CN108235790A - sealant - Google Patents

sealant Download PDF

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Publication number
CN108235790A
CN108235790A CN201680060851.2A CN201680060851A CN108235790A CN 108235790 A CN108235790 A CN 108235790A CN 201680060851 A CN201680060851 A CN 201680060851A CN 108235790 A CN108235790 A CN 108235790A
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CN
China
Prior art keywords
photo
conversion element
electric conversion
sealant
support body
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.)
Pending
Application number
CN201680060851.2A
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Chinese (zh)
Inventor
桥本雄太
今泉雅裕
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Nippon Kayaku Co Ltd
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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
Publication of CN108235790A publication Critical patent/CN108235790A/en
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • 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

Abstract

The present invention relates to a kind of photo-electric conversion element sealants, which is characterized in that the amine containing epoxy resin (a) and as thermal curing agents (b).Photo-electric conversion element sealant can contain thermal curing agents (b), and relative to 1 equivalent of epoxy group in epoxy resin (a), the amount of reactive hydrogen is 0.8~3.0 equivalent in thermal curing agents (b).Thermal curing agents (b) can be amine additives.Thermal curing agents (b) can include at least two amines, which includes 2 undecyl imidazoles.Photo-electric conversion element sealant can contain filler (c).Filler (c) can be selected from one or more of group being made of hydrated magnesium silicate, calcium carbonate, aluminium oxide, crystalline silica and vitreous silica, and its average grain diameter can be less than 50 μm.Photo-electric conversion element sealant can contain silane coupling agent (d).

Description

Sealant
Technical field
The present invention relates to a kind of sealant, there is good adhesiveness under low temperature curing conditions, and particularly suitable for The manufacture of photo-electric conversion element.
Background technology
In recent years, the solar cell to attract attention as clean energy resource is gradually used in general house, but not yet obtains To widely available.As its reason, can include：Due to it's hard to say solar cell its own power generation performance it is very good It is good, therefore have to module is made to maximize, also, the productivity manufactured in module process is relatively low, as a result, cost becomes higher Deng.
Being used in the photo-electric conversion element of solar cell is, usually utilizes the transparent protection material on top and the base of lower part The photoelectric conversion materials such as plate protection materials protection silicon, GaAs, copper indium selenide, photoelectric conversion material and protection are fixed using sealant Material and the element being packaged.Therefore, as be used in manufacture photo-electric conversion element sealant, be requested to have with up and down The adhesiveness of protection materials is good, and flexibility and durability well wait important performances.
At present, as the photo-electric conversion element sealant in solar cell module, from the side such as flexibility and the transparency Face considers, uses the higher ethylene-vinyl acetate copolymer of the containing ratio of such as vinylacetate.However, the copolymer, Heat resistance is insufficient with adhesiveness, therefore, is needed to more promote copolyreaction using organic peroxide etc..This In the case of, the technique that needs following two steps first, makes the ethylene-vinyl acetate for mixing these organic peroxides Secondly the thin slice of copolymer, uses the thin slice sealed photoelectric transition material.Also, in the step of manufacturing thin slice, in order not to make Organic peroxide is decomposed and is needed in low temperature moulding, therefore, it is impossible to improve extrusion forming speed.On the other hand, sealing (Gu Change bonding) photoelectric conversion material the step of in, need the technique by following two steps, that is, pass through laminating machine temporary adhesion The technique of a few minutes~more than ten minutes；Formally bonded at a high temperature of organic peroxide is decomposed in oven dozens of minutes~ The technique of 1 hour.Therefore, it is cumbersome and time consuming when manufacturing photo-electric conversion element, and there are adhesiveness and moisture-resistance reliability The shortcomings that insufficient.And use this photo-electric conversion element solar cell module and solar cell, price costly, And its performance can not be met.
In addition, the sealing material as photo-electric conversion element, at the same time using the copolymer and melting point it is relatively low from During polymers, heat resistance is insufficient, and as solar cell in use, may be deformed due to temperature rise.In addition, in profit When manufacturing photo-electric conversion element with heating and pressurizing method, these sealing materials flow out and may generate burr too much, therefore simultaneously It is undesirable.Moreover, with the enlargement of photo-electric conversion element in recent years, be applied in process the pressure of sealing with it is previous Compared to becoming very large, the length of seal line also becomes more and more longer.It can be seen that it needs to develop a kind of moisture-resistance reliability good It is good, line width narrowization of sealing can be made, the interval between conductive support body can be made to become uniform, and adhesiveness and Flexible good application type sealant.
On the other hand, the method (patent document 1) for using thermosetting epoxy resin as sealant is being studied. In this case, by the way that sealant is coated on conductive support body, and adding the methods of drop coating (dispense), silk-screen printing Heat or after carrying out leveling (leveling) in the case of not heating, is led up and down using alignment mark (alignment mark) fitting Electrical supporter carries out unit making by the technique of crush seal agent.As thermosetting epoxy resin used herein Curing agent, use thermoplastic phenolic resin.However, this photo-electric conversion element sealant, under high temperature and high humidity Long term seal, bond properties is not good enough, has the shortcomings that solution leakage.In addition, when making sealant cures, need 120 DEG C or more high temperature etc. also has the shortcomings that manufacture load is larger.As the method for solving this shortcoming, in patent document 2 Disclose the resin combination using A Hydrogenated Bisphenol A type epoxy resin.However, in this case, also will appear can not assign Long term seal under high-temperature high-humidity, and the phenomenon that solution leakage.
【Patent document】
【Patent document 1】Japanese Patent Laid-Open 2002-368236 bulletins
【Patent document 2】Japanese Patent Laid-Open 2007-087684 bulletins
【Non-patent literature】
【Non-patent literature 1】C.J.Barbe, F Arendse, P Compt and M.Graetzel J.AM.Ceram.Soc., 80,12,3157-71 (1997).
Invention content
The purpose of the present invention is to provide a kind of photo-electric conversion element sealants, are pasted when manufacturing photo-electric conversion element The operation for closing lower conductive support body is easier to, and curing at low temperature and the adhesive strength of obtained sealing, Moisture-resistance reliability, heat resistance etc. are good.That is, the purpose of the present invention is to provide one kind particularly suitable for manufacturing photo-electric conversion element Sealant.
It is that the present inventor etc. study intensively repeatedly as a result, finding to solve with the resin combination of special component Certainly described problem, so as to complete the present invention.
That is, various aspects of the invention are as described below.
[1] a kind of photoelectron conversion element sealants of, which is characterized in that containing epoxy resin (a) and as thermosetting The amine of agent (b).
[2] the photoelectron conversion element sealant described in above-mentioned [1] items of, containing thermal curing agents (b), and relative to 1 equivalent of epoxy group in epoxy resin (a), the amount of reactive hydrogen is 0.8~3.0 equivalent in thermal curing agents (b).
[3] above-mentioned [1] or the photo-electric conversion element sealant described in [2] item, which is characterized in that thermal curing agents (b) are Amine additives.
[4] the photo-electric conversion element sealant in above-mentioned [1] to [3] described in any one, wherein, thermal curing agents (b) Comprising at least two amines, at least one amine with these other than of the amine comprising guanamines and/or imidazoles is at least It is a kind of.
[5] the photo-electric conversion element sealant described in above-mentioned [4] items of, which is characterized in that imidazoles include 2- hendecanes Base imidazoles.
[6] the photo-electric conversion element sealant in above-mentioned [1] to [5] described in any one, contains filler (c).
[7] the photo-electric conversion element sealant described in above-mentioned [6] items of, wherein, filler (c) is selected from by hydration silicon More than one kind or two kinds of group that sour magnesium, calcium carbonate, aluminium oxide, crystalline silica and vitreous silica form, and it is flat Equal grain size is less than 50 μm.
[8] the photo-electric conversion element sealant in above-mentioned [1] to [7] described in any one, contains silane coupling agent (d)。
[9] the photo-electric conversion element sealant described in above-mentioned [8] items of, wherein, silane coupling agent (d) is glycidol Ethoxysilane class or glycidol methoxy silane class.
[10] a kind of photo-electric conversion elements of, including：There is first conductive support body semiconductor to contain layer；Second is conductive Property supporter, there is opposite electrode, it is opposite at a prescribed interval with opposite electrode which set on the semiconductor contains layer Position；Charge transfer layer is located in the gap of the first conductive support body and the second conductive support body；And sealing Pad, set on the peripheral portion of the first conductive support body and the second conductive support body, and surrounds charge transfer layer, wherein, it should Gasket is formed as the photo-electric conversion element described in any one in above-mentioned [1] to [9] with sealant.
[11] one kind has the solar cell of the photo-electric conversion element described in above-mentioned [10] item.
The photo-electric conversion element sealant of the present invention contains amine (the preferably amine addition as thermal curing agents Object), therefore, to the painting work of substrate, stickiness, adhesive strength, up time (working life) at room temperature, low-temperature solid The property changed is good.Therefore, it is very low to the pollution of charge transfer layer in the manufacturing process of photo-electric conversion element.Using this Photo-electric conversion element of the invention obtained from sealant, the power generation performance decline caused by the pollution of charge transfer layer is less, And adhesiveness, moisture-resistance reliability are good.In addition, the photo-electric conversion element of the present invention is used to manufacture opto-electronic conversion with sealant It during element, will not occur that performance is bad, and the element at low temperature with higher reliability can be made in a short time, it can Improve productivity.
Description of the drawings
Fig. 1 is to illustrate the major part of the structure of dye-sensitized photoelectric conversion device prepared by the sealant using the present invention Schematic cross-section.
Symbol description
1st, conductive support body 2, the semiconductor layer by dye sensitization
3rd, opposite electrode 4, charge transfer layer
5th, sealant 6, glass substrate
Specific embodiment
The photo-electric conversion element of the present invention is containing epoxy resin with sealant (hereinafter, being also known as " sealant " sometimes) (a) the photo-electric conversion element hardening resin composition of the amine and as thermal curing agents (b).The sealant, preferably, It is used in photo-electric conversion element as the raw material of following gaskets, which includes：First electric conductivity supports There is body semiconductor to contain layer；Second conductive support body, has opposite electrode, which contains set on the semiconductor Layer and opposite electrode opposite position at a prescribed interval；Charge transfer layer is located in the first conductive support body and second The gap of conductive support body；And gasket, set on the periphery of the first conductive support body and the second conductive support body Portion, and surround charge transfer layer.
The sealant of the present invention unless otherwise indicated, refers both to the composition of the state before heat curing process is carried out.
As the epoxy resin (a) being used in the present invention, being generally used in unimolecule has at least two more than epoxy The epoxy resin of base.As this epoxy resin, can include：For example, phenol aldehyde type epoxy resin, bisphenol A type epoxy resin, Bisphenol f type epoxy resin, biphenyl type epoxy resin, triphenylmenthane type epoxy resin etc..More particularly, it can include： Bisphenol-A, Bisphenol F, bisphenol S, bisphenol fluorene, terpene diphenol, 4,4 '-'-biphenyl diphenol, 2,2 '-'-biphenyl diphenol, 3,3 ', 5,5 '-tetramethyl- [1,1 '-xenyl] -4,4 '-glycol, hydroquinone, resorcinol, naphthalenediol, three-(4- hydroxy phenyls) methane, 1,1,2,2- Four (4- hydroxy phenyls) ethane, phenol (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, benzenediol, dihydroxy naphthalene Deng) and formaldehyde, acetaldehyde, benzaldehyde, parahydroxyben-zaldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, two Cyclopentadiene, furfural, 4,4 '-bis- (chloromethyl) -1,1 '-biphenyl, 4,4 '-bis- (methoxy) -1-1 '-biphenyl, Isosorbide-5-Nitrae-bis- The condensation polymer of (chloromethyl) benzene, Isosorbide-5-Nitrae-bis- (methoxy) benzene etc. and the halogenated bisphenols such as their modifier, tetrabromobisphenol A Class, the glycidol ether compound as derived from alcohols, cycloaliphatic epoxy resin, glycidyl amine type epoxy resin, ethylene oxidic ester The epoxy resin of the solid-states such as type epoxy resin or liquid, but it is not limited to these.These can be used alone, can also be simultaneously Using two or more.These epoxy resin, it is advantageous to reducing the viscosity of photo-electric conversion element sealant of the present invention, it can be normal Fitting operation is carried out under temperature, and can play makes the formation in gap easier act on.And in these epoxy resin, preferably For, using phenol aldehyde type epoxy resin and/or bisphenol A type epoxy resin and/or bisphenol f type epoxy resin, furthermore it is preferred that be, Phenol aldehyde type epoxy resin and bisphenol A type epoxy resin can also be used simultaneously.Additionally, it is preferred that it is that can also use ring simultaneously Two kinds of different epoxy resin of oxygen equivalent.As an embodiment, can use 30~300g/eq epoxy resin and 200~ The mixture of the epoxy resin of 600g/eq.In addition, as an embodiment, the phenolic epoxy of 30~300g/eq can be used The phenol aldehyde type epoxy resin of resin and/or bisphenol A type epoxy resin and/or bisphenol f type epoxy resin and 200~600g/eq and/ Or the mixture of bisphenol A type epoxy resin base/or bisphenol f type epoxy resin.
The sealant of the present invention, in order to reduce pollution of the sealant to charge transfer layer as far as possible, preferably, in sealant Contained hydrolyzable chlorine is as few as possible.Therefore, the amount of hydrolyzable chlorine included in epoxy resin (a), preferably 600ppm Hereinafter, more preferably 500ppm hereinafter, more preferably 400ppm hereinafter, more preferably 300ppm hereinafter, be more preferably 200ppm is hereinafter, most preferably below 100ppm or be actually 0.The amount of hydrolyzable chlorine, can be for example, by will about 0.5g Epoxy resin is dissolved in the dioxanes of 20ml, and after making its reflux 30 minutes using the KOH/ ethanol solutions 5ml of 1N, uses 0.01N Silver nitrate solution titration etc. quantifies.
The content of epoxy resin (a) in the sealant of the present invention, usually 5~80 mass percent, preferably 10~ 70 mass percents, more preferably 20~60 mass percents.
The sealant of the present invention contains the amine as thermal curing agents (b).As these amines, and it is not particularly limited, But preferably using the multifunctional amine in the molecule with 2 or more amino.As having 2 or more amino in the molecule The preferred concrete example of multifunctional amine, can include by diaminodiphenylmethane, diethylenetriamine, triethylene tetramine, diamino Polyamide, amine additives that base diphenyl sulphone (DPS), isophorone diamine, linolenic dimer are synthesized with ethylenediamine etc..Especially A kind of preferred amine is amine additives class.
In addition, the thermal curing agents as the application, preferable use salable cured curing agent at less than 120 DEG C. More preferably, salable cured curing agent at maying be used at less than 110 DEG C.More preferably, it may be used at less than at 105 DEG C Salable cured curing agent most preferably, may be used at 100 DEG C or so (or below 100 DEG C) salable cured curings Agent.
Above-mentioned amine additives are the amino chemical combination as obtained from being chemically reacted epoxy resin and multifunctional amine Object.As the concrete example of amine additives, can include：Trade name, curing agent (hardener) X-3661S, curing agent (hardener) X-3670S (manufacture of ACR Co., Ltd.), (aginomoto is fine by Amicure PN-23, PN-31, PN-40, MY-24 Chemical Co., Ltd. manufactures), NOVACURE HX-3742, HX-3721, HX-3722, HX-3088, HX-3741 (Asahi Chemical Industry's electronics Material Co., Ltd. manufacture) etc. commercially available products.
In addition, " amine additives " of the ingredient of the described sealant as the present invention herein, not comprising as one kind Life is reacted by amine of the epoxy resin (a) with being used as thermal curing agents (b) obtained from implementing heat curing process to sealant Into the amine additives of object.The intention that theoretically there is no restriction, but be to reduce heat due to adding the main purpose of the amine additives Cured temperature, therefore must be the form of addition product before heat cure is carried out.
These amine additives for it is made to play the effect of potential curing agent, preferably, make grain size become smaller and make it equably It is scattered in epoxy resin (a) and uses.By making multifunctional amine or it being made to be chemically reacted to obtain with epoxy resin Amine additives average grain diameter not excessively be more than photo-electric conversion element cell gap (Cell Gap, the first electric conductivity branch The gap of support body and the second conductive support body), it can in two pieces of substrate (conductive support bodies) for being bonded photo-electric conversion element Successfully to form gap.Therefore, average grain diameter typically cell gap hereinafter, preferably 15 μm hereinafter, more preferably For 12 μm hereinafter, more preferably less than 9 μm.The grain size of these amines, can be for example, by laser diffraction/scattering formula granularity point Cloth measuring instrument (dry method) (LMS-30, the manufacture of Co., Ltd. of Seishin Entpr Co., Ltd.) measures.
As the thermal curing agents (b) contained by the sealant of the present invention, guanamines and/or imidazoles can also be used simultaneously At least one amine (preferably above-mentioned amine additives) in addition to this at least one.As can be with guanidine used at the same time Amine, and be not particularly limited, it can include：For example, dicyandiamide, OTBG o tolylbiguanide, acetylguanamine, benzoguanamine (Benzoguanamine), phenylacetyl guanamines etc..
It as can be with imidazoles used at the same time, and be not particularly limited, can include：For example, 2- ethyl imidazol(e)s, 2- Methylimidazole, 2- phenylimidazoles, 2- undecyl imidazoles, 2- heptadecyl imidazoles, 2-ethyl-4-methylimidazole, 2- phenyl -4- Methylimidazole, 1- benzyl -2- phenylimidazoles, 1 benzyl 2 methyl imidazole, 1- 1-cyanoethyl-2-methylimidazoles, 1- cyanoethyls -2- Phenylimidazole, 1- cyanoethyl -2- undecyl imidazoles, 2,4- dicyanos -6 (2 '-methylimidazole (1 ')) ethyl-s-triazine, 2, 4- dicyanos -6 (2 '-undecylimidazole (1 ')) ethyl-s-triazine etc..Wherein, preferably 2-methylimidazole, 2- undecyl miaows Azoles, 2- heptadecyl imidazoles.Sealing characteristics after curability, working life (pot life), curing under from low temperature etc. are examined Consider, more preferably 2- undecyl imidazoles.As thermal curing agents (b), preferably simultaneously using amine additives and guanamines or Imidazoles, more preferably simultaneously using amine additives and imidazoles, most preferably simultaneously using amine additives and 2- undecyls Imidazoles.
In addition, as the thermal curing agents that other can be used simultaneously, can include：For example, phenol-formaldehyde condensation polymer, first Phenol-formaldehyde condensation products, hydroxy benzaldehyde-phenol polycondensate, cresols-naphthols-formaldehyde condensation products, resorcinol-formaldehyde condensation polymer, The multifunctional phenolics such as furfural-phenol polycondensate, α-hydroxyphenyl-ω-hydrogen poly- (two phenylenedimethylidynes-hydroxyphenylene), bis-phenol A, Bisphenol F, bisphenol S, thiodiphenol, 4,4 '-diphenyl phenol, dihydroxy naphthalene, bisphenol fluorene, terpene diphenol, 2,2 '-'-biphenyl diphenol, 3,3 ', 5,5 '-tetramethyl-[1,1 '-biphenyl] -4,4 '-glycol, hydroquinone, resorcinol, naphthalenediol, three-(4- hydroxy benzenes Base) methane, 1,1,2,2- tetra- (4- hydroxy phenyls) ethane, phenol (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline Phenol, benzenediol etc.) and formaldehyde, acetaldehyde, benzaldehyde, parahydroxyben-zaldehyde, salicylaldhyde, parahydroxyacet-ophenone, adjacent hydroxyl Acetophenone, bicyclopentadiene, furfural, 4,4 '-bis- (chloromethyl) -1,1 '-biphenyl, 4,4 '-bis- (methoxy) -1-1 '-connection The condensation polymer and their modifier of benzene, Isosorbide-5-Nitrae '-bis- (chloromethyl) benzene, Isosorbide-5-Nitrae '-bis- (methoxy) benzene etc., tetrabromobisphenol The polyvalent phenols system curing agent such as the condensation product of the halogenated bisphenols class such as A, terpenes and phenol or phthalic anhydride, trimellitic anhydride, Benzenetetrahydride, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, methylnadic anhydride (Methyl nadic Anhydride), the acid anhydride type curing agents such as hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, benzophenonetetracarboxylic acid acid anhydride, carbon atom number are less than 5 Aliphatic hydrazides etc..These can use any one with thermal curing agents used at the same time, can also use 2 simultaneously Kind or more.
These can be with the usage amount of thermal curing agents used at the same time, relative to thermal curing agents (b) in the sealant of the present invention Total amount, usually more than 0 mass percent 50 mass percents are hereinafter, below preferably 30 mass percents.Implement one In mode, sealant can be with thermal curing agents used at the same time not comprising these (other than amine).In another embodiment, it seals The thermal curing agents of agent, can be only made of amine (particularly preferably amine additives class) or by guanamines or imidazoles and Amine (particularly preferably amine additives class) composition in addition to this.
The present invention the photo-electric conversion element thermal curing agents (b) used in sealant content, relative in this hair Epoxy group 1 equivalent of the bright photo-electric conversion element in the epoxy resin (a) used in sealant, activity in thermal curing agents (b) The amount of hydrogen, usually 0.8~3.0 equivalent, preferably 0.8~2.5 equivalent, more preferably 0.8~2.0 equivalent, be more preferably 0.9~2.0 equivalent is most preferably 0.9~1.8 equivalent.In addition, described reactive hydrogen represents and can be with epoxy resin herein The hydrogen atom that the hetero atom for the thermal curing agents that possessed epoxy group is reacted is combined.
As an embodiment, photo-electric conversion element sealant of the invention can be not included in point as curing agent Poly-thiol compound in sub with 2 or more mercaptos and the polyhydrazide chemical combination in the molecule with 2 or more hydrazide groups Any one in object or two kinds.
The photo-electric conversion element sealant of the present invention, can include filler (c) as needed.It is filled out as used The concrete example of agent (c) is filled, can be included：Vitreous silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, Magnesium carbonate, barium sulfate, calcium sulfate, mica, talcum, clay, aluminium oxide (alumina), magnesia, zirconium oxide, aluminium hydroxide, hydrogen Magnesia, hydrated magnesium silicate, calcium silicates, alumina silicate, lithium aluminosilicate, zirconium silicate, barium titanate, glass fibre, carbon fiber, two sulphur Change molybdenum, asbestos etc..Among those, as can preferably enumerate：For example, hydrated magnesium silicate, calcium carbonate, aluminium oxide, crystallization Silica and vitreous silica etc..It can also be to surface treatments such as these implementation chemical treatments.Surface treatment can pass through example Such as silane coupling agent organic compound carries out.These fillers, can use any one or can also mix two kinds with Upper use.The filler (c) that contains of sealant of the present invention, average grain diameter be preferably 50 μm hereinafter, more preferably 40 μm with Under, more preferably 30 μm hereinafter, more preferably 20 μm hereinafter, more preferably 10 μm hereinafter, most preferably less than 5 μm. When being bonded upper and lower base plate during manufacture photo-electric conversion element, by making the average grain diameter of filler for 50 μm hereinafter, can To form appropriate gap.In addition, the average grain diameter of filler herein is, such as laser diffraction/scattering formula granularity is being used In grading curve measured by distribution measuring apparatus, reach the grain size of 50 mass percents from the accumulation of particle smaller.
In the photo-electric conversion element sealant of the present invention, content during using filler (c), usually 0~60 matter Percentage is measured hereinafter, preferably 5~60 mass percents, more preferably 15~50 mass percents.In manufacture photoelectric conversion element During part, due to filler content for 60 mass percents hereinafter, therefore can be formed to keep the appropriate of charge transfer layer Cell gap.
In the photo-electric conversion element sealant of the present invention, in order to improve adhesive strength, silane coupling agent can be used (d).It, then can be with as long as the adhesive strength between sealant and conductive support body can be improved as silane coupling agent (d) It uses.As the concrete example of workable silane coupling agent, can include：3- glycydoxy trimethoxy silicon Alkane, 3- glycydoxies methyldiethoxysilane, 3- glycydoxy methyldiethoxysilanes Wait glycidols methoxy silane class, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, N- phenyl-gamma-amino propyl Trimethoxy silane, N- (2- aminoethyls) 3- aminopropyltriethoxies dimethoxysilane, N- (2- aminoethyls) 3- aminopropyltriethoxies two Methoxy silane, 3-aminopropyltriethoxysilane, 3- mercaptopropyltriethoxysilanes, vinyltrimethoxysilane, N- (2- (vinyl benzyl ammonia) ethyl) 3-aminopropyltriethoxysilane hydrochloride, three ethoxy of 3- methacryloxypropyls Base silane, 3- chloropropyls diethoxy silane, 3- chloropropyl triethoxysilanes, 3- glycydoxy methyl Glycidols Ethoxysilane classes such as diethoxy silane, 3- glycydoxy triethoxysilanes etc..At these In, preferably glycidol Ethoxysilane class or glycidol methoxy silane class.In addition, among those, there is amino Silane coupling agent can obtain good adhesive strength, therefore more preferably.In above-mentioned silane coupling agent, as more excellent The silane coupling agent of choosing can enumerate：For example, N- (2- aminoethyls) 3- aminopropyltriethoxies dimethoxysilane, N- (2- ammonia second Base) 3- aminopropyltriethoxies dimethoxysilane, 3-aminopropyltriethoxysilane, N- (2- (vinyl benzyl ammonia) ethyl) 3- Aminopropyltriethoxywerene werene hydrochloride etc..These silane coupling agents, can use one kind, and can also mix two kinds with Above use.The content for the silane coupling agent being used in the present invention in the photo-electric conversion element sealant of the present invention, is led to It is often 0~2 mass percent hereinafter, preferably 0.1~2 mass percent, more preferably 0.2~1.5 mass percent.This Outside, in one embodiment, the silane coupling agent being used in the present invention, relative to 100 mass parts of epoxy resin (a), such as It is 0~20 mass parts, more typical is 0.1~10 mass parts, preferably 0.5~10 mass parts, more preferably 1~10 mass Part, more preferably more than 1 mass parts to 10 mass parts, most preferably 1.5~8 mass parts.
The photo-electric conversion element sealant of the present invention can include organic solvent, organic filler, stress as needed Releasing agent etc..It, can further additives such as hybrid pigment, leveling agent, antifoaming agent, viscosity modifier in addition, in the encapsulant. Blendable additive, and be not particularly limited, additive amount can also be properly selected according to its purpose.These additives, Preferably, the additive relatively low to the pollution of charge transfer layer.
The photo-electric conversion element sealant of the present invention, can manufacture, that is, by the following method by the epoxy resin (a), the thermal curing agents (b) comprising amine, as needed arbitrarily with filler (c), silane coupling agent (d) and various additions Agent is stirred and is mixed with random order, preferably, them is made to reach each content, then, for example, by three rollers, sand The mixing arrangements such as grinding machine, ball mill uniformly mix.As needed, can also implement after terminating to mix in order to remove impurity Filter is handled.
The photo-electric conversion element sealant of the present invention, is suitable for after 2 pieces of substrates (conductive support body) are bonded from note The autofrettage of the photo-electric conversion element of entrance injection charge transfer layer.This hair clamped by 2 pieces of substrates of being heating and curing can be passed through The weir of bright sealant is sealed.As the method that the sealant of the present invention is coated on substrate, rod coating can be included The rubbing methods such as method, dip coating, spin-coating method, spray coating method, silk screen print method, scraper method, drop-coating (dispensing), can basis Type, the shape of substrate are properly selected or are used simultaneously.From the viewpoint of productivity, it is preferable to use spray coating method, silk screen Print process, drop-coating.The photo-electric conversion element sealant of the present invention, is equally applicable to usually convert light energy into electric energy All photo-electric conversion elements.In order to draw the electric current generated from photo-electric conversion element, solar cell be configured lead and by its As closed circuit.The present invention photo-electric conversion element sealant, be best suited for manufacture dye-sensitized photoelectric conversion device with And the solar cell with the photo-electric conversion element.
Hereinafter, to using the photo-electric conversion element and solar-electricity that the photo-electric conversion element of the present invention manufactured with sealant Pond is described in detail.Embodiment in detail below, is merely illustrative, and the present invention is not limited to these.
In general, dye-sensitized photoelectric conversion device, contains layer to have on surface by the semiconductor of dye sensitization First conductive support body (oxide semiconductor electrode), the second conductive support body and charge as opposite electrode turn Layer is moved to form for main inscape.The photo-electric conversion element sealant of the present invention, is using purpose, bonding first Conductive support body and the second conductive support body, and keep charge transfer layer between two supporters.As electric conductivity branch Support body can make for example with FTO (fluorine-doped tin oxide), ATO (the disastrously miscellaneous tin oxide of antimony), ITO (the disastrously miscellaneous tin oxide of indium) for representative Conductive material the substrates such as glass, plastics, thin polymer film (polymer film), quartz, silicon surface film and It uses.The thickness of substrate, usually 0.01~10mm, shape can take film-form to the various shapes of plate, and two At least one of block substrate can use the substrate with translucency.The electric conductivity of conductive support body, usually 1000 Ω/ cm2Hereinafter, preferably 100 Ω/cm2Below.
As the particle of oxide semiconductor, preferably metal chalcogenide for being used to prepare semiconductor and containing layer.As Its concrete example can include：Titanium (Ti), zinc (Zn), tin (Sn), niobium (Nb), tungsten (W), indium (In), zirconium (Zr), yttrium (Y), lanthanum (La), the oxide of the transition metal such as tantalum (Ta), aluminium (Al) oxide, silicon (Si) oxide, titanium silicon oxide (SiTiO3), calcium Titanium oxide (CaTiO3), barium titanium oxide (BaTiO3) etc. perofskite type oxides etc..Among those, particularly preferably, two Titanium oxide (TiO2), zinc oxide (ZnO), tin oxide (SnO2).It, can be with as preference in addition, these can also be used in mixed way Include SnO2- ZnO mixes class.In the case where mixing class, can also be mixed in the state of particle or following It is mixed under the mud or mushy stage or various composition is laminated in stratiform and is used.In mud or paste The concentration of oxide semiconductor, usually 1~90 mass percent, preferably 5~80 mass percents.Used oxide The primary particle size of semiconductor, usually 1~200nm, preferably 1~50nm.
The preparation method that semiconductor contains layer has, and is made of by depositing directly to be made on substrate oxide semiconductor Film method；On substrate after coating or coating mud or paste, the method that is made by applying pressure；Substrate is made Make the method that it electrically deposits for electrode；On substrate coating or coating mud or paste after, be dried, cure or fire Method etc..As coating or coating, can include：Stick coating method, spin-coating method, spray coating method, silk screen print method, is scraped dip coating The skill in using a kitchen knife in cookery, drop-coating etc..These methods can be properly selected according to type, the shape of substrate or be used simultaneously.From oxide The aspect of performance of semi-conducting electrode considers, preferably, uses the method for mud or paste.Mud, can be by using dividing Powder makes the oxide semiconductor particle of secondary aggegation be dispersed in decentralized medium, make its average 1 grain size be usually 1~ 200nm or predecessor, that is, alkoxide using sol-gal process hydrolysis oxidation object semiconductor etc. are obtained.It is in addition it is also possible to mixed It closes the particle of the different oxide semiconductor of particle diameter distribution and uses.
As the decentralized medium for disperseing mud, as long as being capable of the particle of dispersal oxide semiconductor, then not by special limit System.As decentralized medium, water can be used, the alcohol (alcohol) such as ethyl alcohol (Athanol), terpinol (terpineol), third The organic solvents such as the hydrocarbons such as the ketone such as ketone, acetylacetone,2,4-pentanedione, hexane.These can also be used in mixed way.Become from the viscosity for reducing mud From the aspect of change, it is preferable to use water.
The amicron stablized in order to obtain, can also add dispersion stabilizer etc. in mud.As workable point The concrete example of dispersion stabilizer can include：1 valency alcohol such as the multivalence such as polyethylene glycol alcohol, phenol, octanol etc. itself or they mutually Between copolymer；The celluloses such as hydroxypropyl methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose spread out Biology；Polyacrylamide；Acrylamide, (methyl) acrylic acid or its salt, (methyl) acrylate ((methyl) methyl acrylate, (methyl) ethyl acrylate etc.) etc. itself or mutual copolymer；Acrylamide, (methyl) acrylic acid or its salt, (methyl) The copolymer of the hydrophobic monomers such as acrylate etc. and styrene, ethylene, propylene and for water-soluble polyacrylic derivative； The salt of melamine sulfonic formaldehyde condensation compound；The salt of naphthalene sulfonic acid-formaldehyde condensation product；The lignosulfonates of high molecular weight；Hydrochloric acid, Acid such as nitric acid, acetic acid etc., but it is not limited to these.In addition, these dispersion stabilizers can be used alone, can also 2 kinds with It is upper to use simultaneously.
Among those, preferably, the multivalence such as polyethylene glycol alcohol, phenol, octanol etc. itself or their mutual copolymerization Object, poly- (methyl) acrylic acid, poly- (methyl) sodium acrylate, poly- (methyl) potassium acrylate, poly- (methyl) Lithium acrylate, carboxymethyl are fine Tie up element, hydrochloric acid, nitric acid, acetic acid etc..
It, can be in the base for being used in conductive support body after the mud being coated in conductive support body is dried Processing is fired at the temperature of the melting point (or softening point) of plate below.Firing temperature, usually 100~900 DEG C, preferably 100~600 DEG C.In addition, the firing time and being not particularly limited, but substantially within 4 hours.In conductive support body Semiconductor contains the film thickness of layer, usually 1~50 μm.
In order to improve surface smoothness, layer can also be contained to semiconductor and implements 2 processing (with reference to non-patent literature 1). For example, by will be equipped with the conductive support body direct impregnation of the film that the semiconductor prepared using the method contains layer in The solution such as the alkoxide or chloride, itrated compound, sulfide of the identical metal used when preparing semiconductor and containing layer simultaneously carry out It dries or by arbitrarily selecting further implementation and the identical firing (reheating), semiconductor can be improved and contain layer Smoothness.Herein, it as metal alkoxide, can include：Tetraethyl titanate, isopropyl titanate, tert-butyl alcohol titanium, n- dibutyl-two Acetyl tin etc., and its alcoholic solution can be used.In the case of chloride, it can include：For example, titanium tetrachloride, four Stannic chloride, zinc chloride etc. can use its aqueous solution.The semiconductor being made of obtained oxide semiconductor particle contains The specific surface area of layer, usually 1~1000m2/ g, preferably 10~500m2/g。
Then, it is illustrated to sensitizing dye is carried on the technique that semiconductor contains layer.As sensitizing dye, as long as tool Playing the role of containing with composition semiconductor makes light absorption increase sense together with the semiconductive particles of layer, then is not particularly limited.As increasing Infection material, can be used alone the metal complex dyes comprising metallic elements such as rutheniums or the organic dyestuff not comprising metal, and And it can also be mixed a variety of and used with arbitrary proportion.In the case where being used in mixed way, between various metals Complex dyes, more Arbitrary combination can be carried out between kind organic dyestuff and between metal complex dyes and organic dyestuff.Pass through blended absorbent The different a variety of dyestuffs of wavelength region can use the absorbing wavelength of wider width, can obtain the higher sun of transfer efficiency It can battery.
The metal complex dyes that can be carried, and be not particularly limited, but preferably phthalocyanine and porphyrin etc., more preferably ruthenium Complex compound.In addition, the organic dyestuff that can be carried also is not particularly limited, can include：For example, metal-free phthalocyanine, porphyrin with The methines systems such as cyanine, merocyanine, oxonols (oxonol), triphenylmenthane system, acrylic acid series dyestuff, pyrazolone system methine dyes Dyestuff and xanthene system, anthraquinone system, the dyestuffs such as are at azo system.Preferably, it is speciallyyed permit in Japanese documentation International Publication WO2002-001667 bulletins, Japanese documentation International Publication special permission WO2002-011213 bulletins, Japanese documentation International Publication special permission WO2002-071530 bulletins, Japanese Patent Laid-Open 2002-334729 bulletins, Japan Patent text Offer special open 2003-007358 bulletins, Japanese Patent Laid-Open 2003-017146 bulletins, Japanese Patent Laid-Open 2003-059547 bulletins, Japanese Patent Laid-Open 2003-086257 bulletins, Japanese Patent Laid-Open 2003- No. 115333 bulletins, Japanese Patent Laid-Open 2003-132965 bulletins, Japanese Patent Laid-Open 2003-142172 Bulletin, Japanese Patent Laid-Open 2003-151649 bulletins, Japanese Patent Laid-Open 2003-157915 bulletins, Japan Patent document special open 2003-282165 bulletins, Japanese Patent Laid-Open 2004-014175 bulletins, Japanese documentation Special open 2004-022222 bulletins, Japanese Patent Laid-Open 2004-022387 bulletins, Japanese Patent Laid-Open 2004- No. 227825 bulletins, Japanese Patent Laid-Open 2005-005026 bulletins, Japanese Patent Laid-Open 2005-019130 Bulletin, Japanese Patent Laid-Open 2005-135656 bulletins, Japanese Patent Laid-Open 2006-079898 bulletins, Japan In patent document special open 2006-134649 bulletins, Japanese documentation International Publication special permission WO2006-082061 bulletins etc. Recorded dyestuff.More preferably, methines based dye such as merocyanine and above-mentioned acrylic acid series etc..When mixing a variety of dyestuffs uses Various dyestuffs ratio and be not particularly limited, but be preferably generally, each dyestuff at least use 10 moles of more than %.Make With dissolving the solution of two or more dyestuffs or when the dispersion liquid of dispersion makes the semiconductor contain layer carrying dyestuff, the dyestuff in solution is total Concentration is identical when can be with only carrying a kind of.Solvent when being used as a variety of dyestuffs of mixing, can for oxide semiconductor To use solvent as described above, and used each dyestuff can be the same or different with solvent.
As the method for carrying sensitizing dye, the conductive support body that will contain layer equipped with above-mentioned semiconductor can be included It is impregnated in the method for dispersion liquid that dyestuff is dissolved in the solution of solvent or dyestuff is scattered in solvent.In solution or dispersion liquid Dye strength, can suitably be determined according to the type and solubility of dyestuff.Dipping temperature substantially can be from room temperature to solvent Boiling point, in addition, dip time can be 1 hour~72 hours or so.Workable solvent during as dissolving sensitizing dye Concrete example can include：Methanol, ethyl alcohol, acetone, acetonitrile, dimethyl sulfoxide (DMSO), dimethylformamide, the tert-butyl alcohol, tetrahydrofuran Deng.These can be used alone, and can also be mixed a variety of and used with arbitrary proportion.Sensitizing dye in solution it is dense Degree, usually 1 × 10-6M~1M, preferably 1 × 10-5M~1 × 10-1M.Accordingly, it can obtain as oxide semiconductor electricity Pole use with the conductive support body for containing layer by the semiconductor of dye sensitization.
When dyestuff being carried on semiconductor containing layer, the association of dye granule in order to prevent, under the coexisting of inclusion compound The effect for carrying dyestuff is preferable.Herein, it as inclusion compound, can include：The steroids such as cholic acid, crown ether, cyclodextrin, Calixarenes, polyethylene oxide etc..Preferably, cholic acid, deoxycholic acid, chenodeoxycholic acid, Methyl cholate, sodium taurocholate, ursodeoxycholic The Cholic acids such as acid, polyethylene oxide etc..As the occupation mode of these inclusion compounds, dye solution can be added to, it can also be pre- First inclusion compound, which is dissolved in after solvent, makes dyestuff dissolve or disperse.These inclusion compounds can be used in combination of two or more, ratio It can also arbitrarily select.
In addition it is also possible to contained after it is made to carry dyestuff using the amino-compounds such as 4- tert .-butylpyridines processing semiconductor Layer.Processing method may be used such as dipping and contain layer equipped with the semiconductor of ethanol solution that dyestuff is carried on amino-compound The method of conductive support body etc..
It in opposite electrode, can use on the surface of the conductive support bodies such as FTO conductive glass, be deposited on oxidation also Original is that the electrically conductive microparticles such as the silver of catalyst action, carbon, rhodium, ruthenium or coating are played in the reduction reaction of electrolyte, fires these Substance of the predecessor of electrically conductive microparticle etc..
Then, the photo-electric conversion element for using the present invention is pasted with sealant with the dye equally obtained as described above The conductive support body (oxide semiconductor electrode) and the method for opposite electrode that the semiconductor that material increases sense contains layer are said It is bright.
First, by dispenser (dispenser) in addition to the inlet of charge transfer layer, screen process press etc., The sealant for the present invention for being added to gasket (gap control material) is coated on any one conductive support body with weir shape After the peripheral portion of conducting surface, in a manner of making the conducting surface of the first conductive support body and the second conductive support body facing It is superimposed and heats other conductive support bodies, so as to so that sealant cures.Herein, such as glass can be used as gasket Glass fiber, silicon dioxide microsphere, polymer microballoon etc. can further use the particle of the metal coatings such as golden pearl, Marin Pearl Deng.Its average diameter, although different according to purpose, usually 1~100 μm, preferably 10~40 μm.Its usage amount, phase For 100 mass parts of sealant of the present invention, usually 0.1~10 mass parts, preferably 0.5~5 mass parts, more preferably 1~2.5 mass parts.The heat cure condition of sealant, typically, temperature are 80~120 DEG C, and the time is 1~3 hour.In addition, make For the method for heat cure, the method for being clipped on interlayer and carrying out using the hot press with 2 pieces of heating plates may be used, use folder Method carried out in an oven after tool is fixed etc..The gap of first conductive support body and the second conductive support body, usually 1 ~100 μm, preferably 4~50 μm.
The dye-sensitized photoelectric conversion device of the present invention, by a pair of conductive supporter being equally bonded as described above Gap injection charge transfer layer complete.As charge transfer layer, can use make redox system electrolyte pair and hole Transmission material etc. is dissolved in solvent and the solution in room temperature fuse salt (ionic liquid).It is electrolysed as used redox system Matter can include：By the halogen redox system for forming halide ion as the halide and halogenic molecule of counter ion The metal oxygen of the metal complexes such as electrolyte, hydroferrocyanate-ferricyanate and diamyl iron-diamyl iron ion, cobalt complex etc. It is the organic oxidations such as electrolyte, alkyl hydrosulfide-alkyl disulfide, viologen dye, hydroquinone-quinone reduction system electricity to change reduction Solve matter etc..Preferably, halogen redox system electrolyte.It, can be with as the halogenic molecule in halogen redox system electrolyte It includes：For example, iodine molecule and molecular bromine etc., preferably iodine molecule.In addition, as halide, can include：For example, iodine It is halogenated to change lithium (LiI), sodium iodide (NaI), potassium iodide (KI), cesium iodide (CsI), diiodinating calcium (CaI2), cupric iodide (CuI) etc. Organic 4 grades of the halogens such as metal salt or tetraalkylammonium iodides, iodate imidazoles, 1- methyl -3- alkyl imidazoles iodine, Propidium iodide Ammonium salt etc..Preferably, using iodide ion as counter ion salt class compounds.As its concrete example, can include：Lithium iodide, Sodium iodide, iodate leptodactyline etc..These can be used alone, and can also combine two or more and use.
In addition, when charge transfer layer is made of the solution comprising redox system electrolyte, electricity is used as its solvent The chemical inert substance of aspect.As the concrete example of used solvent, can include：Acetonitrile, valeronitrile, propene carbonate, Ethylene carbonate, 3- methoxypropionitriles, 3- butoxy propionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol (DEG), triethylene glycol, Dimethoxy-ethane, diethyl carbonate, diethyl ether, dimethyl carbonate, 1,2- dimethoxy-ethanes, dimethylformamide, diformazan Base sulfoxide, 1,3-dioxolane, methyl formate, 2- methyltetrahydrofurans, 3- methyl oxazolidine -2- ketone, gamma-butyrolacton, ring fourth Sulfone, tetrahydrofuran, water etc..Among those, preferably, acetonitrile, propene carbonate, ethylene carbonate, 3- methoxypropionitriles, first Oxygroup acetonitrile, ethylene glycol, 3- methyl oxazolidine -2- ketone, gamma-butyrolacton etc..These can be used alone, and can also combine It is two or more and use.The concentration of redox system electrolyte in solution, usually 0.01~99 mass percent, preferably 0.1~90 mass percent.
In addition, when morphosis of the charge transfer layer with the composition comprising redox system electrolyte, as solvent It uses room temperature molten liquid (ionic liquid).As the concrete example of used room temperature molten liquid, can include：1- methyl -3- Alkyl imidazole iodine, tetrafluoroethylene imidazoles, 1- ethyl imidazol(e)s sulfonate, alkyl imidazole trifluoro sulfonamide, 1- methyl pyrroles Cough up alkane iodide etc..In addition, in order to improve the durability of photo-electric conversion element, for example, by being dissolved in low molecular gelling agents Charge transfer layer and thicken either injection simultaneously using the charge transfer layer of active constituent after make its react and be gelled or The gel polymerizeing in advance is made to penetrate into charge transfer layer, so as to realize gel electrolyte.
On the other hand, when charge transfer layer is complete solid-state, hole mobile material and P-type semiconductor can also be used to replace For redox system electrolyte.As used hole mobile material, can include：Amine derivative and polyacetylene, polyphenyl Electric conductive polymers such as amine, polythiophene etc..In addition, as P-type semiconductor, can include：Cupric iodide (CuI), thiocyanic acid are sub- Copper (CuSCn) etc..
After injecting charge transfer layer to the gap of a pair of conductive supporter, the inlet of charge transfer layer is sealed, It can obtain photo-electric conversion element.The sealing material (sealant) of inlet as sealing charge transfer layer, can use different Butene resins, epoxy resin, ultraviolet light (UV) curability acrylic resin etc..
On the other hand, as another production method of photo-electric conversion element, following methods can also be used.That is, arbitrary The peripheral portion of the conducting surface of one conductive support body is not provided with charge transfer layer inlet and sets the weir of sealant, then, Charge transfer layer as hereinbefore is configured to the inside on the weir of sealant, under reduced pressure so that the first conductive support body and Between the facing mode of the conducting surface of second conductive support body is carried and is formed while being bonded another conductive support body Then gap makes sealant cures, so as to obtain photo-electric conversion element.
Fig. 1 is to illustrate the major part of the structure of dye-sensitized photoelectric conversion device prepared by the sealant using the present invention Schematic cross-section.In figure, 1 is the conductive conductive support body in inside, and 2 be to contain layer by the semiconductor of dye sensitization (1 and 2 are referred to as oxide semiconductor electrode), 3 be pair that silver etc. is configured on the conducting surface on the inside of conductive support body Electrode is put, 4 are arranged in the charge transfer layer in the gap of a pair of conductive supporter, and 5 be the sealant of the present invention, and 6 be glass Substrate.Lead is configured, and be inserted into resistance components in-between by the positive electrode and negative electrode in obtained photo-electric conversion element, So as to obtain the solar cell of the present invention.
The sealing material of the present invention, multiple dye-sensitized solar cells of planar configuration are equally applicable to electrical series Large area dye-sensitized solar cell module manufacture.It is well known that the dye-sensitized solar cell of large area Modular structure there are many.The modular structure in any kind can be used in the sealant of the present invention.For example, it can be used in day The dye sensitization with cascaded structure recorded in patent document International Publication special permission WO2009/057704 bulletins etc. is too Positive energy battery module.
The photo-electric conversion element sealant of the present invention, in the manufacturing process of photo-electric conversion element, the coating to substrate Operability, stickiness, adhesive strength, up time (working life) at room temperature, curability at low temperatures are better, and charge is turned The pollution for moving layer is very low.Therefore, by using the photo-electric conversion element of the obtained present invention of the sealant, not by electricity Action caused by the pollution of lotus transfer layer is bad, and adhesiveness, moisture-resistance reliability are good.Moreover, by using the opto-electronic conversion Solar cell prepared by element, manufacture efficiency is higher, and its durability is also relatively good.
【Embodiment】
Hereinafter, the present invention is more specifically described according to embodiment, but the present invention is not limited to these embodiments.
Embodiment 1
As epoxy resin (a) to RE-310S (trade name, bisphenol A type epoxy resin, Nippon Kayaku K. K's system Make, epoxide equivalent 185g/eq., below the amount 400ppm of hydrolyzable chlorine) 90 mass parts addition EP-1001 (trade name, bisphenol-A Type epoxy resin, Mitsubishi chemical Co., Ltd's manufacture, epoxide equivalent 475g/eq.) 10 mass parts and it is heated dissolving.It is inciting somebody to action After the epoxy resin is cooled to room temperature, add as filler (c) SSP-07DM (trade name, surface treated silica, Maximum particle diameter be 0.7 μm) 90 mass parts, KBM-403 (trade name, epoxy silane coupling agent as silane coupling agent (d) (γ-glycidoxypropyltrimethoxysilane alkane), the manufacture of silica gel Co., Ltd. of SHIN-ETSU HANTOTAI) 1 mass parts, and mixed using three rollers Dispersion, and add PN-31 (trade name, epoxy resin amine additives, the aginomoto fine chemistry strain as thermal curing agents (b) Formula commercial firm manufactures, 8.8 μm of average grain diameter) 20 mass parts, it is further mixed and disperseed using three rollers, so as to obtain the photoelectricity of the present invention Conversion element sealant 1.With the viscosity of the E types viscosity meter sealant 1, result 73Pas at 25 DEG C.
Comparative example 1
By 70 mass parts of RE-310S, EPPN-510H (trade name, triphenol methylmethane type ring as epoxy resin (a) Oxygen resin, Nippon Kayaku K. K's manufacture, epoxide equivalent 165g/eq., below the amount 550ppm of hydrolyzable chlorine) 20 mass parts And YD-017 (trade name, bisphenol A-type solid epoxy resin, the manufacture of Dongdu chemical conversion industry Co., Ltd., epoxide equivalent 1900g/eq.) 10 mass parts, PN-152 (trade name, thermoplastic phenolic resin, Japanese chemical drug strain as thermal curing agents (b) Formula commercial firm manufactures, Ahew 100g/eq.) 7.5 mass parts, 1 mass parts of KBM-403 as silane coupling agent (d) add Heat of solution is in 30 mass parts of butyl cellosolve as solvent.After the lysate is cooled to room temperature, further add For using substance (224 DEG C of melting point, the activity of airslide disintegrating mill progress fine grinding as the isopthalic dihydrazide of thermal curing agents (b) Hydrogen equivalent 48.5g/eq., 1.7 μm of average grain diameter, 7 μm of maximum particle diameter) 19 mass parts, the average grain diameter as filler (c) be Less than 0.5 μm 90 mass parts of aluminium oxide and aerosil (fumed silica) 3.5 mass parts, and pass through three rollers Mixing dispersion, 2,4- diamino -6- [2 '-methyl miaows that addition is less than 3 μm as the average grain diameter of curing accelerator thereto Azoles-(1 ')] -5 mass parts of ethyl-s-triazine isocyanuric acid adduct, obtain photo-electric conversion element sealant 2.At 25 DEG C The lower viscosity with the E types viscosity meter sealant 2, result 47Pas.
Embodiment 2
In addition to 90 mass parts of (a) RE-310S in embodiment 1 are changed to 80 mass parts, multi-functional epoxy is added again Resin EPPN-501 (trade name, triphenol methylmethane type epoxy resin, Nippon Kayaku K. K's manufacture, epoxide equivalent 165g/ Eq., below the amount 550ppm of hydrolyzable chlorine) 10 parts, 3 matter will be changed to as 1 mass parts of KBM-403 of silane coupling agent (d) Part is measured, as thermal curing agents (b) addition C11Z (trade name, 2- undecyl imidazoles, four countries are melted into Co., Ltd.'s manufacture) 3 matter It measures other than part, the photo-electric conversion element sealant 3 of the present invention has been obtained using method same as Example 1.At 25 DEG C With the viscosity of the E types viscosity meter sealant 3, result 278Pas.
Embodiment 3
In addition to 90 mass parts of (a) RE-310S in embodiment 1 are changed to 80 mass parts, multi-functional epoxy is added again Resin EPPN-501 (trade name, triphenol methylmethane type epoxy resin, Nippon Kayaku K. K's manufacture, epoxide equivalent 165g/ Eq., below the amount 550ppm of hydrolyzable chlorine) other than 10 parts, the photoelectricity of the present invention has been obtained using method same as Example 1 Conversion element sealant 4.With the viscosity of the E types viscosity meter sealant 4, result 443Pas at 25 DEG C.
Embodiment 4
Other than 1 mass parts of KBM-403 as silane coupling agent (d) in embodiment 1 are changed to 3 mass parts, The photo-electric conversion element sealant 5 of the present invention has been obtained using method same as Example 1.E type viscosity is used at 25 DEG C Meter measures the viscosity of the sealant 5, result 31Pas.
Embodiment 5
In addition to C11Z (trade name, 2- undecyl imidazoles, the four countries as thermal curing agents (b) in addition embodiment 1 Manufactured into Co., Ltd.) other than 3 mass parts, the photo-electric conversion element of the present invention has been obtained using method same as Example 1 With sealant 6.With the viscosity of the E types viscosity meter sealant 6, result 80Pas at 25 DEG C.
[evaluation test 1]
As the Performance Evaluation of each sealant to being made in embodiment 1,3,4,5 and comparative example 1, measure stretching and cut Shearing stress (longitudinal shear strength).In addition, as each close to being made in embodiment 2 and comparative example 1 The Performance Evaluation of agent is sealed, implements the measurement to solvent swell degree.
Tensile shear strength is measured in accordance with the following methods.
A diameter of 50 μm of 1 mass parts of glass fibre as gasket are added, and mixed to each 100 mass parts of sealant Close stirring.The sealant is coated in the conductive support body (FTO glass substrates) of 50mm × 50mm using dispenser, is passed through Heating plate heated and make solvent volatilize after, on the sealant in conductive support body be bonded 2mm × 2mm sheet glass, And make its curing under the conditions of 100 DEG C and 1 hour, tensile shear strength is measured to obtained test film.
【Table 1】
It is measured in accordance with the following methods to solvent swell degree (swellbility).
Each sealant is coated on heat-resistant film using glue spreader (applicator, 200 μm of film thickness), at 100 DEG C And make its curing under conditions of 1 hour.Be applicable in obtained cured film the piercing knife (Punch blade) of 3cm × 3cm and 4 pieces of drift test pieces are made.After the quality (quality before dipping) for measuring each test film, with 3- methoxypropionitriles (3MPN) It is put into togerther in pressure vessel, and pressure vessel is heated 2 hours at 85 DEG C.After heating, pressure vessel is cooled to Room temperature, wiping is attached to the 3MPN on taken out test film, and measures the quality (quality after dipping) of test film.Pass through { (leaching The quality before quality/dipping after stain) -1 } × 100 calculate and acquire solvent impregnated front and rear percent mass penalty, and by 4 pieces of matter The average value of increment rate is measured as swellbility (%).
【Table 2】
Embodiment 2 Comparative example 1
The type of sealant 3 2
Swellbility (%) 2.648 3.83
As shown in the result of table 1 and table 2, sealant 1,4,5,6 of the invention shows higher compared with sealant 2 Adhesive strength.On the other hand, sealant 3 of the invention shows relatively low solvent swell degree compared with sealant 2.These results It has been shown that, since the sealant of the application is conducive to make dye-sensitized solar cell, and at low temperature under low temperature (100 DEG C) Element can be made, therefore can effectively manufacture element i.e. energy saving and with higher reliability.
【Industrial utilizability】
The photo-electric conversion element sealant of the present invention, in the manufacturing process of photo-electric conversion element, the coating to substrate Operability, stickiness, adhesive strength, up time (working life) at room temperature, curability at low temperatures are good, and to electric charge transfer The pollution of layer is very low.Using photo-electric conversion element of the invention obtained from this sealant, not by charge transfer layer Pollution caused by action it is bad, and adhesiveness, moisture-resistance reliability are good.In addition, in the photo-electric conversion element for using the present invention When manufacturing photo-electric conversion element with sealant, it is bad to occur performance, and can improve productivity.

Claims (11)

1. a kind of photo-electric conversion element sealant, which is characterized in that containing epoxy resin (a) and as thermal curing agents (b) Amine.
2. photo-electric conversion element sealant according to claim 1, which is characterized in that containing thermal curing agents (b), relatively 1 equivalent of epoxy group in epoxy resin (a), the amount of reactive hydrogen is 0.8~3.0 equivalent in thermal curing agents (b).
3. photo-electric conversion element sealant according to claim 1 or 2, which is characterized in that thermal curing agents (b) are that amine adds Into object.
4. photo-electric conversion element sealant as claimed in any of claims 1 to 3, which is characterized in that heat cure Agent (b) includes at least two amines, which includes at least one amine with other than these of guanamines and/or imidazoles It is at least one.
5. photo-electric conversion element sealant according to claim 4, which is characterized in that imidazoles include 2- undecyls Imidazoles.
6. photo-electric conversion element sealant as claimed in any of claims 1 to 5, which is characterized in that containing filling out Fill agent (c).
7. photo-electric conversion element sealant according to claim 6, which is characterized in that filler (c) is to select Free water It closes more than one kind or two kinds of group of magnesium silicate, calcium carbonate, aluminium oxide, crystalline silica and vitreous silica composition, and Its average grain diameter is less than 50 μm.
8. photo-electric conversion element sealant as claimed in any of claims 1 to 7, which is characterized in that contain silicon Alkane coupling agent (d).
9. photo-electric conversion element sealant according to claim 8, which is characterized in that silane coupling agent (d) is to shrink Glycerine Ethoxysilane class or glycidol methoxy silane class.
10. a kind of photo-electric conversion element, which is characterized in that including：
First conductive support body contains layer with semiconductor；
Second conductive support body, with opposite electrode, the opposite electrode set on the semiconductor contain layer and opposite electrode with The opposite position in defined interval；
Charge transfer layer is located in the gap of the first conductive support body and the second conductive support body；And
Gasket set on the peripheral portion of the first conductive support body and the second conductive support body, and surrounds charge transfer layer,
The gasket is formed as the photo-electric conversion element described in any one in claim 1 to 9 with sealant.
11. a kind of solar cell with photo-electric conversion element according to any one of claims 10.
CN201680060851.2A 2015-11-09 2016-11-09 sealant Pending CN108235790A (en)

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JP2015219565 2015-11-09
JP2015-219565 2015-11-09
JP2016-148236 2016-07-28
JP2016148236 2016-07-28
PCT/JP2016/083289 WO2017082319A1 (en) 2015-11-09 2016-11-09 Sealing agent

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CN101218707A (en) * 2005-07-07 2008-07-09 日本化药株式会社 Sealing agent for photoelectric converter and photoelectric converter using same
WO2010084939A1 (en) * 2009-01-23 2010-07-29 味の素株式会社 Resin composition
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