WO2006117982A1 - Composition de conversion de fluorescence, procede de conversion de fluorescence, et dispositif utilisant ladite compositiion - Google Patents

Composition de conversion de fluorescence, procede de conversion de fluorescence, et dispositif utilisant ladite compositiion Download PDF

Info

Publication number
WO2006117982A1
WO2006117982A1 PCT/JP2006/307649 JP2006307649W WO2006117982A1 WO 2006117982 A1 WO2006117982 A1 WO 2006117982A1 JP 2006307649 W JP2006307649 W JP 2006307649W WO 2006117982 A1 WO2006117982 A1 WO 2006117982A1
Authority
WO
WIPO (PCT)
Prior art keywords
charge transfer
ferroelectric
fluorine
composition
containing polymer
Prior art date
Application number
PCT/JP2006/307649
Other languages
English (en)
Japanese (ja)
Inventor
Giseop Kwak
Michiya Fujiki
Chisato Okada
Original Assignee
National University Corporation NARA Institute of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by National University Corporation NARA Institute of Science and Technology filed Critical National University Corporation NARA Institute of Science and Technology
Priority to JP2007514549A priority Critical patent/JPWO2006117982A1/ja
Publication of WO2006117982A1 publication Critical patent/WO2006117982A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • Fluorescent color converting composition Fluorescent color converting composition, fluorescent color converting method and device using the composition
  • the present invention relates to a composition containing a charge transfer dye and a ferroelectric fluorine-containing polymer, and to a fluorescent color conversion method and device utilizing a novel function of the composition.
  • Intramolecular charge transfer (ICT) dyes are used as light-emitting / photoelectric conversion materials for ELZPL devices, dye lasers, dye-sensitized solar cells, etc., and their photospecificity varies greatly depending on the polarity of the solvent. It has been known for a long time. For example, a dye laser is most often used as a wavelength tunable laser because a laser having an arbitrary wavelength can be obtained simply by changing the dye solution. However, when changing the oscillation wavelength, it was necessary to take out the dye solution, carefully wash it, and then circulate a new dye solution. In addition, since it is a solution, it has a drawback that it cannot be processed into an arbitrary shape.
  • ICT Intramolecular charge transfer
  • Patent Document 1 There has been proposed a solid-state dye device that does not have such a defect (for example, Patent Document 1). There is no concept of changing the fluorescent color or emission intensity depending on the temperature difference.
  • Patent Document 2 An image record is disclosed (for example, Patent Document 2).
  • the dye used in Patent Document 2 is different from the dye used in the present invention, and utilizes a function of light absorption and heat generation.
  • Patent Document 2 there is no concept of changing the fluorescent color or emission intensity depending on the temperature.
  • Patent Document 1 Japanese Patent Laid-Open No. 2004-346233
  • Patent Document 2 JP-A-3-296769
  • the present invention uses a polymer matrix that exhibits a paraelectric-ferroelectric phase transition, and thereby the fluorescence intensity or wavelength of the ICT type dyes. Discovered a new function that reversibly changes.
  • An object of the present invention is to provide an intramolecular charge transfer type fluorescent dye-dispersed polymer, a fluorescent color conversion method using a novel function of the dispersed polymer, and various devices using them.
  • the above object is achieved by a composition containing a charge transfer dye and a ferroelectric fluorine-containing polymer.
  • the charge transfer dye is at least one selected from the group force consisting of DCM, DCM2, Nile Red, and Coumarin6, and has a high molecular force of ferroelectric fluorine-containing vinylidene fluoride and trifluoro. It is a copolymer with ethylene.
  • the fluorescent color of the composition of the present invention can be changed by a temperature change.
  • FIG. 1 is a graph showing the relationship between the temperature and dielectric constant of a vinylidene fluoride trifluoroethylene copolymer.
  • FIG. 2A UV-vis absorption spectrum of DCM dispersion film.
  • FIG. 2C Fluorescence spectrum of DCM dispersion film.
  • FIG. 3A UV-vis absorption spectrum of DCM2 dispersion film.
  • FIG. 3C Fluorescence spectrum of DCM2 dispersion film.
  • FIG. 4B UV-vis absorption spectrum of Nile Red dispersion film.
  • FIG. 4C Fluorescence spectrum of Nile Red dispersion film.
  • FIG. 4D Fluorescent spectrum of Nile Red dispersion film.
  • FIG. 5A UV-vis absorption spectrum of Coumarin6 dispersion film.
  • FIG. 5B UV-vis absorption spectrum of Coumarin6 dispersion film.
  • FIG. 5C Fluorescence spectrum of Coumarin6 dispersion film.
  • FIG. 5D Fluorescence spectrum of Coumarin6 dispersion film.
  • Charge transfer dyes have a pi-conjugated structure with an electron donor and an acceptor, and their optical properties and nonlinear optical characteristics related to their charge transfer characteristics have been studied.
  • the charge transfer dyes that can be used in the present invention conventionally known dyes can be used, and various commercially available dyes are commercially available from, for example, EXCITON, Aldrich, and Tokyo Chemical Industry.
  • the charge transfer type dye used in this example is a dye having the structure and dye name described below.
  • the dyes described below are intramolecular transfer charge type dyes, and have a dipole moment that is very large. Both the ground state and the excited state have 1 debye or more, and the viewpoint power that the difference is 0.1 debye or more is also selected.
  • a dye that can be used in the present invention from various known dyes, it is preferable to select a dye that can dissolve at least 0.1% in tetrahydrofuran (THF) from the viewpoint described on the left. This is because using a dye that does not dissolve in such a solvent makes it difficult to produce a film in which the dye is uniformly dispersed.
  • THF tetrahydrofuran
  • ferroelectric fluorine-containing polymer used in the present invention a polymer represented by the following general formula [I], which is a copolymer of vinylidene fluoride and trifluoroethylene, is used.
  • X and y are copolymerization ratios.
  • Figure 1 shows the temperature dependence of the dielectric constant of a vinylidene fluoride trifluoroethylene copolymer in which x: y is 52:48.
  • the dielectric constant ( ⁇ ) rapidly changes at a temperature of 50 to 70 ° C., and a paraelectric strong dielectric phase transition occurs.
  • Paraelectric Ferroelectric phase transition is defined as a transition caused by a change in crystal structure between a paraelectric that does not have spontaneous polarization and a ferroelectric that has spontaneous polarization.
  • Dielectric phase transition temperature is defined as the temperature at which spontaneous polarization disappears (Curie temperature).
  • the ratio of x: y is not particularly limited as long as it is a copolymer that causes such a paraelectric ferroelectric phase transition. It is preferable to use a vinylidene fluoride-trifluoroethylene copolymer in which the paraelectric ferroelectric phase transition occurs more rapidly.
  • the dielectric constant was measured by dissolving 2 lOmg of vinylidene fluoride-trifluoroethylene copolymer having x: y of 52:48 in 2ml of organic solvent tetrahydrofuran (THF). Casting and drying were performed using a transparent film prepared.
  • the capacitance C [F] is proportional to the area A [m 2 ] of the electrode plate and inversely proportional to the film thickness L (m) of the film.
  • the ferroelectric fluorine-containing polymer used in the present invention is one that is soluble in tetrahydrofuran (THF) by 0.1% or more and can be used for film formation.
  • a polymer having a dissolution amount lower than 0.1% by weight makes it difficult to produce a uniform film that is difficult to form.
  • a vinylidene fluoride homopolymer having y of 0 cannot be dissolved and a uniform film thickness that is difficult to form cannot be produced.
  • the above-described paraelectric ferroelectric phase transition as the polymer matrix is largely related to changing the fluorescent color emitted by the charge transfer dye by changing the temperature. It is believed that From such a viewpoint, the polymer matrix of the phosphor is not limited to the vinylidene fluoride-trifluoroethylene copolymer represented by the above general formula [I], and other matrices can be used. is expected.
  • the charge transfer dye may be used in an amount ranging from 1 PPM to 10% by weight with respect to the ferroelectric fluorine-containing polymer. Preferably, it is used in the range of 0.01 to less than 1% by weight.
  • the charge transfer dye and the ferroelectric fluorine-containing polymer need to be dissolved in a solvent when a thin film to be described later is formed, and the present invention can be carried out as long as it dissolves.
  • the amount of the charge transfer dye may be appropriately selected within the above range depending on the target fluorescent color, emission intensity, emission degradation rate, and the like.
  • the thin film is prepared by using a predetermined amount of the charge transfer dye and the ferroelectric fluorine-containing polymer in an appropriate solvent such as tetrahydrofuran, methyl ethyl ketone, acetone, black mouth form, ⁇ , ⁇ -dimethylformamide, dimethyl sulfoxide. This can be done by applying and drying a solution dissolved in a solution such as spin coating or solvent casting.
  • the film thickness of the thin film is not particularly limited, but considering the film formability and mechanical strength, the film thickness after drying may be 1 to: LOO / zm.
  • the thin film obtained as described above can change the fluorescent color depending on the temperature.
  • the temperature should be changed between the temperature range and the temperature range that is lower than the transition temperature and higher than the temperature range, taking into account the paraelectric and ferroelectric phase transition temperature of the ferroelectric fluorine-containing polymer used. To do.
  • the change in fluorescent color is caused by a change in fluorescence wavelength and a change in emission intensity.
  • the fluorescent color can be changed in various colors depending on the combination of the phosphor and the fluorinated polymer.
  • the present invention will be described using examples.
  • PVdF—co-TrFE is vinylidene fluoride-3 fluorinated styrene copolymer (copolymer ratio 52:48) (hereinafter referred to as “1 ⁇ (1? -Co- TrFE ”)).
  • the PVdF 2 -co-TrFE dissolves in 100% by weight or more in THF.
  • PVdF-co- Good for both TrFE and DCM! A solution was prepared from THF, which shows solubility.
  • a transparent film film thickness 3 ⁇ m was prepared in a triangular cell by the solvent casting method with a weight ratio of polymer to DCM of 500: 1.
  • the obtained DCM dispersion film was heated from 0 ° C to 90 ° C in 10 ° C increments, and UV-vis absorption 'fluorescence spectrum measurement was performed while gradually cooling down to 90 ° C force 0 ° C in increments of 10 ° C. .
  • FIGS. 2A to 2D show UV-vis absorption and fluorescence spectra of the DCM dispersion film.
  • the UV-vis absorption spectrum was blue-shifted from maxO ° C: 460 nm to 90 ° C: 455.5 nm by heating (Fig. 2A), and returned to its original wavelength by slow cooling (Fig. 2B).
  • Fluorescence spectrum ranges from 0 ° C: 581 nm to 90 ° C: 583.5 nm, heating process (Fig. 2C) ⁇ Power that hardly shifts even in the slow cooling process (Fig. 2D). As a result, the strength decreased.
  • a DCM2 dispersion film was prepared in the same manner as in Example 1 except that DCM2 was used instead of DCM.
  • Figures 3A to 3D show the results of UV-vis absorption and fluorescence spectra.
  • the UV-vis absorption spectrum was blue-shifted from 0 ° C: 500 nm force to 90 ° C: 492.5 nm by calo-heating ( Figure 3A). Furthermore, by slow cooling, the original wavelength was restored from 90 ° C: 492.5 nm force to 0 ° C: 50.5 nm (Fig. 3B).
  • Nile Red dispersion film was prepared in the same manner as in Example 1 except that Nile Red was used instead of DCM.
  • FIGS. 4A to 4D show the results of UV-vis absorption and fluorescence spectra.
  • the UV-vis absorption spectrum was blue-shifted from 0 ° C: 545.5 nm force to 90 ° C: 531.5 nm by heating (Fig. 4A). Furthermore, by slow cooling, the original wavelength returned from 90 ° C: 531.5 nm to 0 ° C: 546 nm (Fig. 4B).
  • the fluorescent color changes reversibly between dark purple and orange by heating and slow cooling. That was observed with the naked eye.
  • a Coumarin6 dispersion film was prepared in the same manner as in Example 1 except that Coumarin6 was used instead of DCM.
  • FIG. 5A to FIG. 5D show the results of UV-vis absorption / fluorescence spectrum of Coumarin 6 dispersion film.
  • the absorption around 390 nm increased and the absorption between 450 and 550 nm decreased during the heating process (Fig. 5A). Furthermore, the absorption was restored by slow cooling (Fig. 5B).
  • a temperature change display element By using the intramolecular charge transfer type fluorescent dye dispersion polymer of the present invention and the fluorescence expression method using the novel function, a temperature change display element, a new type of temperature surface emitting sensor (thermography), temperature ⁇ Polarized wavelength tunable plastic laser 1. It can be applied to stress sensors and bimorph type flat speakers that emit surface light.
  • a composition comprising a charge transfer dye and a ferroelectric fluorine-containing polymer, wherein the charge transfer dye is at least one selected from the group consisting of DCM, DCM2, Nile Red and Coumarin6
  • the dielectric fluorine-containing polymer is a copolymer of vinylidene fluoride and trifluoroethylene.
  • the ferroelectric fluorine-containing polymer is a copolymer of vinylidene fluoride and trifluoroethylene.
  • ferroelectric fluorine-containing polymer is a copolymer of vinylidene fluoride and trifluoroethylene.
  • a temperature change display element having a thin film containing the composition according to any one of 1 to 4 above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lasers (AREA)

Abstract

Cette invention concerne une composition comprenant une matière colorante à transfert de charge, et un polymère ferroélectrique contenant du fluor, ladite matière colorante à transfert de charge étant au moins une matière colorante choisie parmi le DCM, le DCM 2, le rouge nil et la coumarine 6, et ledit polymère ferroélectrique contenant du fluor étant un copolymère de fluorure de vinylidène avec du trifluoroéthylène. L'invention concerne également un procédé de conversion de fluorescence utilisant cette composition, et divers dispositifs les utilisant.
PCT/JP2006/307649 2005-04-28 2006-04-11 Composition de conversion de fluorescence, procede de conversion de fluorescence, et dispositif utilisant ladite compositiion WO2006117982A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007514549A JPWO2006117982A1 (ja) 2005-04-28 2006-04-11 蛍光色変換性組成物、該組成物を使用した蛍光色変換方法およびデバイス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-131793 2005-04-28
JP2005131793 2005-04-28

Publications (1)

Publication Number Publication Date
WO2006117982A1 true WO2006117982A1 (fr) 2006-11-09

Family

ID=37307785

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/307649 WO2006117982A1 (fr) 2005-04-28 2006-04-11 Composition de conversion de fluorescence, procede de conversion de fluorescence, et dispositif utilisant ladite compositiion

Country Status (2)

Country Link
JP (1) JPWO2006117982A1 (fr)
WO (1) WO2006117982A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016204614A (ja) * 2015-04-28 2016-12-08 国立大学法人 筑波大学 強誘電ポリマー球体およびその製造方法
CN111256872A (zh) * 2020-02-24 2020-06-09 复旦大学 一种荧光测温体系、测温方法以及温度检测系统
CN112921435A (zh) * 2021-02-09 2021-06-08 上海大学 一种农用转光遮阳网及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63317544A (ja) * 1987-06-19 1988-12-26 Rikagaku Kenkyusho 高分子フィルム
JPS6416853A (en) * 1987-07-10 1989-01-20 Rikagaku Kenkyusho Increase of pyroelectric current
JPH01266153A (ja) * 1988-04-19 1989-10-24 Mitsubishi Petrochem Co Ltd 帯電防止樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63317544A (ja) * 1987-06-19 1988-12-26 Rikagaku Kenkyusho 高分子フィルム
JPS6416853A (en) * 1987-07-10 1989-01-20 Rikagaku Kenkyusho Increase of pyroelectric current
JPH01266153A (ja) * 1988-04-19 1989-10-24 Mitsubishi Petrochem Co Ltd 帯電防止樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FUJIKI M. ET AL.: "Photophysics and New Functions of Intramolecular Charge Transfer Type Dyes in Various Polymer Matrices", POLYMER PREPRINTS, JAPAN, vol. 54, no. 1, 5 October 2005 (2005-10-05), pages 1337, XP003001632 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016204614A (ja) * 2015-04-28 2016-12-08 国立大学法人 筑波大学 強誘電ポリマー球体およびその製造方法
CN111256872A (zh) * 2020-02-24 2020-06-09 复旦大学 一种荧光测温体系、测温方法以及温度检测系统
CN111256872B (zh) * 2020-02-24 2021-12-03 复旦大学 一种荧光测温材料、测温方法以及温度检测系统
CN112921435A (zh) * 2021-02-09 2021-06-08 上海大学 一种农用转光遮阳网及其制备方法

Also Published As

Publication number Publication date
JPWO2006117982A1 (ja) 2008-12-18

Similar Documents

Publication Publication Date Title
Yuan et al. Carbon quantum dots: an emerging material for optoelectronic applications
Kwon et al. Advanced organic optoelectronic materials: Harnessing excited‐state intramolecular proton transfer (ESIPT) process
JP5080245B2 (ja) 有機半導体を含む電子デバイス
Kozlov et al. Optical properties of molecular organic semiconductor thin films under intense electrical excitation
JP2006236748A (ja) 有機電界発光装置
JP3715978B2 (ja) 有機発光ポリマー
CN102668695A (zh) 附有电极的基板的制备方法
Li et al. Unraveling the energy landscape and energy funneling modulated by hole transport layer for highly efficient perovskite LEDs
WO2006117982A1 (fr) Composition de conversion de fluorescence, procede de conversion de fluorescence, et dispositif utilisant ladite compositiion
Chen et al. Deep-red light-emitting electrochemical cells based on phosphor-sensitized thermally activated delayed fluorescence
Huebner et al. Electroluminescent colloidal inks for flexographic roll-to-roll printing
Cole et al. Inkjet‐printed self‐hosted tadf polymer light‐emitting diodes
Ibnaouf Optical and amplified spontaneous emission from an efficient conducting copolymer (PFO-co-MEH-PPV) in solution
Kwak et al. Polar laser dyes dispersed in polymer matrices: reverification of charge transfer character and new optical functions
Popova et al. Light emitting and electrical properties of pure amorphous thin films of organic compounds containing 2-tert-butyl-6-methyl-4H-pyran-4-ylidene
Buchhauser et al. Characterization of white-emitting copolymers for PLED displays
Gather et al. Improving the lifetime of white polymeric organic light-emitting diodes
Teng et al. Color changeable OLEDs controlled by doping ratio and driving voltage with an anthracene derivative doped layer
Zhang et al. Enhanced amplified spontaneous emission by assistant Förster energy transfer in DCJTB-C545T-Alq 3 coguest-host system
Hagen Enhanced luminous efficiency and brightness using DNA electron blocking layers in bio-organic light emitting diodes
JP4182516B2 (ja) 機能性有機薄膜およびその製造方法
Suzuki Orientational enhancement in the electroluminescence of ionic emissive dyes doped in poly (vinylcarbazole)
Tanaka et al. Selective heat-transfer dye diffusion technique using laser irradiation for polymer electroluminescent devices
JP5415035B2 (ja) 発光性組成物及び有機エレクトロルミネッセンス素子の製造方法
Nüesch et al. Space charge and polarization effects upon doping organic light-emitting diodes with pyran-containing donor-acceptor molecules.

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2007514549

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 06731596

Country of ref document: EP

Kind code of ref document: A1