JP6561888B2 - Sealant composition for organic solar cell and organic solar cell - Google Patents

Description

  The present invention relates to an organic solar cell sealing agent composition and an organic solar cell.

  In organic solar cells such as a dye-sensitized solar cell and a perovskite solar cell, a sealing agent is used to enclose an electrolytic solution.

  The sealing agent is required to have excellent adhesiveness with a base material (electrode base material). Further, the sealing agent is required to have high reliability, that is, low reactivity to the electrolyte. When the reactivity is high, the sealing agent is likely to swell or deteriorate due to the electrolytic solution, leading to a decrease in photoelectric conversion efficiency and leakage of the electrolytic solution.

  In the crosslinkable rubber composition described in Patent Document 1, an ethylene / α-olefin / non-conjugated polyene random copolymer (A) and a hydrosilyl group-containing compound (B) are combined. Since this rubber composition has a low degree of crosslinking, low adhesiveness, and is thermosetting, when this rubber composition is used for sealing, heating is required at the time of sealing. Therefore, there is a concern about the low adhesiveness and the deterioration of the solar cell due to heating.

  Patent Document 2 discloses a dye-sensitized solar cell sealant composition containing a hydrogenated polybutadiene compound having (A) (meth) acrylic groups. However, this sealant composition is inferior in reliability.

  Patent Document 3 discloses a photoelectric conversion element including a polyisobutylene resin-based sealing agent. However, with this polyisobutylene resin-based sealant, curing shrinkage occurs at the time of sealing, resulting in poor adhesion.

Japanese Patent Laying-Open No. 2015-134937 JP 2010-180258 A Table 2007-046499

  Then, an object of this invention is to provide the sealing compound composition for organic solar cells which can form the sealing compound which is excellent in adhesiveness with a base material, and has the reliable sealing performance. Moreover, an object of this invention is to provide the organic type solar cell containing the sealing agent which has a reliable sealing performance.

The sealing composition for organic solar cells according to the present invention is:
(A) a polymer having a liquid cyclic olefin structure;
(B) a (meth) acryloyl group-containing compound;
(C) a photopolymerization initiator;
It is the sealing compound composition for organic type solar cells containing this. When the composition has such a composition, it is possible to form a sealing agent that has excellent adhesion to the substrate and has a highly reliable sealing performance.

  In the sealing composition for organic solar cells according to the present invention, the component (A) is preferably an ethylene-propylene-terpolymer copolymer. Thereby, there exists an effect of coexistence with sealing performance, such as electrolyte solution and a water | moisture content, and adhesiveness with a base material.

  It is preferable that the sealing compound composition for organic solar cells which concerns on this invention contains 0.1-1000 mass parts of (D) fillers with respect to 100 mass parts of components (A). Thereby, there exists an effect which improves a mechanical property.

  It is preferable that the sealing compound composition for organic solar cells which concerns on this invention contains 10-200 mass parts of components (B) with respect to 100 mass parts of components (A). Thereby, there exists an effect of an improvement of sealing performance and adhesiveness.

  The sealing composition for organic solar cells according to the present invention can be suitably used even when the substrate to which the sealing composition for organic solar cells is applied is an organic resin.

  In the sealing composition for organic solar cells according to the present invention, the component (D) is preferably surface-treated. Thereby, there exists an effect called sealing property.

  In the sealing composition for organic solar cells according to the present invention, the component (B) preferably contains a compound having a carboxyl group or an acid anhydride group. Thereby, there exists an effect of adhesiveness with a base material.

  The organic solar cell according to the present invention is an organic solar cell including a cured product of any one of the above-described sealing compositions for organic solar cells. The organic solar cell has high reliability by including such a cured product.

  ADVANTAGE OF THE INVENTION According to this invention, the sealing compound composition for organic solar cells which can form the sealing compound which is excellent in adhesiveness with a base material and has the reliable sealing performance can be provided. ADVANTAGE OF THE INVENTION According to this invention, the organic type solar cell containing the sealing compound which has a reliable sealing performance can be provided.

FIG. 1 is a schematic diagram showing a configuration of an organic solar battery cell produced in the example.

  Hereinafter, embodiments of the present invention will be described. These descriptions are intended to exemplify the present invention and do not limit the present invention in any way.

  In this specification, numerical ranges are intended to include the lower and upper limits of the range, unless otherwise specified. For example, 1-1000 parts by mass is intended to include a lower limit of 1 part by mass and an upper limit of 1000 parts by mass, and means from 1 part by mass to 1000 parts by mass.

(Sealant composition for organic solar cells)
The sealing composition for organic solar cells according to the present invention is:
(A) a polymer having a liquid cyclic olefin structure;
(B) a (meth) acryloyl group-containing compound;
(C) a photopolymerization initiator;
An organic solar cell sealing agent composition (hereinafter sometimes simply referred to as “sealing agent composition”). When the composition has such a composition, it is possible to form a sealing agent that has excellent adhesion to the substrate and has a highly reliable sealing performance.

<(A) component>
The component (A) is a polymer having a liquid cyclic olefin structure. In the present invention, “liquid” means liquid at 23 ° C. Examples of the cyclic olefin structure include a norbornene structure.

一般式（１）中、Ｒ¹は、水素原子または炭素原子数１〜１０のアルキル基であり、Ｒ²は、水素原子または炭素原子数１〜５のアルキル基であり、ｎは、０〜１０の整数である。一般式（２）中、Ｒ³は、水素原子または炭素原子数１〜１０のアルキル基である。 The component (A) includes a structural unit (i) derived from ethylene, a structural unit (ii) derived from an α-olefin having 3 to 20 carbon atoms, and a norbornene compound represented by the following general formula (1) And a structural unit (iii) derived from at least one non-conjugated polyene selected from norbornene compounds represented by the general formula (2).

In General Formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n is 0 to 0. It is an integer of 10. In general formula (2), R < ³ > is a hydrogen atom or a C1-C10 alkyl group.

  Examples of the α-olefin having 3 to 20 carbon atoms constituting the structural unit (ii) include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1 -Nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, and the like. The α-olefin is preferably an α-olefin having 3 to 10 carbon atoms. The α-olefin is more preferably at least one selected from 1-butene, 1-hexene and 1-octene. The α-olefin having 3 to 20 carbon atoms may be used alone or in combination of two or more.

  The non-conjugated polyene constituting the structural unit (iii) is a terminal vinyl group-containing norbornene compound, and is selected from the norbornene compound represented by the general formula (1) and the norbornene compound represented by the general formula (2). At least one.

  In general formula (1), n is an integer of 0-10. n is preferably an integer of 0 to 5.

In General Formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, t-pentyl group, A neopentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. are mentioned. R ¹ is preferably a hydrogen atom, a methyl group or an ethyl group.

In general formula (1), R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As the alkyl group, for example, among the specific examples of the R ^1, include an alkyl group having 1 to 5 carbon atoms. R ² is preferably a hydrogen atom, a methyl group or an ethyl group.

In general formula (2), R < ³ > is a hydrogen atom or a C1-C10 alkyl group. As an alkyl group, the alkyl group quoted by R < ¹ > is mentioned, for example.

  Examples of the norbornene compound represented by the general formula (1) or (2) include 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl)- 2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3 -Dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl) -5-hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) ) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexesyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) ) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like. The norbornene compound is preferably 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- ( 4-pentenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene and 5- (7- 1 or more types selected from octenyl) -2-norbornene.

  As the non-conjugated polyene, in addition to the norbornene compounds represented by the general formulas (1) and (2), as the additional non-conjugated polyene, for example, 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4 A chain non-conjugated diene such as methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene; Cyclic nonconjugated dienes such as indene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, dicyclopentadiene 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-no; Bornene, it may be used in combination non-conjugated polyene such as trienes such as 2-propenyl-2,2-norbornadiene.

  In the case where the norbornene compound represented by the general formulas (1) and (2) and the additional non-conjugated polyene are used in combination, these ratios may be appropriately adjusted and are not particularly limited. For example, with respect to 100 mol% of the norbornene compound represented by the general formulas (1) and (2), the additional non-conjugated polyene is usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol%. Hereinafter, it is more preferably used at 20 mol% or less, particularly preferably at 10 mol% or less.

  The molar ratio ((i) :( ii)) of the structural unit (i) derived from ethylene and the structural unit (ii) derived from the α-olefin having 3 to 20 carbon atoms may be appropriately adjusted. Although not particularly limited, it is usually 35:65 to 95: 5, preferably 40:60 to 90:10, and more preferably 45:55 to 85:15.

  The component (A) is particularly preferably an ethylene-propylene-terpolymer copolymer. Thereby, there exists an effect of coexistence with sealing performance, such as electrolyte solution and a water | moisture content, and adhesiveness with a base material.

  The component (A) preferably has a low viscosity. Therefore, the weight average molecular weight (Mw) of (A) component becomes like this. Preferably it is 10,000 or less, More preferably, it is 2000-6000.

  The iodine value of the component (A) is not particularly limited and may be adjusted as appropriate, but is usually 11 to 55 (g / 100 g), preferably 11 to 30 (g / 100 g), more preferably 11 to 20 (g). / 100 g). By setting the iodine value within the above range, the reactivity with the electrolytic solution can be lowered, the reactivity with the component (B) can be improved, and the reliability can be enhanced.

  (A) The preparation method of a component is not specifically limited, A well-known method can be used. For example, it can be prepared by a method described in a new polymer production process (Industry Research Institute, Inc., pages 309 to 330) or Patent Document 1. For example, the component (A) has a polymerization temperature of 20 to 60 ° C., a polymerization pressure of 0.4 to 5 MPa, a supply amount of non-conjugated polyene and ethylene in the presence of a catalyst mainly containing a vanadium compound and an organoaluminum compound. It is obtained by randomly copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene under a molar ratio (nonconjugated polyene / ethylene) of 0.01 to 0.2.

  The polymer of component (A) may be graft-modified with a graft modifier. The graft modifiers may be used alone or in combination of two or more. Examples of the graft modifier include unsaturated carboxylic acid, acid anhydride of unsaturated carboxylic acid, unsaturated carboxylic acid ester, hydroxyl group-containing ethylenically unsaturated compound, amino group-containing ethylenically unsaturated compound, and epoxy group-containing ethylene. Unsaturated unsaturated compounds, aromatic vinyl compounds, vinyl ester compounds, vinyl chloride and the like.

  Examples of the unsaturated carboxylic acid as the graft modifier include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo (2,2,1) hept-2-ene- Examples include 5,6-dicarboxylic acid.

  Examples of unsaturated carboxylic acid anhydrides as graft modifiers include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo (2,2,1) hept-2-ene-5, Examples include 6-dicarboxylic acid anhydride.

  Examples of the unsaturated carboxylic acid ester as the graft modifier include, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl citraconic acid Dimethyl tetrahydrophthalate, dimethyl bicyclo (2,2,1) hept-2-ene-5,6-dicarboxylate, and the like.

  The amount of the graft modifier used is preferably 0.1 mol or less per 100 g of the polymer before graft modification.

  The method for graft-modifying the component (A) polymer (unmodified polymer) is not particularly limited, and a known method can be appropriately selected and used. For example, a graft-modified polymer can be obtained by reacting an unmodified polymer with a graft modifier in the presence of a radical initiator.

  It does not specifically limit as a radical initiator, It can select suitably and can be used. For example, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, t-butyl Hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl- Dialkyl peroxides such as 2,5-di (t-butylperoxy) hexane and α, α′-bis (t-butylperoxy-m-isopropyl) benzene; t-butylperoxyacetate, t-butylperoxide Oxyisobutyrate, t-butylperoxypivalate, t-butylperoxymaleic acid, t-butylperoxyneode Peroxyesters such as canoate, t-butylperoxybenzoate, di-t-butylperoxyphthalate; ketone peroxides such as dicyclohexanone peroxide; and combinations thereof.

  (A) As a component, you may use a commercial item. Examples of commercially available products include Mitsui EPT series such as PX-068 of ethylene / propylene / terpolymer manufactured by Mitsui Chemicals, Inc.

  (A) A component may be used individually by 1 type or in combination of 2 or more types.

<(B) component>
The component (B) is a (meth) acryloyl group-containing compound. That is, a compound having an acryloyl group and / or a compound having a methacryloyl group. Although not wishing to be bound by theory, it is presumed that the combined use of the component (A) and the component (B) increases the degree of crosslinking and improves the reliability. In addition, when the silane coupling agent used for surface treatment of the (D) component mentioned later has a (meth) acryloyl group, the said silane coupling agent is handled not as (B) component but as a silane coupling agent.

  The component (B) is not particularly limited and can be appropriately selected and used. For example, (meth) acryloyl group-containing carboxylic acids such as acrylic acid and methacrylic acid, and acid anhydrides thereof; (meth) acryloyl having cyclic ether groups such as glycidyl acrylate, tetrahydrofurfuryl acrylate, glycidyl methacrylate, and tetrahydrofurfuryl methacrylate Group-containing compounds: cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, 4-tert-butylcyclohexyl acrylate, 1-adamantanyl acrylate , Cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclopent Monofunctional (meth) acryloyl group-containing compounds having a cyclic aliphatic group such as nyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyl ethyl methacrylate, 4-tert-butylcyclohexyl methacrylate, 1-adamantanyl methacrylate; Acrylate, isononyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate, isoamyl acrylate, lauryl methacrylate, isononyl methacrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, Monofunctional having a chain aliphatic group such as isoamyl methacrylate ( T) Acryloyl group-containing compound; monofunctional (meth) acryloyl group-containing compound having an aromatic ring such as benzyl acrylate, phenoxyethyl acrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate; polyethylene glycol diacrylate Decanediol diacrylate, nonanediol diacrylate, hexanediol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa Polyfunctional (meth) acryloyl group-containing compound such as acrylate And acrylic oligomers such as polypropylene glycol dimethacrylate, urethane dimethacrylate, isoprene dimethacrylate, polybutadiene dimethacrylate, liquid hydrogenated polybutadiene diacrylate, and polyisobutylene dimethacrylate.

  The component (B) preferably contains a compound having a carboxyl group or an acid anhydride group. Thereby, there exists an effect that adhesiveness with a base material improves.

  The amount of component (B) is not particularly limited and may be adjusted as appropriate. The sealing agent composition preferably contains 10 to 200 parts by mass of component (B) with respect to 100 parts by mass of component (A). Thereby, there exists an effect that sealing performance and adhesiveness improve.

<(C) component>
(C) A component is a photoinitiator. (C) A component is not specifically limited, A well-known photoinitiator can be used.

  Examples of the component (C) include acetophenone, 2,2-diethoxyacetophenone, m-chloroacetophenone, p-tert-butyltrichloroacetophenone, 4-dialkylacetophenone, 2-benzylmethyl 2-dimethylamino-1- (4 Acetophenones such as morpholinophenyl) -butanone; benzophenones such as benzophenone; Michler ketones such as Michler ketone; benzyls such as benzyl and benzylmethyl ether; benzoins such as benzoin and 2-methylbenzoin; benzoin methyl ether Benzoin ethers such as benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether; benzyl dimethyl ketals such as benzyl dimethyl ketal; Various carbonyl compounds such as propiophenone, anthraquinone, acetoin, butyroin, toluoin, benzoylbenzoate, α-acyloxime ester, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, Sulfur compounds such as diphenyl disulfide and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one; azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile A peroxide such as benzoyl peroxide or di-tert-butyl peroxide; In addition, phenylglyoxylates; acyl phosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; organic dyes such as boron compounds Compounds, iron-phthalocyanine compounds, and the like. (C) A component may be used individually by 1 type or in combination of 2 or more types.

  The amount of component (C) is not particularly limited and may be adjusted as appropriate. For example, with respect to a total of 100 parts by mass of the component (A) and the component (B), it is usually 0.1 parts by mass or more, preferably 1 part by mass or more, usually 10 parts by mass or less, preferably 5 parts by mass or less.

<(D) component>
(D) A component is a filler. The component (D) is an optional component and has an effect of improving mechanical properties. The component (D) is not particularly limited, and may be selected from known inorganic fillers and organic fillers.

  Examples of the inorganic filler include oxide fillers such as silica, finely divided silicic acid, alumina, magnesium oxide, barium oxide, and calcium oxide; carbon black, graphite; hydroxide fillers such as aluminum hydroxide and magnesium hydroxide; Sedimentary rock fillers such as diatomite and limestone; clay mineral fillers such as kaolinite and montmorillonite; magnetic fillers such as ferrite, iron and cobalt; conductive fillers such as silver, gold, copper and alloys; light calcium carbonate, Heavy calcium carbonate, talc, clay and the like can be mentioned.

  The type of silica is not particularly limited and may be appropriately selected. Examples thereof include fumed silica and precipitated silica.

  The type of carbon black is not particularly limited and may be appropriately selected. For example, SRF, GPF, FEF, HAF, ISAF, SAF, FT, MT and the like can be mentioned.

  As an organic filler, a silicone filler, an epoxy resin filler, a polyamide fiber etc. are mentioned, for example.

  The component (D) is preferably surface-treated. Thereby, there exists an effect called sealing property. The surface treatment method is not particularly limited, and a known surface treatment method can be used. For example, the surface treatment may be performed using a silane coupling agent; a reactive silane such as hexamethyldisilazane, chlorosilane, or alkoxysilane; a low molecular weight siloxane.

  Examples of the silane coupling agent include 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-acryloyloxypropyl. Methyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane; 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3 -Isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane; p-styryl Limethoxysilane, p-styryltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltris (2-methoxyethoxy) silane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-minoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-A Nopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Examples include triethoxysilane and allyltrimethoxysilane.

  The silane coupling agent preferably has an acryloyl group such as 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, and 3-acryloyloxypropylmethyldiethoxysilane. It has a silane coupling agent.

  The amount of component (D) is not particularly limited and may be adjusted as appropriate. The sealing agent composition preferably contains 0.1 to 1000 parts by mass, and more preferably 10 to 300 parts by mass of the (D) filler with respect to 100 parts by mass of the component (A). The shape is not particularly limited, and may be selected as appropriate, such as an indefinite shape such as a grain, a sphere, a plate, or a rod. For example, when the sealant composition of the present invention is used in a dye-sensitized solar cell, the particle size may be selected as appropriate depending on the distance between the photoelectrode and the counter electrode, but is usually 0.001 μm to 500 μm, preferably 0.00. 01 to 50 μm.

(Other ingredients)
In addition to the above-mentioned (A), (B) and (C), the sealant composition is optionally a solvent, a sensitizer, a colorant, a difficult agent used in the component (D) and the sealant composition. A flame retardant, a plasticizer, a polymerization inhibitor, an antioxidant, an antifoaming agent, a coupling agent, a leveling agent, a rheology control agent and the like may be contained.

  The sensitizer is not particularly limited as long as it is usually used, but an aromatic compound that can absorb light having a wavelength of 300 nm or more is preferable. Examples include anthracene compounds, coumarin compounds, carbazole compounds, benzoxazole compounds, naphthalene compounds such as naphthalene and halogenated naphthalene, stilbene compounds, benzidine compounds, pyrene compounds, perylene compounds, naphthalimide compounds, and benzotriazole compounds. . By using such a compound that absorbs ultraviolet rays and emits light as a sensitizer, it is possible to achieve sufficient curing of the adhesive in a light shielding region that is not irradiated by irradiation from one direction. The amount of the sensitizer is not particularly limited and may be adjusted as appropriate. For example, with respect to a total of 100 parts by weight of component (A) and component (B), it is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, usually 10 parts by weight. Part or less, preferably 5 parts by weight or less, more preferably 3 parts by weight or less.

  As the polymerization inhibitor, a polymerization inhibitor can be used in order to maintain the storage stability. However, when the polymerization inhibitor is added in an excessive amount, the storage stability is improved, but the reactivity becomes slow. It is preferable to make it 001-0.1 mass.

  In addition, the sealing agent composition may contain, for example, a liquid saturated elastomer that does not substantially contain a carbon-carbon double bond involved in a radical reaction and exhibits fluidity at 23 ° C.

  Examples of the liquid saturated elastomer include hydrogenated polybutadiene, terminal hydroxyl group-containing hydrogenated polybutadiene, terminal carboxyl group-containing hydrogenated polybutadiene, hydrogenated polyisoprene, terminal hydroxyl group-containing polyisoprene, terminal carboxyl group-containing polyisoprene, and hydrogenated butadiene-isoprene. A copolymer, polyisobutylene, etc. are mentioned. In addition, examples of the liquid saturated elastomer include those having a functional group (terminal functional group) such as a hydroxyl group or a carboxyl group at the terminal.

  In the case of using a liquid saturated elastomer, the blending amount is not particularly limited and may be appropriately adjusted. For example, it is 1 to 50 parts by mass of the liquid saturated elastomer with respect to 100 parts by mass in total of the component (A) and the liquid saturated elastomer.

<Method for Preparing Sealant Composition for Organic Solar Cell>
The preparation method of the organic solar cell sealing agent composition is not particularly limited, and may be prepared using a known method. For example, the above-mentioned components (A), (B), (C) and (D), and other components as necessary are mixed with a known mixing apparatus such as a sand mill, a disper, a colloid mill, a planetary mixer, a kneader. And can be prepared by mixing.

<The hardening method of the sealing compound composition for organic type solar cells>
As energy rays for curing the sealing composition for organic solar cells, ultraviolet rays, visible light, infrared rays, electron beams and the like are used, but ultraviolet rays and electron beams are preferable in order to realize high-speed printing.
As the ultraviolet irradiation device, a light source usually containing light in the range of 200 to 500 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used. On the other hand, when it hardens with an electron beam, the electron beam accelerator which usually has an energy of 100-500 eV can be used.
What is necessary is just to perform hardening conditions etc. on the well-known conditions normally implemented. The cumulative irradiation amount of activation energy is usually 100 to 5000 mJ / cm ² , preferably 200 to 4000 mJ / cm ² .

  Sealing composition for organic solar cell is flexographic printing, gravure printing, screen printing, inkjet printing, offset printing, or bar coating method, dip coating method, flow coating method, spray coating method, spin coating method, roller coating method. It can be used for all kinds of printing and painting such as reverse coating, air knife, dispensing, etc., and can be appropriately selected according to the shape of the substrate to be applied.

<Organic solar cells>
The organic solar cell according to the present invention is an organic solar cell including a cured product of a sealing agent composition for organic solar cells. By including such a cured product, the organic solar cell has high reliability, that is, high photoelectric conversion efficiency maintenance rate.

  Examples of organic solar cells include dye-sensitized solar cells and perovskite solar cells. The organic solar cell according to the present invention is, for example, an organic solar cell sealing agent composition according to the present invention, instead of a conventional sealing agent, as an electrolyte encapsulating member or as a protective layer for a current collector wiring or the like. What is necessary is just to include hardened | cured material, and other structures of organic type solar cells, such as an electrode (photoelectrode), electrolyte solution (electrolyte, solvent), a counter electrode, a protective layer, an antireflection layer, and a gas barrier layer, use a well-known thing. That's fine. Hereinafter, an example of a photoelectrode, an electrolyte layer, and a counter electrode will be described.

<Photoelectrode>
A photoelectrode is not specifically limited, A well-known photoelectrode can be selected suitably and can be used. For example, it may be composed of a photoelectrode substrate, a porous semiconductor fine particle layer formed thereon, and a sensitizing dye layer formed by adsorbing a sensitizing dye on the surface of the porous semiconductor fine particle layer. . The photoelectrode substrate plays a role of supporting a porous semiconductor fine particle layer and the like and a role of a current collector.

  The photoelectrode substrate is not particularly limited, and a known photoelectrode substrate can be appropriately selected and used. For example, a conductive film made of a composite metal oxide such as indium-tin oxide (ITO), indium-zinc oxide (IZO), fluorine-doped tin (FTO), carbon nanotube, A carbon-based conductive film such as graphene, a conductive polymer film such as PEDOT / PSS, etc. and a layer in which these are mixed and laminated, a conductive polymer film such as PEDOT / PSS, etc. and a layer in which these are mixed and laminated Is mentioned.

  Examples of the transparent resin include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr), polysulfone (PSF), Examples include synthetic resins such as polyester sulfone (PES), polyetherimide (PEI), transparent polyimide (PI), and cycloolefin polymer (COP).

  The photoelectrode substrate is preferably an organic resin.

  The porous semiconductor fine particle layer is a porous layer containing semiconductor fine particles. By being a porous layer, the amount of sensitizing dye adsorbed increases, and a dye-sensitized solar cell with high conversion efficiency is easily obtained.

  Examples of the semiconductor fine particles include metal oxide particles such as titanium oxide, zinc oxide, and tin oxide.

  The particle size of semiconductor fine particles (average particle size of primary particles) is not particularly limited, and may be adjusted as appropriate. Preferably it is 2-80 nm, More preferably, it is 2-60 nm. Resistance can be reduced because the particle size is small.

  Although the thickness of a porous semiconductor fine particle layer is not specifically limited, Usually, 0.1-50 micrometers, Preferably it is 5-30 micrometers.

  The formation method of a porous semiconductor fine particle layer is not specifically limited, A well-known method can be selected suitably and can be used. For example, the porous semiconductor fine particle layer can be formed by a known method such as a press method, a hydrothermal decomposition method, an electrophoretic electrodeposition method, or a binder-free coating method.

  The sensitizing dye layer is a layer formed by adsorbing a compound (sensitizing dye) that can be excited by light and pass electrons to the porous semiconductor fine particle layer on the surface of the porous semiconductor fine particle layer.

  The sensitizing dye is not particularly limited, and a sensitizing dye of a known dye-sensitized solar cell can be appropriately selected and used. For example, organic dyes such as cyanine dyes, merocyanine dyes, oxonol dyes, xanthene dyes, squarylium dyes, polymethine dyes, coumarin dyes, riboflavin dyes, perylene dyes; metals such as phthalocyanine complexes and porphyrin complexes of metals such as iron, copper and ruthenium And complex dyes. For example, N3, N719, N749, D102, D131, D150, N205, HRS-1, MK-2 and the like can be mentioned as typical sensitizing dyes.

  The organic solvent for dissolving the dye is preferably degassed and purified by distillation in advance in order to remove moisture and gas present in the solvent. Solvents include alcohols such as methanol, ethanol and propanol, nitriles such as acetonitrile, halogenated hydrocarbons, ethers, amides, esters, carbonates, ketones, hydrocarbons, aromatics, nitromethane and the like. preferable.

  The formation method of a sensitizing dye layer is not specifically limited, A well-known method can be selected suitably and can be used. For example, a sensitizing dye layer is formed by a known method such as a method of immersing a porous semiconductor fine particle layer in a sensitizing dye solution or a method of applying a sensitizing dye solution onto the porous semiconductor fine particle layer. Can do.

  The photoelectrode may be any electrode that can emit light to an external circuit by receiving light, and a known photoelectrode for a dye-sensitized solar cell can be used.

<Electrolyte layer>
The electrolyte layer is a layer for separating the photoelectrode and the counter electrode and efficiently performing charge transfer. The electrolyte layer is not particularly limited, such as a solid, liquid, semi-solid such as a gel. The electrolyte layer usually contains a supporting electrolyte, a redox pair (a pair of chemical species that can be reversibly converted into an oxidized form and a reduced form in a redox reaction), a solvent, and the like.

  Examples of the supporting electrolyte include salts such as alkali metals such as lithium ions and alkaline earth metals, imidazolium ions, compounds having quaternary nitrogen atoms as spiro atoms, and ionic liquids containing cations such as quaternary ammonium ions. Is mentioned.

  As the redox couple, a known one can be used as long as it can reduce the oxidized sensitizing dye. Examples of the redox pair include chlorine compound-chlorine, iodine compound-iodine, bromine compound-bromine, thallium ion (III) -thallium ion (I), ruthenium ion (III) -ruthenium ion (II), copper ion ( II) -copper ion (I), iron ion (III) -iron ion (II), cobalt ion (III) -cobalt ion (II), vanadium ion (III) -vanadium ion (II), manganate ion-per Manganate ion, ferricyanide-ferrocyanide, quinone-hydroquinone, fumaric acid-succinic acid and the like can be mentioned.

  A well-known thing can be used as a solvent for the formation of the electrolyte layer of a solar cell. Examples of the solvent include acetonitrile, methoxyacetonitrile, methoxypropionitrile, N, N-dimethylformamide, ethylmethylimidazolium bistrifluoromethylsulfonylimide, propylene carbonate, glycol ether, and γ-butyllactone.

  The method for forming the electrolyte layer is not particularly limited, and a known method can be appropriately selected and used. For example, it can be formed by applying a solution (electrolyte) containing the constituent components of the electrolyte layer on the photoelectrode; producing a cell having the photoelectrode and the counter electrode, and injecting the electrolyte into the gap. .

(Collector)
It is preferable to arrange a current collecting line on the transparent conductive film of the photoelectrode or the counter electrode, provide a segmented cell portion, and design so that current can be quickly moved in the electrode.
The collector electrode of the photoelectrode and the counter electrode is preferably made of at least one metal selected from silver, copper, aluminum, tungsten, nickel, and chromium, or an alloy thereof. The current collector is preferably formed in a lattice shape on a transparent substrate. As a method for forming the current collector, sputtering, vapor deposition, plating, screen printing, or the like is used.

<Counter electrode>
As the counter electrode, a known counter electrode can be appropriately selected and used. For example, a counter electrode provided with a conductive film and a catalyst layer in this order on a support can be used.

  The support is responsible for supporting the catalyst layer. Examples of the support include a conductive sheet formed using a metal, a metal oxide, a carbon material, a conductive polymer, and the like, and a nonconductive sheet made of a transparent resin or glass.

  As for transparent resin, the transparent resin quoted by the said photoelectrode is mentioned, for example.

  Examples of the conductive film include metals such as platinum, gold, silver, copper, aluminum, indium and titanium; conductive metal oxides such as tin oxide and zinc oxide; indium-tin oxide (ITO) and indium-zinc oxide. Compound (IZO), composite metal oxides such as fluorine-doped tin oxide (FTO); carbon materials such as carbon nanotubes, carbon nanobatts, graphene, and fullerenes; and combinations of two or more thereof.

  The catalyst layer functions as a catalyst when electrons are transferred from the counter electrode to the electrolyte layer in the organic solar cell. As the catalyst layer, a known catalyst layer can be appropriately selected and used. For example, it is preferable to include a conductive polymer, carbon nanostructure, noble metal particles, or both carbon nanostructure and noble metal particles having a catalytic action.

  Examples of the conductive polymer include poly (thiophene-2,5-diyl), poly (3-butylthiophene-2,5-diyl), poly (3-hexylthiophene-2,5-diyl), and poly ( Polythiophene such as 2,3-dihydrothieno- [3,4-b] -1,4-dioxin) (PEDOT); polyacetylene and derivatives thereof; polyaniline and derivatives thereof; polypyrrole and derivatives thereof; poly (p-xylenetetrahydrothiophene) Nium chloride), poly [(2-methoxy-5- (2′-ethylhexyloxy))-1,4-phenylenevinylene], poly [(2-methoxy-5- (3 ′, 7′-dimethyloctyloxy) ) -1,4-phenylenevinylene)], poly [2-2 ′, 5′-bis (2 ″ -ethylhexyloxy) phenyl] -1, - polyphenylene vinylene such as phenylene vinylene]; and the like.

  Examples of the carbon nanostructure include natural graphite, activated carbon, artificial graphite, graphene, carbon nanotube, carbon nanobat, and graphene.

  The noble metal particles are not particularly limited as long as they have a catalytic action, and known noble metal particles can be appropriately selected and used. For example, metal platinum, metal palladium, metal ruthenium, etc. are mentioned.

  The formation method of a catalyst layer is not specifically limited, A well-known method can be selected suitably and can be used. For example, a conductive polymer, carbon nanostructure, noble metal particles, or a mixture obtained by dissolving or dispersing both carbon nanostructures and noble metal particles in an appropriate solvent is applied or sprayed onto the conductive film, It can be performed by drying the solvent of the mixed solution. When carbon nanostructures or noble metal particles are used, a binder may be further added to the mixed solution. As the binder, from the viewpoint of dispersibility of the carbon nanostructure and adhesion to the substrate, a hydroxyl group, a carboxyl group, and a sulfonyl group. It is preferable to use a polymer having a functional group such as a group, a phosphate group, and a sodium salt of these functional groups.

  The catalyst layer is a carbon nanotube (hereinafter referred to as “the average diameter (Av) of carbon nanotubes and a standard deviation (σ) of diameters) satisfying 0.60> 3σ / Av> 0.20 described in JP 2014-120219 A” It may contain a “specific carbon nanotube”. Here, “specific carbon nanotube” is a general term for a set of predetermined carbon nanotubes constituting the carbon nanotube, and “diameter” means an outer diameter of the predetermined carbon nanotube.

  The specific carbon nanotube is a known method, for example, a substrate having a catalyst layer for producing carbon nanotubes (hereinafter sometimes referred to as “catalyst layer for producing CNT”) on the surface (hereinafter referred to as “substrate for producing CNT”) In addition, when a raw material compound and a carrier gas are supplied and carbon nanotubes are synthesized by a chemical vapor deposition method (CVD method), a small amount of oxidant is present in the system, so that CNT It can be obtained by a method (supergrowth method) of dramatically improving the catalytic activity of the production catalyst layer (for example, International Publication No. 2006/011655). Hereinafter, the carbon nanotube produced by the super growth method may be referred to as SGCNT.

  The thickness of the catalyst layer is preferably 0.005 μm to 100 μm.

The amount of the specific carbon nanotube contained in the catalyst layer is preferably 0.1 to 2 × 10 ⁴ mg / m ² , more preferably 0.5 to 5 × 10 ³ mg / m ² .

  For the counter electrode including a catalyst layer composed of specific carbon nanotubes, for example, a dispersion containing specific carbon nanotubes is prepared, this dispersion is applied onto a substrate, and the resulting coating film is dried. The catalyst layer can be formed by forming the catalyst layer.

  Examples of the solvent used for preparing the dispersion include water; alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane and diglyme; N, N-dimethyl. Amides such as formamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane. These solvents can be used alone or in combination of two or more.

  The dispersion liquid may contain a dispersant for improving the dispersibility of the specific carbon nanotube. Preferred dispersants include, for example, known ionic surfactants; nonionic surfactants such as carboxyl methyl cellulose (CMC) and carboxyl methyl cellulose salts; and polymer surfactants such as polystyrene sulfonates such as sodium polystyrene sulfonate. Is mentioned.

  The dispersion may further contain a binder, a conductive aid, a surfactant and the like. These may be appropriately known ones.

  The dispersion can be obtained, for example, by mixing specific carbon nanotubes and, if necessary, other components in a solvent to disperse the carbon nanotubes.

  A known method can be used for the mixing process and the dispersion process. Examples thereof include a method using a nanomizer, an optimizer, an ultrasonic disperser, a ball mill, a sand grinder, a dyno mill, a spike mill, a DCP mill, a basket mill, a paint conditioner, a high-speed stirring device, and the like.

  Although content of the specific carbon nanotube in a dispersion liquid is not specifically limited, Preferably it is 0.001-10 mass% in the whole dispersion liquid, More preferably, it is 0.01-5 mass%.

<Others>
A functional layer such as an antifouling layer, a protective layer such as a hard coat, an antireflection layer, or a gas barrier layer may be provided on one or both of the photoelectrode layer and the counter electrode layer acting as an electrode. A thin film layer of a dense semiconductor (metal oxide TiO ₂ , SnO ₂ , Fe ₂ O ₃ , WO ₃ , ZnO, Nb ₂ O _5, etc.) may be provided as a base layer between the base material and the porous semiconductor layer. . Moreover, you may include the separator for short circuit prevention.

<Extraction electrode>
An extraction electrode can be installed to extract the current from the created module. Usually, the position, material, and production method of the extraction electrode are not particularly limited, and may be performed by a known method. As the material, metals such as aluminum, nickel, stainless steel, copper, gold, silver, solder, pastes such as carbon, conductive tapes, and the like can be used. These can be prepared in a timely manner so as to be extraction electrodes on the negative electrode side and the positive electrode side from the photoelectrode and counter electrode side, respectively.

  The structure of the module is not particularly limited, but includes a Z-type, a W-type, a parallel type, a current collection type, a monolithic type, and the like. A plurality of these modules may be connected in series or in parallel by combining one or two or more. A known method may be used for the connection method, and solder, a metal plate, a cable, a flat cable, a flexible substrate, a cable, or the like may be selected as appropriate.

  In addition to the dye-sensitized solar cell, examples of the perovskite solar cell include perovskite solar cells described in Japanese Patent Application Laid-Open No. 2014-096331, Japanese Patent Application Laid-Open No. 2015-046583, Japanese Patent Application Laid-Open No. 2006-009737, and the like.

<Solar cell module manufacturing method>
The method for producing the module is not particularly limited, and the module can be produced by a known method such as a vacuum bonding method (ODF method) or an end seal method. Examples of the ODF method include a method described in WO2007 / 046499. Examples of the end seal method include a method described in JP-A 2006-004827.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, these Examples aim at the illustration of this invention, and do not limit this invention at all. Unless otherwise specified, the blending amount means parts by mass.

The details of the materials used in the examples are as follows.
Component (A) (Liquid polymer having a cyclic olefin structure)
Liquid EPT: Liquid ethylene-propylene-terpolymer copolymer (product name PX-068 manufactured by Mitsui Chemicals, Inc.)
Component (B) ((meth) acryloyl group-containing compound)
Isobornyl acrylate: Product name manufactured by Kyoeisha Chemical Co., Ltd. Light acrylate (registered trademark) IB-XA
Tricyclodecane dimethanol diacrylate: Product name SR833S manufactured by Sartomer
Methacrylic acid: Liquid hydrogenated polybutadiene diacrylate manufactured by Tokyo Chemical Industry Co., Ltd .: Product name manufactured by Osaka Organic Chemical Industry Co., Ltd. SPBDA-S30
Component (C) (photopolymerization initiator)
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product name IRGACURE (registered trademark) TPO, manufactured by BASF), absorption wavelength over 300 nm)
(D) component (filler)
Silica (fumed silica surface-treated with methacrylic silane): Product name AEROSIL (registered trademark) R711 manufactured by Evonik Degussa GmbH
Silica: Product name AEROSIL (registered trademark) 120 manufactured by Evonik Degussa GmbH
(Other components of the composition)
Liquid polyisobutylene: Nisseki polybutene grade HV-300 M (maleic acid-modified liquid polyisobutylene) manufactured by JX Energy Corporation

Binder-free titanium oxide paste: Product name PECC-C01-06 manufactured by Pexel Technologies Co., Ltd.
Sensitizing dye solution: sensitizing dye ruthenium complex (product name N719 manufactured by Solaronics), solvent acetonitrile, tert-butanol, concentration 0.4 mM

  An organic solar cell having the following configuration was produced.

(1) Preparation of electrolyte solution To be lithium iodide 0.1 mol / L, t-butylpyridine 0.5 mol / L, and 1,2-dimethyl-3-propylimidazolium iodide 0.6 mol / L Added to methoxyacetonitrile. After stirring for 1 hour by vibration with an ultrasonic cleaner, the solution was left in a dark place for 24 hours or more to prepare an electrolytic solution.

(2) Preparation of dye solution 72 mg of a ruthenium complex dye (N719, manufactured by Solaronics) was placed in a 200 mL volumetric flask. 190 mL of dehydrated ethanol was mixed and stirred. After stoppering the volumetric flask, the mixture was stirred for 60 minutes by vibration with an ultrasonic cleaner. After keeping the solution at room temperature, dehydrated ethanol was added to make a total volume of 200 mL to prepare a dye solution.

(3) Creation of module (1) Creation of photoelectrode Conductive electrode substrate (sheet) in which a transparent conductive layer (indium-tin oxide (ITO)) is laminated on a transparent substrate (polyethylene naphthalate film, thickness 200 μm) Resistance 15Ω / sq transmittance 0% @ 300nm, 48% @ 395nm) was created. Laser treatment was performed at intervals according to the photoelectrode cell width to form insulating wires. A high-pressure mercury lamp (rated lamp power 400 W) is placed at a distance of 10 cm from the mask bonding surface, and immediately after irradiation with electromagnetic waves for 1 minute, a binder-free titanium oxide paste containing no polymer component (less than 1% binder, PECC-AW1 -01, manufactured by Pexel Technologies Co., Ltd.) was applied using a Baker type applicator. The paste was heat-dried for 10 minutes in a hot air circulation oven at 150 degrees to form a 1 cm square porous semiconductor fine particle layer (titanium oxide layer). Then, the electroconductive electrode base material in which the porous semiconductor fine particle layer was formed was immersed in the prepared dye solution (40 degreeC), and the pigment | dye was adsorbed, stirring lightly. After 90 minutes, the dye-adsorbed titanium oxide film was taken out from the dye-adsorption container, washed with ethanol and dried to produce a photoelectrode.

(2) Creation of counter electrode A conductive electrode substrate (sheet resistance 150 Ω / sq) obtained by laminating a transparent conductive layer (indium-tin oxide (ITO)) on a transparent substrate (polyethylene naphthalate film, thickness 200 μm). A platinum layer pattern (catalyst layer) was formed on the conductive surface by sputtering to obtain a counter electrode having a light transmittance of about 72% at the catalyst layer forming portion. At this time, when the photoelectrode and the counter electrode are overlapped with their conductive surfaces facing each other, the titanium oxide pattern (porous semiconductor fine particle layer forming portion) and the platinum pattern (catalyst layer forming portion) coincide. It was set as the structure (refer FIG. 1).

(3) Production of organic solar cell The surface of the counter electrode on which the catalyst layer is formed is fixed on an aluminum adsorption plate using a vacuum pump, and the sealant composition shown in Table 1 is titanated with a dispenser by an automatic coating robot. It was applied to the outer peripheral part of the layer (so that the sealant width after bonding was 5.0 mm and the thickness was 30 μm). Further, a conductive resin composition for conducting between the photoelectrode and the counter electrode was similarly applied to the upper part of the silver wiring portion with a dispenser. After that, apply a predetermined amount of the electrolyte prepared as described above to the titanium oxide layer pattern part, and use a self-bonding device so that the rectangular titanium oxide pattern and the same type platinum pattern face each other in a reduced pressure environment. Then, the electrodes were overlapped so that the distance between the electrodes was (30 μm), and light was irradiated from the photoelectrode side with a metal halide lamp (metal halide lamp 30 ° C., integrated light quantity 3000 mJ / cm ² ). Furthermore, it turned over and light irradiation (metal halide lamp 30 degreeC, integrated light quantity 3000mJ / cm < ² >) was performed from the counter electrode side with the metal halide lamp.

  With the formulation shown in Table 1, sealant compositions of Examples and Comparative Examples were prepared. And the adhesiveness (adhesiveness with respect to the base material wetted with electrolyte solution) and reliability of a sealing compound composition were evaluated by the method shown below. The results are also shown in Table 1.

(Adhesion evaluation)
On the ITO surface of the glass substrate or ITO / PEN, an electrolytic solution (lithium iodide 0.1 mol / L, t-butylpyridine 0.5 mol / L, and 1,2-dimethyl-3-propylimidazolium iodide was used. Electrolytic solution in which methoxyacetonitrile is dissolved so as to be 0.6 mol / L) is dropped, and then the sealant composition is wetted with the electrolytic solution glass substrate or ITO / PEN ITO It was dripped on the surface. The sealant composition was cured by irradiating with ultraviolet rays for 10 seconds with a high-pressure mercury lamp (270 mW / cm ² ). In order to remove the electrolyte from the glass plate, the ITO surface of the glass substrate or ITO / PEN is washed with isopropanol, and then the shape of the sealant composition on the glass substrate or the ITO surface of ITO / PEN is observed. Based on the ratio of the remaining area of the sealant composition, the following criteria were used for evaluation.
A: 90% or more of the dropped sealing agent composition adheres to the substrate B: 50% or more and less than 90% of the dropped sealing agent composition adheres to the substrate C: The dropped seal Less than 50% of the agent composition adheres to the substrate

(Reliability evaluation)
The initial photoelectric conversion efficiency was measured, the conversion efficiency after 30 days at room temperature was measured, the maintenance ratio of the conversion efficiency was determined using the following formula, and the reliability was evaluated.
Maintenance rate% = (photoelectric conversion efficiency after 30 days at room temperature) / (initial photoelectric conversion efficiency)
A: 85% or more B: Less than 85%

  As shown in Table 1, in Comparative Example 1 not including the component (A), the reliability was low. Moreover, in Comparative Example 2, the adhesiveness was low, the electrolyte solution leaked, a module could not be created, and the reliability evaluation could not be performed. On the other hand, in an Example, it was excellent in adhesiveness and brought the result with high reliability.

  ADVANTAGE OF THE INVENTION According to this invention, the sealing compound composition for organic solar cells which can form the sealing compound which is excellent in adhesiveness with a base material and has the reliable sealing performance can be provided. ADVANTAGE OF THE INVENTION According to this invention, the organic type solar cell containing the sealing compound which has a reliable sealing performance can be provided.

1: Organic solar battery cell produced in Example 2: PEN
3: ITO
4: PEN
5: ITO
6: Titanium oxide layer (1 cm square)
7: Platinum layer (1cm square)
8: Sealing agent

Claims (8)

(A) a polymer having a liquid cyclic olefin structure;
(B) a (meth) acryloyl group-containing compound;
(C) a photopolymerization initiator;
A sealing agent composition for organic solar cells.   The sealing agent composition for organic solar cells according to claim 1, wherein the component (A) is an ethylene-propylene-terpolymer copolymer.   (A) The sealing compound composition for organic solar cells of Claim 1 or 2 which contains 0.1-1000 mass parts of (D) fillers with respect to 100 mass parts of components.   (A) The sealing compound composition for organic solar cells as described in any one of Claims 1-3 which contains 10-200 mass parts of (B) component with respect to 100 mass parts of components.   The organic solar cell sealing agent composition according to any one of claims 1 to 4, wherein a base material to which the organic solar cell sealing agent composition is applied is an organic resin.   (D) The sealing compound composition for organic solar cells as described in any one of Claims 3-5 by which the component is surface-treated.   (B) The sealing compound composition for organic solar cells as described in any one of Claims 1-6 in which a component contains the compound which has a carboxyl group or an acid anhydride group.   The organic solar cell containing the hardened | cured material of the sealing compound composition for organic solar cells as described in any one of Claims 1-7.

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