JP2008274165A - Fluorescent material - Google Patents
Fluorescent material Download PDFInfo
- Publication number
- JP2008274165A JP2008274165A JP2007121477A JP2007121477A JP2008274165A JP 2008274165 A JP2008274165 A JP 2008274165A JP 2007121477 A JP2007121477 A JP 2007121477A JP 2007121477 A JP2007121477 A JP 2007121477A JP 2008274165 A JP2008274165 A JP 2008274165A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- general formula
- formula
- fluorescent material
- repeating unit
- 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
- 239000000463 material Substances 0.000 title claims abstract description 50
- 229920001721 polyimide Polymers 0.000 claims abstract description 67
- 239000004642 Polyimide Substances 0.000 claims abstract description 63
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 11
- 125000000962 organic group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract 1
- 125000001033 ether group Chemical group 0.000 abstract 1
- 229920005575 poly(amic acid) Polymers 0.000 description 21
- 239000010408 film Substances 0.000 description 20
- 230000005281 excited state Effects 0.000 description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 17
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 17
- 239000010409 thin film Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 229920000642 polymer Chemical class 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- 230000005284 excitation Effects 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000006862 quantum yield reaction Methods 0.000 description 9
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 8
- 238000005102 attenuated total reflection Methods 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- 150000002367 halogens Chemical group 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- -1 polyphenylene vinylene Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 238000005401 electroluminescence Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 241001085205 Prenanthella exigua Species 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 125000005462 imide group Chemical group 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 4
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 0 C*(CCCC1C(CCCC2)C2C(F)(F)F)CC1C(F)(F)F Chemical compound C*(CCCC1C(CCCC2)C2C(F)(F)F)CC1C(F)(F)F 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000006159 dianhydride group Chemical group 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N C1CCCCC1 Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241001422033 Thestylus Species 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- SLPUTJFVMJPMKV-UHFFFAOYSA-N 1-methylpyrrolidin-3-one Chemical compound CN1CCC(=O)C1 SLPUTJFVMJPMKV-UHFFFAOYSA-N 0.000 description 1
- UYPCUJPMHKFVEA-UHFFFAOYSA-N 3,4,6-trifluoro-5-[2,3,5,6-tetrachloro-4-(3,4-dicarboxy-2,5,6-trifluorophenoxy)phenoxy]phthalic acid Chemical compound FC1=C(C(O)=O)C(C(=O)O)=C(F)C(F)=C1OC(C(=C1Cl)Cl)=C(Cl)C(Cl)=C1OC1=C(F)C(F)=C(C(O)=O)C(C(O)=O)=C1F UYPCUJPMHKFVEA-UHFFFAOYSA-N 0.000 description 1
- FKGIWESMZFOQHD-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)cyclohexan-1-amine Chemical compound NC1CCC(C(C(F)(F)F)C(F)(F)F)CC1 FKGIWESMZFOQHD-UHFFFAOYSA-N 0.000 description 1
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- COOWDVCEJFLNBA-UHFFFAOYSA-N 4-[4-(3,4-dicarboxy-2,5,6-trifluorophenoxy)phenoxy]-3,5,6-trifluorophthalic acid Chemical compound C1(=C(C(=C(C(=C1OC1=CC=C(OC2=C(C(=C(C(=C2F)F)C(=O)O)C(=O)O)F)C=C1)F)C(=O)O)C(=O)O)F)F COOWDVCEJFLNBA-UHFFFAOYSA-N 0.000 description 1
- AAYXZWDPJVOEEL-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)cyclohexyl]-3-(trifluoromethyl)cyclohexan-1-amine Chemical compound FC(F)(F)C1CC(N)CCC1C1C(C(F)(F)F)CC(N)CC1 AAYXZWDPJVOEEL-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- BBTGUNMUUYNPLH-UHFFFAOYSA-N 5-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 BBTGUNMUUYNPLH-UHFFFAOYSA-N 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- XCOBLONWWXQEBS-KPKJPENVSA-N N,O-bis(trimethylsilyl)trifluoroacetamide Chemical compound C[Si](C)(C)O\C(C(F)(F)F)=N\[Si](C)(C)C XCOBLONWWXQEBS-KPKJPENVSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- SIOVKLKJSOKLIF-HJWRWDBZSA-N trimethylsilyl (1z)-n-trimethylsilylethanimidate Chemical compound C[Si](C)(C)OC(/C)=N\[Si](C)(C)C SIOVKLKJSOKLIF-HJWRWDBZSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Landscapes
- Electroluminescent Light Sources (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
【課題】白色性の高い優れた蛍光発光特性を有る蛍光材料の提供。
【解決手段】３８０〜５２０ｎｍに蛍光ピークを有するポリイミド単位（１）と、５６０〜７６０ｎｍに蛍光ピークを有するポリイミド単位（２）とを有するポリイミドを含有する蛍光材料である。単位（１）は、式（１）で表わされ、Ｒ２は脂環式構造を含む２価の有機基、Ｒ１は、例えば３，３'，４，４'-ビフェニルエーテル基である。
単位（２）は、単位（１）のＲ１の部分が、例えば３，４，９，１０−ペリレン基である。
【選択図】なしProvided is a fluorescent material having high whiteness and excellent fluorescent emission characteristics.
A fluorescent material containing a polyimide having a polyimide unit (1) having a fluorescence peak at 380 to 520 nm and a polyimide unit (2) having a fluorescence peak at 560 to 760 nm. The unit (1) is represented by the formula (1), R 2 is a divalent organic group containing an alicyclic structure, and R 1 is, for example, a 3,3 ′, 4,4′-biphenyl ether group. .
In the unit (2), the R 1 portion of the unit (1) is, for example, a 3,4,9,10-perylene group.
[Selection figure] None
Description
本発明は、蛍光材料、及びそれを用いた光デバイスに関する。本発明の蛍光材料は、優れた耐熱性を有し可視域の広い波長域にわたる蛍光発光スペクトルを示すものであり、白色又は白色性の高い発光色を示す発光デバイス用材料として使用可能である。 The present invention relates to a fluorescent material and an optical device using the fluorescent material. The fluorescent material of the present invention has excellent heat resistance and exhibits a fluorescence emission spectrum over a wide visible wavelength range, and can be used as a material for a light emitting device that exhibits white or high whiteness emission color.
近年、有機エレクトロルミネッセンス（ＥＬ）素子や、発光型の空間光変調素子、波長変換素子等に使用される有機発光材料として、種々の低分子化合物や高分子化合物が開発されている。発光デバイス等の製造において、低分子化合物を用いる場合、製造プロセスが真空蒸着方式にほぼ制約されるのに対して、高分子化合物は、溶液状態として製膜又はインクジェットプリント方式等により製造できることから、製造コストを安くすることができるという利点を有している。また、高分子化合物は、微細加工なしに微小な塗り分けができる点、そして厚膜を容易に製膜できる等の優れた特徴を有している。そのため、高効率な蛍光発光を示し、かつ発光波長の制御が容易な高分子系の発光材料の開発が望まれている。 In recent years, various low molecular weight compounds and polymer compounds have been developed as organic light emitting materials used for organic electroluminescence (EL) elements, light emitting spatial light modulation elements, wavelength conversion elements and the like. In the production of light emitting devices and the like, when using a low molecular compound, the production process is almost restricted to the vacuum deposition method, whereas the polymer compound can be produced as a solution state by film formation or an inkjet printing method, The manufacturing cost can be reduced. In addition, the polymer compound has excellent features such as the ability to perform minute coating without fine processing and the ability to easily form a thick film. Therefore, it is desired to develop a high-molecular light-emitting material that exhibits high-efficiency fluorescence and can easily control the emission wavelength.
高分子系発光材料としては、ポリ-ｐ-フェニレンやポリフェニレンビニレン等のπ共役型高分子が知られている。しかし、このようなπ共役型高分子は、耐熱性や耐環境性（化学的安定性）が十分でなく、また、製膜や微細加工が容易ではないという問題があった。一方、代表的な耐熱性高分子であるポリイミドは、優れた耐熱性や電気特性を有しており、前駆体であるポリアミド酸が製膜等の加工性に優れていることから、表示用デバイス材料としての用途が期待されている。例えば、非特許文献１には、主鎖や側鎖に蛍光性のフリル基を導入した、青色の蛍光発光を示すポリイミドが開示されており、また、特許文献１及び特許文献２には、発光機能あるいは電荷輸送機能を有するポリイミドを用いた有機ＥＬ素子が開示されている。しかし、上記特許文献及び非特許文献に開示されたポリイミドの蛍光発光は、ポリイミドの主鎖又は側鎖に導入された蛍光性官能基によるものであり、また、その蛍光強度は、ポリイミド分子間の強い相互作用と、それに伴う濃度消失によって、同一の蛍光性官能基を有する低分子化合物の蛍光強度に比べると、その蛍光強度は非常に低いものである。 As polymer light-emitting materials, π-conjugated polymers such as poly-p-phenylene and polyphenylene vinylene are known. However, such a π-conjugated polymer has a problem that heat resistance and environmental resistance (chemical stability) are not sufficient, and film formation and microfabrication are not easy. On the other hand, polyimide, which is a typical heat-resistant polymer, has excellent heat resistance and electrical properties, and the precursor polyamic acid has excellent processability such as film formation. Use as a material is expected. For example, Non-Patent Document 1 discloses a polyimide exhibiting blue fluorescent light emission in which a fluorescent furyl group is introduced into the main chain or side chain, and Patent Document 1 and Patent Document 2 disclose light emission. An organic EL element using a polyimide having a function or a charge transport function is disclosed. However, the fluorescence emission of polyimide disclosed in the above patent document and non-patent document is due to the fluorescent functional group introduced into the main chain or side chain of the polyimide, and the fluorescence intensity is between polyimide molecules. Due to the strong interaction and the accompanying disappearance of concentration, the fluorescence intensity is very low compared to the fluorescence intensity of the low-molecular compound having the same fluorescent functional group.
また、非特許文献２等に開示されているように、ポリイミド自体が紫外線の照射により、可視光の蛍光発光を示すことは、従来から知られていた。この蛍光は、ポリイミドの分子構造中のジアミン部分（電子供与性）と酸無水物部分（電子吸引性）との間で形成される電荷移動錯体（ＣＴＣ）に起因する蛍光（ＣＴ蛍光）である（例えば、非特許文献３参照。）。しかし、芳香族ポリイミドの場合には、ＣＴ相互作用が強くなり、無輻射失活過程が増加するため、その蛍光強度は弱くなる。代表的な全芳香族ポリイミドフィルムであるピロメリット酸無水物と４，４’−ジアミノジフェニルエーテルから合成されるポリイミド（ＰＭＤＡ／ＯＤＡ）においては、通常の蛍光分光計では観測が困難なほどの弱い蛍光しか観測されない。また、非特許文献４には、全芳香族ポリイミドでも、ビフェニルテトラカルボン酸無水物とパラフェニレンジアミンから合成されるポリイミド（ＢＰＤＡ／ＰＤＡ）は相対的に強い蛍光を示すことが報告されている。しかし、既存の蛍光性化合物に比べると、その蛍光強度は非常に弱く、量子収率は１％以下であると考えられる。 In addition, as disclosed in Non-Patent Document 2 and the like, it has been conventionally known that polyimide itself exhibits visible fluorescence by irradiation with ultraviolet rays. This fluorescence is fluorescence (CT fluorescence) resulting from a charge transfer complex (CTC) formed between a diamine portion (electron donating property) and an acid anhydride portion (electron attracting property) in the molecular structure of polyimide. (For example, refer nonpatent literature 3.). However, in the case of aromatic polyimide, the CT interaction becomes strong and the non-radiation deactivation process increases, so the fluorescence intensity becomes weak. In a polyimide (PMDA / ODA) synthesized from pyromellitic anhydride, which is a typical wholly aromatic polyimide film, and 4,4'-diaminodiphenyl ether, weak fluorescence that is difficult to observe with a normal fluorescence spectrometer Only observed. Further, Non-Patent Document 4 reports that polyimide (BPDA / PDA) synthesized from biphenyltetracarboxylic anhydride and paraphenylenediamine exhibits relatively strong fluorescence even in wholly aromatic polyimide. However, compared to existing fluorescent compounds, the fluorescence intensity is very weak, and the quantum yield is considered to be 1% or less.
また、特許文献３には、三次元的な構造を有し、芳香環に直接フッ素が結合した芳香族酸二無水物と脂環式構造を有するジアミンとからなる構造単位を有するポリイミドを用いることで、優れた蛍光発光特性（蛍光強度の強さ、緑色から赤色領域における蛍光波長の制御性、蛍光強度の長期安定性）を有するとともに、耐熱性、化学的安定性、製膜性に優れた蛍光性ポリイミドが得られることが開示されている。また、非特許文献５には、三次元的な構造を有し、電子受容性の低い酸二無水物と脂環式構造を有するジアミンとからなる構造単位を有するポリイミドを用いることで、優れた青色蛍光発光特性を有し、耐熱性、化学的安定性、製膜性に優れた蛍光性ポリイミドが得られることが開示されている。上記特許文献３及び非特許文献５に開示された蛍光性ポリイミドは、蛍光強度が強いものであるが、基本的には単色発光性のものである。 Patent Document 3 uses a polyimide having a three-dimensional structure and having a structural unit composed of an aromatic dianhydride having fluorine directly bonded to an aromatic ring and a diamine having an alicyclic structure. In addition to excellent fluorescence emission characteristics (intensity of fluorescence intensity, controllability of fluorescence wavelength in the green to red range, long-term stability of fluorescence intensity), it also has excellent heat resistance, chemical stability, and film formability It is disclosed that a fluorescent polyimide is obtained. In addition, Non-Patent Document 5 is superior in that it has a three-dimensional structure and uses a polyimide having a structural unit composed of an acid dianhydride having a low electron accepting property and a diamine having an alicyclic structure. It is disclosed that a fluorescent polyimide having blue fluorescent emission characteristics and excellent in heat resistance, chemical stability, and film forming property can be obtained. The fluorescent polyimides disclosed in Patent Document 3 and Non-Patent Document 5 have strong fluorescence intensity, but are basically monochromatic.
照明用途やディスプレイのバックライト等には白色性が必要とされ、このような白色性は、光の３原色（青、緑、赤）に相当するそれぞれの蛍光発光を組み合わせることにより得ることができる。しかし、異なる種類の蛍光性ポリイミドは必ずしも相溶ではないため、容易に組み合わせることができず、また３層を重ねて製膜することは工程が煩雑となる。結果として、白色性の発光を得るためには、単一層のポリイミドで白色性の高い蛍光を高い量子収率で発することが期待される。
従って、本発明の目的は、白色性の高い優れた蛍光発光特性（蛍光強度の強さ、蛍光強度の長期安定性）を有するとともに、耐熱性、化学的安定性、製膜性に優れた白色蛍光材料を提供することにある。
Whiteness is required for lighting applications, display backlights, and the like, and such whiteness can be obtained by combining fluorescent emission corresponding to the three primary colors of light (blue, green, red). . However, since different types of fluorescent polyimides are not necessarily compatible with each other, they cannot be easily combined, and forming a film by stacking three layers makes the process complicated. As a result, in order to obtain white light emission, it is expected that single layer polyimide emits white fluorescent light with a high quantum yield.
Therefore, the object of the present invention is a white having excellent fluorescence emission characteristics (fluorescence intensity, long-term stability of fluorescence intensity) with high whiteness, and excellent heat resistance, chemical stability, and film-forming property. It is to provide a fluorescent material.
本発明者らは、上記目的を達成するため、鋭意検討を重ねた結果、特定の繰り返し単位からなるポリイミドが上記目的を達成し得るという知見を得、その知見を基に鋭意検討を重ねた結果、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have obtained the knowledge that a polyimide composed of a specific repeating unit can achieve the above object, and the results of intensive investigation based on the knowledge The present invention has been completed.
本発明は、上記知見に基づいてなされたものであり、下記一般式（１）で表わされる繰り返し単位であって、該繰り返し単位からなるポリイミドが３８０〜５２０ｎｍに蛍光ピークを有する繰り返し単位と、下記一般式（２）で表わされる繰り返し単位であって、該繰り返し単位からなるポリイミドが５６０〜７６０ｎｍに蛍光ピークを有する繰り返し単位とを有するポリイミドを含有する蛍光材料を提供するものである。
本発明の蛍光材料に含有されるポリイミドを構成する繰り返し単位の好適な例としては、上記一般式（１）におけるＲ１が、下記式（６）〜（１４）からなる群から選択される芳香族基であるものが挙げられる。 As a suitable example of the repeating unit constituting the polyimide contained in the fluorescent material of the present invention, R 1 in the general formula (1) is an fragrance selected from the group consisting of the following formulas (6) to (14). The group which is a group is mentioned.
また、本発明の蛍光材料に含有されるポリイミドを構成する繰り返し単位としては、上記一般式（１）及び（２）におけるＲ２が、脂環式アルキル基であるものが挙げられる。
一般式（２）におけるＲ２としては、トリフルオロメチル基やヘキサフルオロイソプロピリデン基等のペルフルオロアルキル基を有する有機基であってもよい。
また、本発明の蛍光材料に含有されるポリイミドを構成する繰り返し単位としては、上記一般式（１）及び（２）におけるＲ２が、下記式（１５）〜（１９）からなる群から選択されるものが挙げられる。
As the repeating units constituting the polyimide contained in the fluorescent material of the present invention, R 2 in the general formula (1) and (2) may be mentioned those which are alicyclic alkyl group.
R 2 in the general formula (2) may be an organic group having a perfluoroalkyl group such as a trifluoromethyl group or a hexafluoroisopropylidene group.
Moreover, as a repeating unit which comprises the polyimide contained in the fluorescent material of the present invention, R 2 in the general formulas (1) and (2) is selected from the group consisting of the following formulas (15) to (19). Can be mentioned.
上記一般式（１）及び（２）においては、Ｒ２は、単一種類のものであってもよく、又は（１５）〜（１９）のうちの２種以上の構造の混合物であってもよい。
また、本発明の蛍光材料に含有されるポリイミドを構成する繰り返し単位としては、上記一般式（２）におけるＲ３が、下記式（２０）であるものが挙げられる
In the above general formulas (1) and (2), R 2 may be a single type or a mixture of two or more types of (15) to (19). Good.
Moreover, as a repeating unit which comprises the polyimide contained in the fluorescent material of this invention, the thing whose R < 3 > in the said General formula (2) is a following formula (20) is mentioned.
また、本発明は、上記蛍光材料を用いて製造された有機発光デバイスを提供するものである。有機発光デバイスとしては、有機ＥＬ素子、有機レーザー及び空間光変調素子が挙げられる。 Moreover, this invention provides the organic light emitting device manufactured using the said fluorescent material. Examples of the organic light emitting device include an organic EL element, an organic laser, and a spatial light modulation element.
本発明によれば、白色性の高い優れた蛍光発光特性を有し、耐熱性、製膜性に優れ、低吸水性の白色蛍光材料が提供される。 According to the present invention, a white fluorescent material having a high whiteness and excellent fluorescent emission characteristics, excellent heat resistance and film forming property, and low water absorption is provided.
以下に、本発明の蛍光材料を詳細に説明する。
本発明の蛍光材料は、下記一般式（１）で表わされる繰り返し単位であって、該繰り返し単位からなるポリイミドが３８０〜５２０ｎｍに蛍光ピークを有する繰り返し単位と、下記一般式（２）で表わされる繰り返し単位であって、該繰り返し単位からなるポリイミドが５６０〜７６０ｎｍに蛍光ピークを有する繰り返し単位とを有するポリイミドを含有する。
Hereinafter, the fluorescent material of the present invention will be described in detail.
The fluorescent material of the present invention is a repeating unit represented by the following general formula (1), and the polyimide comprising the repeating unit is represented by a repeating unit having a fluorescence peak at 380 to 520 nm and the following general formula (2). It is a repeating unit, The polyimide which consists of this repeating unit contains the polyimide which has a repeating unit which has a fluorescence peak in 560-760 nm.
式（１）中、Ｒ１は、下記一般式（３）又は下記一般式（４）で表わされる４価の芳香族基であり、Ｒ２は脂環式構造を含む２価の有機基である。 In the formula (1), R 1 is a tetravalent aromatic group represented by the following general formula (3) or the following general formula (4), and R 2 is a divalent organic group containing an alicyclic structure. is there.
式（３）中、Ｒ４は炭素−炭素の一重結合、酸素原子、スルホニル基、ハロゲンで置換されていてもよい脂肪族基、１つ以上の２価元素を介した芳香族基のいずれかであるか、又はそれらの組み合わせによって構成される２価の置換基である。
脂肪族基としては、例えばメチレン基、エチレン基、イソプロピリデン基、ヘキサメチレン基等の長鎖アルキル基等が挙げられる。これらの脂肪族基は、フッ素、塩素、臭素、ヨウ素等のハロゲンで置換されていてもよい。また、１つ以上の２価元素を介した芳香族基とは、例えば酸素原子（-Ｏ-）を介して結合した芳香族基やスルホニル基（-ＳＯ２-）を介して結合した芳香族基を意味するものとし、この芳香族基はフッ素、塩素、臭素、ヨウ素等のハロゲンで置換されていてもよい。
In formula (3), R 4 is any one of a carbon-carbon single bond, an oxygen atom, a sulfonyl group, an aliphatic group optionally substituted with halogen, and an aromatic group via one or more divalent elements. Or a divalent substituent constituted by a combination thereof.
Examples of the aliphatic group include a long chain alkyl group such as a methylene group, an ethylene group, an isopropylidene group, and a hexamethylene group. These aliphatic groups may be substituted with halogens such as fluorine, chlorine, bromine and iodine. The aromatic group via one or more divalent elements is, for example, an aromatic group bonded via an oxygen atom (—O—) or an aromatic group bonded via a sulfonyl group (—SO 2 —). This aromatic group may be substituted with a halogen such as fluorine, chlorine, bromine or iodine.
式（４）中、Ｒ４及びＲ５は、同一であっても異なっていてもよく、炭素−炭素の一重結合、酸素原子、スルホニル基、ハロゲンで置換されていてもよい脂肪族基、１つ以上の２価元素を介した芳香族基のいずれかであるか、又はそれらの組み合わせによって構成される２価の置換基である。
脂肪族基としては、例えばメチレン基、エチレン基、イソプロピリデン基、ヘキサメチレン基等の長鎖アルキル基等が挙げられる。これらの脂肪族基は、フッ素、塩素、臭素、ヨウ素等のハロゲンで置換されていてもよい。また、１つ以上の２価元素を介した芳香族基とは、例えば酸素原子を介して結合した芳香族基や、スルホニル基を介して結合した芳香族基を意味するものとし、この芳香族基はフッ素、塩素、臭素、ヨウ素等のハロゲンで置換されていてもよい。
In the formula (4), R 4 and R 5 may be the same or different and are a carbon-carbon single bond, an oxygen atom, a sulfonyl group, an aliphatic group optionally substituted with halogen, 1 It is a divalent substituent that is either an aromatic group via two or more divalent elements, or a combination thereof.
Examples of the aliphatic group include a long chain alkyl group such as a methylene group, an ethylene group, an isopropylidene group, and a hexamethylene group. These aliphatic groups may be substituted with halogens such as fluorine, chlorine, bromine and iodine. The aromatic group via one or more divalent elements means, for example, an aromatic group bonded via an oxygen atom or an aromatic group bonded via a sulfonyl group. The group may be substituted with a halogen such as fluorine, chlorine, bromine or iodine.
一般式（２）中、Ｒ３は、下記一般式（５）、又は下記一般式（４２）で表される４価の芳香族基を示す。 In the general formula (2), R 3 represents a tetravalent aromatic group represented by the following general formula (5) or the following general formula (42).
上記一般式（５）においては、ｎは１以上の整数であり、好ましくは１〜３の整数であり、例えば、下記式（２０）〜（２２）の中から選択され、３つ以上のナフタレン環を含む場合、その中の２個のナフタレン環をつなぐ構造は共有結合１本であってもよい。そのような場合は、Ｒ３は、上記式（４２）で表わされる。式（４２）で表わされる４価の置換基の具体例としては、下記式（２３）、（２４）で表わされる置換基が挙げられる。 In the said General formula (5), n is an integer greater than or equal to 1, Preferably it is an integer of 1-3, for example, is chosen from following formula (20)-(22), and is 3 or more naphthalene When a ring is included, the structure connecting two naphthalene rings therein may be one covalent bond. In such a case, R 3 is represented by the above formula (42). Specific examples of the tetravalent substituent represented by the formula (42) include substituents represented by the following formulas (23) and (24).
本発明の蛍光材料は、上記一般式（１）で表わされる繰り返し単位、及び上記一般式（２）で表わされる繰り返し単位を有するポリイミド共重合体を含み、一般式（１）中のＲ１が４価の芳香族基であり、吸水性が低く、蛍光性の光学用デバイスとして用いるのに好適である。また、一般式（１）及び一般式（２）中のＲ２に脂環式構造を有するので、ポリイミド分子内及び分子間の電荷移動相互作用が抑制される。従って、本発明の蛍光材料は高い蛍光強度を発現できる。上記一般式（１）で表わされる繰り返し単位を有するポリイミドは紫外長波長域から可視短波長〜中波長域にかけての蛍光発光、すなわち紫〜青〜緑色の蛍光発光（蛍光ピーク波長３８０〜５２０ｎｍ、好ましくは４００〜４５０ｎｍ）を示す。一方、上記一般式（２）で表わされる繰り返し単位を有するポリイミドは、赤色の鮮やかな蛍光発光（蛍光ピーク波長５６０〜７２６０ｎｍ好ましくは６５０〜７００ｎｍ）を示す。 The fluorescent material of the present invention includes a polyimide copolymer having a repeating unit represented by the above general formula (1) and a repeating unit represented by the above general formula (2), wherein R 1 in the general formula (1) is It is a tetravalent aromatic group, has low water absorption, and is suitable for use as a fluorescent optical device. Further, since the R 2 of the general formulas (1) and (2) having an alicyclic structure, charge transfer interactions between polyimide intramolecular and are suppressed. Therefore, the fluorescent material of the present invention can exhibit high fluorescence intensity. The polyimide having the repeating unit represented by the general formula (1) is fluorescent emission from the ultraviolet long wavelength region to the visible short wavelength to medium wavelength region, that is, purple to blue to green fluorescent emission (fluorescence peak wavelength of 380 to 520 nm, preferably Represents 400 to 450 nm). On the other hand, the polyimide having the repeating unit represented by the general formula (2) exhibits bright red fluorescence (fluorescence peak wavelength of 560 to 7260 nm, preferably 650 to 700 nm).
これらの共重合体の発光機構を図１に示す。
これらの共重合体が白色性の高い蛍光発光を示すのは、構成成分である一般式（１）で表わされる繰り返し単位、及び一般式（２）で表わされる繰り返し単位の蛍光発光機構が独立のものとして残っているだけではなく、前者の蛍光スペクトルが後者の励起スペクトル（蛍光発光を引き起こすための光吸収能のスペクトル）と重畳しているために、前者の光照射によって獲得されたエネルギーが後者へ移動し、結果として長波長域（黄〜赤色域）での蛍光発光も惹起することに由来する（図１に示す発光機構）。すなわち、構成成分である一般式（１）で表わされる繰り返し単位を波長２８０〜３７０ｎｍの紫外光で照射すると、一般式（１）で表わされる繰り返し単位の酸二無水物部分に存在する電子は、まず励起状態１に励起され、その励起状態からの直接的な発光緩和として波長３８０〜４８０ｎｍの蛍光を示す。しかし、そのエネルギーのほとんどは、励起状態での分子間あるいは分子内でのエネルギー移動機構を通じて一般式（２）で表わされる繰り返し単位に移動し、この励起状態２からの発光緩和として波長５００〜７００ｎｍの蛍光を示す。この励起状態２は、一般式（２）で表わされる繰り返し単位を紫外光あるいは可視短波長光で照射した場合の垂直励起状態に相当し、この励起によっても電荷分布がそれほど変化しないため局所励起状態（Locally Excited State）と呼ばれる。一方、一般式（２）で表わされる繰り返し単位は、同一分子間で相互作用し会合体の励起状態(Excited Aggregate State)を形成することが可能であり、その励起状態３のエネルギー順位は第一励起状態や第二励起状態よりも低い。分子間あるいは分子内でのエネルギー移動機構を通じて、励起状態２から励起状態３へのエネルギー移動が引き続いて惹起され、この励起状態３からの蛍光発光は波長５５０〜８００ｎｍに観測される。結果として、非占軌道にある電子を励起状態１のみに励起することで、励起状態１から励起状態２そして励起状態３への連続的なエネルギー移動が起こり、それぞれの励起状態からの蛍光発光が合算されて観測されるため、蛍光スペクトルが可視域全体に広がって白色性の高い蛍光発光を示す。従って、一般式（１）で表わされる繰り返し単位の蛍光と一般式（２）で表わされる繰り返し単位の蛍光の成分比が、共重合体の蛍光スペクトル形状を決定する最も重要な要素であり、したがって白色度の高い蛍光発光を得るためには、２成分の構造式の組み合わせに応じてその共重合比が精密に制御される必要がある。また、白色の蛍光を高効率的で発光させるための最適の励起波長は、一般式（１）で表わされる繰り返し単位単独での励起波長にほぼ等しくなるので、白色蛍光ポリイミドの励起波長を制御するためには、一般式（１）で表わされる繰り返し単位の構造を、所望の励起波長を有するものとする必要がある。
The light emission mechanism of these copolymers is shown in FIG.
These copolymers exhibit fluorescence with high whiteness because the fluorescent light emission mechanism of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) is independent. Not only remains, but because the former fluorescence spectrum is superimposed on the latter excitation spectrum (the spectrum of light absorption ability to cause fluorescence emission), the energy acquired by the former light irradiation is the latter. As a result, fluorescence emission in the long wavelength region (yellow to red region) is also induced (the light emission mechanism shown in FIG. 1). That is, when the repeating unit represented by the general formula (1) as a constituent component is irradiated with ultraviolet light having a wavelength of 280 to 370 nm, the electrons present in the acid dianhydride part of the repeating unit represented by the general formula (1) are: First, it is excited to the excited state 1 and shows fluorescence having a wavelength of 380 to 480 nm as direct light emission relaxation from the excited state. However, most of the energy is transferred to the repeating unit represented by the general formula (2) through an energy transfer mechanism between molecules in the excited state or within the molecule, and a wavelength of 500 to 700 nm as emission relaxation from the excited state 2. The fluorescence of is shown. This excited state 2 corresponds to a vertical excited state in the case where the repeating unit represented by the general formula (2) is irradiated with ultraviolet light or visible short wavelength light. (Locally Excited State). On the other hand, the repeating unit represented by the general formula (2) can interact between the same molecules to form an excited aggregate state, and the energy level of the excited state 3 is first. It is lower than the excited state and the second excited state. The energy transfer from the excited state 2 to the excited state 3 is subsequently induced through an intermolecular or intramolecular energy transfer mechanism, and the fluorescence emission from the excited state 3 is observed at a wavelength of 550 to 800 nm. As a result, continuous excitation of energy from excited state 1 to excited state 2 and excited state 3 occurs by exciting electrons in the unoccupied orbital state only to excited state 1, and fluorescence emission from each excited state occurs. Since they are added together and observed, the fluorescence spectrum spreads over the entire visible range and exhibits high whiteness fluorescence. Therefore, the component ratio of the fluorescence of the repeating unit represented by the general formula (1) and the fluorescence of the repeating unit represented by the general formula (2) is the most important factor determining the fluorescence spectrum shape of the copolymer. In order to obtain fluorescence with high whiteness, the copolymerization ratio needs to be precisely controlled according to the combination of the structural formulas of the two components. In addition, the optimum excitation wavelength for emitting white fluorescence with high efficiency is substantially equal to the excitation wavelength of the repeating unit represented by the general formula (1) alone, so the excitation wavelength of the white fluorescent polyimide is controlled. For this purpose, the structure of the repeating unit represented by the general formula (1) needs to have a desired excitation wavelength.
上記一般式（１）で表わされる繰り返し単位と、上記一般式（２）で表わされる繰り返し単位との共重合比は、好ましくは９７：３〜９９．９９：０．０１（モル比）であり、更に好ましくは９９．５：０．５〜９９．９９：０．０１（モル比）である。共重合比を上記範囲とするには、ポリイミドを合成する際に、上記一般式（１）で表わされる繰り返し単位を得るための酸二無水物、上記一般式（２）で表わされる繰り返し単位を得るための酸二無水物の使用量を調整することによって達成することができる。 The copolymerization ratio of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) is preferably 97: 3 to 99.99: 0.01 (molar ratio). More preferably, it is 99.5: 0.5 to 99.99: 0.01 (molar ratio). In order to make the copolymerization ratio within the above range, when synthesizing polyimide, an acid dianhydride for obtaining a repeating unit represented by the above general formula (1), a repeating unit represented by the above general formula (2) It can be achieved by adjusting the amount of acid dianhydride used to obtain.
本発明の蛍光材料に含有されるポリイミドとしては、例えば、下記式（２５）〜（３６）で表わされる繰り返し単位のいずれかと、下記式（３７）又は（３８）のいずれかで表わされる繰り返し単位とを含有するポリイミドが挙げられる。 As the polyimide contained in the fluorescent material of the present invention, for example, any of the repeating units represented by the following formulas (25) to (36) and the repeating unit represented by any of the following formulas (37) or (38) And polyimide containing.
本発明の蛍光材料に含有されるポリイミドの分子量は、その蛍光特性が発揮される範囲であれば特に限定されないが、その前駆体（ポリアミド酸あるいはポリアミド酸エステル）の分子量として対数粘度換算で０.０５〜５.０(ｄｌ／ｇ)（温度３０℃の有機溶媒中、濃度０.５ｇ／ｄｌ）の範囲であることが好ましい。 The molecular weight of the polyimide contained in the fluorescent material of the present invention is not particularly limited as long as the fluorescence characteristics are exhibited, but the molecular weight of the precursor (polyamic acid or polyamic acid ester) is 0. It is preferably in the range of 05 to 5.0 (dl / g) (concentration 0.5 g / dl in an organic solvent at a temperature of 30 ° C.).
本発明の蛍光材料に含有されるポリイミドの製造方法に特に制限はないが、例えば、前記の２種類の酸二無水物からなる混合物と前記のジアミン化合物とを重縮合して得られるポリアミド酸を、加熱閉環することによって製造することができる。加熱閉環する方法に特に制限はなく、従来公知の方法が用いられる。 Although there is no restriction | limiting in particular in the manufacturing method of the polyimide contained in the fluorescent material of this invention, For example, the polyamic acid obtained by polycondensing the mixture which consists of said 2 types of acid dianhydrides, and said diamine compound is used. It can be produced by heating and ring closure. There is no restriction | limiting in particular in the method of carrying out a heating ring closure, A conventionally well-known method is used.
酸二無水物としては、例えば、ピロメリット酸二無水物、１，４−ビス（３，４−ジカルボキシフェノキシ）ベンゼン二無水物、３,３',４,４'ーオキシビスフタル酸二無水物、３,３',４,４'-ビフェニルテトラカルボン酸二無水物、３,３',４,４'-ベンゾフェノンテトラカルボン酸二無水物、２,２ービス（３,４ージカルボキシ）プロパン二無水物、ビス（３,４ージカルボキシ）メタン二無水物等が挙げられる。なお、これらと同じ基本骨格を有するテトラカルボン酸やその酸塩化物、エステル化物等も、本発明の蛍光材料に含有されるポリイミド共重合体を製造するための原料として用いることができる。
用いられる酸二無水物はとしては、例えば、下記一般式（１）で表わされる繰り返し単位を得るためには下記一般式式（３９）、（４０）で表わされるものが、下記一般式（２）で表わされる繰り返し単位を得るためには下記一般式式（４１）で表されるものが挙げられる。
Examples of the acid dianhydride include pyromellitic dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 3,3 ′, 4,4′-oxybisphthalic acid Anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxy) propane And dianhydrides and bis (3,4-dicarboxy) methane dianhydrides. Tetracarboxylic acids having the same basic skeleton as those, acid chlorides and esterified products thereof can also be used as raw materials for producing the polyimide copolymer contained in the fluorescent material of the present invention.
Examples of the acid dianhydride used include those represented by the following general formulas (39) and (40) in order to obtain a repeating unit represented by the following general formula (1). In order to obtain a repeating unit represented by the following formula (41), one represented by the following general formula (41) may be mentioned.
上記一般式（３９）及び（４０）においては、Ｒ４、Ｒ５は炭素−炭素の一重結合又はフッ素以外のハロゲン原子（塩素、臭素、ヨウ素）を含んでいてもよく、２，２−ビス（３，４−ジカルボキシトリフルオロフェノキシ）プロパン二無水物や１，４−ビス（３，４−ジカルボキシトリフルオロフェノキシ）ベンゼン二無水物、１，４−ビス（３，４−ジカルボキシトリフルオロフェノキシ）テトラクロロベンゼン二無水物、２，２’，５，５’，６，６’−ヘキサフルオロ−３，３’，４，４’，−ビフェニルテトラカルボン酸二無水物等が挙げられる。 In the general formulas (39) and (40), R 4 and R 5 may contain a carbon-carbon single bond or a halogen atom other than fluorine (chlorine, bromine, iodine), and 2,2-bis (3,4-dicarboxytrifluorophenoxy) propane dianhydride, 1,4-bis (3,4-dicarboxytrifluorophenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxytri Fluorophenoxy) tetrachlorobenzene dianhydride, 2,2 ′, 5,5 ′, 6,6′-hexafluoro-3,3 ′, 4,4 ′,-biphenyltetracarboxylic dianhydride and the like.
ジアミン化合物としては、例えば、１，４−ジアミノシクロヘキサン、４，４’−ジアミノジシクロヘキシルメタン、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビシクロヘキサン、２，２’−ビス（４−アミノシクロヘキシル）−ヘキサフルオロプロパン、ビス（３-アミノプロピルジメチルシリル）エーテル等やこれらの構造異性体が挙げられる。 Examples of the diamine compound include 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 2,2′-bis (trifluoromethyl) -4,4′-diaminobicyclohexane, 2,2′-bis. Examples include (4-aminocyclohexyl) -hexafluoropropane, bis (3-aminopropyldimethylsilyl) ether, and structural isomers thereof.
以下に、本発明の蛍光材料を用いた、フィルムの製造方法の一例を示す。
まず、極性有機溶媒中で、３，３’，４，４’，−ビフェニルテトラカルボン酸二無水物と３,４,９,１０-ペリレンテトラカルボン酸二無水物の任意のモル比の混合物を４，４’−ジアミノジシクロヘキシルメタンとを重縮合し、ポリアミド酸溶液を得る。この時、Ｎ，Ｏ−ビス（トリメチルシリル）アセトアミドやＮ，Ｏ−ビス（トリメチルシリル）トリフルオロアセトアミドのようなシリルエステル化物を混合すると、原料の会合体や生成物の不溶化（ゲル化）が起こりにくくなる。用いられる極性有機溶媒としては、例えば、Ｎ−メチル−４−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等が挙げられる。重合溶液中の原料化合物の濃度は、好ましくは５〜４０重量％であり、更に好ましくは１０〜２５重量％である。この反応を下記式に示す。
Below, an example of the manufacturing method of a film using the fluorescent material of this invention is shown.
First, in a polar organic solvent, a mixture of 3,3 ′, 4,4 ′,-biphenyltetracarboxylic dianhydride and 3,4,9,10-perylenetetracarboxylic dianhydride in an arbitrary molar ratio is prepared. Polycondensation with 4,4′-diaminodicyclohexylmethane gives a polyamic acid solution. At this time, when a silyl esterified product such as N, O-bis (trimethylsilyl) acetamide or N, O-bis (trimethylsilyl) trifluoroacetamide is mixed, insolubilization (gelation) of the raw material aggregates and products hardly occurs. Become. Examples of the polar organic solvent used include N-methyl-4-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide and the like. The concentration of the raw material compound in the polymerization solution is preferably 5 to 40% by weight, more preferably 10 to 25% by weight. This reaction is shown in the following formula.
上述のようにして得られたポリアミド酸溶液を、溶融石英板上に回転塗布し、窒素雰囲気下で、例えば７０℃程度の温度と３００℃程度の温度の２段階で加熱し、イミド化する。この反応を下記式に示す。加熱の例としては、例えば、７０℃で１時間、３００℃で１時間３０分のように行ってもよい。イミド化後、空気中あるいは水中で石英板から剥離することによりポリイミドフィルムを得る。石英板からの剥離が困難な場合は、ポリアミド酸溶液をアルミ板上に回転塗布し、熱イミド化後、基板ごと１０％塩酸に浸しアルミ板を溶解することにより、ポリイミドフィルムを得る。 The polyamic acid solution obtained as described above is spin-coated on a fused quartz plate, and heated in two stages, for example, at a temperature of about 70 ° C. and a temperature of about 300 ° C. in a nitrogen atmosphere, and imidized. This reaction is shown in the following formula. As an example of heating, for example, the heating may be performed at 70 ° C. for 1 hour and at 300 ° C. for 1 hour 30 minutes. After imidation, a polyimide film is obtained by peeling from the quartz plate in air or water. When peeling from the quartz plate is difficult, the polyimide film is obtained by spin-coating the polyamic acid solution on the aluminum plate, thermal imidization, and then immersing the substrate together with 10% hydrochloric acid to dissolve the aluminum plate.
ポリアミド酸の合成方法としては、上記のように極性有機溶媒を用いて合成する方法の他、原料である酸二無水物とジアミン化合物の昇華性を利用して、真空蒸着重合法により基板上で合成する方法が挙げられる。この場合のポリイミドフィルムの合成方法としては、具体的には、酸二無水物モノマーとジアミンモノマーを、真空槽内でそれぞれの蒸着源を加熱して蒸発させ、基板上でポリアミド酸を合成し、さらにこれを不活性気体中で加熱して、脱水閉環することによりポリイミド薄膜を得ることができる。また、必要に応じてピリジン／無水酢酸などの閉環触媒と脱水剤の組み合わせによる化学処理を行ってイミド化してもよい。 As a method for synthesizing the polyamic acid, in addition to the method of synthesizing using a polar organic solvent as described above, the sublimation property of the acid dianhydride and the diamine compound as raw materials is used to form a polyamic acid on a substrate by a vacuum deposition polymerization method. The method of synthesizing is mentioned. As a method for synthesizing the polyimide film in this case, specifically, an acid dianhydride monomer and a diamine monomer are evaporated by heating respective vapor deposition sources in a vacuum chamber, and a polyamic acid is synthesized on the substrate. Furthermore, a polyimide thin film can be obtained by heating this in inert gas and carrying out dehydration ring closure. Further, if necessary, imidization may be performed by chemical treatment with a combination of a ring-closing catalyst such as pyridine / acetic anhydride and a dehydrating agent.
本発明の蛍光材料は、有機ＥＬ素子、有機レーザー、空間光変調素子等の有機発光デバイスの材料として用いることができる。例えば、本発明の蛍光材料のフィルムを発光層／受光層として用いて、透明基板／透明電極／電荷輸送層／発光層／受光層／電極の積層体を形成することにより有機ＥＬ素子にすることができる。
その他、通信用の光導波路や光源、光ファイバー増幅器、蛍光増白剤、塗料、インク、蛍光コレクタ、シンチレータ、植物育成用フィルム等に利用することができる。
The fluorescent material of the present invention can be used as a material for organic light-emitting devices such as organic EL elements, organic lasers, and spatial light modulation elements. For example, using the film of the fluorescent material of the present invention as a light emitting layer / light receiving layer, an organic EL device is formed by forming a laminate of transparent substrate / transparent electrode / charge transport layer / light emitting layer / light receiving layer / electrode. Can do.
In addition, it can be used for optical waveguides and light sources for communication, optical fiber amplifiers, optical brighteners, paints, inks, fluorescent collectors, scintillators, plant growth films, and the like.
以下に、実施例を示して本発明を具体的に説明するが、これらにより本発明は何ら制限を受けるものではない。
実施例１
三角フラスコに、３，３’，４，４’，−ビフェニルテトラカルボン酸二無水物（ｓ-ＢＰＤＡ）０．３０４ｇ（１．０３ｍｍｏｌ）、３,４,９,１０-ペリレンテトラカルボン酸二無水物（ＰＴＤＡ）０．０００４０５ｇ（０．００１０３ｍｍｏｌ）、及び４，４’−ジアミノジシクロヘキシルメタン（ＤＣＨＭ）０．２１７ｇ（１．０３ｍｍｏｌ）を加え、溶液の原材料の濃度が１０重量％になるようにＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）４．６９ｇを加えた。三角フラスコ中の溶液を窒素雰囲気中、室温で２４時間攪拌し、ポリアミド酸のＤＭＡｃ溶液を得た。得られたポリアミド酸のＤＭＡｃ溶液を直径７５ｍｍの石英板上に回転塗布し、窒素雰囲気下、７０℃で１時間、３００℃で１時間３０分、２段階で昇温して加熱イミド化を行った。加熱イミド化によって形成された層を石英板から剥離して蛍光材料であるを含むポリイミド薄膜を得た。
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.
Example 1
Into an Erlenmeyer flask, 0.304 g (1.03 mmol) of 3,3 ′, 4,4 ′,-biphenyltetracarboxylic dianhydride (s-BPDA), 3,4,9,10-perylenetetracarboxylic dianhydride Product (PTDA) 0.000405 g (0.00103 mmol) and 4,4′-diaminodicyclohexylmethane (DCHM) 0.217 g (1.03 mmol) are added, and the concentration of the raw materials in the solution is 10 wt%. , 4.69 g of N-dimethylacetamide (DMAc) was added. The solution in the Erlenmeyer flask was stirred in a nitrogen atmosphere at room temperature for 24 hours to obtain a DMAc solution of polyamic acid. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 300 ° C. for 1 hour 30 minutes, and heated for imidization. It was. The layer formed by heating imidization was peeled from the quartz plate to obtain a polyimide thin film containing a fluorescent material.
得られたポリイミド薄膜の赤外吸収スペクトルを減衰全反射（ＡＴＲ）法により測定したところ、１７７７ｃｍ-１及び１７１９ｃｍ-１にイミド基のカルボニルに特有の吸収が観察され、またポリアミド酸において観測される１６７７ｃｍ-１、１６３７ｃｍ-１のアミド結合特有の吸収が消失しており、イミド化が完全に進行したことが確認できた。得られた薄膜の膜厚を触針式膜厚計で測定したところ、３．２μｍであった。得られたポリイミド薄膜の蛍光発光スペクトルを励起波長３６５ｎｍ、蛍光観測波長３００〜８００ｎｍで測定した。結果を図２に示す。図２から明らかなように、波長３５０〜７５０ｎｍにおいて強い蛍光が観測された。図２において縦軸は蛍光強度、横軸は波長（ｎｍ）を示している。図２に示すように、実施例１で得られた蛍光材料は、蛍光波長が可視域全体に広がっており、明るい白色の蛍光を示している。そこで、この白色発光ポリイミドの蛍光量子収率を、Y. Geng ら, J. Am. Chem. Soc., 124, 8337 (2002)に記載の方法によって測定した。
すなわち、高透明性かつ無蛍光であるポリメチルメタクリレート樹脂中にアントラセンを１×１０-2 mol/l の濃度で溶解させたフィルム状試料を調製し、この蛍光強度を測定するとともに、アントラセンの蛍光量子収率を０．２８として校正して、上記で得られた白色蛍光材料の蛍光量子収率を見積もったところ０．１５８であった。
The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm -1 and 1719 cm -1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm −1 and 1637 cm −1 disappeared, and it was confirmed that imidization proceeded completely. When the film thickness of the obtained thin film was measured with a stylus type film thickness meter, it was 3.2 μm. The fluorescence emission spectrum of the obtained polyimide thin film was measured at an excitation wavelength of 365 nm and a fluorescence observation wavelength of 300 to 800 nm. The results are shown in FIG. As is clear from FIG. 2, strong fluorescence was observed at a wavelength of 350 to 750 nm. In FIG. 2, the vertical axis represents fluorescence intensity, and the horizontal axis represents wavelength (nm). As shown in FIG. 2, the fluorescent material obtained in Example 1 has a fluorescent wavelength extending over the entire visible range, and shows bright white fluorescence. Therefore, the fluorescence quantum yield of this white light-emitting polyimide was measured by the method described in Y. Geng et al., J. Am. Chem. Soc., 124, 8337 (2002).
That is, a film sample prepared by dissolving anthracene at a concentration of 1 × 10 −2 mol / l in a highly transparent and non-fluorescent polymethylmethacrylate resin was prepared, and the fluorescence intensity was measured and the anthracene fluorescence was measured. When the quantum yield was calibrated as 0.28 and the fluorescence quantum yield of the white fluorescent material obtained above was estimated, it was 0.158.
実施例２
三角フラスコに、２,２−ビス（３,４−ジカルボキシ）プロパン二無水物（ＢＳＡＡ）０．３７０ｇ（０．７１２ｍｍｏｌ）、３,４,９,１０-ペリレンテトラカルボン酸二無水物（ＰＴＤＡ）０．０００２８０ｇ（０．０００７１２ｍｍｏｌ）、及び４，４’−ジアミノジシクロヘキシルメタン（ＤＣＨＭ）０．１５０ｇ（０．７１２ｍｍｏｌ）を加え、溶液の原材料の濃度が１０重量％になるようにＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）４．６９ｇを加えた。三角フラスコ中の溶液を窒素雰囲気中、室温で２４時間攪拌し、ポリアミド酸のＤＭＡｃ溶液を得た。得られたポリアミド酸のＤＭＡｃ溶液を直径７５ｍｍの石英板上に回転塗布し、窒素雰囲気下、７０℃で１時間、３００℃で１時間３０分、２段階で昇温して加熱イミド化を行った。加熱イミド化によって形成された層を石英板から剥離して蛍光材料であるを含むポリイミド薄膜を得た。
Example 2
Into an Erlenmeyer flask, 0.370 g (0.712 mmol) of 2,2-bis (3,4-dicarboxy) propane dianhydride (BSAA), 3,4,9,10-perylenetetracarboxylic dianhydride (PTDA) ) 0.000280 g (0.000712 mmol) and 4,4′-diaminodicyclohexylmethane (DCHM) 0.150 g (0.712 mmol) are added, and the N, N— 4.69 g of dimethylacetamide (DMAc) was added. The solution in the Erlenmeyer flask was stirred in a nitrogen atmosphere at room temperature for 24 hours to obtain a DMAc solution of polyamic acid. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 300 ° C. for 1 hour 30 minutes, and heated for imidization. It was. The layer formed by heating imidization was peeled from the quartz plate to obtain a polyimide thin film containing a fluorescent material.
上述のようにして得られたポリイミド薄膜の赤外吸収スペクトルを減衰全反射（ＡＴＲ）法により測定したところ、１７７７ｃｍ-１及び１７１９ｃｍ-１にイミド基のカルボニルに特有の吸収が観察され、またポリアミド酸において観測される１６７７ｃｍ-１、１６３７ｃｍ-１のアミド結合特有の吸収が消失しており、イミド化が完全に進行したことが確認できた。得られた薄膜の膜厚を触針式膜厚計で測定したところ、３．２μｍであった。得られたポリイミド薄膜の蛍光発光スペクトルを励起波長３６５ｎｍ、蛍光観測波長３００〜８００ｎｍで測定した。結果を図２に示す。図２から明らかなように、波長３５０〜７５０ｎｍにおいて強い蛍光が観測された。図２において縦軸は蛍光強度、横軸は波長（ｎｍ）を示している。図２に示すように、実施例２で得られた蛍光材料は、蛍光波長が可視域全体に広がっており、明るい白色の蛍光を示している。そこで、この白色発光ポリイミドの蛍光量子収率を実施例１と同様にして測定したところ、上記で得られた白色蛍光材料の蛍光量子収率を見積もったところ０．１９２であった。 When the infrared absorption spectrum of the polyimide thin film obtained as described above was measured by the attenuated total reflection (ATR) method, absorption specific to carbonyl of the imide group was observed at 1777 cm −1 and 1719 cm −1. 1677Cm -1 observed in acid, have disappeared amide bond characteristic absorption of 1637 cm -1, it was confirmed that the imidization proceeded completely. When the film thickness of the obtained thin film was measured with a stylus type film thickness meter, it was 3.2 μm. The fluorescence emission spectrum of the obtained polyimide thin film was measured at an excitation wavelength of 365 nm and a fluorescence observation wavelength of 300 to 800 nm. The results are shown in FIG. As is clear from FIG. 2, strong fluorescence was observed at a wavelength of 350 to 750 nm. In FIG. 2, the vertical axis represents fluorescence intensity, and the horizontal axis represents wavelength (nm). As shown in FIG. 2, the fluorescent material obtained in Example 2 has a fluorescent wavelength that extends over the entire visible range, and shows bright white fluorescence. Therefore, when the fluorescence quantum yield of this white light emitting polyimide was measured in the same manner as in Example 1, the fluorescence quantum yield of the white fluorescent material obtained above was estimated to be 0.192.
実施例３
三角フラスコに、３，３’，４，４’，−ビフェニルテトラカルボン酸二無水物（ｓ-ＢＰＤＡ）０．８４６ｇ（２．８７ｍｍｏｌ）、３,４,９,１０-ペリレンテトラカルボン酸二無水物（ＰＴＤＡ）０．００１１３ｇ（０．００２８７ｍｍｏｌ）、及びビス（３-アミノプロピルジメチルシリル）エーテル（ＡＰＭＤＳ）０．７１４ｇ（２．８７ｍｍｏｌ）を加え、溶液の原材料の濃度が２５重量％になるようにＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）４．６９ｇを加えた。三角フラスコ中の溶液を窒素雰囲気中、室温で２４時間攪拌し、ポリアミド酸のＤＭＡｃ溶液を得た。得られたポリアミド酸のＤＭＡｃ溶液を直径７５ｍｍの石英板上に回転塗布し、窒素雰囲気下、７０℃で１時間、２２０℃で１時間３０分、２段階で昇温して加熱イミド化を行った。加熱イミド化によって形成された層を石英板から剥離して蛍光材料であるを含むポリイミド薄膜を得た。
Example 3
Into an Erlenmeyer flask, 0.846 g (2.87 mmol) of 3,3 ′, 4,4 ′,-biphenyltetracarboxylic dianhydride (s-BPDA), 3,4,9,10-perylenetetracarboxylic dianhydride Product (PTDA) 0.00113 g (0.00287 mmol) and bis (3-aminopropyldimethylsilyl) ether (APMDS) 0.714 g (2.87 mmol) are added so that the concentration of raw materials in the solution is 25% by weight. Was added with 4.69 g of N, N-dimethylacetamide (DMAc). The solution in the Erlenmeyer flask was stirred in a nitrogen atmosphere at room temperature for 24 hours to obtain a DMAc solution of polyamic acid. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 220 ° C. for 1 hour 30 minutes, and heated for imidization. It was. The layer formed by heating imidization was peeled from the quartz plate to obtain a polyimide thin film containing a fluorescent material.
得られたポリイミド薄膜の赤外吸収スペクトルを減衰全反射（ＡＴＲ）法により測定したところ、１７７７ｃｍ-１及び１７１９ｃｍ-１にイミド基のカルボニルに特有の吸収が観察され、またポリアミド酸において観測される１６７７ｃｍ-１、１６３７ｃｍ-１のアミド結合特有の吸収が消失しており、イミド化が完全に進行したことが確認できた。得られた薄膜の膜厚を触針式膜厚計で測定したところ、６．５μｍであった。得られたポリイミド薄膜の蛍光発光スペクトルを励起波長３６５ｎｍ、蛍光観測波長３００〜８００ｎｍで測定した。結果を図２に示す。図２から明らかなように、波長３５０〜８００ｎｍにおいて強い蛍光が観測された。図２において縦軸は蛍光強度、横軸は波長（ｎｍ）を示している。図２に示すように、実施例３で得られた蛍光材料は、蛍光波長が可視域全体に広がっており、明るい白色の蛍光を示している。そこで、この白色発光ポリイミドの蛍光量子収率を実施例１と同様にして測定したところ０．１２６であった。 The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm -1 and 1719 cm -1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm −1 and 1637 cm −1 disappeared, and it was confirmed that imidization proceeded completely. It was 6.5 micrometers when the film thickness of the obtained thin film was measured with the stylus type film thickness meter. The fluorescence emission spectrum of the obtained polyimide thin film was measured at an excitation wavelength of 365 nm and a fluorescence observation wavelength of 300 to 800 nm. The results are shown in FIG. As is clear from FIG. 2, strong fluorescence was observed at a wavelength of 350 to 800 nm. In FIG. 2, the vertical axis represents fluorescence intensity, and the horizontal axis represents wavelength (nm). As shown in FIG. 2, the fluorescent material obtained in Example 3 has a fluorescent wavelength that extends over the entire visible range, and shows bright white fluorescence. Therefore, the fluorescence quantum yield of this white light-emitting polyimide was measured in the same manner as in Example 1, and found to be 0.126.
実施例４
三角フラスコに、３，３’，４，４’，−ビフェニルテトラカルボン酸二無水物（ｓ-ＢＰＤＡ）０．７１６ｇ（２．４４ｍｍｏｌ）、３,４,９,１０-ペリレンテトラカルボン酸二無水物（ＰＴＤＡ）０．０００９５９ｇ（０．００２４３ｍｍｏｌ）、４，４’−ジアミノジシクロヘキシルメタン（ＤＣＨＭ）０．３５８９ｇ（１．７０６ｍｍｏｌ）、及びビス（３-アミノプロピルジメチルシリル）エーテル（ＡＰＭＤＳ）０．１８２ｇ（０．７３１ｍｍｏｌ）を加え、溶液の原材料の濃度が１８重量％になるようにＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）５．６２ｇを加えた。三角フラスコ中の溶液を窒素雰囲気中、室温で２４時間攪拌し、ポリアミド酸のＤＭＡｃ溶液を得た。得られたポリアミド酸のＤＭＡｃ溶液を直径７５ｍｍの石英板上に回転塗布し、窒素雰囲気下、７０℃で１時間、２２０℃で１時間３０分、２段階で昇温して加熱イミド化を行った。加熱イミド化によって形成された層を石英板から剥離して蛍光材料であるを含むポリイミド薄膜を得た。
Example 4
Into an Erlenmeyer flask, 0.716 g (2.44 mmol) of 3,3 ′, 4,4 ′,-biphenyltetracarboxylic dianhydride (s-BPDA), 3,4,9,10-perylenetetracarboxylic dianhydride Product (PTDA) 0.000959 g (0.00243 mmol), 4,4′-diaminodicyclohexylmethane (DCHM) 0.3589 g (1.706 mmol), and bis (3-aminopropyldimethylsilyl) ether (APMDS) 0.182 g (0.731 mmol) was added, and 5.62 g of N, N-dimethylacetamide (DMAc) was added so that the concentration of the raw material of the solution was 18% by weight. The solution in the Erlenmeyer flask was stirred in a nitrogen atmosphere at room temperature for 24 hours to obtain a DMAc solution of polyamic acid. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 220 ° C. for 1 hour 30 minutes, and heated for imidization. It was. The layer formed by heating imidization was peeled from the quartz plate to obtain a polyimide thin film containing a fluorescent material.
得られたポリイミド薄膜の赤外吸収スペクトルを減衰全反射（ＡＴＲ）法により測定したところ、１７７７ｃｍ-１及び１７１９ｃｍ-１にイミド基のカルボニルに特有の吸収が観察され、またポリアミド酸において観測される１６７７ｃｍ-１、１６３７ｃｍ-１のアミド結合特有の吸収が消失しており、イミド化が完全に進行したことが確認できた。得られた薄膜の膜厚を触針式膜厚計で測定したところ、１０．４μｍであった。得られたポリイミド薄膜の蛍光発光スペクトルを励起波長３６５ｎｍ、蛍光観測波長３００〜８００ｎｍで測定した。結果を図２に示す。図２から明らかなように、波長３５０〜７５０ｎｍにおいて強い蛍光が観測された。結果を図２に示した。図２において縦軸は蛍光強度、横軸は波長（ｎｍ）を示している。図２に示すように、実施例４で得られた蛍光材料は、蛍光波長が可視域全体に広がっており、明るい白色の蛍光を示している。そこで、この白色発光ポリイミドの蛍光量子収率を実施例１と同様にして測定したところ０．１５２であった。 The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm -1 and 1719 cm -1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm −1 and 1637 cm −1 disappeared, and it was confirmed that imidization proceeded completely. It was 10.4 micrometers when the film thickness of the obtained thin film was measured with the stylus type film thickness meter. The fluorescence emission spectrum of the obtained polyimide thin film was measured at an excitation wavelength of 365 nm and a fluorescence observation wavelength of 300 to 800 nm. The results are shown in FIG. As is clear from FIG. 2, strong fluorescence was observed at a wavelength of 350 to 750 nm. The results are shown in FIG. In FIG. 2, the vertical axis represents fluorescence intensity, and the horizontal axis represents wavelength (nm). As shown in FIG. 2, the fluorescent material obtained in Example 4 has a fluorescent wavelength extending over the entire visible range, and shows bright white fluorescence. Therefore, the fluorescence quantum yield of this white light-emitting polyimide was measured in the same manner as in Example 1, and found to be 0.152.
図２から明らかなように、実施例１〜４得られた蛍光材料を波長３００〜３６５ｎｍの紫外光を照射して励起したところ、その発光波長は、全て３５０〜７００ｎｍと可視域に広く存在し、しかもその発光強度は目視で容易に確認できるほど高効率であることから、白色の発光デバイス用材料として好適であることが確認された。 As is clear from FIG. 2, when the fluorescent materials obtained in Examples 1 to 4 were excited by irradiating with ultraviolet light having a wavelength of 300 to 365 nm, the emission wavelengths were all widely in the visible range of 350 to 700 nm. And since the light emission intensity is so efficient that it can be easily confirmed visually, it was confirmed that it was suitable as a white light emitting device material.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007121477A JP2008274165A (en) | 2007-05-02 | 2007-05-02 | Fluorescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007121477A JP2008274165A (en) | 2007-05-02 | 2007-05-02 | Fluorescent material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2008274165A true JP2008274165A (en) | 2008-11-13 |
Family
ID=40052555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007121477A Pending JP2008274165A (en) | 2007-05-02 | 2007-05-02 | Fluorescent material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2008274165A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021106823A1 (en) | 2019-11-29 | 2021-06-03 | キヤノン株式会社 | Display device and apparatus |
-
2007
- 2007-05-02 JP JP2007121477A patent/JP2008274165A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021106823A1 (en) | 2019-11-29 | 2021-06-03 | キヤノン株式会社 | Display device and apparatus |
| EP4050384A1 (en) | 2019-11-29 | 2022-08-31 | Canon Kabushiki Kaisha | Display device and apparatus |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6225659B2 (en) | Diamine containing hexafluoroisopropanol group, polyimide and polyamide using the same, cyclized product thereof, and production method thereof | |
| TWI889648B (en) | Polymers for use in electronic devices | |
| TWI808096B (en) | Low-color polymers for use in electronic devices | |
| JP5748774B2 (en) | Polyimide composite, polyamic acid solution, method for producing polyimide composite, and film comprising polyimide composite | |
| JP2009149787A (en) | Fluorescent material | |
| TW201604191A (en) | Tetracarboxylic dianhydride, polylysine, polyimine, and the production method thereof, and polylysine solution | |
| Kung et al. | Synthesis and characterization of novel electroactive polyamides and polyimides with bulky 4‐(1‐adamantoxy) triphenylamine moieties | |
| JP6706771B2 (en) | Organic light emitting material exhibiting room temperature phosphorescence and optical device using the same | |
| CN109503837B (en) | A kind of polyimide with photochromic properties and its preparation method and application | |
| JP2004307857A (en) | Fluorescent polyimide | |
| JP5028626B2 (en) | Fluorescent material | |
| Damaceanu et al. | Photo-optical properties of poly (oxadiazole-imide) s containing naphthalene rings | |
| JP2005320393A (en) | Fluorescent material | |
| JP2025183287A (en) | Polymers for use in electronic devices | |
| JP2025134775A (en) | Polymers for use in electronic devices | |
| Liang et al. | Photoluminescence properties of novel fluorescent polyimide based on excited state intramolecular proton transfer at the end groups | |
| JP4947546B2 (en) | Fluorescent material and optical device using the same | |
| JP2008274165A (en) | Fluorescent material | |
| JP2008297354A (en) | Blue light emitting polyimide | |
| CN112673011B (en) | Polymers used in electronic devices | |
| JP2021080451A (en) | Polymer with tunable refractive index | |
| CN106797683B (en) | Organic electroluminescent substrate and use its display of organic electroluminescence | |
| JP5265994B2 (en) | Fluorescent polymer and optical device using the same | |
| EP1953845A1 (en) | Blue light-emitting device containing polyimide | |
| KR20050120749A (en) | Perdeuterated poliimides, method for the production and use thereof in the form of transparent materials in the range of 2500-3500 cm-1 |