JP2006012673A - Dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell prevented from leakage of electrolyte solution, capable of reducing the number of components by eliminating spacers, and obtaining high durability. <P>SOLUTION: The solar cell comprises a first and second transparent substrates 1 and 1A faced each other with a small interval, a sealing peripheral wall 5 which glues peripheral parts of these first and second transparent substrates 1 and 1A, an electrolyte solution 6 sealed between these substrates 1 and 1A. The sealing peripheral wall 5 is a finite form of silicon adhesive 10. Since the sealing peripheral wall 5 is made of silicon adhesive excellent in adhesion, chemical resistance, waterproof, weather resistance and environmental condition; there is no danger of leakage of electrolyte solution 6. Then spacers can be eliminated to reduce the number of components. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dye-sensitized solar cell (also referred to as a dye-sensitized solar cell) that converts light energy such as sunlight into electrical energy.

  Conventionally, a pn junction type of a silicon semiconductor has been widely known as a solar cell. However, since a dye-sensitized type was proposed in 1991, a dye-sensitized type has attracted attention. This dye-sensitized solar cell is also called a wet solar cell because the electrolyte solution is sealed inside, and has a feature that manufacturing equipment and cost are low.

  Although this type of dye-sensitized solar cell is not shown, the first and second transparent substrates facing each other, the sealant interposed between the peripheral edges of the first and second transparent substrates, And a spacer interposed between and closely adhered to the second transparent substrate, and an electrolyte solution sealed between the first and second transparent substrates (Patent Documents 1, 2, 3, 4, 5). , 6).

  A transparent conductive film as an electrode is formed on the inner surface of the first transparent substrate, and a porous film is formed on the transparent conductive film by uniformly applying and heating titanium oxide particles. A dye is adsorbed on the porous film. The second transparent substrate is formed as a conductive substrate by forming a transparent conductive film on the opposite surface. The sealant is formed into a frame shape using, for example, liquid polyisobutylene.

In the dye-sensitized solar cell having such a configuration, when light is applied to the first transparent substrate, the dye absorbs the light and emits electrons, and the electrons move to the porous film and become a transparent conductive film. It is transmitted. And an electron moves to the transparent conductive film of a 2nd transparent substrate, reduces the ion in electrolyte solution, and the reduced ion is oxidized again on a pigment | dye. By repeating these, electric energy is generated.
JP 2004-95248 A JP 2000-173680 A Japanese Patent Laid-Open No. 11-288745 JP 2000-348783 A JP 2001-185244 A JP 2000-30367 A

  In the conventional dye-sensitized solar cell, as described above, the sealing agent is simply interposed between the peripheral portions of the first and second transparent substrates, and the sealing agent is compressed as the first and second transparent substrates are compressed. May flow out and the electrolyte solution may leak, so there is a problem that the number of parts cannot be reduced by omitting the spacer made of solid packing. Further, depending on the type of the electrolyte solution, strong durability is required, but the conventional sealant and the spacer cannot satisfy the necessity.

  The present invention has been made in view of the above, eliminates the possibility of leakage of the electrolyte solution, can reduce the number of parts by omitting the spacers, and can obtain strong durability It aims to provide a battery.

In order to solve the above-described problems, the present invention includes a sealing peripheral wall that joins the peripheral portions of a pair of transparent substrates, and an electrolyte solution that is filled between the pair of transparent substrates, and converts and uses light energy. There,
The sealing peripheral wall is a fixed silicone adhesive.
In addition, it is preferable to set it as the range of 30-500, when the plasticity at the time of non-hardening of a silicone adhesive is measured with a Williams plasticity meter.

  Here, the pair of transparent substrates in the claims may be the same size or not, and may or may not be flexible. Examples of the transparent substrate include glass with FTO having weather resistance, glass with ITO having a smooth surface, conductive PET film, and the like. Examples of the supporting electrolyte of the electrolyte solution include cations such as lithium ions and anions such as chlorine ions. Examples of the redox substance in the electrolyte include an iodine-iodine mixture and a bromine-bromine mixture. Furthermore, as the solvent of the electrolyte solution, a mixed solution of acetonitrile and ethylene carbonate or the like is used.

  According to the present invention, it is possible to eliminate the possibility that the electrolyte solution leaks from the dye-sensitized solar cell. Therefore, there is an effect that the number of parts can be reduced by omitting the spacer. Moreover, strong durability can be obtained.

  Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. The dye-sensitized solar cell according to the present embodiment has a slight gap of 30 to 50 μm as shown in FIGS. Opposing first and second transparent substrates 1 and 1A, endless sealing peripheral walls 5 for bonding the peripheral portions of the first and second transparent substrates 1 and 1A, and first and second transparent substrates An electrolyte solution 6 for electron exchange enclosed between the substrates 1 and 1A and the sealing peripheral wall 5 is provided, and the sealing peripheral wall 5 is made to be a silicone adhesive 10.

  As the first and second transparent substrates 1 and 1A, for example, conductive glass (TCO) thinly deposited with a compound (ITO) composed of 95% indium oxide and 5% tin oxide is used on a glass plate. It has heat resistance against heat of about 500 ° C.

  The first transparent substrate 1 is formed by laminating and forming a transparent conductive film 2 as an electrode on the surface facing the second transparent substrate 1A, and uniformly applying and heating titanium oxide particles on the transparent conductive film 2. As a result, the porous film 3 is laminated and the dye 4 made of a ruthenium complex or the like that efficiently absorbs sunlight (see the arrow in FIG. 2) is adsorbed to the porous film 3. The second transparent substrate 1A is formed by laminating and forming a transparent conductive film 2A as an electrode on the opposite surface.

  As the electrolyte solution 6, phosphoric acid, sulfuric acid, a mixed acid thereof, an aqueous solution in which a glycerin base and a metal acetate are dissolved are used. Examples of the glycerin base include sodium glycerophosphate and calcium glycerophosphate, but calcium glycerophosphate which is easily soluble in water is preferable. The metal acetate is not particularly limited, but in particular, acetate of alkali metal (lithium, sodium, potassium, rubidium, cesium), acetate of alkaline earth metal (magnesium, calcium, strontium, barium) Is good.

  The silicone adhesive 10 is made of a regular silicone material having weather resistance, heat resistance, etc., and is formed into a filament, tape shape, strip shape, string shape, and the peripheral edge of the porous film of the first transparent substrate 1 In addition to being bonded to the peripheral edge of the transparent conductive film of the second transparent substrate 1 </ b> A, it functions as a spacer in addition to the hollow sealing peripheral wall 5. This silicone adhesive 10 does not deviate from the rubber cross-linked body and needs to maintain its shape. Therefore, the plasticity of the uncured silicone adhesive 10 is preferably in the range of 30 to 500 when measured with a Williams plasticity meter.

  This is because, when the plasticity is less than 30, when the silicone adhesive 10 is made into an uncured fixed-form shape, or shape retention after molding is lowered, it becomes difficult to maintain any shape. . Conversely, when the plasticity of the silicone adhesive 10 exceeds 500, it is extremely difficult to remove bubbles remaining at the interface when the silicone adhesive 10 is bonded to the first and second transparent substrates 1 and 1A. If air bubbles remain at the interface, the contact area between the silicone adhesive 10 and the first and second transparent substrates 1 and 1A decreases, leading to a decrease in adhesive strength.

  As the silicone adhesive 10, a silicone rubber adhesive by any crosslinking method such as radical reaction, addition reaction with a platinum catalyst, condensation reaction, ultraviolet ray, electron beam curing, etc. can be used. However, in practice, the silicone adhesive 10 that crosslinks by an addition reaction or a condensation reaction is preferable from an economical and physical viewpoint.

I) Condensation-curable silicone adhesive This adhesive generally has the following basic composition.
(1) Polyorganosiloxane: a main component of a condensation-curable silicone adhesive, which is a diorganopolysiloxane represented by the following general formula (1) or (2).

（式中、Ｒは置換又は非置換の一価炭化水素基、Ｘは酸素原子又は炭素数１〜８の二価炭化水素基、ｎはジオルガノポリシロキサンの２５℃における粘度を１００，０００ｍＰａ・ｓ以上、好ましくは１，０００，０００ｍＰａ・ｓ以上とする数である）

(In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group, X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is a viscosity of the diorganopolysiloxane at 25 ° C. of 100,000 mPa · s or more, preferably 1,000,000 mPa · s or more)

（式中、Ｙは加水分解性基、ａは２又は３、Ｒ、Ｘ、ｎは上記と同様である）

(Wherein Y is a hydrolyzable group, a is 2 or 3, R, X, and n are the same as above)

  Here, R is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group or an octyl group, a cycloalkyl group such as a cyclohexyl group or a cyclopentyl group, a vinyl group, a propenyl group, a butenyl group, or a heptenyl. Group, hexenyl group, alkenyl group such as allyl group, phenyl group, tolyl group, xylyl group, naphthyl group, aryl group such as diphenyl group, aralkyl group such as benzyl group, phenylethyl group, or the carbon atom of these groups Identical or different non-selective groups selected from a chloromethyl group, a trifluoropropyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, etc. in which some or all of the bonded hydrogen atoms are substituted with halogen atoms, cyano groups, etc. Substitution or substitution is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms.

X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, the divalent hydrocarbon group is _{- (CH 2) m - (} m is 1-8) is represented by. Among these, an oxygen atom and —CH ₂ CH ₂ — are preferable.

n is a number that makes the viscosity of the diorganopolysiloxane at 25 ° C. 100,000 mPa · s or more, preferably 1,000,000 mPa · s or more.
Y is a hydrolyzable group, specifically, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group, a ketoxime group such as a dimethylketoxime group or a methylethylketoxime group, an acyloxy group such as an acetoxy group, Examples thereof include alkenyloxy groups such as isopropenyloxy group and isobutenyloxy group.

  Such a diorganopolysiloxane can be produced by a known method such as obtaining a cyclic siloxane or a linear oligomer which is a monomer of various organopolysiloxanes by an equilibrium reaction with an acid or base catalyst.

When a branched structure is introduced into the diorganopolysiloxane, a silane or siloxane containing SiO _3/2 units and / or SiO _4/2 units is added at a level at which the diorganopolysiloxane does not gel during the equilibration polymerization. Is the ordinary method. Furthermore, it is preferable that the low molecular weight siloxane is removed from the diorganopolysiloxane by stripping or washing. When such an organosiloxane is used, the initial contamination can be reduced.

(2) Crosslinking agent: As the crosslinking agent, a silane having two or more, preferably three or more hydrolyzable groups in one molecule, or a partial hydrolysis condensate thereof is used. In this case, hydrolyzable groups include alkoxy groups such as methoxy, ethoxy and butoxy groups, ketoximes such as dimethyl ketoxime and methylethyl ketoxime, acyloxy groups such as acetoxy, isopropenyloxy and isobutyl. Examples thereof include alkenyloxy groups such as a tenenyloxy group, amino groups such as an N-butylamino group and N, N-diethylamino group, and amide groups such as an N-methylacetamide group. Among these, an alkoxy group, a ketoxime group, an acyloxy group, and an alkenyloxy group are preferable.

  The compounding amount of the crosslinking agent is 1 to 50 parts, preferably 2 to 30 parts, more preferably 5 to 20 parts per 100 parts of diorganopolysiloxane (parts by mass).

(3) Curing catalyst: The silicone rubber adhesive composition according to the present invention is accelerated by the use of a curing catalyst. Examples of the curing catalyst include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetona). ) Titanic acid ester or titanium chelate compound such as titanium, titanium isopropoxyoctylene glycol, zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron-2-ethylhexoate, cobalt-2-ethylhe Organometallic compounds such as xoate, manganese-2-ethylhexoate, cobalt naphthenate, alkoxyaluminum compound, 3-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxy Aminoalkyl group-substituted alkoxysilanes such as silane, amine compounds such as hexylamine and dodecylamine phosphate and salts thereof, quaternary ammonium salts such as benzyltriethylammonium acetate, alkali metals such as potassium acetate, sodium acetate and lithium oxalate Lower fatty acid salt, dialkylhydroxylamine such as dimethylhydroxylamine, diethylhydroxylamine, tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane, etc. Examples thereof include silane or siloxane containing guanidyl group. These are not limited to one type, and may be used as a mixture of two or more types.

  In addition, the compounding quantity of a curing catalyst is 0-20 parts with respect to 100 parts of said diorganopolysiloxane, Preferably it is 0.001-10 parts, More preferably, 0.01-5 parts is good.

(4) Filler: In the composition of the silicone rubber adhesive according to the present invention, it is preferable to use one or more fillers for the purpose of reinforcement in addition to the above components. Examples of the filler include fumed silica, precipitated silica, silica whose surface is hydrophobized with an organosilicon compound, quartz powder, carbon black, talc, zeolite, bentonite and other reinforcing agents, asbestos, glass fiber Examples thereof include fibrous fillers such as carbon fibers and organic fibers, and basic fillers such as calcium carbonate, zinc carbonate, zinc oxide, magnesium oxide, and celite. Of these fillers, silica, calcium carbonate, zeolite and the like are preferable, and particularly, fumed silica and calcium carbonate whose surfaces have been subjected to a hydrophobic treatment are preferable.

  The blending amount of the filler may be selected depending on the purpose and the kind of the filler, but is 1 to 500 parts, particularly 5 to 100 parts, with respect to 100 parts of the diorganopolysiloxane (1) component of the base polymer. preferable.

(5) Adhesive imparting component: As an adhesion promoter, amino group-containing organoalkoxysilane such as γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-glycidoxypropyl Examples include epoxy group-containing organoalkoxysilanes such as trimethoxysilane, mercapto group-containing organoalkoxysilanes such as γ-mercaptopropyltrimethoxysilane, and reaction mixtures of amino group-containing organoalkoxysilanes and epoxy group-containing organoalkoxysilanes. The compounding quantity of this component is 0.1-5 mass parts normally with respect to 100 mass parts of (1) component.

II) Addition reaction curable silicone adhesive This adhesive generally has the following basic composition.
(1) ′ Polyorganosiloxane: a main component of an addition reaction curable silicone adhesive composition, characterized by having an average of two or more alkenyl groups in one molecule. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group, and a vinyl group is preferable.

  Examples of organic groups bonded to silicon atoms other than alkenyl groups in this component include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups and other alkyl groups; phenyl groups, tolyl groups, xylyl groups, etc. Aryl groups; halogenated alkyl groups such as 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. are exemplified, preferably methyl group.

  Examples of the molecular structure of this component include a straight chain, a partially branched straight chain, a branched chain, a net, and a dendritic. The viscosity of this component at 25 ° C. is 100,000 mPa · s or more, preferably 1,000,000 mPa · s or more.

As the polyorganosiloxane of this component, molecular chain both ends dimethylvinylsiloxy group-blocked polydimethylsiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked dimethyl Siloxane / methylvinylsiloxane copolymer, siloxane unit represented by the formula: (CH ₃ ) ₃ SiO _1/2 and siloxane unit represented by the formula: (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 : _{Polyorganosiloxanes} composed of siloxane units represented by SiO _4/2 , some or all of the methyl groups of these polyorganosiloxanes are alkyl groups such as ethyl groups and propyl groups; aryl groups such as phenyl groups and tolyl groups; Polyorgano substituted with halogenated alkyl group such as 3,3,3-trifluoropropyl group Rokisan, allyl some or all of the vinyl groups of these polyorganosiloxanes, polyorganosiloxanes substituted with alkenyl groups such as propenyl group, and mixtures of two or more of these polyorganosiloxanes are exemplified.

(2) 'Hydrogenated polyorganosiloxane: This polyorganosiloxane acts as a curing agent for the present composition, and has an average of two or more silicon-bonded hydrogen atoms in one molecule. . Examples of the organic group bonded to the silicon atom in this component include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an aryl group such as a phenyl group, a tolyl group, and a xylyl group; -Halogenated alkyl groups such as a chloropropyl group and a 3,3,3-trifluoropropyl group are exemplified, and a methyl group is preferred.

  Examples of the molecular structure of this component include linear, partially branched, branched, network, and dendritic. The viscosity of this component at 25 ° C. is not limited, but is preferably in the range of 1 to 1,000,000 mPa · s, more preferably in the range of 1 to 10,000 mPa · s.

The polyorganosiloxane of this component includes polydimethylsiloxane blocked with a dimethylhydrogensiloxy group blocked at both ends of the molecular chain, a polymethylhydrogensiloxane blocked with a trimethylsiloxy group blocked at both ends of the molecular chain, a trimethylsiloxy blocked dimethylsiloxane / methylhydrogen at both ends of the molecular chain. Siloxane copolymer, cyclic polymethylhydrogensiloxane, polyorganosiloxane comprising a siloxane unit represented by the formula: (CH ₃ ) ₂ HSiO _1/2 and a siloxane unit represented by the formula: SiO _4/2 , and these polyorganos Polysiloxanes in which some or all of the methyl groups of siloxane are substituted with alkyl groups such as ethyl groups and propyl groups; aryl groups such as phenyl groups and tolyl groups; and halogenated alkyl groups such as 3,3,3-trifluoropropyl groups. Organosiloxanes and their A mixture of two or more types of reorganosiloxane is exemplified, and the resulting cured product has improved mechanical properties, particularly elongation, so that polyorganosiloxane and molecular chain having silicon-bonded hydrogen atoms only at both ends of the molecular chain. A mixture of polyorganosiloxane having a silicon atom bond in the side chain is preferred.

  In this composition, the content of this component is such that the molar ratio of silicon atom-bonded hydrogen atoms in this component to the alkenyl group in component (1) ′ is in the range of 0.01 to 20, preferably Is an amount that falls within the range of 0.1 to 10, particularly preferably an amount that falls within the range of 0.1 to 5. This is because if the content of this component is less than the lower limit of the above range, the resulting adhesive tends not to be sufficiently cured. On the other hand, when the upper limit of the above range is exceeded, the mechanical properties of the obtained cured adhesive product tend to be lowered.

  When using a mixture of polyorganosiloxane having silicon-bonded hydrogen atoms only at both ends of the molecular chain and polyorganosiloxane having silicon-bonded side chains in the molecular chain, the former polyorganosiloxane content Is an amount such that the molar ratio of silicon-bonded hydrogen atoms in this component to the alkenyl group in component (1) ′ is in the range of 0.01 to 10, preferably in the range of 0.1 to 10. In particular, an amount in the range of 0.1 to 5 is good.

  The content of the latter polyorganosiloxane is preferably such that the molar ratio of silicon-bonded hydrogen atoms in this component to alkenyl groups in (1) ′ component is in the range of 0.5 to 20, Further, the amount is preferably in the range of 0.5 to 10, and the amount in the range of 0.5 to 5 is particularly optimal.

(3) Curing catalyst: Platinum catalyst for addition reaction includes platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complex of platinum and diketone, complex of chloroplatinic acid and olefins, platinum chloride Examples include complexes of acid and alkenylsiloxane, and those in which these are supported on a carrier such as alumina, silica, or carbon black. Among these, a complex of chloroplatinic acid and an alkenylsiloxane is preferable because of its high catalytic activity as an addition reaction catalyst. Particularly, a chloroplatinic acid and divinyltetramethyldisiloxane complex as disclosed in JP-B-42-22924 is preferred. Is preferred.
The addition amount of this component is 1 to 1000 parts by mass, preferably 1 to 100 parts by mass as platinum metal atoms, per 1 part by mass of (1) ′ component.

(4) 'Filler: The filler is added to improve the mechanical strength of the present composition, and a compound usually used for blending silicone rubber is used. Examples of this component include fumed silica, precipitated silica, calcined silica, pulverized quartz, and powder obtained by surface-treating these silica powders with an organosilicon compound such as organoalkoxysilane, organohalosilane, or organosilazane. In particular, in order to sufficiently improve the mechanical strength of the resulting cured adhesive, it is preferable to use silica powder having a BET specific surface area of 50 m ² / g or more as this component.

  In this composition, the content of this component is arbitrary, but in order to improve the mechanical strength of the resulting silicone rubber cured product, (1) 1-1000 parts by weight of 100 parts by weight of component. It is preferable to be within the range, more preferably within the range of 1 to 400 parts by mass. In addition, in the present composition, as other optional components, for example, fumed titanium oxide, carbon black, carbon nanotube, diatomaceous earth, iron oxide, aluminum oxide, alumina silicate, calcium carbonate, zinc oxide, aluminum hydroxide, Inorganic fillers such as silver, gold and nickel, inorganic and organic fillers plated with gold or silver; a filler obtained by treating the surface of these fillers with the above organosilicon compound may be contained.

(5) 'Adhesiveness imparting component: This is for imparting and improving the adhesiveness in order for this addition reaction curable silicone adhesive to function as an adhesive. This includes methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, bis (trimethoxysilyl) propane, silane coupling agents such as bis (trimethoxysilyl) hexane, and partial hydrolysates thereof; epoxy group, acid anhydride group, Organic compounds having an α-cyanoacryl group and siloxane compounds containing these groups, or organic compounds or siloxane compounds having both of these groups and alkoxysilyl groups; tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetra (2- D (Ruhexyl) titanate, titanium ethyl acetonate, titanium acetyl acetonate, etc. titanium compounds; ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum tris (acetylacetonate), Aluminum compounds such as aluminum monoacetylacetonate bis (ethyl acetoacetate); zirconium compounds such as zirconium acetylacetonate, zirconium butoxyacetylacetonate, zirconium bisacetylacetonate, and zirconium ethylacetoacetate may be contained. The content of these adhesion-imparting agents is not limited, but is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of (1) ′ component.

  This composition contains 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-phenyl-1-butyn-3-ol for adjusting curability. Acetylene compounds such as 3-methyl-3-penten-1-yne, ene-yne compounds such as 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3 , 5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, silanol group-blocked methylvinylsiloxane, both molecular chains Organosiloxane compounds having 5% by weight or more of vinyl groups in one molecule such as terminal silanol-blocked methylvinylsiloxane / dimethylsiloxane copolymer; Triazoles such as benzotriazole, phosphite S, mercaptans, preferably contains a curing inhibitor such as hydrazines. Although content of these hardening inhibitors is not limited, It is good to exist in the range of 0.001-5 mass parts with respect to 100 mass parts of (1) 'component.

  The method of preparing this composition is not limited, and can be prepared by mixing other optional components as necessary. However, (1) or (1) ′ component and (4) Alternatively, it is preferable to add the remaining components to the base compound prepared by heating and mixing the component (4) ′.

  In addition, when it is necessary to add other arbitrary components, you may add when preparing a base compound. Moreover, when this changes in quality by heat mixing, it is preferable to add when adding (2)-(4) component or (2) '-(4)' component. Moreover, when preparing a base compound, the said organosilicon compound may be added and the surface of (3) or (3) 'component may be processed in-situ. When preparing the adhesive, a known kneading apparatus such as a two-roll, a kneader mixer, or a loss mixer can be used.

III) Organicated Oxide Curing Silicone Adhesive When the organopolysiloxane composition is a curable silicone rubber composition based on an organic peroxide, the organopolysiloxane used as the base polymer is preferably a gum. And those having a viscosity at 25 ° C. of 100,000 mPa · s or more, preferably 1,000,000 mPa · s or more and having at least two alkenyl groups such as vinyl groups in the molecular chain terminal and / or molecular chain.

  An organic peroxide is used as the curing catalyst. Examples of this organic peroxide include alkyl organic peroxides such as dicumyl peroxide and di-t-butyl peroxide, and acyl organic peroxides such as benzoyl peroxide and 2,4-dichlorobenzoyl peroxide. Oxides are used as suitable compounds. The blending amount is preferably 0.1 to 10 parts by mass, particularly 0.2 to 5 parts by mass with respect to 100 parts by mass of the base polymer organopolysiloxane.

IV) Radiation-curable silicone adhesive When the organopolysiloxane composition is a radiation-curable silicone rubber composition, the organopolysiloxane used as the base polymer includes a vinyl group in the molecular chain terminal and / or molecular chain, Those having two or more aliphatic unsaturated groups such as an allyl group, an alkenyloxy group, an acrylic group, and a methacryl group, a mercapto group, an epoxy group, and a hydrosilyl group are used. Its viscosity at 25 ° C. is 100,000 mPa · s or more, preferably 1,000,000 mPa · s or more.

  As a reaction initiator, known acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone, 3- Chloroxanthol, 3,9-dichloroxanthol, 3-chloro-8-nonylxanthol, benzoin, benzoin methyl ether, benzoin butyl ether, (4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothioxanthone Torr, and the like. The blending amount is preferably 0.1 to 20 parts by mass, particularly 0.5 to 10 parts by mass with respect to 100 parts by mass of the base polymer organopolysiloxane.

  The adhesion of the silicone adhesive 10 can be improved by applying a primer to the first and second transparent substrates 1 and 1A. Most of the primers are obtained by dispersing a surface treatment agent containing various substances in a solvent. In this primer, the surface treatment agent is preferably a silane coupling agent. This silane coupling agent is preferably blended in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the solvent.

  Here, the preferable blending amount of the silane coupling agent is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the dispersion solvent. If the amount is less than this range, sufficient adhesion cannot be obtained. This is because harmful effects occur. On the contrary, if it exceeds this range, the adverse effect that the workability deteriorates occurs.

  As the silane coupling agent, epoxy group-containing silanes or partial hydrolysis condensates thereof, (meth) acrylic group-containing silanes or partial hydrolysis condensates thereof, vinyl group-containing silanes or partial hydrolysis condensates thereof, It is preferable to use one or two or more substances selected from the group consisting of cyclic siloxanes, chain siloxanes, and cyanuric ring-containing organosilicon compounds.

  Examples of the epoxy group-containing silane include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 2- (3,4-epoxy Examples include cyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl (methyl) triethoxysilane.

  Examples of the (meth) acryl group-containing silane include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropyl (methyl) dimethoxysilane. Examples of the vinyl group-containing silane include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and the like.

  Examples of the cyclic siloxane include 3-glycidoxypropyl group-containing methylhydrogen cyclic tetrasiloxane, 3-methacryloxypropyl group-containing methylhydrogen cyclic tetrasiloxane, 3-glycidoxypropyl group-containing methylmethoxy cyclic siloxane, Methylhydrogen cyclic siloxane having 3-glycidoxypropyl group and 2- (trimethoxysilyl) ethyl group, methylhydrogen cyclic siloxane having 3-methacryloxypropyl group and 2- (trimethoxysilyl) ethyl group, 2 -[(3-trimethoxysilyl) propyloxycarbonyl] propyl group-containing methylhydrogen cyclic siloxane and the like.

  Examples of the chain siloxane include 3-glycidoxypropyl group-containing methylmethoxysiloxane, 3-glycidoxy group and methylhydrogensiloxane having a vinyl group, 3-glycidoxy group and 2- (trimethoxysilyl) ethyl group. Examples thereof include methylsiloxane. Examples of the cyanuric ring-containing organosilicon compound include tris (3-trimethoxysilylpropyl) isocyanurate.

  These primers can be applied by a coating machine such as a spray coater or a roll coater, or the first and second transparent substrates 1 and 1A can be dipped and applied in the primer solution.

  From the viewpoint of ensuring durability, a metal foil, a film, and / or a fiber cloth (not shown) are selectively provided or laminated on the surface, back surface, or inside of the silicone adhesive 10. Although it does not specifically limit as metal foil, Gold, silver, copper, nickel, iron, tin, aluminum foil, etc. are mention | raise | lifted. The thickness of the metal foil is preferably in the range of 5 to 500 μm. This is because workability becomes difficult when the thickness is less than 5 μm, and flexibility is impaired when the thickness exceeds 500 μm.

  The material of the film is not particularly limited, but various organic polymer films made of polyethylene terephthalate, vinyl chloride, or the like are used. The thickness of this film should just be 5-500 micrometers. This is because workability is difficult if it is less than 5 μm, and flexibility is impaired if it exceeds 500 μm. The material of the fiber cloth is not particularly limited, but the thickness is in the range of 5 to 500 μm. This is because workability is difficult when the thickness is less than 5 μm, and flexibility is impaired when the thickness exceeds 500 μm.

  According to the above configuration, the sealing peripheral wall 5 interposed and bonded between the peripheral portions of the first and second transparent substrates 1 and 1A has a fixed shape excellent in adhesiveness, chemical resistance, water resistance, weather resistance, and environmental conditions. Therefore, there is no possibility that the electrolyte solution 6 leaks. Therefore, the number of parts can be reduced by omitting the spacer. Moreover, durability of the sealing surrounding wall 5 can be improved. Further, since the sealing peripheral wall 5 is not liquid, the adhesive can be set very easily. Furthermore, since it is not necessary to increase the viscosity of the silicone adhesive 10 in particular, adhesion of the adhesive does not become difficult and the thickness is not uniform.

It is a section explanatory view showing an embodiment of a dye sensitizing type solar cell concerning the present invention. It is principal part cross-sectional explanatory drawing which shows embodiment of the dye-sensitized solar cell which concerns on this invention. It is a perspective explanatory view showing a silicone adhesive in an embodiment of a dye-sensitized solar cell according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st transparent substrate 1A 2nd transparent substrate 2 Transparent conductive film 3 Porous film 4 Dye 5 Sealing peripheral wall 6 Electrolyte solution 10 Silicone adhesive

Claims (2)

A dye-sensitized solar cell that includes a sealing peripheral wall that joins the peripheral portions of a pair of transparent substrates, and an electrolyte solution that is filled between the pair of transparent substrates, and uses conversion of light energy,
A dye-sensitized solar cell, characterized in that a sealing peripheral wall is a regular silicone adhesive. The dye-sensitized solar cell according to claim 1, wherein a plasticity of the silicone adhesive when uncured is in a range of 30 to 500 when measured with a Williams plasticity meter.

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