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WO2017082319A1 - Produit d'étanchéité - Google Patents

Produit d'étanchéité Download PDF

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Publication number
WO2017082319A1
WO2017082319A1 PCT/JP2016/083289 JP2016083289W WO2017082319A1 WO 2017082319 A1 WO2017082319 A1 WO 2017082319A1 JP 2016083289 W JP2016083289 W JP 2016083289W WO 2017082319 A1 WO2017082319 A1 WO 2017082319A1
Authority
WO
WIPO (PCT)
Prior art keywords
photoelectric conversion
agent
sealing agent
conversion element
conversion elements
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/083289
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English (en)
Japanese (ja)
Inventor
雄太 橋本
今泉　雅裕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
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 Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to KR1020187012829A priority Critical patent/KR20180081725A/ko
Priority to JP2017550372A priority patent/JP6802802B2/ja
Priority to CN201680060851.2A priority patent/CN108235790A/zh
Publication of WO2017082319A1 publication Critical patent/WO2017082319A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/804—Materials of encapsulations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic 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
    • 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
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention relates to a sealing agent particularly suitable for the production of a photoelectric conversion element having excellent adhesiveness under low temperature curing conditions.
  • Photoelectric conversion elements used in solar cells generally protect photoelectric conversion materials such as silicon, gallium-arsenic, copper-indium-selenium with an upper transparent protective material and a lower substrate protective material. Are fixed with a sealant and packaged. For this reason, as a sealing agent used for manufacture of a photoelectric conversion element, it is requested
  • an ethylene-vinyl acetate copolymer having a high vinyl acetate content is used as a sealing agent for a photoelectric conversion element in a solar cell module from the viewpoint of flexibility and transparency.
  • the copolymer since the copolymer has insufficient heat resistance and adhesiveness, it is necessary to use an organic peroxide or the like for the purpose of further promoting the copolymerization reaction.
  • an ethylene-vinyl acetate copolymer sheet containing these organic peroxides is first prepared, and then a photoelectric conversion material is sealed using this sheet, which requires a two-step process.
  • the heat resistance is not sufficient, and there is a risk of deformation due to a temperature rise during use as a solar cell.
  • these sealing materials may flow out more than necessary, which is not preferable.
  • the stress applied to the seal portion during the processing process has become much larger than before, and the seal line length has also become longer. From these facts, it is excellent in moisture resistance reliability, enables the line width of the seal to be narrowed, makes the interval between the conductive supports uniform, and further provides a coating type sealant with excellent adhesion and flexibility. Development is required.
  • thermosetting epoxy resin As a sealing agent, the sealing agent is applied to the conductive support by a method such as dispenser or screen printing, and after leveling without heating or heating, the upper and lower conductive supports are bonded together using alignment marks, and the sealing agent The cell is manufactured by the process of pressing the.
  • a curing agent for the thermosetting epoxy resin used here a phenol novolac resin is used.
  • such a sealant for a photoelectric conversion element has the disadvantage that the adhesion performance is inferior in terms of long-term sealing under high temperature and high humidity, and the electrolyte solution leaks.
  • Patent Document 2 discloses a resin composition using a hydrogenated bisphenol type epoxy resin. However, in this case as well, long-term sealing under high temperature and high humidity cannot be imparted, and an electrolyte leakage phenomenon is shown.
  • the object of the present invention is to facilitate the bonding operation of the upper and lower conductive supports at the time of manufacturing the photoelectric conversion element, and to cure at a low temperature, and to obtain the adhesive strength, moisture resistance reliability and heat resistance of the obtained seal part. It is providing the sealing agent for photoelectric conversion elements excellent in property etc. That is, an object of the present invention is to provide a sealing agent particularly suitable for manufacturing a photoelectric conversion element.
  • each aspect of the present invention is as follows. [1]. (A) An epoxy resin and (b) an amine as a thermosetting agent, and a sealing agent for a photoelectric conversion element. [2].
  • the above [1] contains (b) a thermosetting agent in an amount such that (b) active hydrogen in the thermosetting agent is 0.8 to 3.0 equivalents with respect to 1 equivalent of epoxy group in the epoxy resin. ]
  • the sealing agent for photoelectric conversion elements of a term [3].
  • thermosetting agent for a photoelectric conversion element according to the above item [1] or [2], wherein the thermosetting agent is an amine adduct. [4].
  • thermosetting agent contains at least two amines including at least one of guanamines and / or imidazoles and at least one of other amines.
  • the sealing agent for photoelectric conversion elements as described in any one of term. [5].
  • the sealing agent for a photoelectric conversion element as described in the above item [4], wherein the imidazole comprises 2-undecylimidazole. [6].
  • C The sealing agent for photoelectric conversion elements according to any one of [1] to [5], which contains a filler. [7].
  • the filler is one or more selected from the group consisting of hydrous magnesium oxalate, calcium carbonate, aluminum oxide, crystalline silica and fused silica, and the average particle size is 50 ⁇ m or less.
  • a first conductive support having a semiconductor-containing layer; a second conductive support having a counter electrode provided at a position where the semiconductor-containing layer and the counter electrode face each other at a predetermined interval;
  • a photoelectric transfer element including a charge transfer layer sandwiched between gaps of the conductive support, and a seal provided in a peripheral portion of the first and second conductive supports and surrounding the charge transfer layer,
  • the photoelectric conversion element whose seal
  • a solar cell comprising the photoelectric conversion element as described in the above item [10].
  • the sealing agent for photoelectric conversion elements of the present invention contains amines (preferably amine adducts) as a thermosetting agent, it can be applied to a substrate, workability, bonding strength, and usable time at room temperature (pot Life) and low temperature curability. Therefore, the contamination property with respect to the charge transfer layer in the manufacturing process of the photoelectric conversion element is extremely low.
  • the photoelectric conversion element of the present invention obtained by using such a sealing agent has little deterioration in power generation performance due to contamination of the charge transfer layer, and is excellent in adhesiveness and moisture resistance reliability.
  • a photoelectric conversion element is produced using the photoelectric conversion element sealing agent of the present invention, it is possible to produce a low-temperature and high-reliability element in a short time without causing poor performance. Increase productivity.
  • the sealing agent for photoelectric conversion elements of the present invention includes (a) an epoxy resin and (b) a curable resin composition for a photoelectric conversion element containing amines as a thermosetting agent. It is a thing.
  • the sealing agent is preferably a first conductive support having a semiconductor-containing layer, and a second conductive having a counter electrode provided at a position where the semiconductor-containing layer and the counter electrode face each other at a predetermined interval.
  • the sealant of the present invention refers to a composition in a state before being subjected to a thermosetting process.
  • an epoxy resin having at least two epoxy groups in one molecule is usually used.
  • examples of such epoxy resins include novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, and triphenylmethane type epoxy resins.
  • bisphenol A bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyl Tophenone, o-hydroxyacetophenone
  • These may be used alone or in combination of two or more.
  • These epoxy resins are useful for lowering the viscosity of the sealing agent for photoelectric conversion elements of the present invention, and can have a function of enabling a bonding operation at room temperature and facilitating gap formation.
  • these epoxy resins the use of a novolac type epoxy resin and / or a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin is preferable, and the combined use of a novolac type epoxy resin and a bisphenol A type epoxy resin is also preferable.
  • a mixture of 30-300 g / eq epoxy resin and 200-600 g / eq epoxy resin may be used.
  • 30 to 300 g / eq novolac type epoxy resin and / or bisphenol A type epoxy resin and / or bisphenol F type epoxy resin 200 to 600 g / eq novolak type epoxy resin and / or bisphenol A Mixtures of type epoxy resin and / or bisphenol F type epoxy resin may be used.
  • the sealing agent of the present invention preferably has as little hydrolyzable chlorine as possible contained in the sealing agent in order to minimize contamination of the charge transfer layer by the sealing agent. Therefore, the (a) epoxy resin also preferably has a hydrolyzable chlorine content of 600 ppm or less, more preferably 500 ppm or less, still more preferably 400 ppm or less, and even more preferably 300 ppm or less. Preferably, those below 200 ppm are even more preferred, most preferably below 100 ppm or substantially zero.
  • the amount of hydrolyzable chlorine is determined by, for example, dissolving about 0.5 g of epoxy resin in 20 ml of dioxane, refluxing with 5 ml of 1N KOH / ethanol solution for 30 minutes, and titrating with 0.01N silver nitrate solution. can do.
  • the content of the (a) epoxy resin in the sealing agent of the present invention is usually 5 to 80% by mass, preferably 10 to 70% by mass, more preferably 20 to 60% by mass.
  • the sealing agent of this invention contains amines as (b) thermosetting agent.
  • amines are not particularly limited, but polyfunctional amines having two or more amino groups in the molecule are preferably used.
  • Preferred examples of polyfunctional amines having two or more amino groups in the molecule are synthesized from diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, linolenic acid dimer and ethylenediamine. Examples thereof include polyamide resins and amine adducts.
  • One particularly preferred amine is an amine adduct.
  • curing agent which enables seal hardening at less than 120 degreeC can be used preferably. More preferably, a curing agent that enables seal curing at less than 110 ° C. can be used. More preferably, it is less than 105 ° C., most preferably around 100 ° C. (or below 100 ° C.), and a curing agent that enables seal hardening can be used.
  • the amine adduct is an amine compound obtained by chemically reacting an epoxy resin with polyfunctional amines.
  • product names Hardener X-3661S, Hardener X-3670S (manufactured by ARC Corporation), Amicure PN-23, PN-31, PN-40, MY-24 (Ajinomoto Fine Techno)
  • Commercial products such as NOVACURE HX-3742, HX-3721, HX-3722, HX-3088, HX-3741 (manufactured by Asahi Kasei E-Materials Co., Ltd.).
  • the “amine adduct” as a component of the sealant of the present invention mentioned here is a reaction product of (a) an epoxy resin and (b) amines obtained by subjecting the sealant to a thermosetting process. It does not contain amine adducts as one of the above. Although not intending to be bound by theory, this amine adduct is added primarily for the purpose of lowering the temperature of thermosetting, so it needs to be in the form of an adduct before being subjected to thermosetting.
  • These amine adducts are preferably used by being finely dispersed in the particle size (a) and uniformly dispersed in the epoxy resin so as to act as a latent curing agent.
  • the average particle size of the amine adduct obtained by chemically reacting polyfunctional amines or this with an epoxy resin is the cell gap of the photoelectric conversion element (the distance between the first conductive support and the second conductive support). When the two substrates (conductive support) of the photoelectric conversion elements are bonded together, the gap can be formed successfully. Therefore, the average particle diameter may be usually not more than the cell gap, preferably not more than 15 ⁇ m, more preferably not more than 12 ⁇ m, and still more preferably not more than 9 ⁇ m.
  • the particle size of these amines can be measured, for example, with a laser diffraction / scattering particle size distribution analyzer (dry type) (LMS-30, manufactured by Seishin Enterprise Co., Ltd.).
  • thermosetting agent contained in the sealant of the present invention at least one of guanamines and / or imidazoles and at least one of other amines (preferably the above-mentioned amine adduct) are used in combination. May be.
  • the guanamines that can be used in combination are not particularly limited, and examples thereof include dicyandiamide, o-toluyl biguanide, acetoguanamine, benzoguanamine, and phenylacetoguanamine.
  • Imidazoles that can be used in combination are not particularly limited, and examples thereof include 2-ethylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2 -Undecylimidazole, 2,4-dicyano-6 (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4-dicyano-6 (2'-undecylimidazole (1')) ethyl- Examples thereof include s-triazine.
  • thermosetting agent is preferably a combination of an amine adduct and guanamines or imidazoles, more preferably a combination of an amine adduct and imidazoles, and most preferably a combination of an amine adduct and 2-undecylimidazole.
  • thermosetting agents that can be used in combination include, for example, phenol-formaldehyde polycondensate, cresol-formaldehyde polycondensate, hydroxybenzaldehyde-phenol polycondensate, cresol-naphthol-formaldehyde polycondensate, resorcin-formaldehyde polycondensation.
  • thermosetting agents that can be used in combination may be used, or two or more of them may be used in combination.
  • the amount of these thermosetting agents that can be used in combination is usually 0% by mass or more and 50% by mass or less, preferably 30% by mass or less, based on the total amount of (b) the thermosetting agent in the sealing agent of the present invention.
  • the sealant does not contain a thermosetting agent (other than amines) that can be used in combination.
  • the thermosetting agent of the sealant consists only of amines (particularly preferably amine adducts) or only guanamines or imidazoles and other amines (particularly preferably amine adducts). It's okay.
  • thermosetting agent used for the sealing agent for photoelectric conversion elements of this invention is used for the sealing agent for photoelectric conversion elements of this invention
  • the active hydrogen in the thermosetting agent is usually 0.8 to 3.0 equivalents, preferably 0.8 to 2.5 equivalents, more preferably 0.8 to 2.0 equivalents, still more preferably 0.8.
  • the amount is 9 to 2.0 equivalents, most preferably 0.9 to 1.8 equivalents.
  • the active hydrogen here means a hydrogen atom bonded to a hetero atom of a thermosetting agent capable of reacting with an epoxy group of the epoxy resin.
  • the sealing agent for photoelectric conversion elements of the present invention is either a polythiol compound having two or more thiol groups in the molecule and a polyhydrazide compound having two or more hydrazide groups in the molecule as a curing agent, or It may not include both.
  • the sealing agent for photoelectric conversion elements of the present invention can contain (c) a filler as necessary.
  • a filler as necessary.
  • Specific examples of the filler (c) used include fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina (aluminum oxide) ), Magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, hydrous magnesium silicate, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc. Is mentioned.
  • hydrous magnesium oxalate calcium carbonate, aluminum oxide, crystalline silica, fused silica and the like.
  • surface treatment such as chemical treatment.
  • the surface treatment can be performed, for example, with an organic compound such as a silane coupling agent. Any one of these fillers may be used, or two or more kinds may be mixed and used.
  • the filler (c) that can be contained in the sealant of the present invention preferably has an average particle size of 50 ⁇ m or less, more preferably an average particle size of 40 ⁇ m or less, and even more preferably an average particle size of 30 ⁇ m or less.
  • the average particle diameter of the filler is, for example, a particle diameter in which the accumulation from the smaller particles becomes 50% by mass in a particle diameter distribution curve measured using a laser diffraction / scattering particle size analyzer. It is.
  • the content in the case of using the filler is usually 0 to 60% by mass, preferably 5 to 60% by mass, more preferably 15 to 50% by mass in the sealing agent for photoelectric conversion elements of the present invention. .
  • the content of the filler is 60% by mass or less, it is possible to form an appropriate cell gap for holding the charge transfer layer when a photoelectric conversion element is formed.
  • silane coupling agent can be used for the photoelectric conversion element sealing agent of the present invention in order to improve the adhesive strength.
  • Any silane coupling agent can be used as long as it improves the adhesive strength between the sealing agent and the conductive support.
  • Specific examples of silane coupling agents that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, glycidylmethoxysilanes such as 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3 -Aminopropylmethyldimethoxysilane, 3-aminopropylmethyl
  • glycidyl ethoxysilanes or glycidyl methoxysilanes are preferable.
  • a silane coupling agent having an amino group is preferable for obtaining good adhesive strength.
  • N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropyl are more preferable.
  • silane coupling agents may be used alone or in combination of two or more.
  • the content of the silane coupling agent used in the present invention is usually 0 to 2% by mass or less, preferably 0.1 to 2% by mass, more preferably 0.2 to 1% in the sealing agent for photoelectric conversion elements of the present invention. 0.5% by mass.
  • the silane coupling agent used in the present invention is, for example, 0 to 20 parts by mass, typically 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (a). Parts, preferably 0.5 to 10 parts by weight, more preferably 1 to 10 parts by weight, even more preferably more than 1 part by weight and up to 10 parts by weight, most preferably 1.5 to 10 parts by weight. 8 parts by mass.
  • the sealing agent for photoelectric conversion elements of the present invention may contain an organic solvent, an organic filler, a stress relaxation agent and the like as necessary.
  • additives such as pigments, leveling agents, antifoaming agents and viscosity modifiers can be further blended with the sealing agent.
  • Additives that can be blended are not particularly limited, and the amount added may be appropriately selected depending on the purpose. These additives are preferably those having low contamination to the charge transfer layer.
  • the sealing agent for photoelectric conversion elements of the present invention comprises (a) an epoxy resin, (b) a thermosetting agent containing amines, and optionally (c) a filler, (d) a silane coupling agent, and various additives. , In any order, preferably so as to achieve each of the above-mentioned contents, with stirring if necessary, and then by uniformly mixing with a mixing device such as a three roll, sand mill, ball mill, etc. Can do. If necessary, a filtration treatment may be performed to remove impurities after mixing is completed.
  • the sealing agent for photoelectric conversion elements of the present invention is suitable for a method for producing a photoelectric conversion element in which a charge transfer layer is injected from an injection port after two substrates (conductive support) are bonded together. Sealing can be performed by heating and curing a weir of the sealing agent of the present invention sandwiched between two substrates.
  • Examples of the method for applying the sealant of the present invention to a substrate include bar coater methods, dip coating methods, spin coating methods, spray methods, screen printing methods, doctor blade methods, dispensing methods, and the like. Depending on the form, it can be appropriately selected or used in combination. From the viewpoint of productivity, it is preferable to use a spray method, a screen printing method, or a dispensing method.
  • the sealing agent for photoelectric conversion elements of the present invention can be applied to any photoelectric conversion element that can generally convert light energy into electric energy.
  • a lead wire is arranged so that a current generated from the photoelectric conversion element can be taken out, and a closed circuit is taken as a solar cell.
  • the sealing agent for photoelectric conversion elements of the present invention is particularly suitable for producing a dye-sensitized photoelectric conversion element and a solar cell having the photoelectric conversion element.
  • a dye-sensitized photoelectric conversion element includes a first conductive support (oxide semiconductor electrode) having a semiconductor-containing layer sensitized with a dye on the surface, a second conductive support as a counter electrode, The charge transfer layer is configured as a main component.
  • the sealing agent for photoelectric conversion elements of this invention is used in order to adhere
  • the conductive support examples include conductive materials typified by FTO (fluorine-doped tin oxide), ATO (antimony-doped tin oxide), and ITO (indium-doped tin oxide), glass, plastic, polymer film, quartz, silicon, and the like.
  • a thin film on the surface of the substrate is used.
  • the thickness of the substrate is usually 0.01 to 10 mm, and the shape can take various forms from a film shape to a plate shape, but at least one of the two substrates is a light-transmitting substrate.
  • the conductivity of the conductive support is usually 1000 [Omega] / cm 2 or less, preferably 100 [Omega / cm 2 or less.
  • metal chalcogenide fine particles are preferable.
  • TiO 2 , ZnO, and SnO 2 are particularly preferable.
  • These may be used in combination, and a preferred example is a SnO 2 —ZnO mixed system.
  • the components may be mixed in the form of fine particles, mixed in a slurry or paste state described below, or the respective components may be used in layers.
  • the concentration of the oxide semiconductor in the slurry or paste is usually 1 to 90% by mass, preferably 5 to 80% by mass.
  • the primary particle size of the oxide semiconductor used is usually 1 to 200 nm, preferably 1 to 50 nm.
  • the method for preparing a semiconductor-containing layer includes a method of directly forming a thin film made of an oxide semiconductor on a substrate by vapor deposition, a method of applying or coating a slurry or paste on a substrate, and then applying pressure, and a substrate as an electrode. And a method of electrically depositing, applying or coating a slurry or paste on a substrate, drying, curing or firing.
  • the coating or coating method include a bar coater method, a dip coating method, a spin coating method, a spray method, a screen printing method, a doctor blade method, and a dispensing method. These methods can be appropriately selected or used in combination depending on the type and form of the substrate.
  • the slurry is obtained by dispersing finely aggregated oxide semiconductor fine particles in a dispersion medium using a dispersant so that the average primary particle diameter is usually 1 to 200 nm, or by a sol-gel method. It can be obtained by hydrolyzing alkoxide or the like, which is a precursor of an oxide semiconductor.
  • oxide semiconductor particles having different particle size distributions may be mixed and used.
  • the dispersion medium for dispersing the slurry is not particularly limited as long as the oxide semiconductor fine particles can be dispersed.
  • organic solvents such as water, alcohols such as ethanol and terpineol, ketones such as acetone and acetylacetone, and hydrocarbons such as hexane are used. These may be used as a mixture. Use of water is preferable in that the viscosity change of the slurry is reduced.
  • a dispersion stabilizer or the like may be added to the slurry.
  • the dispersion stabilizer to be used include polyhydric alcohols such as polyethylene glycol, monohydric alcohols such as phenol and octyl alcohol, or co-condensates between these; hydroxypropyl methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, Cellulose derivatives such as carboxymethyl cellulose; polyacrylamide; acrylamide, (meth) acrylic acid or its salt, (meth) acrylic acid ester (methyl (meth) acrylate, ethyl (meth) acrylate), etc.
  • Co-condensate a polyacrylic acid derivative that is a water-soluble copolymer of acrylamide, (meth) acrylic acid or a salt thereof, (meth) acrylic acid ester and the like and a hydrophobic monomer such as styrene, ethylene, propylene, etc.
  • Lignin sulfonate of a high molecular weight salt of naphthalenesulfonic acid-formaldehyde condensate; salts of melamine sulfonic acid formaldehyde condensate hydrochloric acid, nitric acid, but such acids such as acetic acid, but is not limited thereto.
  • These dispersion stabilizers may be used alone or in combination of two or more.
  • polyhydric alcohols such as polyethylene glycol, self or co-condensates such as phenol and octyl alcohol, poly (meth) acrylic acid, poly (meth) acrylic acid sodium salt, poly (meth) acrylic acid potassium salt , Lithium poly (meth) acrylate, carboxymethylcellulose, hydrochloric acid, nitric acid, acetic acid and the like are preferable.
  • a baking treatment can be performed at a temperature below the melting point (or softening point) of the substrate used for the conductive support.
  • the firing temperature is usually 100 to 900 ° C., preferably 100 to 600 ° C.
  • the firing time is not particularly limited, but is generally within 4 hours.
  • the thickness of the semiconductor-containing layer provided on the conductive support is usually 1 to 50 ⁇ m.
  • the semiconductor-containing layer may be subjected to secondary treatment (see Non-Patent Document 1).
  • a conductive support in which a thin film of a semiconductor-containing layer prepared by the above method is provided in a solution of the same metal alkoxide or chloride, nitride, sulfide, etc., used for the preparation of the semiconductor-containing layer
  • the smoothness of the semiconductor-containing layer can be enhanced by directly immersing and drying the body, or optionally further firing (re-firing) as described above.
  • examples of the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyltin, and an alcohol solution thereof is used.
  • chloride for example, titanium tetrachloride, tin tetrachloride, zinc chloride and the like can be mentioned, and an aqueous solution thereof is used.
  • the specific surface area of the semiconductor-containing layer comprising oxide semiconductor fine particles obtained in this manner is usually 1 to 1000 m 2 / g, preferably 10 to 500 m 2 / g.
  • the sensitizing dye is not particularly limited as long as it has a function of sensitizing light absorption together with the semiconductor fine particles constituting the semiconductor-containing layer.
  • a metal complex dye containing a metal element such as ruthenium or an organic dye not containing a metal may be used alone, or several kinds may be mixed and used at an arbitrary ratio.
  • any of a plurality of types of metal complex dyes, a plurality of types of organic dyes, and a combination of a metal complex dye and an organic dye may be used. By mixing a plurality of types of dyes having different absorption wavelength regions, a wide absorption wavelength can be used, and a solar cell with high conversion efficiency can be obtained.
  • the metal complex dye that can be supported is not particularly limited, but phthalocyanine, porphyrin, and the like are preferable, and a ruthenium complex is more preferable.
  • organic dyes that can be supported such as metal-free phthalocyanines, porphyrins and cyanines, merocyanines, oxonol, triphenylmethane, acrylic acid dyes, pyrazolone methine dyes, and other xanthene dyes. Azo-type, anthraquinone-type, and perylene-type dyes.
  • each dye in the case of using a mixture of plural kinds of dyes is not particularly limited, but in general, it is preferable to use each dye at least about 10 mol% or more.
  • the total concentration of the dyes in the solution may be the same as when only one kind is supported.
  • the solvents described above with respect to the oxide semiconductor can be used, and the solvents for the respective dyes to be used may be the same or different.
  • Examples of the method of supporting the sensitizing dye include a method of immersing the conductive support provided with the semiconductor-containing layer in a solution obtained by dissolving the dye in a solvent or a dispersion obtained by dispersing the dye in the solvent.
  • concentration of the dye in the solution or dispersion may be determined as appropriate depending on the type and solubility of the dye.
  • the immersion temperature is generally from room temperature to the boiling point of the solvent, and the immersion time may be about 1 hour to 72 hours.
  • Specific examples of the solvent that can be used to dissolve the sensitizing dye include methanol, ethanol, acetone, acetonitrile, dimethyl sulfoxide, dimethylformamide, t-butanol, tetrahydrofuran and the like.
  • the concentration of the sensitizing dye in the solution is usually 1 ⁇ 10 ⁇ 6 M to 1M, preferably 1 ⁇ 10 ⁇ 5 M to 1 ⁇ 10 ⁇ 1 M.
  • the dye When the dye is supported on the semiconductor-containing layer, it is effective to support the dye in the presence of the inclusion compound in order to prevent the association of the dye particles.
  • the clathrate compound include steroidal compounds such as cholic acid, crown ether, cyclodextrin, calixarene, polyethylene oxide and the like. Preferred are cholic acid, deoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester, cholic acids such as sodium cholate and ursodeoxycholic acid, polyethylene oxide and the like.
  • these inclusion compounds they may be added to the dye solution, or the dye may be dissolved or dispersed after the inclusion compound is dissolved in a solvent in advance.
  • the semiconductor-containing layer may be treated with an amine compound such as 4-t-butylpyridine.
  • an amine compound such as 4-t-butylpyridine.
  • the treatment method for example, a method of immersing a conductive support provided with a semiconductor-containing layer carrying a dye in an ethanol solution of an amine compound is employed.
  • the counter electrode is formed by depositing conductive fine particles such as platinum, carbon, rhodium, ruthenium, etc., which act catalytically on the reduction reaction of the redox electrolyte, on the surface of a conductive support such as FTO conductive glass, or the like.
  • conductive fine particles such as platinum, carbon, rhodium, ruthenium, etc.
  • coated and baked the precursor of electroconductive fine particles are used.
  • the conductive support (oxide semiconductor electrode) and the counter electrode having the semiconductor-containing layer sensitized with the dye obtained as described above are used for the photoelectric conversion element sealing agent of the present invention.
  • a method of bonding will be described.
  • the sealant of the present invention to which a spacer (gap control material) is added is dispensed by a dispenser, a screen printing machine, etc., leaving the injection port of the charge transfer layer at the periphery of the conductive surface of one of the conductive supports.
  • the other conductive support can be overlaid and heated to cure the sealant so that the conductive surfaces of the first and second conductive supports face each other.
  • the spacer for example, glass fiber, silica beads, polymer beads and the like, and fine particles coated with metal such as gold pearl and silver pearl are used.
  • the average diameter varies depending on the purpose, but is usually 1 to 100 ⁇ m, preferably 10 to 40 ⁇ m.
  • the amount used is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, and more preferably 1 to 2.5 parts by weight with respect to 100 parts by weight of the sealant of the present invention.
  • the heat curing conditions for the sealant are usually 80 to 120 ° C. for 1 to 3 hours.
  • the gap between the first and second conductive supports is usually 1 to 100 ⁇ m, preferably 4 to 50 ⁇ m.
  • the dye-sensitized photoelectric conversion element of the present invention is completed by injecting a charge transfer layer into the gap between the pair of conductive supports bonded together as described above.
  • a charge transfer layer a solution in which a redox electrolyte pair, a hole transport material, or the like is dissolved in a solvent or a room temperature molten salt (ionic liquid) is used.
  • the redox electrolyte used include halogen compounds having halogen ions as counter ions and halogen redox electrolytes composed of halogen molecules, metals such as ferrocyanate-ferricyanate, ferrocene-ferricinium ions, and cobalt complexes.
  • Examples thereof include metal redox electrolytes such as complexes, and organic redox electrolytes such as alkylthiol-alkyl disulfides, viologen dyes, and hydroquinone-quinones.
  • a halogen redox electrolyte is preferred.
  • Examples of halogen molecules in the halogen redox electrolyte include iodine molecules and bromine molecules, and iodine molecules are preferable.
  • Examples of the halogen compound include metal halide salts such as LiI, NaI, KI, CsI, CaI 2 and CuI, tetraalkylammonium iodide, imidazolium iodide, 1-methyl-3-alkylimidazolium iodide.
  • organic quaternary ammonium salts of halogen such as pyridinium iodide.
  • Salt compounds having iodine ions as counter ions are preferred. Specific examples thereof include lithium iodide, sodium iodide, trimethylammonium iodide salt and the like. These may be used alone or in combination of two or more.
  • an electrochemically inert solvent is used as the solvent.
  • the solvent used include acetonitrile, valeronitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, 3-butoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dimethoxy.
  • the concentration of the redox electrolyte in the solution is usually 0.01 to 99% by mass, preferably 0.1 to 90% by mass.
  • a solvent used as a solvent is a room temperature melt (ionic liquid).
  • the room temperature melt used include 1-methyl-3-alkylimidazolium iodide, vinylimidazolium tetrafluoride, 1-ethylimidazolesulfonate, alkylimidazolium trifluoromethylsulfonylimide, 1-methyl Examples thereof include pyrrolidinium iodide.
  • a low molecular gelling agent is dissolved in the charge transfer layer to increase the viscosity, or the charge transfer layer combined with the reactive component is reacted after injection. It is possible to obtain a gel electrolyte by gelling, or by impregnating a charge transfer layer into a previously polymerized gel.
  • a hole transport material or a P-type semiconductor can be used instead of the redox electrolyte.
  • the hole transport material used include conductive polymers such as amine derivatives, polyacetylene, polyaniline, and polythiophene.
  • the P-type semiconductor include CuI and CuSCN.
  • a photoelectric conversion element can be obtained by injecting the charge transfer layer into the gap between the pair of conductive supports and then sealing the injection port of the charge transfer layer.
  • a sealing material for sealing the injection port of the charge transfer layer, isobutylene resin, epoxy resin, UV curable acrylic resin, or the like can be used.
  • the following method can also be adopted as another method for producing a photoelectric conversion element. That is, a sealant weir is provided in the periphery of the conductive surface of one of the conductive supports without providing the charge transfer layer injection port, and then the same charge transfer layer as described above is placed inside the sealant weir. Place and paste the other conductive support so that the conductive surfaces of the first and second conductive supports face each other under reduced pressure, form a gap at the same time, and then cure the sealant Thus, a photoelectric conversion element can be obtained.
  • FIG. 1 is a schematic cross-sectional view of the relevant part for explaining the structure of a dye-sensitized photoelectric conversion element prepared using the sealant of the present invention.
  • 1 is a conductive support having conductivity inside
  • 2 is a semiconductor-containing layer sensitized by a dye (1 and 2 are collectively referred to as an oxide semiconductor electrode)
  • 3 is a conductive support.
  • 4 is a charge transfer layer disposed in a gap between a pair of conductive supports
  • 5 is a sealant of the present invention
  • 6 is a glass substrate.
  • the solar cell of this invention can be obtained by arrange
  • the sealing material of the present invention can also be applied to the production of a large-area dye-sensitized solar cell module in which a plurality of dye-sensitized solar cells arranged in a plane are electrically connected in series.
  • a large-area dye-sensitized solar cell module in which a plurality of dye-sensitized solar cells arranged in a plane are electrically connected in series.
  • module structures for dye-sensitized solar cells with a large area are known.
  • the sealant of the present invention can be used for any kind of module structure. For example, it can also be used for a dye-sensitized solar cell module having a series connection structure described in International Publication No. WO2009 / 057704.
  • the sealing agent for photoelectric conversion elements of the present invention is excellent in coating workability, bonding properties, adhesive strength, usable time at room temperature (pot life), and low-temperature curability in the manufacturing process of photoelectric conversion elements, Very low contamination to the charge transfer layer. Therefore, the photoelectric conversion element of the present invention obtained using the sealant is free from malfunction due to contamination of the charge transfer layer, and is excellent in adhesion and moisture resistance reliability. And the solar cell prepared using this photoelectric conversion element can be manufactured efficiently, and is excellent in its durability.
  • Example 1 As an epoxy resin, RE-310S (trade name, bisphenol A type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 185 g / eq., Hydrolyzed chlorine amount of 400 ppm or less) was added to 90 parts by mass of EP-1001 (trade name) Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 475 g / eq.) 10 parts by mass was added and dissolved by heating.
  • RE-310S trade name, bisphenol A type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 185 g / eq., Hydrolyzed chlorine amount of 400 ppm or less
  • thermosetting agent 31 (trade name, epoxy resin amine adduct, manufactured by Ajinomoto Fine Techno Co., Ltd., average particle size 8.8 ⁇ m) 20 parts by mass, and further mixed and dispersed by three rolls, the sealing agent for photoelectric conversion elements of the present invention (1) was obtained. It was 73 Pa * s when the viscosity at 25 degrees C of this sealing agent (1) was measured with the E-type viscosity meter.
  • This solution was cooled to room temperature and then (b) finely pulverized with a jet mill of isophthalic acid dihydrazide as a thermosetting agent (melting point 224 ° C., active hydrogen equivalent 48.5 g / eq., Average particle size 1.7 ⁇ m). (Maximum particle size 7 ⁇ m) 19 parts by mass, (c) 90 parts by mass of alumina having an average particle size of 0.5 ⁇ m or less and 3.5 parts by mass of fumed silica as a filler were added and mixed by three rolls.
  • Example 2 90 parts by mass of (a) RE-310S in Example 1 was changed to 80 parts by mass, and a new multifunctional epoxy resin EPPN-501 (trade name, trisphenol methane novolak type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., 10 parts of epoxy equivalent 165 g / eq., Amount of hydrolyzed chlorine of 550 ppm or less) (d) 1 part by weight of KBM-403 was changed to 3 parts by weight as a silane coupling agent, and (b) as a thermosetting agent A sealing agent (3) for photoelectric conversion elements of the present invention was obtained in the same manner as in Example 1 except that 3 parts by mass of C11Z (trade name, 2-undecylimidazole, manufactured by Shikoku Kasei Co., Ltd.) was added. It was 278 Pa * s when the viscosity at 25 degrees C of this sealing agent (3) was measured with the E-type viscosity meter.
  • EPPN-501 trade name, trisphenol methan
  • Example 3 90 parts by mass of (a) RE-310S in Example 1 was changed to 80 parts by mass, and a new multifunctional epoxy resin EPPN-501 (trade name, trisphenol methane novolak type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., (Epoxy equivalent 165 g / eq., Hydrolyzed chlorine content 550 ppm or less) Except for adding 10 parts, a sealing agent (4) for photoelectric conversion elements of the present invention was obtained in the same manner as in Example 1. It was 443 Pa.s when the viscosity at 25 degrees C of this sealing agent (4) was measured with the E-type viscosity meter.
  • EPPN-501 trade name, trisphenol methane novolak type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., (Epoxy equivalent 165 g / eq., Hydrolyzed chlorine content 550 ppm or less
  • Example 4 In the same manner as in Example 1 except that 1 part by mass of KBM-403 is changed to 3 parts by mass as (d) the silane coupling agent in Example 1, a sealing agent (5) for photoelectric conversion elements of the present invention is obtained. It was. It was 31 Pa * s when the viscosity at 25 degrees C of this sealing agent (5) was measured with the E-type viscosity meter.
  • Example 5 The photoelectric conversion element of the present invention is the same as Example 1 except that 3 parts by mass of C11Z (trade name, 2-undecylimidazole, manufactured by Shikoku Kasei Co., Ltd.) is added as the thermosetting agent in Example 1 (b). A sealing agent (6) was obtained. The viscosity of this sealing agent (6) at 25 ° C. was 80 Pa ⁇ s as measured with an E-type viscometer.
  • C11Z trade name, 2-undecylimidazole, manufactured by Shikoku Kasei Co., Ltd.
  • the shear bond strength was measured by the following method. 1 part by mass of glass fiber having a diameter of 50 ⁇ m was added as a spacer to 100 parts by mass of each sealing agent, and mixed and stirred. This sealant is applied onto a 50 mm ⁇ 50 mm conductive support (FTO glass substrate) with a dispenser, and the solvent is volatilized by heating with a hot plate, and then the sealant on the conductive support is 2 mm ⁇ 2 mm. Glass pieces were bonded together and cured at 100 ° C. for 1 hour, and the shear strength of the obtained test pieces was measured.
  • the solvent swelling degree was measured by the following method. Each sealant was applied onto a heat-resistant film using an applicator (film thickness 200 ⁇ m) and cured under conditions of 100 ° C. for 1 hour. Four punched test pieces were produced by applying a 3 cm ⁇ 3 cm punch blade to the obtained cured film. After measuring the mass of each test piece (mass before immersion), it was placed in a pressure vessel together with 3-methoxypropionitrile (3MPN), and the pressure vessel was heated at 85 ° C. for 2 hours. After the heating, the pressure vessel was cooled to room temperature, 3MPN adhering to the taken-out test piece was wiped off, and the mass of the test piece (mass after immersion) was measured. The mass increase rate before and after solvent immersion was calculated from ⁇ (mass after immersion / mass before immersion) -1 ⁇ ⁇ 100, and the average value of the mass increase rates of the four sheets was taken as the degree of swelling (%).
  • the sealing agents (1), (4), (5) and (6) of the present invention showed higher adhesive strength than the sealing agent (2).
  • the sealing agent (3) of the present invention showed a lower degree of solvent swelling than the sealing agent (2).
  • the sealing agent for photoelectric conversion elements of the present invention is excellent in coating workability, bonding properties, adhesive strength, usable time at room temperature (pot life), and low-temperature curability in the manufacturing process of photoelectric conversion elements, Very low contamination to the charge transfer layer.
  • the photoelectric conversion element of the present invention obtained using such a sealant has no malfunction due to contamination of the charge transfer layer, and has excellent adhesion and moisture resistance reliability.
  • a performance defect does not arise and productivity can be improved.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Sealing Material Composition (AREA)
  • Photovoltaic Devices (AREA)
  • Hybrid Cells (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne un produit d'étanchéité pour élément de conversion photoélectrique, caractérisé en ce qu'il contient (a) une résine époxy et (b) une amine comme agent thermodurcissable. Le produit d'étanchéité pour élément de conversion photoélectrique peut contenir l'agent thermodurcissable (b) dans une quantité à laquelle la teneur en hydrogène actif dans l'agent thermodurcissable (b) est de 0,8 à 3,0 équivalents pour 1 équivalent de groupes époxy dans la résine époxy (a). L'agent thermodurcissable (b) peut être un adduit amine. L'agent thermodurcissable (b) peut comprendre au moins deux amines comprenant le 2-undecylimidazole. Le produit d'étanchéité pour élément de conversion photoélectrique peut contenir (c) une charge. La charge (c) peut être une ou plusieurs substances choisies dans le groupe constitué par le silicate de magnésium hydraté, le carbonate de calcium, l'oxyde d'aluminium, la silice cristalline et la silice fondue, et peut avoir un diamètre de particules moyen inférieur ou égal à 50 µm. Le produit d'étanchéité pour élément de conversion photoélectrique peut contenir (d) un agent de couplage silane.
PCT/JP2016/083289 2015-11-09 2016-11-09 Produit d'étanchéité Ceased WO2017082319A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002368236A (ja) * 2001-06-04 2002-12-20 Nippon Kayaku Co Ltd シール剤
WO2007007671A1 (fr) * 2005-07-07 2007-01-18 Nippon Kayaku Kabushiki Kaisha Agent d’étanchéité pour convertisseur photoélectrique et convertisseur photoélectrique utilisant ledit agent
WO2010084939A1 (fr) * 2009-01-23 2010-07-29 味の素株式会社 Composition de résine
WO2015068787A1 (fr) * 2013-11-08 2015-05-14 味の素株式会社 Composition de resine d'etancheite contenant de l'hydrotalcite et feuille d'etancheite

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JP4918975B2 (ja) 2005-09-21 2012-04-18 株式会社スリーボンド 色素増感型太陽電池用シール剤
KR101156534B1 (ko) * 2009-12-28 2012-06-20 삼성에스디아이 주식회사 광전변환소자
JP2014120431A (ja) * 2012-12-19 2014-06-30 Nippon Kayaku Co Ltd 色素増感型太陽電池用シール剤及びそれを用いた色素増感太陽電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002368236A (ja) * 2001-06-04 2002-12-20 Nippon Kayaku Co Ltd シール剤
WO2007007671A1 (fr) * 2005-07-07 2007-01-18 Nippon Kayaku Kabushiki Kaisha Agent d’étanchéité pour convertisseur photoélectrique et convertisseur photoélectrique utilisant ledit agent
WO2010084939A1 (fr) * 2009-01-23 2010-07-29 味の素株式会社 Composition de résine
WO2015068787A1 (fr) * 2013-11-08 2015-05-14 味の素株式会社 Composition de resine d'etancheite contenant de l'hydrotalcite et feuille d'etancheite

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