NIPPON CARBIDEINDUSTRIES company; trade(brand)name " CK-102 ") 24mg and curing catalysts (NIPPONCARBIDE INDUSTRIES company; trade(brand)name " CK-901 ") 12mg mixes, and obtains photoabsorption pigment composition.
Embodiment 6
In embodiment 5; two [4-morpholino base alkylsulfonyls-1 that replacement obtains in embodiment 1; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 120mg (0.188 micromole); and two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper complex 121mg (0.188 micromole) that use obtains in embodiment 2; in addition operation similarly to Example 5 obtains photoabsorption pigment composition.
Embodiment 7
In embodiment 5; two [4-morpholino base alkylsulfonyls-1 that replacement obtains in embodiment 1; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 120mg (0.188 micromole); and two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel complex 119mg (0.188 micromole) that use obtains in embodiment 3; in addition operation similarly to Example 5 obtains photoabsorption pigment composition.
Embodiment 8
In embodiment 5; two [4-morpholino base alkylsulfonyls-1 that replacement obtains in embodiment 1; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 120mg (0.188 micromole); and two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper complex 120mg (0.188 micromole) that use obtains in embodiment 4; in addition operation similarly to Example 5 obtains photoabsorption pigment composition.
Comparative example 1
In embodiment 5; two [4-morpholino base alkylsulfonyls-1 that replacement obtains in embodiment 1; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 120mg (0.188 micromole); and tetra-n-butyl ammonium=two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel 165mg (0.188 micromole) that use obtains in Production Example 1; in addition operation similarly to Example 5 obtains photoabsorption pigment composition.
Comparative example 2
In embodiment 5; two [4-morpholino base alkylsulfonyls-1 that replacement obtains in embodiment 1; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 120mg (0.188 micromole); and tetra-n-butyl ammonium=two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper 166mg (0.188 micromole) that use obtains in Production Example 2; in addition operation similarly to Example 5 obtains photoabsorption pigment composition.
Comparative example 3
Except in embodiment 5, do not use two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel complex 120mg (0.188 micromole) of in embodiment 1, obtaining in addition, operation obtains photoabsorption pigment composition similarly to Example 5.
[photoabsorption pigment composition is to the impact assessment of tackiness agent curing characteristics]
For the photoabsorption pigment composition that obtains in embodiment 5～8 and comparative example 1～3, investigation is to the influence of the curing characteristics of the tackiness agent of coexistence.As investigation method be: after obtaining above-mentioned each photoabsorption pigment composition, immediately with its all amount add among methyl ethyl ketone 6g and mix, modulate pigment solution thus, measure its viscosity through the time change.It should be noted that viscosity is to use viscometer (TOKIMEC of Co., Ltd., trade(brand)name " DIGITAL VISCOMETERDVH-EII "), down measures at 80 ℃.The viscosity that to measure each pigment solution through the time change and be shown in Table 1.
Table 1
| Viscosity (mPas) | 0 hour | 1 hour | 2 hours |
| Embodiment 5 | 120 | 200 | 273 |
| Embodiment 6 | 122 | 212 | 276 |
| Embodiment 7 | 126 | 226 | 280 |
| Embodiment 8 | 123 | 207 | 271 |
| Comparative example 1 | 118 | 245 | 444 |
| Comparative example 2 | 122 | 233 | 453 |
| Comparative example 3 | 120 | 195 | 267 |
As shown in Table 1, the viscosity of the pigment solution of the photoabsorption pigment composition that use obtains in embodiment 5～8 through the time change, with comparing of comparative example 1～2, highly stable, in addition, the difference that changes with the viscosity of the pigment solution that does not contain title complex of comparative example 3 is little.By these results as can be known, the photoabsorption pigment composition that obtains in embodiment 5～8 is very little to the influence of curing characteristics of the tackiness agent of coexistence.
Embodiment 9
Two [4-morpholino base alkylsulfonyls-1 that will in embodiment 1, obtain; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 6.4mg (0.01 micromole), side sour cyanines pigment (FEW company; trade(brand)name " Rn638 ") 2.7mg (0.01 micromole) and acrylic resin 2.0g mix; obtain photoabsorption pigment composition; in this photoabsorption pigment composition, add chloroform 24.0g, the modulation pigment solution.Whole amounts of this pigment solution are coated on the polyester film with the coiling rod, and dry at normal temperatures, the thickness that obtains filming is the photoabsorption part of 10 μ m.
Embodiment 10
In embodiment 9; two [4-morpholino base alkylsulfonyls-1 that replacement obtains in embodiment 1; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 6.4mg (0.01 micromole); and two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper complex 6.4mg (0.01 micromole) that use obtains in embodiment 2; in addition operation similarly to Example 9, the thickness that obtains filming is the photoabsorption part of 10 μ m.
Embodiment 11
In embodiment 9; two [4-morpholino base alkylsulfonyls-1 that replacement obtains in embodiment 1; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 6.4mg (0.01 micromole); and two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel complex 6.4mg (0.01 micromole) that use obtains in embodiment 3; in addition operation similarly to Example 9, the thickness that obtains filming is the photoabsorption part of 10 μ m.
Embodiment 12
In embodiment 9; two [4-morpholino base alkylsulfonyls-1 that replacement obtains in embodiment 1; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 6.4mg (0.01 micromole); and two [4-piperidino-(1-position only) alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] copper complex 6.4mg (0.01 micromole) that use obtains in embodiment 4; in addition operation similarly to Example 9, the thickness that obtains filming is the photoabsorption part of 10 μ m.
Comparative example 4
Except in embodiment 9; nickel complex 6.4mg (0.01 micromole) in addition not use two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, the S '] that obtains in embodiment 1; operation similarly to Example 9, the thickness that obtains filming is the photoabsorption part of 10 μ m.
Comparative example 5
In embodiment 9; two [4-morpholino base alkylsulfonyls-1 that replacement obtains in embodiment 1; 2-diphenyl disulfide alkoxide-S; S '] nickel complex 6.4mg (0.01 micromole); and tetra-n-butyl ammonium=two [4-morpholino base alkylsulfonyl-1,2-diphenyl disulfide alkoxide-S, S '] nickel 8.8mg (0.01 micromole) that use obtains in Production Example 1; operation similarly to Example 9 in addition, the thickness that obtains filming is the photoabsorption part of 10 μ m.
[evaluation of the light absorpting ability of photoabsorption part]
For the photoabsorption part that in embodiment 9～12 and comparative example 4～5, obtains, for investigate light absorpting ability through the time change, carry out following model experiment.At first, for each photoabsorption part, use spectrophotometric determination specific wavelength (measure wavelength: the transmissivity of 550nm) locating, as transmissivity before the test.Then, use minienvironment tester (ESPEC company trade(brand)name " SU-240 "), similarly be determined at 80 ℃ of transmissivities after leaving standstill 100 hours with above-mentioned, as test back transmissivity.To the transmissivity that each photoabsorption part is measured be shown in Table 2.
Table 2
| Transmissivity (%) before the test | Test back transmissivity (%) | |
| Embodiment 9 | 17.0 | 23.2 |
| Embodiment 10 | 17.6 | 22.9 |
| Embodiment 11 | 18.0 | 23.0 |
| Embodiment 12 | 18.6 | 23.5 |
| Comparative example 4 | 19.5 | 41.7 |
| Comparative example 5 | 16.5 | 22.4 |
As shown in Table 2, the variable quantity of the photoabsorption part that in embodiment 9～12, obtains from transmissivity before testing to test back transmissivity, with comparing of comparative example 4, very little, in addition, with the use of comparative example 5 difference of variable quantity of transmissivity of photoabsorption part of substituted benzene dithiol metal complex salt little.By these results as can be known, the photoabsorption part that in embodiment 9～12, obtains, can fully suppress light absorpting ability through the time change.
Claims (4)
1, a kind of substituted benzene dithiol metal complex, with general formula (1) expression,
In the formula, R
1And R
2Independent separately, the expression carbonatoms is 1～6 alkyl, carbonatoms is 1～8 alkylamino, morpholino base with substituting group or unsubstituted, piperidino-(1-position only) with substituting group or unsubstituted, pyrrolidyl with substituting group or unsubstituted, the thiomorpholine with substituting group or unsubstituted have the piperazinyl of substituting group or unsubstituted or have substituting group or the phenyl of unsubstituted for base; M represents transition metal atoms.
2, substituted benzene dithiol metal complex as claimed in claim 1, wherein, the represented transition metal atoms of M is copper, cobalt or nickel in the general formula (1).
3, a kind of photoabsorption pigment composition contains claim 1 or 2 described substituted benzene dithiol metal complexes and optical absorption pigment and forms.
4, a kind of photoabsorption part is coated the described photoabsorption pigment composition of claim 3 on the substrate and is obtained.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007259115 | 2007-10-02 | ||
| JP2007259115 | 2007-10-02 |
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| CN101402594A true CN101402594A (en) | 2009-04-08 |
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| CNA2008101669192A Pending CN101402594A (en) | 2007-10-02 | 2008-09-26 | Substituted benzene dithiol metal complex and photoabsorption pigment composition containing the same |
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| Country | Link |
|---|---|
| JP (1) | JP2009102617A (en) |
| KR (1) | KR20090034279A (en) |
| CN (1) | CN101402594A (en) |
| TW (1) | TW200916450A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003221523A (en) * | 2002-01-31 | 2003-08-08 | Sumitomo Seika Chem Co Ltd | Near infrared ray absorbent pigment and near infrared ray absorber using the pigment |
| JP2006291183A (en) * | 2005-03-16 | 2006-10-26 | Sumitomo Seika Chem Co Ltd | Light absorbing dyestuff and light absorbing material comprising the same |
| CN101117445A (en) * | 2006-08-01 | 2008-02-06 | 住友精化株式会社 | Optical absorption pigment and optical absorption material |
| CN101148546A (en) * | 2006-09-22 | 2008-03-26 | 住友精化株式会社 | Light absorbing dyestuff composition |
-
2008
- 2008-09-03 TW TW097133723A patent/TW200916450A/en unknown
- 2008-09-10 JP JP2008232364A patent/JP2009102617A/en active Pending
- 2008-09-26 CN CNA2008101669192A patent/CN101402594A/en active Pending
- 2008-09-29 KR KR1020080095427A patent/KR20090034279A/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003221523A (en) * | 2002-01-31 | 2003-08-08 | Sumitomo Seika Chem Co Ltd | Near infrared ray absorbent pigment and near infrared ray absorber using the pigment |
| JP2006291183A (en) * | 2005-03-16 | 2006-10-26 | Sumitomo Seika Chem Co Ltd | Light absorbing dyestuff and light absorbing material comprising the same |
| CN101117445A (en) * | 2006-08-01 | 2008-02-06 | 住友精化株式会社 | Optical absorption pigment and optical absorption material |
| CN101148546A (en) * | 2006-09-22 | 2008-03-26 | 住友精化株式会社 | Light absorbing dyestuff composition |
Non-Patent Citations (1)
| Title |
|---|
| DIETER SELLMANN,ET AL.: "Transition metal complexes with sulfur ligands Part CXLIV. Square planar nickel complexes with NiS4 cores in three different oxidation states: synthesis, X-ray structural and spectroscopic studies", 《INORGANICA CHIMICA ACTA》 * |
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| KR20090034279A (en) | 2009-04-07 |
| TW200916450A (en) | 2009-04-16 |
| JP2009102617A (en) | 2009-05-14 |
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