WO2018042642A1 - Particule de luminophore, composition de formation d'un matériau d'étanchéité, matériau d'étanchéité, et module de cellule solaire - Google Patents

Particule de luminophore, composition de formation d'un matériau d'étanchéité, matériau d'étanchéité, et module de cellule solaire Download PDF

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WO2018042642A1
WO2018042642A1 PCT/JP2016/075907 JP2016075907W WO2018042642A1 WO 2018042642 A1 WO2018042642 A1 WO 2018042642A1 JP 2016075907 W JP2016075907 W JP 2016075907W WO 2018042642 A1 WO2018042642 A1 WO 2018042642A1
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sealing material
phosphor particles
meth
hollow core
phosphor
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PCT/JP2016/075907
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English (en)
Japanese (ja)
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祐巳 乾
野尻　剛
琢 澤木
悟史 黒澤
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日立化成株式会社
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Priority to PCT/JP2016/075907 priority Critical patent/WO2018042642A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • 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
    • H01L31/042—PV modules or arrays of single PV cells
    • 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

Definitions

  • the present invention relates to phosphor particles, a composition for forming a sealing material, a sealing material, and a solar cell module.
  • a general solar cell module has a configuration as shown in FIG. 5, for example.
  • a general solar battery module 100 includes a cover glass 11, a sealing layer 12, a solar battery cell 13, a back surface sealing material layer 14, and a support base 15 in this order from the light receiving surface side.
  • the surface cover glass 11 is generally made of tempered glass with an emphasis on impact resistance. Moreover, in order to improve adhesiveness with the sealing layer 12 (usually also referred to as resin or filler mainly composed of ethylene vinyl acetate copolymer), the surface on the sealing layer side of the cover glass 11 is embossed. The concavo-convex pattern is given. In addition, the uneven
  • a solar cell 13 for example, a crystalline silicon solar cell
  • a tab wire (not shown) are arranged below the cover glass 11 serving as a surface protective layer. 12 and the back surface sealing material layer 14. Further, a support base 15 is disposed on the back side of the solar cell module 100.
  • spectral mismatch spectral mismatch
  • Patent Document 1 a conventional wavelength conversion material has been developed as an additive in a sealing layer on the light receiving surface side of a solar battery cell.
  • a wavelength conversion material is introduced to correct the spectral mismatch.
  • the present invention has been made in view of the above problems, and is a phosphor particle excellent in the effect of improving photoelectric conversion efficiency, and a sealing material-forming composition and a sealing material formed using the aforementioned phosphor particles. And it aims at providing a solar cell module.
  • the present invention includes the following embodiments.
  • Porous hollow core particles having an air part with a refractive index of 1, a refractive index n1 of 1.20 to 1.80, and having at least one of a porous structure and a hollow structure;
  • a phosphor particle that covers at least a part of the hollow core particle, contains a transparent resin and a fluorescent material, and has a shell layer having a refractive index n2 of 1.20 to 1.80.
  • ⁇ 3> The phosphor particles according to ⁇ 1> or ⁇ 2>, wherein the shell layer contains a polymer of a vinyl compound.
  • ⁇ 4> The phosphor particles according to any one of ⁇ 1> to ⁇ 3>, wherein the porous hollow core particles contain a polymer of a vinyl compound.
  • ⁇ 5> Any one of ⁇ 1> to ⁇ 4>, comprising two or more porous hollow core particles, wherein the shell layer covers at least a part of the two or more porous hollow core particles.
  • the fluorescent substance particle as described in one.
  • ⁇ 6> The phosphor particles according to any one of ⁇ 1> to ⁇ 5>, wherein the volume is smaller than the volume of a sphere having a diameter of 150 ⁇ m.
  • ⁇ 7> The phosphor particles according to any one of ⁇ 1> to ⁇ 6>, which are spherical.
  • ⁇ 8> The phosphor particles according to any one of ⁇ 1> to ⁇ 7>, wherein the outer surface has an uneven shape derived from the porous hollow core particles.
  • a composition for forming a sealing material comprising a sealing resin and the phosphor particles according to any one of ⁇ 1> to ⁇ 8>.
  • a solar battery module having a solar battery cell and the sealing material according to ⁇ 10> provided on the light receiving surface side of the solar battery cell.
  • the present invention can provide phosphor particles excellent in the effect of improving photoelectric conversion efficiency, and a composition for forming a sealing material, a sealing material, and a solar cell module formed using the above-described phosphor particles.
  • Example 2 It is an image at the time of observing the cross section of the fluorescent substance particle in Example 1 with an optical microscope.
  • 2 is an SEM image of phosphor particles (particles having a diameter of about 20 ⁇ m) in Example 1.
  • 2 is an SEM image of phosphor particles (particles having a diameter of about 50 ⁇ m) in Example 1.
  • 2 is an SEM image of porous hollow core particles used in Example 1. It is the schematic diagram which showed the structure of the general solar cell module.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the content rate or content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. It means the total content or content of substances.
  • the term “layer” or “film” refers to a part of the region in addition to the case where the layer or the film is formed when the region where the layer or film exists is observed. It is also included when it is formed only.
  • laminate indicates that layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.
  • (meth) acryloyloxy group means at least one of acryloyloxy group and methacryloyloxy group
  • (meth) acryl means at least one of acryl and methacryl
  • (meth) acrylate Means at least one of acrylate and methacrylate.
  • vinyl resin means a resin containing a vinyl compound as a polymerization component
  • “vinyl compound” means a compound having at least one ethylenically unsaturated bond.
  • transparent means that the transmittance of light having a wavelength of 400 nm to 800 nm at an optical path length of 1 cm is 90% or more.
  • the phosphor particles of the present embodiment have a porous portion having an air portion with a refractive index of 1, a refractive index n1 of 1.20 to 1.80, and having at least one of a porous structure and a hollow structure. Particles and a shell layer covering at least a part of the porous hollow core particles, containing a transparent resin and a fluorescent material, and having a refractive index n2 of 1.20 to 1.80.
  • the refractive index n1 and the refractive index n2 may be the same value or different values.
  • the shell layer in the phosphor particles may contain other components.
  • the phosphor particles of the present embodiment include a shell layer containing a fluorescent substance, the wavelength conversion effect of converting light that does not contribute to power generation (for example, ultraviolet light) into light in a wavelength region that can contribute to power generation.
  • the phosphor particles can be used for a member constituting a solar cell module, for example. More specifically, the phosphor particles can be used for forming a sealing material, and when the phosphor particles are used for forming a sealing material for a solar battery module, the power generation efficiency of the solar battery cell is improved. be able to.
  • the phosphor particles have an air portion having a refractive index of 1, and cover at least a part of the porous hollow core particles having a refractive index n1 of 1.20 to 1.80 and the porous hollow core particles. And a shell layer having a refractive index n2 of 1.20 to 1.80. Therefore, there is a difference in refractive index between the porous hollow core particles (parts other than the air part) and the air part, and between the air part and the shell layer, so that one or more interfaces having different refractive indices exist. is doing. As a result, when the phosphor particles are used to form a sealing material for a solar cell module, incident sunlight, light reflected from the solar cells, etc.
  • the fluorescent substance contained in the shell layer of the porous hollow core particles converts light in a wavelength region that has a small contribution to solar power generation in the diffused light into light in a wavelength region that has a large contribution to power generation. Is emitted (emits light). And since the light which a fluorescent material emits injects into a photovoltaic cell and contributes to electric power generation, it is thought that electric power generation efficiency is improving.
  • the phosphor particles include porous hollow core particles having an air part with a refractive index of 1 and a refractive index n1 of 1.20 to 1.80.
  • the porous hollow core particle means a core particle having at least one of a porous structure and a hollow structure, and the porous structure is a structure having a plurality of openings (pores) on the particle surface.
  • the hollow structure means a structure in which at least one cavity that is not open is present inside the particle. Moreover, it is preferable that the hollow structure has a plurality of cavities that are not open inside the particles.
  • the proportion of the air part in the porous hollow core particles is preferably 40% by volume or more, and more preferably 50% by volume or more.
  • the proportion of the air portion in the porous hollow core particles can be measured, for example, by a mercury intrusion method using a mercury intrusion porosimeter.
  • the refractive index n1 of the porous hollow core particles is preferably 1.20 to 1.80, more preferably 1.30 to 1.70. Since the refractive index n1 of the porous hollow core particles is in this range, when the phosphor particles are used for forming a sealing material for a solar cell module, the sunlight incident from various angles is less reflected loss. It can be introduced into a battery cell.
  • the volume of the porous hollow core particles is preferably smaller than the volume of a sphere having a diameter of 50 ⁇ m, and more preferably smaller than the volume of a sphere having a diameter of 30 ⁇ m, from the viewpoint of improving light utilization efficiency.
  • the volume of the porous hollow core particles is preferably larger than the volume of a sphere having a diameter of 1 ⁇ m from the viewpoint of efficiently diffusing incident sunlight, light reflected from a solar battery cell, etc., and having a diameter of 5 ⁇ m. More preferably, it is larger than the volume of the sphere.
  • the volume of the porous hollow core particles can be measured by, for example, an SEM image.
  • the porous hollow core particles are not particularly limited, and commercially available ones may be used. Examples of commercially available products include “ADVANCEL HB-2051” and “ADVANCEL HB-4051” manufactured by Tokuyama Sekisui Industry Co., Ltd.
  • the porous hollow core particles are made of, for example, a vinyl resin that is a polymer formed by polymerizing or copolymerizing a vinyl compound.
  • a vinyl resin that is a polymer formed by polymerizing or copolymerizing a vinyl compound.
  • the vinyl compounds and vinyl resins exemplified in the item of the shell layer described later can be used.
  • a conventionally known method can be adopted, a method of foaming a foaming agent contained in resin particles (for example, vinyl resin particles), and a volatile property encapsulated in the resin.
  • resin particles for example, vinyl resin particles
  • volatile property encapsulated in the resin examples thereof include a method of gasifying and expanding a substance, and a method of injecting a gas such as air into a molten resin.
  • the hollow or porous structure for example, as a method for producing porous hollow core particles, for example, in a dispersion medium containing a polar solvent as a main component, oil droplets containing a vinyl compound and an organic solvent are used. Dispersing and polymerizing the oil droplets to give vinyl resin particles, and then removing the organic solvent encapsulated in the vinyl resin particles from the resin particles to produce porous hollow core particles with the resin particles hollow. It is done. More specifically, the method described in JP-A No. 2003-181274 can be employed as a method for producing the porous hollow core particles.
  • the phosphor particles cover at least a part of the porous hollow core particles and include a shell layer containing a transparent resin and a fluorescent material and having a refractive index n2 of 1.20 to 1.80.
  • the shell layer contains a transparent resin.
  • the transparent resin can be appropriately selected depending on the application, and examples thereof include a vinyl resin that is a polymer formed by polymerizing or copolymerizing a vinyl compound.
  • the vinyl resin examples include (meth) acrylic resin, polyethylene, polystyrene, polyvinyl chloride, and a copolymer containing a polymerization component of these resins in the polymerization component.
  • a (meth) acrylic resin is preferable from the viewpoint of suppressing light scattering.
  • Examples of the vinyl compound forming the vinyl resin include a monofunctional vinyl compound and a bifunctional or higher polyfunctional vinyl compound. Moreover, you may combine a monofunctional vinyl compound and a polyfunctional vinyl compound more than bifunctional as a vinyl compound. The monofunctional vinyl compound and the bifunctional or higher polyfunctional vinyl compound may be used alone or in combination of two or more.
  • the monofunctional vinyl compound examples include a compound having a (meth) acryloyloxy group such as a (meth) acryl monomer and a (meth) acryl oligomer, and other vinyl compounds. It is preferable that the vinyl compound which forms a vinyl resin, especially a (meth) acrylic resin contains a (meth) acrylic monomer.
  • (Meth) acrylic acid, (meth) acrylic acid ester, etc. are mentioned as (meth) acrylic monomer.
  • (meth) acrylic acid esters include alkyl (meth) acrylates, alkenyl (meth) acrylates, urethane (meth) acrylates, among which alkyl (meth) acrylates and alkenyl (meth) acrylates are preferred, and alkyl (meth) ) Acrylate is more preferred.
  • the alkyl moiety or alkenyl moiety of the (meth) acrylic acid ester may be linear, branched or cyclic.
  • the alkyl part or the alkenyl part may be unsubstituted or may have a substituent.
  • substituents include a phenyl group, a group having a cyclic structure such as a heterocyclic ring, a hydroxyl group, an amino group, an alkoxy group, and a halogen atom.
  • (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meta ) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, pentamethylpiperidyl (meth) acrylate, urethane (meth) acrylate (tolylene diisocyanate and 2-hydroxyethyl Meth) reaction of acrylic acid ester, a reaction
  • vinyl compounds include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, diacetone acrylamide, styrene, vinyl toluene, ethylene, vinyl chloride and the like. These other vinyl compounds are compounds that can be copolymerized with a compound having a (meth) acryloyloxy group such as a (meth) acrylic monomer or a (meth) acrylic oligomer.
  • the polyfunctional vinyl compound having two or more functions is not particularly limited, and is trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, and PO-modified trimethylolpropane.
  • the bifunctional or higher polyfunctional vinyl compound may be, for example, a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid.
  • bifunctional or higher polyfunctional vinyl compound examples include compounds obtained by adding an ⁇ , ⁇ -unsaturated carboxylic acid to a polyvalent glycidyl group-containing compound (trimethylolpropane triglycidyl ether tri (meth) acrylate, Bisphenol A diglycidyl ether di (meth) acrylate, etc.), esterified products of polycarboxylic acids (phthalic anhydride, etc.) and substances having hydroxyl and ethylenically unsaturated groups (2-hydroxyethyl (meth) acrylate, etc.), etc. Also mentioned.
  • a polyvalent glycidyl group-containing compound trimethylolpropane triglycidyl ether tri (meth) acrylate, Bisphenol A diglycidyl ether di (meth) acrylate, etc.
  • esterified products of polycarboxylic acids phthalic anhydride, etc.
  • the content of the bifunctional or higher polyfunctional vinyl compound in the vinyl compound used for forming the vinyl resin is preferably 0.1% by mass to 50% by mass with respect to the total mass of the vinyl compound. 0.5% by mass to 10% by mass is more preferable.
  • the mass ratio of the monofunctional vinyl compound to the polyfunctional vinyl compound used to form the vinyl resin is: It is preferably 5: 1 to 100: 1, more preferably 10: 1 to 50: 1, and even more preferably 15: 1 to 30: 1.
  • the shell layer contains a fluorescent material.
  • the shell layer contains a fluorescent substance, and light in a wavelength region that has a small contribution to solar power generation among incident sunlight has a large contribution to power generation. It is possible to use sunlight efficiently and stably by converting to light in the wavelength range.
  • the shell layer may be, for example, a layer in which a fluorescent material is dispersed in a transparent resin.
  • Fluorescent material is not particularly limited, and examples thereof include organic phosphors, inorganic phosphors, transition metal complexes, rare earth metal complexes, and the like.
  • a fluorescent substance may be used individually by 1 type, or may use 2 or more types together.
  • the organic phosphor is not particularly limited, and includes at least one of naphthalene, anthracene, perylene, pyrene, porphyrin, carbazole, quinoline, thiazole, oxazole, thiadiazole, diazole, triazole, alloxazine, cyanine, pyridine, rhodamine, dibenzofuran skeleton and the like.
  • the compound which has the above is mentioned.
  • organic phosphors may be used. Commercially available products include “Lumogen F Violet 570”, “Lumogen F Yellow 083”, “Lumogen F Orange 240”, “Lumogen F Red 300”, “Lumogen F Red 300”, and “Rhogen F Red 300” of Taoka Chemical Industry Co., Ltd. “B”, “Sumiplast Yellow FL7G” by Sumika Finechem Co., Ltd., “MACROLEX Fluorescent Red G” from Bayer, “MACROLEX Fluorescent Yellow 10GN”, and the like.
  • the inorganic phosphor is not particularly limited, and examples thereof include calcium halophosphate phosphor, phosphate phosphor, aluminate phosphor, zinc sulfide phosphor, zinc oxide phosphor, and rare earth oxide phosphor.
  • inorganic phosphors include X-ray and radiation-excited phosphors such as NaI: Ti, CaWO 4 : Pb, Gd 2 O 2 S: Tb, BaSi 2 O 5 : Pb, Sr 2 P 2 O 7 : Eu.
  • BaMg 2 Al 16 O 27 Eu, BaMg 2 Al 16 O 27 : Eu, Mn, BaMgAl 10 O 17 : Eu, Mn, MgWO 4 : Pb, 3Ca 3 (PO 4 ) 2 .Ca (F, Cl) 2 : Sb, Mn, MgGa 2 O 4: Mn, 0.5MgF 2 ⁇ 3.5MgO ⁇ GeO 2: Mn, Ga 2 O 4: Mn, Zn 2 SiO 4: Mn, MgAl 11 O 19: Ge, Tb, Y 2 SiO 5 : Ce, Tb, Y 2 O 2 S: Eu, La 2 O 2 S: Eu, Y 2 O 3 : Eu, YVO 4 : Eu, (Sr, Mg, Ba) 3 (PO 4 ) 2 : Sn, 3.
  • the transition metal complex is not particularly limited as long as it has a transition metal and a ligand coordinated to the transition metal.
  • Examples of the transition metal constituting the transition metal complex include ruthenium, rhodium, osmium, iridium, rhenium, platinum and the like.
  • the ligand constituting the transition metal complex is not particularly limited as long as it can be coordinated to the transition metal, and can be appropriately selected according to the transition metal to be used. Among these, an organic ligand is preferable from the viewpoint of luminous efficiency.
  • Examples of the ligand constituting the transition metal complex include 1,10-phenanthroline, 2-2′-bipyridyl, 2-2′-6,2 ′′ -terpyridyl, 4,7-diphenyl-1,10-phenanthroline, Examples include 2- (2-pyridyl) benzimidazole, triphenylphosphine oxide, tri-n-butylphosphine oxide, tri-n-octylphosphine oxide, tri-n-butylphosphate, and the like.
  • the rare earth metal complex is not particularly limited as long as it has a rare earth metal and a ligand coordinated to the rare earth metal.
  • the rare earth metal constituting the rare earth metal complex is preferably at least one of europium and samarium, more preferably europium, from the viewpoint of luminous efficiency.
  • the ligand constituting the rare earth metal complex is not particularly limited as long as it can be coordinated to the rare earth metal, and can be appropriately selected according to the rare earth metal used. Among these, from the viewpoint of luminous efficiency, an organic ligand is preferable, and an organic ligand capable of forming a complex with at least one of europium and samarium is more preferable.
  • 1,10-phenanthroline, 2-2′-bipyridyl, 2-2′-6,2 ′′ -terpyridyl, 4,7-diphenyl-1,10-phenanthroline examples include 2- (2-pyridyl) benzimidazole, triphenylphosphine oxide, tri-n-butylphosphine oxide, tri-n-octylphosphine oxide, tri-n-butylphosphate, and the like.
  • the rare earth metal complex includes Eu (TTA) 3 Phen ((1,10-phenanthroline) tris [4,4,4-trifluoro-1- (2-thienyl) -1,3- from the viewpoint of wavelength conversion efficiency. Butanedionate] europium (III)), Eu (BMPP) 3 Phen ((1,10-phenanthroline) tris [1- (pt-butylphenyl) -3- (N-methyl-3-pyrrole) -1 , 3-propanedionate] europium (III)), Eu (BMDBM) 3 Phen ((1,10-phenanthroline) tris [1- (pt-butylphenyl) -3- (p-methoxyphenyl) -1 , 3-propanedionate] europium (III)) and the like.
  • TTA 3 Phen A method for producing Eu (TTA) 3 Phen is described in, for example, Masa Mitsushi, Shinji Kikuchi, Tokuji Miyashita, Yutaka Amano, J. et al. Mater. Chem. Reference may be made to the method disclosed in 2003, 13, 285-2879.
  • a commercially available product may be used as the rare earth metal complex.
  • Commercially available products include “Lumisis E 400” from Central Techno Co., Ltd.
  • the fluorescent substance may be incorporated in the main chain or side chain in the transparent resin.
  • the fluorescent substance can be incorporated into the main chain or the side chain in the vinyl resin by copolymerizing a fluorescent substance having a polymerizable structure (for example, vinyl group) and a vinyl compound.
  • the fluorescent material is an organic phosphor
  • the organic phosphor is stabilized by being immobilized in the main chain or side chain where the organic phosphor is formed, so that the light resistance of the phosphor particles can be improved. it can.
  • the fluorescent substance preferably has a maximum absorption wavelength of 250 nm to 400 nm and a maximum emission wavelength of 400 nm to 800 nm from the viewpoint of correcting a spectral mismatch between the sunlight spectrum and the sensitivity of the solar battery cell.
  • the content of the fluorescent substance in the shell layer is 0.0001 parts by mass to 10 parts by mass with respect to 100 parts by mass of the shell layer from the viewpoint of excitation wavelength, emission wavelength, quantum efficiency, and phosphor particle transmittance.
  • the amount is preferably 0.001 to 1 part by mass.
  • the content of the fluorescent substance in the shell layer is 0.0001 part by mass or more, a sufficient wavelength conversion effect tends to be easily obtained.
  • the content of the fluorescent substance in the shell layer is 10 parts by mass or less, light in a region that contributes greatly to solar power generation among incident sunlight is easily transmitted to the solar battery cell, and the photoelectric conversion efficiency is increased. There is a tendency to increase.
  • the content of the fluorescent substance in the phosphor particles is 0.00005% by mass to 10% by mass with respect to the total mass of the phosphor particles in terms of excitation wavelength, emission wavelength, quantum efficiency, and phosphor particle transmittance. Preferably, it is 0.0001% by mass to 5% by mass, and more preferably 0.001% by mass to 1% by mass.
  • the phosphor content in the phosphor particles is 0.00005% by mass or more, a sufficient wavelength conversion effect tends to be easily obtained.
  • the content of the fluorescent substance in the phosphor particles is 10% by mass or less, light in a region that greatly contributes to photovoltaic power generation among incident sunlight is easily transmitted to the solar battery cell, and the photoelectric conversion efficiency. Tend to increase.
  • a polymerization initiator When the vinyl compound is polymerized to obtain a vinyl resin, a polymerization initiator may be used.
  • the polymerization initiator include a photopolymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator, and a radical polymerization initiator is preferable.
  • the radical polymerization initiator is not particularly limited, and examples thereof include organic peroxides that generate free radicals by heat, radical polymerization initiators having an azo group, and the like.
  • the organic peroxide is not particularly limited, and is isobutyl peroxide, ⁇ , ⁇ ′bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, di- -S-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl neodecanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethyl peroxyneo Decanoate, di-2-ethoxyethyl peroxydicarbonate, di (ethylhexyl) peroxydicarbonate, t-hexyl neodecanoate, dimethoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) Peroxydicarbonate, t-butyl pero
  • the radical polymerization initiator having an azo group is not particularly limited, and azobisisobutyronitrile (AIBN, trade name “V-60”, Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2- Methylisobutyronitrile) (trade name “V-59”, Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2,4-dimethylvaleronitrile) (trade name “V-65”, Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd.), dimethyl-2,2′-azobis (isobutyrate) (trade name “V-601”, Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (4-methoxy-2,4-dimethylvalero) Nitrile) (trade name “V-70”, Wako Pure Chemical Industries, Ltd.).
  • AIBN azobisisobutyronitrile
  • V-60 Wako Pure Chemical Industries, Ltd.
  • the amount of the polymerization initiator (preferably a radical polymerization initiator) can be appropriately selected according to the type of vinyl compound or the refractive index of the vinyl resin to be formed. Specifically, the amount of the radical polymerization initiator used is preferably 0.01% by mass to 2% by mass and more preferably 0.1% by mass to 1% by mass with respect to the vinyl compound.
  • a radical scavenger When obtaining a vinyl resin by polymerizing a vinyl compound, a radical scavenger may be used together with a radical polymerization initiator.
  • the radical scavenger is not particularly limited as long as it suppresses deterioration of the fluorescent substance derived from the radical polymerization initiator and a shell layer containing a desired fluorescent substance can be obtained.
  • the hindered amine radical scavenger is not limited. Hindered phenol radical scavenger, phosphorus radical scavenger, sulfur radical scavenger and the like.
  • a radical scavenger may be used individually by 1 type, or may use 2 or more types together.
  • the amount of the radical scavenger used is appropriately selected within the range where phosphor particles are obtained without impeding the progress of radical polymerization and various properties such as transparency and refractive index are not impaired.
  • the amount of the radical scavenger used can be 0.01 to 5% by mass, preferably 0.1 to 2% by mass, based on the vinyl compound.
  • the refractive index n2 of the shell layer is preferably 1.20 to 1.80, and more preferably 1.40 to 1.70. When the refractive index n2 of the shell layer is within this range, sunlight incident from various angles can be efficiently introduced into the solar battery cell with little reflection loss.
  • the refractive index n2 of the shell layer may be equal to or higher than the refractive index n1 of the porous hollow core particles. From the viewpoint of efficiently diffusing light at various incident angles, the refractive index n2 of the shell layer is It is preferable that it is larger than the refractive index n1 of the hollow core particles.
  • the thickness of the shell layer is not particularly limited, and is preferably 1 nm to 40 ⁇ m, for example, and more preferably 1 nm to 30 ⁇ m.
  • the thickness of the shell layer means the shortest distance from the surface of the shell layer to the porous hollow core particles.
  • the phosphor particles contain two or more porous hollow core particles, and the shell layer may cover at least a part of the two or more porous hollow core particles. Two or more porous hollow core particles may be covered.
  • the volume of the phosphor particles is preferably smaller than the volume of a sphere having a diameter of 150 ⁇ m, and more preferably smaller than the volume of a sphere having a diameter of 100 ⁇ m, from the viewpoint of improving the light utilization efficiency.
  • the volume of the phosphor particles is preferably larger than the volume of a sphere having a diameter of 5 ⁇ m, from the viewpoint of efficiently diffusing incident sunlight, light reflected from a solar battery cell, etc. More preferably larger than the volume. Note that the volume of the phosphor particles can be measured by, for example, an SEM image.
  • the phosphor particles are preferably spherical.
  • the spherical shape includes not only a true spherical shape but also an elliptical or substantially spherical shape.
  • the ratio of the major axis to the minor axis is 3 or less, preferably 2 or less, more preferably 1.5 or less, the phosphor particles are judged to be spherical. May be.
  • the major axis is the length of the longest part of the phosphor particles projected in the two-dimensional visual field in the SEM image.
  • the minor axis is the length of the shortest part orthogonal to the major axis.
  • the phosphor particles may have an uneven shape on the outer surface, for example, an uneven shape derived from porous hollow core particles on the outer surface.
  • having an uneven shape derived from porous hollow core particles on the outer surface means that an uneven shape corresponding to the uneven shape of the porous hollow core particles is present on the outer surface of the phosphor particles.
  • the phosphor particles may be spherical and have an uneven shape on the outer surface.
  • the method for producing the phosphor particles of the present embodiment is not particularly limited, and for example, a well-known production method in which the fluorescent material and the porous hollow core particles are dispersed using a transparent resin as a dispersion medium can be used.
  • a vinyl compound is polymerized (preferably suspension polymerization) in a composition containing a fluorescent substance, porous hollow core particles, and a vinyl compound forming a vinyl resin. By this, it is possible to employ a method for producing phosphor particles.
  • a method of producing phosphor particles by suspension polymerization first, other components such as a fluorescent substance, porous hollow core particles, a vinyl compound, and a polymerization initiator (preferably a radical polymerization initiator) as necessary Is added to the solvent to prepare a composition (suspension). Next, at least a part of the porous hollow core particles is heated by the shell layer containing the vinyl resin and the fluorescent substance while heating the prepared suspension to polymerize the vinyl compound to produce a vinyl resin granule. A granular material covered with is formed.
  • a polymerization initiator preferably a radical polymerization initiator
  • composition for forming sealing material contains a sealing resin and the phosphor particles of the present embodiment.
  • the composition for forming a sealing material according to this embodiment is used for forming a sealing material.
  • the composition for forming a sealing material contains a sealing resin (transparent sealing resin).
  • a sealing resin transparent sealing resin
  • a photocurable resin, a thermosetting resin, a thermoplastic resin, or the like is preferably used. More specifically, examples of the sealing resin include ethylene-vinyl acetate copolymer (EVA).
  • the composition for forming a sealing material may contain other components other than the sealing resin and the phosphor particles.
  • other components include known additives such as a polymerization initiator, a plasticizer, a flame retardant, a crosslinking aid, an adhesion aid, an ultraviolet absorber, a stabilizer, and an antioxidant.
  • the content of the phosphor particles in the encapsulant-forming composition is 0 with respect to 100 parts by mass of the encapsulant-forming composition from the viewpoints of excitation wavelength, emission wavelength, quantum efficiency, and phosphor particle transmittance. It is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass. When the content of the phosphor particles is 0.001 parts by mass or more, a sufficient wavelength conversion effect tends to be easily obtained. In addition, when the content of the phosphor particles is 10 parts by mass or less, light in a region that greatly contributes to solar power generation in incident sunlight is easily transmitted to the solar battery cell, and the photoelectric conversion efficiency tends to increase. There is.
  • the ratio of the total volume of the phosphor particles smaller than the volume of the sphere having a diameter of 150 ⁇ m to the total volume of the phosphor particles is preferably 50% or more
  • the ratio of the total volume of the phosphor particles smaller than the volume of the sphere having a diameter of 100 ⁇ m to the total volume of the phosphor particles is more preferably 50% or more
  • the composition for forming a sealing material from the viewpoint of efficiently diffusing incident sunlight, light reflected from the solar battery cell, etc., it is larger than the volume of a sphere having a diameter of 10 ⁇ m with respect to the total volume of the phosphor particles.
  • the ratio of the total volume of the phosphor particles is preferably 50% or more, and the ratio of the total volume of the phosphor particles larger than the volume of the sphere having a diameter of 15 ⁇ m to the total volume of the phosphor particles is more preferably 50% or more. preferable.
  • the sealing material of this embodiment is formed from the composition for sealing material formation of this embodiment.
  • the sealing material of this embodiment is used for a solar cell module or the like.
  • the sealing material is manufactured by curing (preferably, thermosetting) a sealing resin contained in the composition for forming a sealing material.
  • the sealing material is preferably in the form of a sheet from the viewpoint of easy handling.
  • the sheet-like encapsulant is produced, for example, by sandwiching the encapsulant-forming composition between release sheets and pressurizing and heating the encapsulant-forming composition using a press.
  • the thickness of the sealing material is, for example, preferably 1 ⁇ m to 1000 ⁇ m, and more preferably 10 ⁇ m to 800 ⁇ m.
  • the solar cell module of this embodiment has a solar cell and the sealing material of this embodiment provided on the light receiving surface side of the solar cell.
  • the solar cell module of this embodiment should just have the sealing material of this embodiment provided in the light-receiving surface side of the photovoltaic cell at least. Therefore, even if the sealing material of this embodiment is provided in the back surface side, the sealing material different from the sealing material of this embodiment may be provided.
  • the manufacturing method of a solar cell module is not specifically limited, It can manufacture by a well-known method.
  • the solar cell module includes, for example, an antireflection film, a surface protective layer (for example, protective glass and a protective film), a sealing material of the present embodiment, a solar cell, a back surface side sealing material, and a support substrate (for example, a back film). , Cell electrodes, tab lines and the like.
  • a surface protective layer for example, protective glass and a protective film
  • a sealing material of the present embodiment a solar cell
  • a back surface side sealing material for example, a back film
  • a support substrate for example, a back film.
  • Cell electrodes, tab lines and the like Cell electrodes, tab lines and the like.
  • the light transmissive layer having light transmittance an antireflection film, a protective glass, a sealing material, a solar battery cell (for example, SiNx of solar battery cell: H layer and Si layer), and the like. Can be mentioned.
  • the stacking order of the light-transmitting layers is usually an antireflection film, a surface protective layer, a sealing material, and a solar battery cell that are formed as necessary in order from the light receiving surface of the solar battery module.
  • the stacking order of the solar battery modules is an antireflection film, a surface protective layer, a sealing material, a solar battery cell, a back surface side sealing material, and a support substrate that are formed as necessary in order from the light receiving surface.
  • the refractive index of the sealing material is arranged on the light incident side from the sealing material.
  • Light-transmitting layer that is, a solar cell (for example, SiNx: H of a solar cell) higher than the refractive index of the light-transmitting layer, that is, the antireflection film, the protective glass, etc.
  • the refractive index is preferably lower than the refractive index of the layer (also referred to as “cell antireflection film” and Si layer).
  • the refractive index of the light-transmitting layer disposed on the light incident side from the sealing material is preferably 1.25 to 1.45.
  • the refractive index is preferably 1.45 to 1.55.
  • the refractive index of the light transmissive layer disposed on the light incident side of the encapsulant, that is, the SiNx: H layer (cell antireflection film) of the solar battery cell is preferably 1.9 to 2.1,
  • the refractive index of the Si layer or the like is preferably 3.3 to 3.4.
  • the refractive index of the sealing material is preferably 1.5 to 2.1, and more preferably 1.5 to 1.9.
  • a solar cell module can be manufactured by, for example, laminating and laminating an antireflection film, a surface protective layer, the sealing material of this embodiment, a solar battery cell, a back surface side sealing material, and a support substrate in this order.
  • a laminating method for obtaining a solar cell module a known method can be adopted. For example, a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, a method using a nip roll, etc. Is mentioned.
  • the encapsulant may contain phosphor particles. preferable.
  • the solar cell module of the present invention is not limited to a configuration in which phosphor particles are included in the sealing material.
  • the layer containing the phosphor particles according to the present embodiment may be disposed in the path until the incident light reaches the solar cell. Therefore, for example, not only the above-described sealing material may include phosphor particles, but the surface protective layer may include phosphor particles, and the solar cell on the light-receiving surface of the solar battery cell or the surface protective layer may be used.
  • a light transmissive layer containing phosphor particles may be separately provided on the battery cell side surface (that is, between the surface protective layer and the sealing material). The light transmissive layer can be formed, for example, by applying and drying a coating liquid containing phosphor particles and a binder resin on the surface protective layer.
  • FIG. 1 is an image when the cross section of the phosphor particles of Example 1 is observed with an optical microscope.
  • FIG. 1 it was confirmed that the porous hollow core particles were covered with the shell layer.
  • the SEM image of the fluorescent substance particle obtained in Example 1 is shown in FIG.2 and FIG.3.
  • FIG. 2 spherical phosphor particles with more irregularities were confirmed on the surface having a diameter of about 20 ⁇ m, and in FIG. 3, spherical phosphor particles having fewer irregularities were confirmed on the surface having a diameter of about 50 ⁇ m.
  • the SEM image of the porous hollow core particle used in Example 1 is shown in FIG.
  • the refractive index n1 of the porous hollow core particles and the refractive index n2 of the shell layer were measured to be 1.30 and 1.52, respectively.
  • Comparative Example 1 In Comparative Example 1, instead of the phosphor particles obtained in Example 1, commercially available Lumisis E 400 manufactured by Central Techno Co., Ltd. was used.
  • Comparative Example 2 polymer particles containing no porous hollow core particles were obtained in the same manner as in Example 1 except that ADVANCEL HB-2051 manufactured by Tokuyama Sekisui Industry Co., Ltd. was not used.
  • the phosphor particles of Example 1, the phosphor material of Comparative Example 1, and the polymer particles of Comparative Example 2 were used for the production of a sealing material forming composition, a sealing material, and a solar cell module as described later.
  • composition for forming sealing material 100 g of ethylene-vinyl acetate resin (Tosoh Corporation, trade name: Ultrasen 634 (“Ultrasen” is a registered trademark)) as a transparent sealing resin, peroxide thermal radical initiator (Arkema Yoshitomi Corporation, Luperox 101 (“ “Lupelox” is a registered trademark)) 1.5 g, a silane coupling agent (Toray Dow Corning Co., Ltd., trade name: SZ6030) 0.5 g, and 1 g of the phosphor particles obtained in Example 1 are mixed. Was kneaded with a roll mixer adjusted to 90 ° C. to obtain a composition for forming a sealing material.
  • Ultrasen 634 Ultrasen 634
  • Luperox 101 “Lupelox” is a registered trademark)
  • silane coupling agent Toray Dow Corning Co., Ltd., trade name: SZ6030
  • Comparative Example 1 and Comparative Example 2 instead of the phosphor particles 1g obtained in Example 1, 0.001 g of the fluorescent substance and the polymer obtained in Comparative Example 2 were used. A composition for forming a sealing material was obtained using 1 g of each particle.
  • ⁇ Production of solar cell module> On the tempered glass (manufactured by Asahi Glass Co., Ltd.) as the cover glass, the sealing material prepared as described above is placed, and the photovoltaic cell on which the electromotive force can be taken out is placed on the light receiving surface. I put it to become. Furthermore, a back surface side sealing material, a PET film (trade name: A-4300, manufactured by Toyobo Co., Ltd.) as a support substrate is placed, and using a vacuum laminator, a hot plate 150 ° C., vacuum 10 minutes, pressurization 15 minutes. Lamination was performed under conditions to produce a solar cell module.
  • a PET film trade name: A-4300, manufactured by Toyobo Co., Ltd.
  • a solar simulator (Wacom Denso Co., Ltd., trade name: WXS-155S-10, AM1.5G) was used as a simulated solar ray, and the current-voltage characteristics were measured using an IV curve tracer (Eihiro Seiki Co., Ltd., trade name: MP-).

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Abstract

Cette particule de luminophore présente : une particule creuse poreuse formant noyau, qui présente une section d'air ayant un indice de réfraction de 1, un indice de réfraction (n1) de 1,20 à 1,80, et une structure poreuse et/ou une structure creuse ; et une couche d'écorce, qui recouvre au moins une partie de la particule creuse poreuse formant noyau, contenant une résine transparente et une substance fluorescente, et présente un indice de réfraction (n2) de 1,20 à 1,80.
PCT/JP2016/075907 2016-09-02 2016-09-02 Particule de luminophore, composition de formation d'un matériau d'étanchéité, matériau d'étanchéité, et module de cellule solaire WO2018042642A1 (fr)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
JP2002180041A (ja) * 2000-12-18 2002-06-26 Sumitomo Chem Co Ltd 蛍光性粒子
JP2009280489A (ja) * 2008-04-23 2009-12-03 Commissariat A L'energie Atomique オルガノランタニド化合物を含むシリカ粒子、その調製方法及びその使用
JP2010209314A (ja) * 2009-03-06 2010-09-24 Korea Inst Of Science & Technology ナノ粒子・多孔体複合ビーズ及びその製造方法
JP2013087241A (ja) * 2011-10-20 2013-05-13 Hitachi Chemical Co Ltd 被覆蛍光材料、波長変換型太陽電池封止材、太陽電池モジュール及びこれらの製造方法
JP2013194160A (ja) * 2012-03-21 2013-09-30 Hitachi Chemical Co Ltd 粒子状太陽電池用波長変換材料
JP2016014096A (ja) * 2014-07-01 2016-01-28 古河電気工業株式会社 紫外励起蛍光粒子、これを用いた検出方法、画像表示方法、画像表示スクリーンおよび画像表示装置
JP2016516853A (ja) * 2013-03-20 2016-06-09 コーニンクレッカ フィリップス エヌ ヴェＫｏｎｉｎｋｌｉｊｋｅ Ｐｈｉｌｉｐｓ Ｎ．Ｖ． 多孔質粒子内の封止量子ドット

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002180041A (ja) * 2000-12-18 2002-06-26 Sumitomo Chem Co Ltd 蛍光性粒子
JP2009280489A (ja) * 2008-04-23 2009-12-03 Commissariat A L'energie Atomique オルガノランタニド化合物を含むシリカ粒子、その調製方法及びその使用
JP2010209314A (ja) * 2009-03-06 2010-09-24 Korea Inst Of Science & Technology ナノ粒子・多孔体複合ビーズ及びその製造方法
JP2013087241A (ja) * 2011-10-20 2013-05-13 Hitachi Chemical Co Ltd 被覆蛍光材料、波長変換型太陽電池封止材、太陽電池モジュール及びこれらの製造方法
JP2013194160A (ja) * 2012-03-21 2013-09-30 Hitachi Chemical Co Ltd 粒子状太陽電池用波長変換材料
JP2016516853A (ja) * 2013-03-20 2016-06-09 コーニンクレッカ フィリップス エヌ ヴェＫｏｎｉｎｋｌｉｊｋｅ Ｐｈｉｌｉｐｓ Ｎ．Ｖ． 多孔質粒子内の封止量子ドット
JP2016014096A (ja) * 2014-07-01 2016-01-28 古河電気工業株式会社 紫外励起蛍光粒子、これを用いた検出方法、画像表示方法、画像表示スクリーンおよび画像表示装置

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