CN1230487C - 红色荧光材料及包含此材料的组合物 - Google Patents
红色荧光材料及包含此材料的组合物 Download PDFInfo
- Publication number
- CN1230487C CN1230487C CNB018234763A CN01823476A CN1230487C CN 1230487 C CN1230487 C CN 1230487C CN B018234763 A CNB018234763 A CN B018234763A CN 01823476 A CN01823476 A CN 01823476A CN 1230487 C CN1230487 C CN 1230487C
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- Prior art keywords
- red fluorescence
- fluorescence material
- amino groups
- present
- alkyl
- 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.)
- Expired - Fee Related
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- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title abstract description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract 2
- 125000004663 dialkyl amino group Chemical group 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- 125000003368 amide group Chemical group 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- -1 polyoxyethylene Polymers 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- 125000001246 bromo group Chemical group Br* 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 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
- ZUCHUQKVYXMZJU-UHFFFAOYSA-N C1=CC=C(C=C1)C(=O)C(=O)CCC(F)(F)F Chemical compound C1=CC=C(C=C1)C(=O)C(=O)CCC(F)(F)F ZUCHUQKVYXMZJU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- DVQGYGDSAGBRSZ-UHFFFAOYSA-N bis(1-cyclohexylcyclohexa-2,4-dien-1-yl)methanone Chemical class C1C=CC=CC1(C1CCCCC1)C(=O)C1(C2CCCCC2)CC=CC=C1 DVQGYGDSAGBRSZ-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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- OCPQNNYHIOZPGF-UHFFFAOYSA-N europium;perchloric acid Chemical compound [Eu].OCl(=O)(=O)=O OCPQNNYHIOZPGF-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5345—Complexes or chelates of phosphine-oxides or thioxides with metallic compounds or metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pyrane Compounds (AREA)
Abstract
一种荧光强度得到提高的红色荧光材料，以及包含此材料的油墨组合物。所述的红色荧光材料可用通式(1)表示：其中，X1和X2各自独立地表示氢原子、卤原子、烷基、烷氧基、羟基、氨基、烷基氨基、二烷基氨基、芳基或芳烷基。Y表示含有1-10个碳原子的氟代烃基。Z1、Z2和Z3各自独立地表示氢原子、卤原子、烷基、烷氧基、羟基、氨基、烷基氨基、二烷基氨基、芳基或芳烷基。
Description
发明领域
本发明涉及一种化合物及其组合物，所述化合物在可见光下无色，但在UV光照射下发出有色可见光。更具体地，本发明涉及一种红色荧光材料及其组合物，所述材料有优良的发射强度。
发明背景
我们已经知道这样一类化合物，它们在可见光下无色，但在UV光辐射下发出红光，如三(噻吩甲酰基三氟丙酮酸)铕配合物、三(苯甲酰基三氟丙酮酸)铕配合物等。这些化合物可用于各种油墨等。这些化合物的发射强度相对较高；不过，需要的是发射量子效率更高的红色荧光材料。
本发明的目的是提供一种红色荧光材料及包含此材料的油墨组合物。所述材料在UV光辐射下发出红光，稳定性好，荧光发射强度较常规材料有更大的提高。
发明概述
为克服上述问题，本发明的发明人做了大量研究，获得了一种铕配合物，它含有萘基三氟丙酮酸盐衍生物和三苯基氧化膦衍生物配体，由此得到一种红色发光组合物，它具有优良的荧光发射强度。
也就是说，本发明涉及
(1)由如下通式(1)表示的红色荧光材料，
(在通式中，X1和X2各自独立地表示氢原子、卤原子、烷基、烷氧基、羟基、氨基、烷基氨基、二烷基氨基、芳基或芳烷基。Y表示含有1-10个碳原子的氟代烃基。Z1、Z2和Z3各自独立地表示氢原子、卤原子、烷基、烷氧基、羟基、氨基、烷基氨基、二烷基氨基、芳基或芳烷基。)
(2)上面(1)所述的红色荧光材料，其中X1和X2各自是氢原子；
(3)上面(1)或(2)所述的红色荧光材料，其中Y是三氟甲基；
(4)上面(1)、(2)或(3)所述的红色荧光材料，其中Z1、Z2和Z3是表示氢原子；和
(5)一种油墨组合物，其含有(1)-(4)中任一项所述的红色荧光材料。
发明的最佳实施方式
下面将详细解释本发明。
本发明红色荧光材料由上述通式(1)表示，在通式(1)中，X1和X2或Z1、Z2和Z3各自独立地表示氢原子、卤原子、烷基、烷氧基、羟基、氨基、烷基氨基、二烷基氨基、芳基或芳烷基。卤原子可以是氯原子、氟原子、溴原子和碘原子。此外，所述烷基、烷氧基、烷基氨基和二烷基氨基等当中的烷基表示直链或支链、饱和烃基。至于芳基，可以是苯基、甲苯基、萘基等。至于芳烷基，可以是苄基、苯乙基等。
这些基团中，可优选为氢原子、卤原子、烷基和烷氧基，至于烷基和烷氧基，优选那些含1-6个碳原子的基团。更加优选的基团是氢原子、氯原子、甲基和乙基。
Y表示含有1-10个碳原子的氟代烃基。作为具体实例，可以提到全氟烷基，如三氟甲基、五氟乙基、七氟丙基、十七氟辛基等，或者一氟甲基、二氟甲基、三氟乙基、四氟丙基、八氟戊基等。这些基团中，可优选为全氟烷基，如三氟甲基、五氟乙基、十七氟辛基等。更加优选的是三氟甲基。
通式(1)所示化合物可如下面合成实施例所述进行合成。即，在(例如)醇或丙酮中，在氢氧化钠存在下，三苯基氧化膦和(例如)全氟烷基-1-(2-萘基)-1，3-丁二酮等与高氯酸铕或氯化铕反应，反应温度宜为0-80℃，由此合成通式(1)所示化合物。
通式(1)所示化合物的实例列于表1。表中取代基的取代位有如下位置关系：X是2-萘基上的取代基，Z为2位与P成邻位，Ph表示苯基，Bz表示苄基。
化合物实例
表1
| 化合物实例号 | X1 | X2 | Y | Z1 | Z2 | Z3 |
| 2 | H | H | CF3 | H | H | H |
| 4 | H | H | C8F17 | H | H | H |
| 5 | 6-CH3 | H | CF3 | H | H | H |
| 6 | 3-OCH3 | H | CF3 | H | H | H |
| 7 | H | H | CF3 | 4-CH3 | 4-CH3 | 4-CH3 |
| 8 | 3-CH3 | 7-CH3 | CF3 | 4-CH3 | 4-CH3 | 4-CH3 |
| 9 | 3-CH3 | 6-CH3 | C6F13 | H | H | H |
| 10 | H | H | CF3 | 4-OCH3 | 4-OCH3 | 4-OCH3 |
| 11 | H | H | CF3 | 4-Cl | 4-Cl | 4-Cl |
| 12 | 6-OH | H | C6F13 | 4-OH | 4-OH | 4-OH |
| 13 | H | H | CH2CF2CHF2 | H | H | H |
| 14 | 6-Bz | H | CF3 | H | H | H |
| 15 | 6-Ph | H | CF3 | H | H | H |
| 16 | 4-Br | H | CF3 | H | H | H |
混合至少一种或多种通式(1)所示化合物、各种溶剂、树脂粘合剂，如果需要，再加上其他添加剂，如染料、颜料、表面活性剂等，可以得到本发明的红色荧光材料组合物，它可以用于各种油漆、油墨等。
本发明可用的溶剂有水；醇溶剂，如甲醇、乙醇、异丙醇、乙二醇、二甘醇、丙二醇、聚乙二醇、丙三醇等；酮类溶剂，如丙酮、甲乙酮、环己酮等；非质子极性溶剂，如二甲基甲酰胺、二甲基亚砜、甲基吡咯烷酮等；酯类溶剂，如乙酸乙酯、乙酸丁酯等；芳烃类溶剂，如甲苯、二甲苯等；含卤素溶剂，如氯仿等；溶纤剂系列，如甲基溶纤剂、丁基溶纤剂等。这些溶剂可单独使用或以混合状态使用。
本发明可用的树脂粘合剂有丙烯酸类树脂，如聚丙烯酸酯树脂、聚甲基丙烯酸酯树脂、聚甲基丙烯酸甲酯等；聚乙烯吡咯烷酮；聚乙烯醇；聚丁基缩丁醛；聚乙酸乙烯酯；聚碳酸酯；环氧树脂；聚氨酯树脂；尼龙树脂；纤维素，如甲基纤维素、乙基纤维素、乙酰基纤维素、硝基纤维素等；聚烯烃。用于油墨的清漆的例子有，用于聚酰胺基油性油墨的清漆，用于纤维素油墨的清漆，用于丙烯酸类油墨的清漆等。
对于本发明的红色荧光材料包含于树脂中的情况，诸如聚苯乙烯等的树脂与本发明的红色荧光材料混合在一起，加热、熔融并溶解，然后用注塑机制成树脂板；或者例如，将甲基丙烯酸酯单体和聚合引发剂与本发明的红色荧光材料混合，随后用UV灯照射UV光，进行聚合；或者例如，将聚丁基缩丁醛树脂溶解于溶剂中，与本发明的红色荧光材料混合，随后进行旋涂，由此可获得树脂膜等。如果要将本发明的红色荧光材料施加于各种油墨清漆中，举例来说，可将本发明的红色荧光材料溶解于丙烯酸甲酯聚合物的二甲苯或甲乙酮溶液中，制成组合物，此组合物可涂敷于美术纸等之上。如果要将本发明的红色荧光油墨施加于油墨中，用于喷墨印刷机等，举例来说，可将本发明的红色荧光材料溶解于各种溶剂；如果需要，可加入添加剂，如表面张力调节剂、粘度调节剂、电导率调节剂、粘合剂树脂、表面活性剂等；由此可获得油墨组合物。
在本发明中，组合物中的红色荧光材料的浓度虽然因应用领域的不同而各异，但通常在0.001％-10％(重量)范围内，宜在0.01％-3％(重量)范围内。
实施例
下面将结合实施例更加具体地解释本发明。不过，本发明不受限于这些实施例。在实施例中，如果不特别指明，“份”指重量份。
实施例1(化合物(2)的合成)
室温下混合50份乙醇、2.4份4，4，4-三氟烷基-1-(2-萘基)-1，3-丁二酮、1.7份三苯基氧化膦和3.6份10％氢氧化钠，向此溶液中滴加1.1份六水合氯化铕溶解于30份水所得的溶液，接着搅拌2小时。反应完成后，过滤白色固体沉淀，洗涤、干燥，由此获得4份以下化学式所示化合物(2)。
吸收光谱(甲醇)中最大吸收波长：331nm
荧光光谱(甲醇)中最大激发波长：333nm
荧光光谱(甲醇)中最大荧光波长：613nm
熔点：80℃左右
分解温度：310℃左右(由TG-DTA测定)
元素分析：
碳：60.81％(理论值：62.28％)
氢：3.64％(理论值：3.62％)
实施例2(油墨的制备)
将一份化合物(2)溶解于80份甲乙酮中，随后加入10份乙酸乙酯、6份乙醇、2份N-甲基-2-吡咯烷酮、1份硫氰酸钠和1份氯乙烯-乙酸乙烯酯共聚物，搅拌使之溶解，接着过滤溶液，由此得到本发明的油墨组合物。本发明的油墨组合物在保存期间既不沉淀，也不分离，即便长期保存，其物理性质也不发生变化。如果在喷墨印刷机上用此组合物制作印刷品，当用UV光照射时，事实证实印刷品能显示很好的颜色。
实施例3(油墨的制备)
在25份乙醇中溶解1份化合物(2)，然后加入74份凹印油墨用NC清漆，同时搅拌使之溶解，由此得到用于凹印油墨的组合物。本发明的油墨组合物在储存期间既不沉淀，也不分离，即便长期储存，其物理性质也不发生变化。用刮条涂布器将所述组合物涂布在美术纸上并干燥。证实，当用UV光照射美术纸时，它显示很好的颜色。
实施例4(油墨的制备)
在25份甲乙酮和25份甲苯中溶解1份化合物(2)，向此溶液中加入25份二季戊四醇六丙烯酸酯、25份丙烯酸苯基缩水甘油酯和3份作为光聚合引发剂的1-环己基苯基酮，搅拌使之溶解，由此得到可用UV固化的油墨组合物。本发明的油墨组合物在储存期间既不沉淀，也不分离，即便长期储存，其物理性质也不发生变化。用刮条涂布器将所述组合物涂布在美术纸上，然后干燥，再用高压汞蒸气灯以100mJ/cm2的能量照射，由此得到固化膜。证实，当用UV光照射美术纸时，它显示很好的颜色。
比较例1
比较了下式所示化合物(3)与本发明的化合物(2)的荧光强度[在甲醇中，浓度10μg/ml，激发波长333nm，荧光检测波长613nm(Hitachi Ltd.生产的F-4010光谱荧光光度计)]，其中化合物(3)是用4，4，4-三氟烷基-1-(2-噻吩甲基)-1，3-丁二酮代替实施例1中的4，4，4-三氟烷基-1-(2-萘基)-1，3-丁二酮获得的。从下面表2可以明显看出，本发明的红色荧光材料具有更强的荧炮发射强度。
表2
| 样品 | 荧光发射强度 |
| 实施例1中的化合物(2) | 3000 |
| 比较例1中的化合物(3) | 1500 |
本发明的效果
根据本发明，获得一种红色荧光材料和包含此材料的组合物，所述材料与传统材料相比，荧光发射强度得到增强，并且在UV光照射下发出红光。此外，该化合物在有机溶剂中具有高的溶解性，用它能获得稳定的油墨组合物。由于发射强度好，该荧光材料在油墨中的用量可以减少，同时考虑到该组合物的稳定性得到提高而成本得到降低，它具有很高的应用价值。
Claims (5)
1.一种由如下通式(1)表示的红色荧光材料，
在通式中，X1和X2各自独立地表示氢原子、卤原子、具有1-6个碳原子的烷基、具有1-6个碳原子的烷氧基、羟基、选自苯基和甲苯基的芳基或选自苄基和苯乙基的芳烷基；Y表示含有1-10个碳原子的氟代烃基；Z1、Z2和Z3各自独立地表示氢原子、卤原子、具有1-6个碳原子的烷基、具有1-6个碳原子的烷氧基、或羟基。
2.权利要求1所述的红色荧光材料，其中X1和X2各自是氢原子。
3.权利要求1所述的红色荧光材料，其中Y是三氟甲基。
4.权利要求1所述的红色荧光材料，其中Z1、Z2和Z3各自是氢原子。
5.一种油墨组合物，其包含权利要求1-4任一项所述的红色荧光材料。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001109876A JP4466940B2 (ja) | 2000-04-10 | 2001-04-09 | 赤色蛍光材料およびそれを含有する組成物 |
| PCT/JP2001/005990 WO2003008516A1 (fr) | 2001-04-09 | 2001-07-10 | Matiere rouge fluorescente et composition contenant cette matiere |
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| CN1529743A CN1529743A (zh) | 2004-09-15 |
| CN1230487C true CN1230487C (zh) | 2005-12-07 |
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| US (1) | US20050011405A1 (zh) |
| EP (1) | EP1405892B1 (zh) |
| CN (1) | CN1230487C (zh) |
| CA (1) | CA2452243A1 (zh) |
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| WO (1) | WO2003008516A1 (zh) |
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| JP2008297250A (ja) * | 2007-05-31 | 2008-12-11 | Toshiba Corp | 蛍光性希土類錯体、ならびにそれを用いた発光素子、セキュリティー媒体、および照明装置 |
| US8664425B2 (en) * | 2010-02-02 | 2014-03-04 | Honeywell International Inc. | Bluegreen fluorescent compounds |
| JP5880387B2 (ja) * | 2012-10-16 | 2016-03-09 | 富士ゼロックス株式会社 | 静電荷像現像用透明トナー、静電荷像現像剤、トナーカートリッジ、画像形成方法及び画像形成装置 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3539941A (en) * | 1968-08-22 | 1970-11-10 | American Cyanamid Co | Liquid lanthanide chelate luminescent system with synergic agent |
| JPS63150358A (ja) * | 1986-12-15 | 1988-06-23 | Asahi Chem Ind Co Ltd | 螢光塗料組成物 |
| US5011816A (en) * | 1990-03-13 | 1991-04-30 | Eastman Kodak Company | Receiver for thermally-transferable fluorescent europium complexes |
| US5006503A (en) * | 1990-03-13 | 1991-04-09 | Eastman Kodak Company | Thermally-transferable fluorescent europium complexes |
| DE69510921T2 (de) * | 1995-05-25 | 1999-12-30 | Nycomed Amersham Plc, Little Chalfont | Fluoreszente Verbindungen |
| JPH11255700A (ja) * | 1998-03-12 | 1999-09-21 | Taiho Ind Co Ltd | アセチルアセトン系金属錯体及びその合成法、並びにそれを用いた有機多層型エレクトロルミネッセンス素子 |
| GB0119726D0 (en) * | 2001-08-14 | 2001-10-03 | Qinetiq Ltd | Triboluminescent materials and devices |
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2001
- 2001-07-10 US US10/482,610 patent/US20050011405A1/en not_active Abandoned
- 2001-07-10 CA CA002452243A patent/CA2452243A1/en not_active Abandoned
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| Publication number | Publication date |
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| DE60115107T2 (de) | 2006-07-20 |
| EP1405892B1 (en) | 2005-11-16 |
| DE60115107D1 (de) | 2005-12-22 |
| US20050011405A1 (en) | 2005-01-20 |
| CN1529743A (zh) | 2004-09-15 |
| EP1405892A4 (en) | 2005-03-02 |
| EP1405892A1 (en) | 2004-04-07 |
| CA2452243A1 (en) | 2003-01-30 |
| WO2003008516A1 (fr) | 2003-01-30 |
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