KR20180081725A - Seal - Google Patents

Abstract

The present invention relates to a sealant for an optoelectronic conversion element, which comprises (a) an epoxy resin and (b) an amine as a heat curing agent. The sealing agent for optoelectronic conversion elements may contain (b) a thermosetting agent in an amount such that (a) 0.8 to 3.0 equivalents of active hydrogen in (b) the thermosetting agent is added to 1 equivalent of the epoxy group in the epoxy resin. (b) The thermosetting agent may be an amine adduct. The thermosetting agent (b) may contain at least two amines including 2-undecylimidazole. The sealing agent for the optoelectronic conversion element may contain (c) a filler. (c) The filler may be one or more kinds selected from the group consisting of hydrated magnesium silicate, calcium carbonate, aluminum oxide, crystalline silica and fused silica, and the average particle diameter thereof may be 50 탆 or less. The sealing agent for the optoelectronic conversion element may contain (d) a silane coupling agent.

Description

Seal

The present invention relates to a sealant particularly suitable for the production of a photoelectric conversion element, which has excellent adhesiveness under low-temperature curing conditions.

Solar cells, which are attracting attention as a clean energy source, have recently been used for general residential use, but they have not yet reached a sufficient level of supply. The reason for this is that it is difficult to say that the solar cell itself has sufficiently excellent power generation performance, so that it is difficult to increase the module size, and the productivity in module manufacture is low, and as a result, And the like.

Photoelectric conversion elements used in solar cells are generally formed by protecting a photoelectric conversion material such as silicon, gallium-arsenic and copper-indium-selenium with a transparent protection material on the top and a substrate protection material on the bottom, Fixed and packaged. For this reason, the sealant used in the production of the photoelectric conversion element is required to have good adhesiveness to the upper and lower protective materials, and excellent flexibility and durability.

For example, an ethylene-vinyl acetate copolymer having a high vinyl acetate content has been used as a sealing agent for a photoelectric conversion element in a solar cell module from the viewpoints of flexibility and transparency. However, since the copolymer is insufficient in heat resistance and adhesiveness, it is necessary to use an organic peroxide or the like for the purpose of further promoting the copolymerization reaction. In this case, a two-step process is required in which a sheet of the ethylene-vinyl acetate copolymer in which these organic peroxides are blended is first prepared, and then the photoelectric conversion material is sealed using this sheet. In the sheet production step, it is necessary to perform molding at a low temperature such that the organic peroxide is not decomposed, so that the extrusion rate can not be increased. On the other hand, in the step of sealing the photoelectric conversion material (curing and bonding), a step of temporarily bonding the substrate with the laminator for several minutes to several tens of minutes, It is necessary to carry out a two-step process consisting of a step of bonding over time. Therefore, there is a problem in that labor and time are required for the production of the photoelectric conversion element, and the adhesiveness and humidity resistance reliability are not sufficient. The solar cell module and the solar cell using such a photoelectric conversion element are expensive and can not satisfy their performance.

Further, when a copolymer of the above-mentioned copolymer and an ionomer having a low melting point is used as a sealing material for a photoelectric conversion element, the heat resistance is insufficient and there is a risk of being deformed due to a rise in temperature at the time of use as a solar cell. Further, when the photoelectric conversion element is manufactured by a hot pressing method, these sealing materials may flow out more than necessary, which may cause burrs. In addition, with the recent increase in the size of the photoelectric conversion element, the stress applied to the seal portion during the processing process is remarkably larger than that of the prior art, and the seal line length is also increased. From these viewpoints, it is necessary to develop a coating type sealing agent which is excellent in moisture and humidity reliability, can narrow the line width of the seal, can make the intervals between the conductive supports uniform, and has excellent adhesion and flexibility. .

On the other hand, a method of using a thermosetting epoxy resin as a sealant has been studied (Patent Document 1). In this case, the sealing agent is applied to a conductive support by a method such as dispenser or screen printing, leveling is performed without heating or heating, then the upper and lower conductive supports are bonded using alignment marks, Has been produced. As the curing agent of the thermosetting epoxy resin used herein, a phenol novolac resin is used. However, such a sealing agent for a photoelectric conversion element is inferior in adhesion performance to a long-term sealing property under high temperature and high humidity, and has a problem that an electrolyte is leaked. Further, there is also a problem that a manufacturing load is large, for example, a high temperature of 120 DEG C or more is required at the time of sealing hardening. As a method for solving this problem, Patent Document 2 discloses a resin composition using a hydrogenated bisphenol type epoxy resin. However, in this case too, long-term sealing property under high temperature and high humidity can not be given, and an event that an electrolyte is leaked appears.

Japanese Patent Application Laid-Open No. 2002-368236 Japanese Patent Application Laid-Open No. 2007-087684

 C. J. Barbe, F. Arendse, P. Compt and M. Graetzel J. Am. Ceram. Soc., 80, 12, 3157-71 (1997).

It is an object of the present invention to provide a photoelectric conversion element which is easy to bond the upper and lower conductive supports at the time of manufacturing the photoelectric conversion element and which is excellent in curing at a low temperature and in the adhesive strength of the obtained sealing portion, And the like. That is, an object of the present invention is to provide a sealant particularly suitable for manufacturing a photoelectric conversion element.

As a result of intensive studies, the inventors of the present invention have found that a resin composition having a specific composition solves the above problems, and has accomplished the present invention.

That is, each aspect of the present invention is as follows.

[One]. A sealant for optoelectronic conversion element characterized by containing amines as (a) an epoxy resin and (b) a thermosetting agent.

[2]. The optoelectronic conversion element seal (1) according to the above item (1), which contains the thermosetting agent (b) in an amount such that the active hydrogen in the thermosetting agent is 0.8 to 3.0 equivalents relative to 1 equivalent of the epoxy group in the epoxy resin .

[3]. The sealant for a photoelectric conversion element according to the above [1] or [2], wherein the thermosetting agent (b) is an amine adduct.

[4]. 1] to [3], wherein the thermosetting agent (b) comprises at least two amines including at least one of guanamine and / or imidazoles and at least one other amine. Wherein the photoelectric conversion element is a transparent electrode.

[5]. The sealant for a photoelectric conversion element according to the above item [4], wherein the imidazoles include 2-undecylimidazole.

[6]. The sealant for a photoelectric conversion element according to any one of (1) to (5) above, which contains (c) a filler.

[7]. (c) the filler is one or more selected from the group consisting of hydrated magnesium silicate, calcium carbonate, aluminum oxide, crystalline silica and fused silica, and the average particle diameter of the filler is not more than 50 占 퐉, ] The sealant for a photoelectric conversion element according to item [

[8]. (d) a sealing agent for a photoelectric conversion element according to any one of [1] to [7], which contains a silane coupling agent.

[9]. (d) a sealant for a photoelectric conversion element according to the above item [8], wherein the silane coupling agent is glycidylethoxysilane or glycidylmethoxysilane.

[10]. A first conductive support having a semiconductor-containing layer, a second conductive support having an opposing electrode formed at a position where the semiconductor-containing layer and the counter electrode are opposed to each other at a predetermined interval, a charge transfer layer sandwiched between the first and second conductive support, And a seal which is formed at a peripheral portion of the first and second conductive supports and surrounds the charge transfer layer, wherein the seal is a photoelectric conversion element according to any one of the items [1] to [9] Wherein the photoelectric conversion element is a seal formed of a sealant.

[11]. A solar cell comprising the photoelectric conversion element according to the item [10].

Since the sealant for photoelectric conversion element of the present invention contains amines (preferably amine adduct) as a heat curing agent, it is preferable that the sealing performance, bonding property, adhesive strength, , And is excellent in low temperature curability. Therefore, the staining property to the charge transport layer in the manufacturing process of the photoelectric conversion element is very low. The photoelectric conversion element of the present invention obtained by using such a sealant is excellent in adhesiveness and humidity resistance reliability with less deterioration of power generation performance due to contamination of the charge transport layer. Further, when the photoelectric conversion element is manufactured using the photoelectric conversion element of the present invention, it is possible to manufacture the element with low performance and high reliability in a short time without causing a performance failure, Thereby enabling improvement.

1 is a schematic cross-sectional view of a main part for explaining the structure of a dye-sensitized photoelectric conversion element prepared using the sealant of the present invention.

(Mode for carrying out the invention)

The photoelectric conversion element sealing agent for a photoelectric conversion element of the present invention (hereinafter sometimes referred to simply as a "sealing agent") is a curable resin composition for an optoelectronic conversion element containing (a) an epoxy resin and (b) an amine as a heat curing agent. The sealing material preferably includes a first conductive support having a semiconductor-containing layer, a second conductive support having an opposing electrode formed at a position where the semiconductor-containing layer and the opposing electrode face each other at a predetermined interval, And a seal which is formed in the peripheral portion of the first and second conductive supports and surrounds the charge transfer layer, and is used as a raw material of the seal.

The sealant of the present invention refers to a composition before being subjected to a heat curing process unless otherwise specified.

As the epoxy resin (a) used in the present invention, an epoxy resin having at least two or more epoxy groups in one molecule is generally used. Examples of such epoxy resins include novolak type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, and triphenylmethane type epoxy resins. More specifically, there may be mentioned bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'- - [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis -Hydroxyphenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, Hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (Methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene and 1,4-bis (methoxymethyl) benzene, and modifications thereof, tetrabromobisphenol Do something like A There may be mentioned solid or liquid epoxy resins such as glycidyl ether compounds derived from glycidyl ether bisphenols, glycidyl ether compounds derived from alcohols, alicyclic epoxy resins, glycidyl amine type epoxy resins and glycidyl ester type epoxy resins. It is not. These may be used alone, or two or more of them may be used in combination. These epoxy resins are advantageous for lowering the viscosity of the photoelectric conversion element sealant of the present invention and can have a function of enabling a bonding operation at room temperature and facilitating formation of a gap. Among these epoxy resins, the use of a novolak type epoxy resin and / or a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin is preferable, and a combination use of a novolak type epoxy resin and a bisphenol A type epoxy resin desirable. It is also preferable to use a combination of two kinds of epoxy resins different in epoxy equivalent. In one embodiment, a mixture of 30 to 300 g / eq. Of epoxy resin and 200 to 600 g / eq. Of epoxy resin may be used. In an embodiment of the present invention, there is provided an epoxy resin composition comprising 30 to 300 g / eq. Of a novolak type epoxy resin and / or a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin, 200 to 600 g / eq. / Or a mixture of a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin may be used.

It is preferable that the sealing agent of the present invention has as little hydrolyzable chlorine contained in the sealing agent as possible in order to minimize contamination of the charge transporting layer by the sealing agent. Therefore, the amount of the hydrolyzable chlorine contained in the epoxy resin (a) is preferably 600 ppm or less, more preferably 500 ppm or less, more preferably 400 ppm or less, even more preferably 300 ppm or less, more preferably 200 ppm or less Most preferably 100 ppm or less, 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, titrating with 0.01 N silver nitrate solution .

The content of the epoxy resin (a) in the sealing agent of the present invention is usually 5 to 80 mass%, preferably 10 to 70 mass%, and more preferably 20 to 60 mass%.

The sealant of the present invention contains (b) amines as a heat curing agent. These amines are not particularly limited, but multifunctional amines having two or more amino groups in the molecule are preferably used. Specific preferred examples of polyfunctional amines having two or more amino groups in the molecule include diamines such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, linolenic acid dimer and ethylenediamine A polyamide resin to be synthesized, and an amine duct. One particularly preferred amine is an amine adduct.

As the heat curing agent in the present invention, a curing agent which enables seal curing at less than 120 ° C can be preferably used. More preferably, a curing agent which enables seal curing at a temperature lower than 110 ° C can be used. More preferably less than 105 ° C, and most preferably about 100 ° C or less (or at 100 ° C or less), which enables seal curing.

The amine adduct is an amine compound obtained by chemically reacting an epoxy resin with polyfunctional amines. As concrete examples of the amine duct, there can be mentioned a product name, Hardener X-3661S, Hardener X-3670S (manufactured by A-Si Aluminum), Amicure PN-23, PN-31, PN-40, MY- Nova Cure HX-3742, HX-3721, HX-3722, HX-3088 and HX-3741 (manufactured by Asahi Kasei Chemicals Co., Ltd.).

The term " amine adduct " as a sealant component of the present invention referred to here means an amine adduct as one of reaction products of (a) epoxy resin and (b) amine obtained by subjecting a sealant to a heat- . Although not intending to be bound by theory, this amine adduct is added mainly for the purpose of lowering the temperature of the heat curing, and therefore it is necessary to form the adduct before it is thermally cured.

It is preferable that these amine ducts are dispersed uniformly in the epoxy resin (a) so as to function as a latent curing agent. The average particle diameter of the amine adduct obtained by chemical reaction between the polyfunctional amine or epoxy resin and the polyfunctional amine is prevented from becoming excessively larger than the cell gap of the photoelectric conversion element (the distance between the first conductive support and the second conductive support) (Electroconductive substrate) of the present invention can be smoothly formed. Therefore, the average particle diameter thereof is usually not more than the cell gap, preferably not more than 15 mu m, more preferably not more than 12 mu m, further preferably not more than 9 mu m. The particle diameters of these amines can be measured by, for example, a laser diffraction / scattering type particle size distribution analyzer (dry type) (LMS-30, manufactured by Seishin Kogyo Co., Ltd.).

As the heat curing agent (b) contained in the sealant of the present invention, at least one of guanamine and / or imidazoles and at least one of the other amines (preferably, the amine adduct) may be used in combination good. The guanamine which can be used in combination is not particularly limited, and examples thereof include dicyandiamide, o-toluylbiguanide, acetoguanamine, benzoguanamine, and phenylacetoguanamine.

Examples of imidazoles that can be used in combination include, but are not limited to, 2-ethylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1 2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-dicyano- (1 ')) ethyl-s-triazine, 2,4-dicyano-6 (2'-undecylimidazole . Among them, 2-methylimidazole, 2-undecylimidazole and 2-heptadecylimidazole are preferable. It is more preferable that 2-undecylimidazole is used from the viewpoints of curability at low temperature, pot life, and seal characteristics after curing. As the thermosetting agent (b), it is preferable to use an amine adduct in combination with guanamine or imidazoles, more preferably an amine adduct and an imidazol in combination, and the amine adduct and 2-undecylimidazole Combined use is most preferred.

Examples of other heat curing agents that can be used in combination include phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates, hydroxybenzaldehyde-phenol polycondensates, cresol-naphthol-formaldehyde polycondensates, resorcin- Polyfunctional novolacs such as formaldehyde polycondensate, furfural-phenol polycondensate,? -Hydroxyphenyl-? -Hydopoly (biphenyldimethylene-hydroxyphenylene), bisphenol A, bisphenol F, bisphenol S, Dihydroxynaphthalene, fluorene bisphenol, terpenediphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1, 4'-diol, hydroquinone, resorcin, naphthalene diol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ) Ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, etc.), formaldehyde, Hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) - biphenylylene, (Methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis ), Polycondensation products of benzene and the like and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, condensation products of terpenes and phenols, or polyhydric phenol compounds such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, Acid anhydride-based curing agents such as maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and anhydrous benzophenonetetracarboxylic acid, aliphatic hydrazides having 5 or less carbon atoms Drew There. Any of these thermosetting agents that can be used together may be used either singly or in combination.

The amount of the thermosetting agent which 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 the thermosetting agent (b) in the sealing agent of the present invention. In one embodiment, the sealant does not include any thermosetting agents (other than amines) that may be used in combination. In another embodiment, the heat curing agent for the sealant may be selected from amines (particularly preferably amine adducts), guanamine or imidazoles and other amines (particularly preferably amine adducts) It may be done by only.

The content of the thermosetting agent (b) used in the photoelectric conversion element-sealing material of the present invention is preferably such that the amount of the thermosetting agent (b) contained in the thermosetting agent (b) relative to 1 equivalent of the epoxy group in the epoxy resin The amount of active hydrogen 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 0.9 to 2.0 equivalents, and most preferably 0.9 to 1.8 equivalents. The term "active hydrogen" as used herein means a hydrogen atom bonded to a hetero atom of a thermosetting agent capable of reacting with an epoxy group of an epoxy resin.

In one embodiment, the sealing agent for a photoelectric conversion element of the present invention is a resin composition containing, as a curing agent, a polythiol compound having two or more thiol groups in a molecule and a polyhydrazide compound having two or more hydrazide groups in the molecule, It does not matter if you do not include both.

The sealant for a photoelectric conversion element of the present invention may contain (c) a filler, if necessary. Specific examples of the filler (c) used are fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina Magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, hydrated magnesium silicate, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide and asbestos. Of these, preferred are magnesium hydrate, calcium carbonate, aluminum oxide, crystalline silica, and fused silica. They may be subjected to surface treatment by chemical treatment or the like. The surface treatment can be performed, for example, by an organic compound such as a silane coupling agent. Any of these fillers may be used, or two or more fillers may be used in combination. The filler (c) to be contained in the sealant of the present invention preferably has an average particle diameter of 50 탆 or less, more preferably 40 탆 or less, more preferably 30 탆 or less, More preferably 20 μm or less, still more preferably 10 μm or less, and most preferably 5 μm or less. When the average particle diameter is 50 占 퐉 or less, it is possible to form an appropriate gap at the time of joining the upper and lower substrates at the time of manufacturing the photoelectric conversion element. The average particle diameter of the filler herein is, for example, a particle diameter at which the accumulation from the smaller particles is 50 mass% in the particle size distribution curve measured using a laser diffraction / scattering type particle size analyzer.

The content of the filler (c) when used is usually 0 to 60 mass% or less, preferably 5 to 60 mass%, and more preferably 15 to 50 mass%, in the photoelectric conversion element sealant of the present invention. When the content of the filler is 60 mass% or less, it is possible to form a suitable cell gap for storing and holding the charge transport layer when the photoelectric conversion element is produced.

In the photoelectric conversion element sealant of the present invention, (d) a silane coupling agent may be used in order to improve the adhesive strength. As the silane coupling agent (d), any material may be used as long as it improves the bonding strength between the sealing agent and the conductive support. Specific examples of silane coupling agents that can be used include glycidylmethoxysilanes such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl ) Ethyltrimethoxysilane, N-phenyl- gamma -aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercapto Propyltriethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltriethoxysilane hydrochloride, 3-methacryloxypropyltriethoxysilane, 3-chloropropylmethyl And glycidyl ethoxysilanes such as diethoxysilane, 3-chloropropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Of these, glycidyl ethoxysilanes or glycidyl methoxysilanes are preferred. Among them, a silane coupling agent having an amino group is preferable in obtaining a good bonding strength. More preferred among the above silane coupling agents are N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (2- (vinylbenzylamino) ethyl) -Aminopropyltriethoxysilane hydrochloride, and the like. These 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, preferably 0.1 to 2% by mass, and more preferably 0.2 to 1.5% by mass in the photoelectric conversion element sealant of the present invention. In one embodiment, 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, per 100 parts by mass of the epoxy resin (a) Preferably from 0.5 to 10 mass parts, more preferably from 1 to 10 mass parts, still more preferably from 1 mass parts to 10 mass parts, and most preferably from 1.5 to 8 mass parts.

The sealing agent for a photoelectric conversion element of the present invention may contain, if necessary, an organic solvent, an organic filler, a stress relaxation agent and the like. Further, additives such as a pigment, a leveling agent, a defoaming agent, and a viscosity adjusting agent may be added to the sealing agent. The additive that can be blended is not particularly limited, and the amount thereof to be added may be suitably selected in accordance with the purpose. These additives preferably have a low staining property with respect to the charge transporting layer.

The sealing agent for a photoelectric conversion element of the present invention can be obtained by a method comprising the steps of (a) providing an epoxy resin, (b) a thermosetting agent comprising amines, optionally (c) a filler, (d) a silane coupling agent, , Preferably the above-mentioned respective contents, with stirring, if necessary. Subsequently, the mixture can be uniformly mixed by a mixing device such as a three-roll mill, a sand mill or a ball mill. If necessary, filtration may be performed to remove impurities after mixing.

The sealing agent for a photoelectric conversion element of the present invention is suitable for a method of forming a photoelectric conversion element for injecting a charge transfer layer from an injection port after joining two substrates (conductive support). Sealing can be performed by thermally curing the weir of the sealant of the present invention sandwiched between two substrates. Examples of the method of applying the sealant of the present invention to a substrate include a coating method such as 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. , It is possible to appropriately select or combine them depending on the form. From the viewpoint of productivity, it is preferable to use a spray method, a screen printing method, and a dispensing method. The sealant for a photoelectric conversion element of the present invention can be generally applied to any photoelectric conversion element capable of converting light energy into electric energy. A lead wire is disposed so as to take out a current generated from the photoelectric conversion element, and a closed circuit is used as a solar cell. INDUSTRIAL APPLICABILITY The sealing agent for a photoelectric conversion element of the present invention is particularly suitable for the production of a dye-sensitized photoelectric conversion element and a solar cell having the photoelectric conversion element.

Hereinafter, the photoelectric conversion element and the solar cell manufactured using the photoelectric conversion element sealant of the present invention will be described in detail. The following specific embodiments are merely examples, and the present invention is not limited thereto.

In general, the dye-sensitized photoelectric conversion element comprises a first conductive support (oxide semiconductor electrode) having on its surface a semiconductor-containing layer formed by increasing or decreasing a dye, a second conductive support as a counter electrode, and a charge transfer layer as main components do. The sealing agent for a photoelectric conversion element of the present invention is used for adhering the first and second conductive support members and for maintaining the charge transfer layer between both the support members. As the conductive support, a conductive material typified by FTO (fluorine-doped tin oxide), ATO (antimony doped tin oxide), or ITO (indium-doped tin oxide) Is thinned on the surface of the substrate. The thickness of the substrate is usually 0.01 to 10 mm, and its shape can take various forms from a film shape to a plate shape, but a substrate having light transparency is used for at least one of the two substrates. The conductivity of the conductive support is usually 1000 Ω / cm 2 or less, preferably 100 Ω / cm 2 or less.

As the oxide semiconductor used for preparing the semiconductor-containing layer, fine particles of metal carboxylate are preferable. Specific examples thereof include oxides of transition metals such as Ti, Zn, Sn, Nb, W, In, Zr, Y, La and Ta, oxides of Al, oxides of Si, perovskia such as SiTiO ₃ , CaTiO ₃ and BaTiO ₃ Oxide and the like. Of these, TiO ₂ , ZnO and SnO ₂ are particularly preferable. These may be used in combination, and a SnO ₂ -ZnO mixed system is a preferable example. In the case of a mixed system, they may be mixed in the state of fine particles, mixed in the slurry or paste state described below, or the respective components may be used in the form of layers. The concentration of the oxide semiconductor in the slurry or paste is usually 1 to 90 mass%, preferably 5 to 80 mass%. The primary particle diameter of the oxide semiconductor to be used is usually 1 to 200 nm, preferably 1 to 50 nm.

A method of 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 forming a slurry or paste on the substrate by applying or coating the substrate, A method in which a slurry or paste is applied or coated on a substrate, followed by drying, curing, or firing. Examples of the coating or coating method include a bar coater method, a dip coating method, a spin coating method, a spraying method, a screen printing method, a doctor blade method and a dispensing method. These methods can be suitably selected or used in combination according to the type and form of the substrate. For the performance of the oxide semiconductor electrode, a method using a slurry or paste is preferred. The slurry can be prepared, for example, by dispersing fine particles of an oxide semiconductor which are secondary agglomerated in a dispersion medium so as to have an average primary particle size of usually 1 to 200 nm or by using a sol- And the like. In addition, fine particles of oxide semiconductors having different particle diameter distributions may be mixed and used.

The dispersion medium for dispersing the slurry is not particularly limited as long as it can disperse fine particles of an oxide semiconductor. As the dispersion medium, water, an alcohol such as ethanol and terpineol, an organic solvent such as ketone such as acetone, acetyl acetone, or hydrocarbons such as hexane is used. They may be mixed and used. Use of water is preferable in that the viscosity change of the slurry is reduced.

For the purpose of obtaining stable primary microparticles, a dispersion stabilizer or the like may be added to the slurry. Specific examples of the dispersion stabilizer to be used include polyvalent alcohols such as polyethylene glycol, monohydric alcohols such as phenol and octyl alcohol, or co-condensation products of these monomers; Cellulose derivatives such as hydroxypropylmethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose; Polyacrylamides; Acrylamide, (meth) acrylic acid or its salt, (meth) acrylic acid ester (methyl (meth) acrylate, ethyl (meth) acrylate); Acrylate, (meth) acrylic acid or its salt, (meth) acrylic acid ester or the like and a hydrophobic monomer such as styrene, ethylene or propylene; Salts of melamine sulfonic acid formaldehyde condensates; Salts of naphthalenesulfonic acid formaldehyde condensates; High molecular weight ligninsulfonic acid salts; Hydrochloric acid, nitric acid, acetic acid and the like, but the present invention is not limited thereto. These dispersion stabilizers may be used alone or in combination of two or more.

Of these, polyvalent alcohols such as polyethylene glycol, magnetic materials such as phenol and octyl alcohol or co-condensation products of these materials, poly (meth) acrylic acid, sodium poly (meth) acrylate, poly (meth) Lithium, carboxymethylcellulose, hydrochloric acid, nitric acid, acetic acid and the like are preferable.

After the slurry coated on the conductive support is dried, the firing treatment can be performed at a temperature not higher than the melting point (or softening point) of the substrate used for the conductive support. The firing temperature is usually 100 to 900 占 폚, preferably 100 to 600 占 폚. The firing time is not particularly limited, but is usually within 4 hours. The film thickness of the semiconductor-containing layer formed on the conductive support is usually 1 to 50 mu m.

For the purpose of improving the surface smoothness, the semiconductor-containing layer may be subjected to secondary treatment (see Non-Patent Document 1). For example, the conductive support on which the thin film of the semiconductor containing layer prepared by the above method is formed is directly immersed in a solution of an alkoxide, a chloride, a nitride or a sulfide of the same metal as that used for preparing the semiconductor containing layer, (Re-firing) in the same manner as described above, the smoothness of the semiconductor-containing layer can be enhanced. Examples of the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyltin and the like, and an alcohol solution thereof is used. Examples of the chloride include titanium tetrachloride, tin tetrachloride and zinc chloride, and an aqueous solution thereof is used. The semiconductor-containing layer formed of the oxide semiconductor fine particles thus obtained has a specific surface area of usually 1 to 1000 m 2 / g, preferably 10 to 500 m 2 / g.

Next, the step of supporting the sensitizing dye on the semiconductor-containing layer will be described. The sensitizing dye is not particularly limited as long as it has an effect of increasing or decreasing light absorption together with the semiconductor fine particles constituting the semiconductor-containing layer. As the sensitizing dye, a metal complex dye containing a metal element such as ruthenium or an organic dye not containing a metal may be used singly or several kinds may be mixed in an arbitrary ratio. When used in combination, it is possible to use any of plural kinds of metal complex dyes, a plurality of kinds of organic dyes, and a combination of metal complex dyes and organic dyes. By mixing a plurality of types of dye having different absorption wavelength regions, a wide absorption wavelength can be utilized, and a solar cell with high conversion efficiency can be obtained.

The metal complex dye which can be supported is not particularly limited, but phthalocyanine and porphyrin are preferable, and ruthenium complex is more preferable. There is no particular limitation on the organic pigments that can be carried, and examples thereof include organic pigments such as nonmetallic phthalocyanine, porphyrin, cyanine, meloxicane, oxolin, triphenylmethane, acrylic acid based pigments, pyrazolone based methine pigments, Based pigments, azo pigments, azotite pigments, azo pigments, anthraquinone pigments, and perylene pigments. International Patent Publication Nos. WO2002-001667, WO2002-011213, WO2002-071530, JP-A 2002-334729, JP-A 2003-007358, JP-A 2003 -017146, JP-A-2003-059547, JP-A-2003-086257, JP-A-2003-115333, JP-A-2003-132965, JP-A-2003-142172, Japanese Unexamined Patent Application Publication No. 2003-151649, Japanese Unexamined Patent Application Publication No. 2003-157915, Japanese Unexamined Patent Publication No. 2003-282165, Japanese Unexamined Patent Application Publication No. 2004-014175, Japanese Unexamined Patent Publication No. 2004-022222, Japanese Unexamined Patent Application, 022387, 2004-227825, 2005-005026, 2005-019130, 2005-135656, 2006-079898, and Japan Patent Publication 2006-134649, International Patent Publication No. WO2006-082061, etc. Implicit that the dye is preferred. Melocyanine and the methine-based coloring matters such as the acrylic acid-based ones described above. The ratio of each coloring matter when a plurality of kinds of coloring matters are mixed is not particularly limited, but it is generally preferable to use at least about 10 mole% of each coloring matter. When the dye is supported on the semiconductor-containing layer by using a solution or a dispersed dispersion in which two or more coloring matters are dissolved, the concentration of the coloring matter in the solution may be the same as in the case of carrying only one kind. As the solvent in the case of using a mixture of plural kinds of coloring matters, the above-mentioned solvents for the oxide semiconductor can be used, and the solvents for the respective coloring materials to be used may be the same or different.

As a method of supporting the sensitizing dye, a method of immersing a conductive support in which the semiconductor containing layer is formed in a solution in which the dye is dissolved in a solvent or a dispersion in which a dye is dispersed in a solvent can be mentioned. The concentration of the dye in the solution or dispersion may be suitably determined according to 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 to 72 hours. Specific examples of the solvent which can be used for dissolving the sensitizing dye include methanol, ethanol, acetone, acetonitrile, dimethylsulfoxide, dimethylformamide, t-butanol, tetrahydrofuran and the like. These may be used alone, or a plurality of them may be mixed at an arbitrary ratio. The concentration of the sensitizing dye in the solution is usually 1 × 10 ^-6 M to ¹ M, preferably 1 × 10 ^-5 M to ¹ × 10 ^-1 M. In this way, a conductive support having a semiconductor-containing layer increased or decreased in coloring matter, which is used as an oxide semiconductor electrode, is obtained.

When the dye is supported on the semiconductor-containing layer, it is effective to carry the dye under the coexistence of the inclusion compound in order to prevent association of the dye particles. Examples of the inclusion compound include steroid compounds such as cholic acid, crown ether, cyclodextrin, calixarene, and polyethylene oxide. Preferable examples include colonic acid, deoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester, sodium choloric acid, colsic acid such as ursodeoxycholic acid, and polyethylene oxide. The use of these inclusion compounds may be added to the coloring matter solution, or the coloring matter may be dissolved or dispersed after the inclusion compound is dissolved in the solvent in advance. These inclusion compounds can be used in combination of two or more kinds, and the ratio thereof can be arbitrarily selected.

Further, after supporting the dye, the semiconductor containing layer may be treated with an amine compound such as 4-t-butylpyridine. A treatment method is, for example, a method of immersing a conductive support on which a semiconductor containing layer carrying a dye is formed in an ethanol solution of an amine compound.

On the surface of a conductive support such as an FTO conductive glass or the like, conductive fine particles such as platinum, carbon, rhodium, or ruthenium, which act catalytically in the reduction reaction of the redox electrolyte, are deposited on the counter electrode, or precursors of these conductive fine particles are coated , Fired and the like are used.

Next, a method of bonding the conductive support (oxide semiconductor electrode) having the semiconductor-containing layer increased and decreased to the dye obtained as described above and the counter electrode using the photoelectric conversion element sealant of the present invention will be described.

First, a sealant of the present invention to which a spacer (gap control member) is added is applied in a beam shape to a peripheral portion of a conductive surface of one of the conductive supports by a dispenser, a screen printer, etc. leaving the injection port of the charge- The other conductive supporter may be overlapped with each other so that the conductive surfaces of the first and second conductive supporters face each other, and the sealing agent may be cured by heating. Here, as the spacer, for example, glass fiber, silica beads, polymer beads, and further metal-coated fine particles such as gold puffs and silver puffs are used. The average diameter thereof varies depending on the purpose, but is usually 1 to 100 占 퐉, preferably 10 to 40 占 퐉. The amount thereof is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, and more preferably 1 to 2.5 parts by mass based on 100 parts by mass of the sealing material of the present invention. The heat curing of the sealant is usually carried out at 80 to 120 DEG C for 1 to 3 hours. As a method for heating and curing, a method of sandwiching sandwiches with a hot press machine having two thermal plates, a method of fixing them in a jig, and a method of performing them in an oven can be adopted. The gap between the first and second conductive supports is usually 1 to 100 占 퐉, preferably 4 to 50 占 퐉.

The dye-sensitized photoelectric conversion element of the present invention is completed by injecting a charge-transporting layer into the gap between a pair of conductive supports bonded in the above-described manner. As the charge transporting layer, a solution obtained by dissolving a redox electrolyte pair or a hole transporting material in a solvent or a room temperature molten salt (ionic liquid) is used. Examples of the redox electrolyte used include a halogen redox electrolyte composed of a halogen compound having a halogen ion as a bion and a halogen molecule, a metal complex such as a ferrocenate-ferricyanide, a ferrocene-ferricinium ion, a cobalt complex, etc. Redox electrolyte such as a metal oxide redox electrolyte, alkylthiol-alkyl disulfide, viologen dye, hydroquinone-quinone, and the like. A halogen redox electrolyte is preferable. Examples of the halogen molecule in the halogen redox electrolyte include iodine molecules and bromine molecules, and iodine molecules are preferred. In addition, the halogen compound, for example a halogenated metal salt such as LiI, NaI, KI, CsI, CaI _2, CuI, or tetraalkylammonium iodide, imidazolium iodide, 1-methyl-3-alkyl imidazole Organic quaternary ammonium salts of halogens such as zirconium iodide and pyridinium iodide, and the like. A salt compound having an iodine ion as a bionic ion is preferable. Specific examples thereof include lithium iodide, sodium iodide, and trimethylammonium iodide. These may be used alone, or two or more kinds may be used in combination.

Further, when the charge transporting layer is composed of a solution containing a redox type electrolyte, an electrochemically inactive one is used as the solvent. Specific examples of the solvent to be used include acetonitrile, valeronitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, 3-butoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol , Triethylene glycol, dimethoxyethane, diethyl carbonate, diethyl ether, dimethyl carbonate, 1,2-dimethoxyethane, dimethylformamide, dimethylsulfoxide, 1,3-dioxolane, methyl formate, 2- Methyl tetrahydrofuran, 3-methyloxazolidin-2-one,? -Butyrolactone, sulfolane, tetrahydrofuran, water and the like. Of these, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, 3-methyloxazolidin-2-one and? -Butyrolactone are preferable. These may be used alone or in combination of two or more. The concentration of the redox electrolyte in the solution is usually 0.01 to 99% by mass, preferably 0.1 to 90% by mass.

Further, when the charge transporting layer is formed in the form of a composition containing an oxidation-reduction type electrolyte, a room temperature melt (ionic liquid) is used as a solvent. Specific examples of the room temperature melt to be used include 1-methyl-3-alkylimidazolium iodide, vinylimidazolium tetrafluoride, 1-ethylimidazole sulfonate, alkylimidazolium trifluoromethylsulfonyl Amide, 1-methylpyrrolidinium iodide, and the like. Further, for the purpose of improving the durability of the photoelectric conversion element, for example, by dissolving a low molecular weight gelling agent in the charge transporting layer to increase its viscosity, or by reacting the charge transporting layer in combination with the reactive component after injection, Alternatively, it is possible to obtain a gel electrolyte by impregnating the charge transport layer with a gel which has been previously polymerized.

On the other hand, in the case of a completely solid charge transporting layer, a hole transporting material or a P-type semiconductor may be used instead of the redox type electrolyte. Examples of the hole transporting material to be used include amine derivatives, and conductive polymers such as polyacetylene, polyaniline and polythiophene. Examples of the P-type semiconductor include CuI and CuSCN.

A photoelectric conversion element can be obtained by injecting the charge transport layer into the gap between the pair of conductive supports and then sealing the injection port of the charge transport layer. As the sealing material (sealant) for sealing the injection port of the charge transporting layer, an isobutylene resin, an epoxy resin, an UV-curable acrylic resin, or the like can be used.

On the other hand, as another manufacturing method of the photoelectric conversion element, the following method can also be employed. That is, a beam of sealing agent is formed in the periphery of the conductive surface of either one of the conductive supports without forming the charge transfer layer injection port, and then the same charge transfer layer as above is disposed inside the beam of the sealing agent, The other conductive support is put on the other conductive support so that the conductive surfaces of the first and second conductive supports face each other, the gap is formed and the gap is formed, and then the sealing agent is cured to obtain the photoelectric conversion element.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic cross-sectional view of a main part for explaining the structure of a dye-sensitized photoelectric conversion element prepared using the sealant of the present invention. FIG. In the figure, reference numeral 1 denotes a conductive support having conductivity on the inside, reference numeral 2 denotes a semiconductor-containing layer formed by increasing or decreasing a dye (1 and 2 are referred to as an oxide semiconductor electrode), reference numeral 3 denotes platinum Reference numeral 4 denotes a charge transfer layer disposed in a gap between the pair of conductive supports, reference numeral 5 denotes a sealing agent of the present invention, and reference numeral 6 denotes a glass substrate. The solar cell of the present invention can be obtained by disposing a lead line between the positive electrode and the negative electrode of the thus obtained photoelectric conversion element and inserting a resistance component therebetween.

The sealing agent of the present invention can be applied to the fabrication 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. There are several types of modular structures of large-sized, dye-sensitized solar cells. The sealant of the present invention can be used for any type of module structure. For example, it can be used in a dye-sensitized solar cell module having a series connection structure described in International Patent Publication No. WO2009 / 057704.

INDUSTRIAL APPLICABILITY The sealing agent for photoelectric conversion element of the present invention is excellent in workability of application to a substrate, bonding property, adhesive strength, usable time at room temperature (pot life), low temperature curability, The staining property to the mobile layer is very low. Therefore, the photoelectric conversion element of the present invention obtained by using the sealant has no malfunction due to contamination of the charge transport layer, and is excellent in adhesiveness and moisture resistance reliability. A solar cell prepared using the photoelectric conversion element can be efficiently produced and has excellent durability.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Example 1]

(trade name: bisphenol A) was added to 90 parts by mass of (a) RE-310S (trade name, bisphenol A type epoxy resin, available from Nippon Kayaku Co., Ltd., epoxy equivalent: 185 g / eq. A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 475 g / eq.) Were added and heated to dissolve. After the epoxy resin was cooled to room temperature, 90 parts by mass of SSP-07DM (trade name, surface-treated silica, maximum particle size 0.7 탆) as a filler (c), KBM-403 (trade name, epoxy silane coupling agent And 1 part by mass of a crosslinking agent (? -Glycidoxypropyltrimethoxysilane), manufactured by Shin-Etsu Silicones Co., Ltd.) were added and mixed and dispersed by a three-roll roll. (B) PN- 20 parts by mass, average particle size of 8.8 mu m, manufactured by Ajinomoto Fine Techno Co., Ltd.) was further added and mixed and dispersed by a three-roll mill to obtain a sealing agent (1) for a photoelectric conversion element of the present invention. The viscosity of this sealing agent (1) at 25 캜 was measured by an E-type viscometer, and found to be 73 Pa s.

[Comparative Example 1]

70 parts by mass of RE-310S as an epoxy resin, EPPN-501H (trade name, trisphenol methan novolak type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 165 g / eq., hydrolyzed chlorine content of 550 ppm or less) And 10 parts by mass of YD-017 (trade name, bisphenol A type solid epoxy resin, manufactured by Toto Kasei Kogyo K.K., epoxy equivalent: 1900 g / eq.) As a thermosetting agent, 7.5 parts by mass of active hydrogen equivalent 100 g / eq., Manufactured by Nippon Kayaku Co., Ltd.), 1 part by mass of KBM-403 as a silane coupling agent was added to 30 parts by mass of ethylene glycol dibutyl ether as a solvent . This solution was cooled to room temperature and further finely pulverized by a jet mill of isophthalic acid dihydrazide as a thermosetting agent (melting point: 224 deg. C, active hydrogen equivalent: 48.5 g / eq., Average particle diameter: 19 parts by mass as a filler, 90 parts by mass of alumina having an average particle size of 0.5 占 퐉 or less and 3.5 parts by mass of fumed silica were mixed and dispersed by a three-roll mill, 5 parts by mass of a 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine isocyanuric acid adduct having a size of 3 μm or less was added thereto to obtain a photoelectric conversion element- 2). The viscosity of this sealant (2) at 25 캜 was measured by an E-type viscometer to be 47 Pa s.

[Example 2]

90 parts by mass of RE-310S (a) in Example 1 was changed to 80 parts by mass, and a polyfunctional epoxy resin EPPN-501 (trade name, trisphenol methanovolactic epoxy resin, manufactured by Nippon Kayaku Co., 10 parts by mass of epoxy equivalent weight of 165 g / eq., Hydrolysis chlorine content of not more than 550 ppm), (d) 1 part by mass of KBM-403 as a silane coupling agent was changed to 3 parts by mass, and (b) C11Z -Undecylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) were added in the same manner as in Example 1, to thereby obtain a photoelectric conversion element-sealing material (3) of the present invention. The viscosity of this sealing agent (3) at 25 캜 was measured by an E-type viscometer to be 278 Pa s.

[Example 3]

90 parts by mass of RE-310S (a) in Example 1 was changed to 80 parts by mass, and a polyfunctional epoxy resin EPPN-501 (trade name, trisphenol methanovolactic epoxy resin, manufactured by Nippon Kayaku Co., An epoxy equivalent of 165 g / eq., And a hydrolysis chlorine content of 550 ppm or less) were added, to obtain a photoelectric conversion element-sealing material (4) of the present invention. The viscosity of this sealant (4) at 25 캜 was measured by an E-type viscometer and found to be 443 Pa s.

[Example 4]

(5) of the present invention was obtained in the same manner as in Example 1, except that 1 part by mass of KBM-403 as the silane coupling agent (d) in Example 1 was changed to 3 parts by mass . The viscosity of this sealant (5) at 25 캜 was measured by an E-type viscometer to be 31 Pa s.

[Example 5]

Except that 3 parts by mass of C11Z (trade name, 2-undecylimidazole, manufactured by Shikoku Kasei K.K.) as the heat curing agent (b) in Example 1 was added to the photoelectric conversion layer of the present invention. Thereby obtaining a conversion element sealing material (6). The viscosity of this sealant (6) at 25 캜 was measured by an E-type viscometer to be 80 Pa s.

[Evaluation test 1]

The shear bond strengths were measured as performance evaluations of the respective sealants produced in Examples 1, 3, 4, and 5 and Comparative Example 1. As performance evaluations of the sealants produced in Example 2 and Comparative Example 1, solvent swelling degree was measured.

The shear bond strength was measured by the following method.

1 part by mass of glass fiber having a diameter of 50 占 퐉 was added as a spacer to 100 parts by mass of each seal, followed by mixing and stirring. This sealant was applied on a conductive support (FTO glass substrate) of 50 mm x 50 mm with a dispenser, and the solvent was evaporated by heating with a hot plate. Then, on the sealant on the conductive support, 2 mm x 2 mm glass Piece was joined and cured under the condition of 100 占 폚 for 1 hour, and the shear bond strength of the obtained test piece was measured.

The swelling degree (swelling degree) of the solvent was measured by the following method.

Each sealant was coated on a heat-resistant film using an applicator (film thickness: 200 mu m), and cured at 100 DEG C for 1 hour. Four pieces of punching test pieces were produced by applying a punch blade of 3 cm x 3 cm to the obtained cured film. After the mass of each test piece (mass before immersion) was measured, it was put in a pressure vessel together with 3-methoxypropionitrile (3 MPN), and the pressure vessel was heated at 85 캜 for 2 hours. After completion of the heating, the pressure-resistant container was cooled to room temperature, and 3MPN attached to the test piece taken out was wiped off to measure the mass of the test piece (mass after immersion). From the calculation of {(mass after immersion / mass after immersion) -1} x 100, the mass increase rate before and after solvent immersion was determined, and the average value of the four mass increase rates was defined as the swelling degree (%).

As shown in Table 1 and Table 2, the sealing agents (1), (4), (5) and (6) of the present invention exhibited higher adhesive strength than the sealing agent (2). On the other hand, the sealing agent (3) of the present invention exhibited a lower degree of solvent swelling as compared with the sealing agent (2). These results suggest that the present sealing material is useful for fabricating a dye-sensitized solar cell device at a low temperature (100 ° C) and can be fabricated at a low temperature, so that it is effective for energy saving and high reliability device manufacturing have.

(Industrial availability)

INDUSTRIAL APPLICABILITY The sealing agent for photoelectric conversion element of the present invention is excellent in workability of application to a substrate, bonding property, adhesive strength, usable time at room temperature (pot life), low temperature curability, The staining property to the mobile layer is very low. The photoelectric conversion element of the present invention obtained by using such a sealant has no malfunction due to contamination of the charge transport layer, and is excellent in adhesiveness and moisture resistance reliability. In addition, when the photoelectric conversion element is manufactured using the photoelectric conversion element-sealing material of the present invention, the performance is not defective and the productivity can be improved.

1: conductive support
2: Semiconductor containing layer increased or decreased by dye
3: opposite electrode
4: charge transport layer
5: Sealant
6: glass substrate

Claims (11)

A sealant for optoelectronic conversion element characterized by containing amines as (a) an epoxy resin and (b) a thermosetting agent. The method according to claim 1,
(b) a thermosetting agent in an amount such that (a) the amount of active hydrogen in the thermosetting agent is 0.8 to 3.0 equivalents relative to 1 equivalent of the epoxy group in the epoxy resin. 3. The method according to claim 1 or 2,
(b) a sealant for a photoelectric conversion element, wherein the heat curing agent is an amine duct. 4. The method according to any one of claims 1 to 3,
(b) the sealant for a photoelectric conversion element, wherein the heat curing agent comprises at least two amines including at least one of guanamine and / or imidazoles and at least one of other amines. 5. The method of claim 4,
A sealant for a photoelectric conversion element, characterized in that the imidazoles include 2-undecylimidazole. 6. The method according to any one of claims 1 to 5,
(c) a filler. The method according to claim 6,
(c) the filler is one or more kinds selected from the group consisting of hydrated magnesium silicate, calcium carbonate, aluminum oxide, crystalline silica and fused silica, and the average particle diameter thereof is 50 탆 or less, Sealing system. 8. The method according to any one of claims 1 to 7,
(d) a silane coupling agent. 9. The method of claim 8,
(d) the silane coupling agent is glycidylethoxysilane or glycidylmethoxysilane. A first conductive support having a semiconductor-containing layer, a second conductive support having an opposing electrode formed at a position where the semiconductor-containing layer and the counter electrode are opposed to each other at a predetermined interval, a charge transfer layer sandwiched between the first and second conductive support, And a seal which is formed in the peripheral portion of the first and second conductive supports and surrounds the charge transporting layer, wherein the seal is the seal for a photoelectric conversion element according to any one of claims 1 to 9 Photoelectric conversion element, which is a zero-formed seal. A solar cell comprising the photoelectric conversion element according to claim 10.

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