WO2014065190A1 - Complexe de terre rare et son application - Google Patents

Complexe de terre rare et son application Download PDF

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Publication number
WO2014065190A1
WO2014065190A1 PCT/JP2013/078194 JP2013078194W WO2014065190A1 WO 2014065190 A1 WO2014065190 A1 WO 2014065190A1 JP 2013078194 W JP2013078194 W JP 2013078194W WO 2014065190 A1 WO2014065190 A1 WO 2014065190A1
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Prior art keywords
rare earth
ligand
complex
earth element
mmol
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PCT/JP2013/078194
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English (en)
Japanese (ja)
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上遠野　正孝
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株式会社クレハ
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Priority to JP2014543257A priority Critical patent/JPWO2014065190A1/ja
Publication of WO2014065190A1 publication Critical patent/WO2014065190A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/92—Ketonic chelates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • 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
    • 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
    • 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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • 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
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Definitions

  • the present invention relates to rare earth complexes and uses of the complexes.
  • Wind power, solar power, geothermal heat, etc. are attracting attention as clean energy sources that have no emissions that affect the environment.
  • Solar cells capable of directly converting sunlight into electrical energy are a promising source of electrical energy and have been actively put into practical use in recent years.
  • Solar cells photoelectrically convert sunlight into electrical energy using photoelectric conversion materials, but the wavelength of light that can be effectively converted by photoelectric conversion materials is determined for each material, and other wavelengths are effective. It was not available.
  • Crystalline silicon solar cells using crystalline silicon as a photoelectric conversion material have been put into practical use as typical solar cells.
  • crystalline silicon has low sensitivity to ultraviolet rays contained in a large amount of sunlight, and power generation efficiency is low. It was about 10 to 20%.
  • a wavelength conversion type solar cell encapsulating sheet containing a fluorescent material having an absorption wavelength peak at 300 to 450 nm and an ultraviolet absorber is known (see, for example, Patent Document 1).
  • Patent Document 1 by providing the wavelength conversion type solar cell encapsulating sheet on the light receiving surface side of the solar cell, the wavelength of ultraviolet light contained in sunlight is converted, and the power generation efficiency of the solar cell is improved.
  • the purpose of this sheet is to ensure the weather resistance of the sheet by containing an ultraviolet absorber.
  • a fluorescent resin composition comprising an organic rare earth metal complex that emits fluorescence in the wavelength range of 550 to 900 nm and an ethylene-vinyl acetate copolymer is used as a sealant between the front cover and the crystalline silicon cell.
  • a solar cell module has been proposed (see, for example, Patent Document 2). In patent document 2, the power generation efficiency of a solar cell is raised by using the said sealing agent.
  • the present invention has been made in view of the above prior art, and absorbs ultraviolet light to blue light, which can be used as a wavelength conversion sheet used as a constituent member of a solar cell module or the like, or as a sealant.
  • An object of the present invention is to provide a rare earth complex that emits light and has heat resistance superior to that of a conventionally known europium complex, and uses of the complex.
  • the rare earth complex of the present invention is a complex containing at least one rare earth element selected from Pr, Eu, Sm, Tb, Dy, Ho, and Er
  • the rare earth element includes the following general formula (A): At least one ligand (a) selected from the group of ligands represented by formula (I) is coordinated with 0.3 to 0.7 per rare earth element, and the rare earth element has the following general formula: At least one ligand (b) selected from the ligand group represented by (B) is coordinated 0.8 to 1.2 per rare earth element, At least one ligand (c) selected from the group of ligands represented by the following general formula (C) is coordinated 1.6 to 2.4 per rare earth element, When the number of ligands (a) per element is ⁇ and the number of ligand
  • X 1 and X 2 are each independently an aromatic ring, a heteroaromatic ring, —C (CH 3 ) 3 , —CH 3 , —CF 3 , — C 2 F 5 , —C 3 F 7 , or —C 4 F 9. )
  • the rare earth complex preferably contains at least one rare earth element selected from Eu, Sm, and Tb.
  • the 2 ⁇ + ⁇ is preferably 3.0.
  • the resin composition of the present invention contains the rare earth complex and a resin.
  • the resin solution of the present invention contains the rare earth complex, a resin and a solvent.
  • the wavelength conversion sheet of this invention consists of the said resin composition.
  • the sealing agent of this invention consists of the said resin composition.
  • mode of the solar cell module of this invention it has at least a photovoltaic cell and the said wavelength conversion sheet,
  • the said wavelength conversion sheet is arrange
  • the solar cell module has at least a solar cell, the sealant, and a front cover, and the sealant is interposed between the solar cell and the front cover. It is characterized by containing.
  • the rare earth complex of the present invention is a complex that absorbs ultraviolet light to blue light and emits light, and has heat resistance superior to that of conventionally known europium complexes. For this reason, the rare earth complex of this invention can be used for the wavelength conversion sheet
  • the rare earth complex of the present invention is a complex containing at least one rare earth element selected from Pr, Eu, Sm, Tb, Dy, Ho, and Er.
  • the rare earth element is represented by the following general formula (A).
  • At least one ligand (c) selected from the ligand group represented by the formula (C) is coordinated 1.6 to 2.4 per rare earth element, and the rare earth element 1
  • ⁇ is the number of ligands (a) per unit and ⁇ is the number of ligands (c)
  • 2 ⁇ + ⁇ is Characterized in that it is a 1.0 to 3.4.
  • At least one ligand (a) selected from the ligand group represented by the general formula (A) is also simply referred to as a ligand (a), and the general formula (B)
  • At least one ligand (b) selected from the represented ligand group is also simply referred to as ligand (b), and at least selected from the ligand group represented by the general formula (C).
  • One type of ligand (c) is also simply referred to as ligand (c).
  • X 1 and X 2 are each independently an aromatic ring, a heteroaromatic ring, —C (CH 3 ) 3 , —CH 3 , —CF 3 , — C 2 F 5 , —C 3 F 7 , or —C 4 F 9. )
  • the rare earth complex of the present invention contains at least one rare earth element selected from Pr, Eu, Sm, Tb, Dy, Ho, and Er as the rare earth element.
  • the wavelength at which the rare earth complex is excited and the emission wavelength are mainly determined by the type of rare earth element.
  • the rare earth element is preferable because it absorbs ultraviolet light to blue light, is excited, and crystal silicon emits light having a wavelength (550 to 1000 nm) having high photoelectric conversion efficiency as fluorescence.
  • the excitation wavelength of Pr is 450 nm
  • the emission wavelength is 600 nm
  • the excitation wavelength of Eu is 330 to 430 nm
  • the emission wavelengths are 570 nm, 580 nm, 620 nm, and 630 nm.
  • Excitation wavelengths are 360 nm and 410 nm, emission wavelengths are 560 nm, 610 nm, and 635 nm, excitation wavelengths of Tb are 200 to 350 nm, emission wavelengths are 490 nm, 550 nm, 590 nm, and 625 nm, and excitation wavelengths of Dy are 200 340 nm, emission wavelength 490 nm, 570 nm, 2400 nm, Ho excitation wavelength 380 nm, emission wavelength 620 nm, 2000 nm, Er excitation wavelength 400 nm, emission wavelength 610 nm, 970 nm, 1500-1600 A m.
  • the rare earth element is preferably at least one rare earth element selected from Eu, Sm and Tb from the viewpoint of wavelength conversion efficiency.
  • the rare earth complex of the present invention usually has two of the rare earth elements per molecule.
  • the rare earth complex of the present invention has the ligand (a), the ligand (b), and the ligand (c).
  • the rare earth complex of the present invention has a ligand (a).
  • the ligand (a) has two diketonate structures that are bidentate ligands in the ligand. That is, the ligand (a) is a bisdiketonate ligand.
  • the present inventors have found that the rare earth complex of the present invention having a bisdiketonate ligand having a specific structure is superior in heat resistance as compared with a conventionally known europium complex. In addition, the rare earth complex of the present invention has sufficient emission characteristics.
  • X 1 and X 2 possessed by each ligand are each independently an aromatic ring, a heteroaromatic ring, —C (CH 3 ) 3 , —CH 3 , —CF 3 , —C 2 F 5 , —C 3 F 7 , or —C 4 F 9 .
  • X 1 and X 2 may be the same or different, and when a plurality of ligands (a) are present, each X 1 and X 2 may be the same or different.
  • the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl ring, and a benzene ring and a naphthalene ring are preferable.
  • heteroaromatic ring examples include a thiophene ring, a furan ring, and a pyridine ring, and a thiophene ring is preferable.
  • X 1 and X 2 are preferably a heteroaromatic ring, an aromatic ring, —C (CH 3 ) 3 , —CH 3 , —CF 3 , and preferably a heteroaromatic ring, an aromatic ring, or —CF 3 . It is more preferable from the viewpoint of high fluorescence quantum efficiency and emission intensity of the complex.
  • the at least one ligand (a) selected from the ligand group represented by the general formula (A) is at least selected from the ligand group represented by the general formula (A ′). It is preferable that it is a kind of ligand from a viewpoint of the heat resistance and wavelength conversion characteristic of a complex.
  • the rare earth complex of the present invention has a ligand (b).
  • the ligand (b) is a ligand having a bipyridine skeleton or a phenanthroline skeleton, and coordinates to a rare earth element as a bidentate ligand.
  • the rare earth complex of the present invention having the ligand (b) is excellent in heat resistance as compared with a conventionally known europium complex.
  • the at least one ligand (b) selected from the ligand group represented by the general formula (B) is at least selected from the ligand group represented by the general formula (B ′).
  • a kind of ligand is preferable from the viewpoints of emission intensity and heat resistance.
  • the rare earth complex of the present invention has a ligand (c).
  • the ligand (c) has one diketonate structure which is a bidentate ligand in the ligand. That is, the ligand (c) is a diketonate ligand.
  • the inventors of the present invention have a rare earth complex having a heat resistance higher than that of a conventionally known europium complex even when it has a diketonate ligand having a specific structure. It was found to be excellent in properties.
  • the at least one ligand (c) selected from the ligand group represented by the general formula (C) is at least selected from the ligand group represented by the general formula (C ′).
  • a kind of ligand is preferable from the viewpoints of high fluorescence quantum yield and emission intensity.
  • ligands (a) are coordinated per rare earth element.
  • the ligand (a) is preferably 0.4 to 0.6 coordinated per rare earth element, and more preferably 0.5 coordinated.
  • ligands (b) are coordinated per rare earth element.
  • the ligand (b) is preferably 0.9 to 1.1 coordinated per rare earth element, more preferably 1.0 coordinated.
  • ligands (c) are coordinated per rare earth element.
  • the ligand (c) is preferably 1.8 to 2.2 coordinated per rare earth element, more preferably 2.0 coordinated.
  • 2 ⁇ + ⁇ is 3.0 to 3.4, where ⁇ is the number of ligands (a) per rare earth element and ⁇ is the number of ligands (c). Preferably, it is 3.0 to 3.2, more preferably 3.0 to 3.1, and particularly preferably 3.0.
  • the ligand (a) has two diketonate structures in the ligand, and the ligand (c) has one diketonate structure in the ligand,
  • the 2 ⁇ + ⁇ indicates how many diketonate structures are coordinated with one rare earth element. That is, the rare earth complex of the present invention preferably has 3.0 to 3.4 diketonate structures coordinated to one rare earth element.
  • the rare earth element used in the present invention is trivalent and stably present. Therefore, 3.0 rare earth elements, ligand (a), ligand (b) and coordination can be obtained by coordination of 3.0 diketonate structures. The entire ligand (c) is neutralized in charge and constitutes a stable rare earth complex.
  • the rare earth element, the ligand (a), the ligand (b) and the ligand (c) as a whole are negatively charged.
  • the rare earth complex of the present invention further has a counter cation.
  • Examples of the counter cation include at least one counter cation (d) selected from the group of counter cations represented by the following general formula (D).
  • the rare earth complex of the present invention has a specific rare earth element, a ligand (a), a ligand (b), and a ligand (c), and these have the specific amounts described above.
  • the ligand (a) constituting the rare earth complex of the present invention is a bisdiketonate having two diketonate structures, and the two diketonate structures are usually coordinated to different rare earth elements. Further, as described above, the rare earth complex of the present invention usually has two of the rare earth elements per molecule.
  • two diketonate structures of the ligand (a) are coordinated to different rare earth elements, and one ligand (b) is coordinated to each rare earth element. It is a structure in which two ligands (c) are coordinated.
  • the method for producing the rare earth complex of the present invention is not particularly limited. For example, it can be produced by the following method.
  • the method for producing a rare earth complex of the present invention includes a compound that becomes a ligand (a) by reacting and coordinating with a compound containing a rare earth element, a compound constituting the ligand (b), and a rare earth element.
  • the rare earth complex of the present invention is produced by adding a compound containing the rare earth element or a solution of the compound to a solution containing the compound that becomes the ligand (c) by reaction and coordination with the compound, and reacting the compound. A method is mentioned.
  • a compound that becomes a ligand (a) and a compound that becomes a ligand (c) are used by coordination with the compound containing the rare earth element.
  • Hydrate may be sufficient as the compound which comprises a ligand (b), and a compound containing rare earth elements.
  • Examples of the compound that becomes the ligand (a) by coordinating to the compound containing the rare earth element include at least one compound selected from the group of compounds represented by the following general formula (A ′′). .
  • Examples of the compound that becomes the ligand (c) by coordinating with the compound containing the rare earth element include at least one compound selected from the group of compounds represented by the following general formula (C ′′). .
  • the at least one compound selected from the compound group represented by the general formula (A ′′) and the at least one compound selected from the compound group represented by the general formula (C ′′) are so-called keto- Depending on the enol tautomerism, there may be a case where a diketone structure is taken, and a case where a structure consisting of a ketone and an enol is taken as shown in the formula, but in the present invention, the two are not particularly distinguished.
  • Examples of the compound constituting the ligand (b) include at least one compound selected from the group of compounds represented by the following general formula (B ′′).
  • the rare earth element-containing compound examples include the rare earth element chlorides, bromides, acetates, oxides, and the like.
  • the compound containing the rare earth element is preferably the chloride or bromide of the rare earth element described above.
  • the method for producing the rare earth complex of the present invention will be described in more detail.
  • the method for producing the rare earth complex of the present invention first, by coordinating to the compound containing the rare earth element, the ligand (a) and the compound containing the rare earth element are coordinated.
  • the compound to be the ligand (c) is dissolved in a solvent to obtain a solution (i).
  • a base or an aqueous solution thereof is added to the solution (i), and then a compound constituting the ligand (b) is added to obtain a solution (ii).
  • a compound containing a rare earth element is added to the solution (ii) to obtain the rare earth complex of the present invention as a solid.
  • the rare earth complex of the present invention can be produced by recovering the solid by an arbitrary method and purifying it as necessary.
  • an organic solvent or a mixed solvent of an organic solvent and water is usually used.
  • a polar organic solvent is preferably used, and specific examples thereof include tetrahydrofuran (THF), ethanol, methanol, isopropyl alcohol, dioxane and the like.
  • the base examples include sodium hydroxide and triethylamine.
  • the compound constituting the ligand (b) may be a hydrate.
  • the rare earth complex may be a hydrate as described above.
  • the compound which becomes a ligand (a) is coordinated by coordinating to the compound which becomes a ligand (a) by coordinating to the compound containing the rare earth element, the compound constituting the ligand (b), and the compound containing the rare earth element.
  • the amount of the compound used as the child (c) should be appropriately selected according to the amount of the ligand (a), ligand (b) and ligand (c) in the rare earth complex to be obtained. Is possible.
  • the amount of the base used is usually in the range of a total amount to an excess amount of 2 times mole of the added ligand (a) and 1 time mole of the added ligand (c). Preferably, it is used in the range of a total amount of 1.5 times the total amount of 2 times mole of the added ligand (a) and 1 time mole of the added ligand (c).
  • the said rare earth complex when manufacturing the said rare earth complex by the said method, it is normally performed at room temperature and a normal pressure, However Heating, pressure reduction, pressurization, etc. may be performed as needed.
  • Heating, pressure reduction, pressurization, etc. may be performed as needed.
  • the rare earth complex of the present invention absorbs ultraviolet light to blue light and emits light, it can be used as a light emitting material for various applications. Since the rare earth complex of the present invention is excellent in heat resistance, it is preferably used as one of materials that constitute a solar cell module, for example, for applications exposed to light such as sunlight for a long period of time.
  • the resin composition may be obtained by directly mixing or kneading the rare earth complex of the present invention with a resin, or a resin solution containing the rare earth complex of the present invention, a resin and a solvent. After the preparation, the resin composition may be obtained by removing the solvent.
  • the resin is not particularly limited, and examples thereof include polyvinyl acetal such as polyvinyl butyral, acrylic resin, polycarbonate, polystyrene, polyolefin, polyvinyl chloride, epoxy resin, fluororesin, and ethylene-vinyl acetate copolymer.
  • polyvinyl acetal such as polyvinyl butyral, acrylic resin, polycarbonate, polystyrene, polyolefin, polyvinyl chloride, epoxy resin, fluororesin, and ethylene-vinyl acetate copolymer.
  • the resin composition usually contains the rare earth complex of the present invention in an amount of 0.0001 to 30 parts by weight, preferably 0.0005 to 20 parts by weight, more preferably 100 parts by weight of the resin. 0.001 to 10 parts by mass is contained.
  • the resin solution usually contains 0.0001 to 30 parts by mass, preferably 0.0005 to 20 parts by mass, more preferably 0 to 100 parts by mass of the rare earth complex of the present invention. 001 to 10 parts by mass.
  • the resin solution usually contains 100 to 100000 parts by mass, preferably 500 to 50000 parts by mass, and more preferably 1000 to 10000 parts by mass of the solvent with respect to 100 parts by mass of the resin.
  • the resin composition and the resin solution may contain other additives.
  • additives include a plasticizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a dehydrating agent, an adhesion adjusting agent, a silane coupling agent, a pigment, a crosslinkable monomer, and a polymerization initiator.
  • the amount of these additives used varies depending on the application, but is usually in the range of 0.001 to 50 parts by mass with respect to 100 parts by mass of the resin.
  • plasticizer examples include 3GO (triethylene glycol bis (2-ethylhexanoate)).
  • Applications of the rare earth complex of the present invention include a wavelength conversion sheet made of the resin composition and a sealant made of the resin composition.
  • the wavelength conversion sheet of the present invention comprises the resin composition.
  • the wavelength conversion sheet of the present invention absorbs ultraviolet light to blue light, and crystalline silicon can be wavelength-converted to 550 to 1000 nm having high photoelectric conversion efficiency. By arranging the conversion sheet, it is possible to improve the power generation efficiency of the solar cell module.
  • the method for producing the wavelength conversion sheet is not particularly limited, but the method for producing the wavelength conversion sheet by applying the resin solution described above and removing the solvent, melt-kneading the resin composition, and extruding into a sheet form The method of manufacturing a wavelength conversion sheet by doing is mentioned.
  • the thickness of the wavelength conversion sheet of the present invention is usually 10 to 1000 ⁇ m.
  • the sealing agent of this invention consists of the said resin composition.
  • the wavelength conversion sheet of the present invention absorbs ultraviolet light to blue light, and crystalline silicon can be wavelength-converted to 550 to 1000 nm having high photoelectric conversion efficiency. It is possible to improve the power generation efficiency of the solar cell module by containing the above-mentioned sealant.
  • the solar cell module of the present invention uses the wavelength conversion sheet and / or the sealant as one of its constituent members.
  • the solar cell module of the present invention includes at least a solar cell and the wavelength conversion sheet, and the solar cell module in which the wavelength conversion sheet is disposed on the light receiving surface side of the solar cell, or at least a solar cell.
  • Examples of the solar battery module include a cell, the sealing agent, and a front cover, and the sealing agent is contained between the solar battery cell and the front cover.
  • each member such as a solar battery cell, a front cover, and a back cover that constitute the solar battery module of the present invention.
  • members used for solar cell modules such as an antireflection film.
  • DBM-DBM (1,3-bis (3-phenyl-3-oxopropanoyl) benzene) (94.5 mg, 0.255 mmol) was weighed and dissolved in chloroform (8 ml).
  • DBM-DBM (94.5 mg, 0.255 mmol) was weighed into a 50 ml eggplant flask and THF / ethanol / water (10/5/5 ml) was added. Thereto, 1M aqueous sodium hydroxide solution (0.51 ml, 0.51 mmol) was added at room temperature, followed by ethanol solution (2 ml) of 1,10-phenanthroline monohydrate (33.7 mg, 0.170 mmol) and dissolved. I let you.
  • TTA-TTA (305 mg, 0.750 mmol) was weighed and dissolved in chloroform (50 ml). Thereto, a methanol solution (5 ml) of europium chloride hexahydrate (183 mg, 0.500 mmol) and a methanol solution (2 ml) of triethylamine (151 mg, 1.50 mmol) were successively added dropwise at room temperature. After stirring for 1 hour, the produced precipitate was centrifuged, washed with chloroform, methanol, water and ether and dried to obtain 260 mg of a pale yellow powder (Eu complex (c4)) (yield 68%).
  • TTA 222 mg, 1.00 mmol
  • TTA-TTA 102 mg, 0.250 mmol
  • 3GO triethylene glycol bis (2-ethylhexanoate)
  • PVB polyvinyl butyral
  • the viscous solution obtained by stirring was spread on a Teflon (registered trademark) plate, and after removing volatile components overnight at room temperature, it was pressed at 120 ° C. and 15 MPa for 3 minutes with a small press machine manufactured by ASONE, about 0.3 mm thick A sheet containing 0.02% by mass of the Eu complex was prepared.
  • the viscous solution obtained by stirring was spread on a Teflon (registered trademark) plate, and after removing volatile components overnight at room temperature, it was pressed at 120 ° C. and 15 MPa for 3 minutes with a small press machine manufactured by ASONE, about 0.3 mm thick A sheet containing 0.2% by mass of the Eu complex was prepared.
  • the sheet was placed on a slide glass, heated at 200 ° C. for 15 minutes (in a warm air dryer), and 615 nm when the sheet before and after heating was irradiated with 366 nm ultraviolet light with a BLAK-RAY lamp (MODEL UVL-21) was measured with a spectro multichannel photodetector (manufactured by Otsuka Electronics; Photo, MCPD-100, MCPD-3000).
  • the emission intensity before heating was subtracted from the emission intensity after heating to calculate the amount of decrease in emission intensity before and after heating.
  • TTA 4,4,4-trifluoro-1-thienyl-1,3-butanedione
  • TTA 444 mg, 2.00 mmol
  • TFT 204 mg, 0.50 mmol
  • the viscous solution obtained by stirring was spread on a Teflon (registered trademark) plate, volatile components were removed overnight at room temperature, and then pressed at 120 ° C. and 15 MPa for 3 minutes with a small press machine. Was made.
  • the Sm complexes (6) and (7) obtained in the examples are superior in light resistance and heat resistance compared to the Sm complex (c5) obtained in the comparative example. Moreover, the current value increased by using the Sm complex.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Sealing Material Composition (AREA)

Abstract

　Le but de la présente invention est de fournir un complexe de terre rare ayant une résistance à la chaleur supérieure par rapport à des complexes d'europium selon l'état de la technique, et de fournir une application dudit complexe. Ce complexe de terre rare est un complexe contenant un élément terre rare tel que Eu, dans lequel un ligand (a) sélectionné dans le groupe constitué par des ligands représentés par la formule générale (A) est coordiné à l'élément terre rare à raison de 0,3 à 0,7 ligand par atome de l'élément terre rare, un ligand spécifique (b) possédant un squelette bipyridine ou un squelette phénanthroline est coordiné à l'élément terre rare à raison de 0,8 à 1,2 ligand par atome de l'élément terre rare, un ligand spécifique (c) ayant une structure dicétonate en son sein est coordiné à l'élément terre rare à raison de 1,6 à 2,4 ligands par atome de l'élément terre rare et, si le nombre de ligands (a) par atome de l'élément terre rare est défini par α, et si le nombre de ligands (c) est défini par γ, alors 2α + γ s'inscrit dans la plage de 3,0 à 3,4.
PCT/JP2013/078194 2012-10-24 2013-10-17 Complexe de terre rare et son application WO2014065190A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023282236A1 (fr) * 2021-07-05 2023-01-12 東ソー株式会社 Complexe de terre rare

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JP2001094128A (ja) * 1999-09-22 2001-04-06 Sharp Corp 太陽電池モジュール及びその製造方法
JP2007291063A (ja) * 2006-03-27 2007-11-08 Ushio Chemix Kk １０配位希土類錯体及び９配位希土類錯体
WO2008047427A1 (fr) * 2006-10-18 2008-04-24 National Institute Of Advanced Industrial Science And Technology Composition de résine fluorescente et module de batterie solaire utilisant ladite composition
WO2011040391A1 (fr) * 2009-09-29 2011-04-07 日立化成工業株式会社 Matériau fluorescent permettant de convertir des longueurs d'onde, composition de résine permettant de convertir des longueurs d'onde et contenant le matériau fluorescent, module de cellule solaire produit à l'aide du matériau fluorescent ou de la composition de résine, procédé de production d'une composition de résine permettant de convertir des longueurs d'onde, et procédé de production d'un module de cellule solaire
WO2011126118A1 (fr) * 2010-04-09 2011-10-13 日立化成工業株式会社 Luminophore sphérique, matériau d'étanchéité pour batterie solaire à conversion de longueur d'ondes, module de batterie solaire et procédé pour les produire
JP2011210891A (ja) * 2010-03-29 2011-10-20 Hitachi Chem Co Ltd 波長変換型太陽電池封止シート、及び太陽電池モジュール
WO2012077485A1 (fr) * 2010-12-06 2012-06-14 日立化成工業株式会社 Luminophore sphérique, matériau de scellement pour batteries solaires de type à conversion de longueur d'onde, module de batterie solaire, et procédé pour la fabrication de ceux-ci

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001094128A (ja) * 1999-09-22 2001-04-06 Sharp Corp 太陽電池モジュール及びその製造方法
JP2007291063A (ja) * 2006-03-27 2007-11-08 Ushio Chemix Kk １０配位希土類錯体及び９配位希土類錯体
WO2008047427A1 (fr) * 2006-10-18 2008-04-24 National Institute Of Advanced Industrial Science And Technology Composition de résine fluorescente et module de batterie solaire utilisant ladite composition
WO2011040391A1 (fr) * 2009-09-29 2011-04-07 日立化成工業株式会社 Matériau fluorescent permettant de convertir des longueurs d'onde, composition de résine permettant de convertir des longueurs d'onde et contenant le matériau fluorescent, module de cellule solaire produit à l'aide du matériau fluorescent ou de la composition de résine, procédé de production d'une composition de résine permettant de convertir des longueurs d'onde, et procédé de production d'un module de cellule solaire
JP2011210891A (ja) * 2010-03-29 2011-10-20 Hitachi Chem Co Ltd 波長変換型太陽電池封止シート、及び太陽電池モジュール
WO2011126118A1 (fr) * 2010-04-09 2011-10-13 日立化成工業株式会社 Luminophore sphérique, matériau d'étanchéité pour batterie solaire à conversion de longueur d'ondes, module de batterie solaire et procédé pour les produire
WO2012077485A1 (fr) * 2010-12-06 2012-06-14 日立化成工業株式会社 Luminophore sphérique, matériau de scellement pour batteries solaires de type à conversion de longueur d'onde, module de batterie solaire, et procédé pour la fabrication de ceux-ci

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023282236A1 (fr) * 2021-07-05 2023-01-12 東ソー株式会社 Complexe de terre rare

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