JP2005302564A - Sealing agent for dye-sensitized solar battery - Google Patents

Sealing agent for dye-sensitized solar battery Download PDF

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JP2005302564A
JP2005302564A JP2004117856A JP2004117856A JP2005302564A JP 2005302564 A JP2005302564 A JP 2005302564A JP 2004117856 A JP2004117856 A JP 2004117856A JP 2004117856 A JP2004117856 A JP 2004117856A JP 2005302564 A JP2005302564 A JP 2005302564A
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acrylate
dye
sensitized solar
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sealing agent
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Katsuhiko Kishi
克彦 岸
Kazuhiro Furuya
和寛 古谷
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ThreeBond Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealing agent composition having excellent durability against electrolyte used for a dye-sensitized solar battery, excellent in adhering properties to a transparent substrate, having reliable sealing properties. <P>SOLUTION: The photocuring sealing agent for dye-sensitized solar battery contains compounds expressed in (A) to (D) . (A) denotes 100 pts. wt. of (meta)acrylate containing 10-20C straight chain aliphatic hydrocarbon in a molecule, (B) denotes 5 to 15 pts. wt. of alicyclic (meta)acrylate, (C) denotes 10 pts. wt. or more of styrene group thermoplastic elastomer shown by formula stated elsewhere and (D) denotes a photopolymerization initiator, wherein, the sum of X<SB>1</SB>and X<SB>2</SB>denote an integer of 20 to 30, the sum of Y<SB>1</SB>and Y<SB>2</SB>denote an integer of 65 to 74, and Z is an integer of 1 to 5. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は紫外線または電子線等の活性エネルギー線の照射により速やかに重合し、硬化物を与える重合性組成物で、特に色素増感型太陽電池用シール剤として使用される。   The present invention is a polymerizable composition that rapidly polymerizes upon irradiation with active energy rays such as ultraviolet rays or electron beams to give a cured product, and is particularly used as a sealant for a dye-sensitized solar cell.

近年、色素増感型太陽電池と呼ばれる太陽電池が開発されている。色素増感型太陽電池は１９９１年にグレッツェルらが雑誌Ｎａｔｕｒｅにて発表された新しいタイプの有機半導体型太陽電池で、従来のシリコーン半導体型太陽電池とは異なるメカニズムによって作動し、製造コストが安いという利点によって注目をされている。またこの太陽電池は、内部に有機溶剤系の電解液を封入してあることから湿式太陽電池とも呼ばれる。この太陽電池は、光透過性を有する電極基板間に積層された光透過性を有する導電層と受光に伴い電子を放出する色素と、光電極に対して所定の間隔を隔てて対面すると共に導電性を有する対極と、光極と対極との間に配置された流動性を有する電解質層を有する。   In recent years, solar cells called dye-sensitized solar cells have been developed. The dye-sensitized solar cell is a new type of organic semiconductor solar cell that was published in 1991 by Gretzel et al. In the magazine Nature. It operates by a mechanism different from conventional silicone semiconductor solar cells and is said to be cheap to manufacture. Has been noticed by the benefits. This solar cell is also called a wet solar cell because an organic solvent-based electrolyte is sealed inside. This solar cell has a light-transmitting conductive layer laminated between light-transmitting electrode substrates, a dye that emits electrons upon receiving light, and a photoelectrode facing the photoelectrode with a predetermined distance and being conductive. And a fluid electrolyte layer disposed between the photoelectrode and the counter electrode.

電池内に存在する電解液は太陽電池が発電を行うために必至成分であり、通常は極性の高い有機溶剤にヨウ素を溶解させたものを用いる。よってこの電解液が漏洩することは電池の性能低下に大きく起因すると考えられ、そのため電解液の漏洩防止は太陽電池の信頼性を得るためには電解液の封止は重要技術である。   The electrolyte present in the battery is an indispensable component for the solar battery to generate power, and usually an iodine solution dissolved in a highly polar organic solvent is used. Therefore, it is considered that the leakage of the electrolytic solution is largely caused by a decrease in the performance of the battery. Therefore, the prevention of the leakage of the electrolytic solution is an important technique for sealing the electrolytic solution in order to obtain the reliability of the solar cell.

色素増感型太陽電池用の封止剤についてはこれまでに幾つかの発明事例が存在する。例えば特開２００４−６３２８号公報、特開２００３−１６８４９３号公報、特開２００３−１６８４９４号公報、特開２００３−１８８３９４号公報にはアイオノマーを用いたシート状の封止剤が電池作成時に用いられている。特開２０００−１７３６８０号公報によれば、受光電極と対極とを重ねるように組み合わせると共に電極間には、シール用樹脂を塗った封止用の固形物を介在させる技術が開示されている。また液状の樹脂を太陽電池用の封止剤として使用する発明も既知であり、シール用樹脂として特開２０００−１７３６８０号公報や特開２００２−３６８２３６号公報には、受光電極と対極とを重ねるように組み合わせると共に電極間のシール用剤としてエポキシ系樹脂とシリコーン系樹脂が用いられており、また特開２００２−３１３４４３号公報及び特開２００４−９５２４８号公報においては反応性ポリイソブチレンが、特開２００３−２２３９３９号公報においてはガラス転移点が８０℃以上の硬質な樹脂との表現でエポキシ樹脂、ウレタンアクリレート系樹脂、エポキシアクリレート系樹脂が用いられている。   There have been several examples of inventions related to a sealant for a dye-sensitized solar cell. For example, JP-A-2004-6328, JP-A-2003-168493, JP-A-2003-168494, and JP-A-2003-188394 use a sheet-like sealant using an ionomer at the time of battery preparation. ing. Japanese Unexamined Patent Publication No. 2000-173680 discloses a technique in which a light receiving electrode and a counter electrode are combined so as to overlap each other, and a sealing solid material coated with a sealing resin is interposed between the electrodes. In addition, an invention using a liquid resin as a sealing agent for solar cells is also known, and Japanese Patent Application Laid-Open Nos. 2000-173680 and 2002-368236 disclose a sealing resin in which a light receiving electrode and a counter electrode are stacked. In addition, an epoxy resin and a silicone resin are used as a sealing agent between the electrodes, and in Japanese Patent Application Laid-Open Nos. 2002-31443 and 2004-95248, reactive polyisobutylene is disclosed in In 2003-223939, an epoxy resin, a urethane acrylate resin, and an epoxy acrylate resin are used in terms of a hard resin having a glass transition point of 80 ° C. or higher.

さらに最近では電解液を封止する技術でなく、漏洩の少ない電解液の開発が盛んに行われている。例えば電解液を高分子ゲル中に分散および含浸させる技術によりセルの信頼性を向上させる技術もある。具体的には特開２００２−２８９２６８号公報、特開２００２−２９９６６５号公報、特開２００４−８７２０２号公報、特開２００３−１３２９６４号公報には高分子ゲル中に電解液を封じ込めることで電解液の漏洩を防止する手法が考案されている。
特開２００４−９５２４８号公報 特開２００３−２２３９３９号公報 特開２００４−６３２８号公報 特開２００３−１６８４９３号公報 特開２００３−１８８３９４号公報 特開２０００−１７３６８０号公報 特開２００２−３６８２３６号公報 特開２００２−３１３４４３号公報 特開２００２−２８９２６８号公報 特開２００２−２９９６６５号公報 特開２００４−８７２０２号公報 特開２００３−１３２９６４号公報 In recent years, not only a technique for sealing an electrolytic solution but also an electrolytic solution with little leakage has been actively developed. For example, there is a technique for improving cell reliability by a technique of dispersing and impregnating an electrolytic solution in a polymer gel. Specifically, JP-A-2002-289268, JP-A-2002-299665, JP-A-2004-87202, and JP-A-2003-132964 disclose that an electrolyte is contained in a polymer gel. A technique has been devised to prevent leakage.
JP 2004-95248 A JP 2003-223939 A JP 2004-6328 A JP 2003-168493 A JP 2003-188394 A JP 2000-173680 A JP 2002-368236 A JP 2002-313443 A JP 2002-289268 A JP 2002-299665 A JP 2004-87202 A JP 2003-132964 A

本発明は、色素増感型太陽電池に使用される電解液に対して優れた耐性を有し、かつ透明基板との接着性に優れ、信頼性の高いシール性能を有する封止剤組成物を提供することを目的とする。   The present invention provides an encapsulant composition having excellent resistance to an electrolyte solution used in a dye-sensitized solar cell, excellent adhesion to a transparent substrate, and having a reliable sealing performance. The purpose is to provide.

本発明者は各種の材質の電池シール部についての電解質層に対する膨潤性、密着性等の改善を鋭意検討してきた結果、
（Ａ）分子内に炭素数１０〜２０の直鎖脂肪族炭化水素を有する（メタ）アクリレート １００重量部
（Ｂ）脂環式（メタ）アクリレート ５〜１５重量部
（Ｃ）下記一般式で示されるスチレン系熱可塑性エラストマー １０重量部以上

Figure 2005302564
なお、式中のＸ１，Ｘ２は、Ｘ１及びＸ２の合計で２５〜３０整数を表し、またＹ１，Ｙ２は、Ｙ１及びＹ２の合計で６５〜７４の整数を表し、Ｚは１〜５の整数を表す。
（Ｄ）光重合開始剤
上記（Ａ）〜（Ｄ）を主成分とする光硬化性の色素増感型太陽電池用シール剤とすることで前記課題を解決した。 As a result of earnestly examining the improvement of swellability, adhesion, etc. to the electrolyte layer of the battery seal portion of various materials,
(A) (meth) acrylate having a straight chain aliphatic hydrocarbon having 10 to 20 carbon atoms in the molecule 100 parts by weight (B) alicyclic (meth) acrylate 5 to 15 parts by weight (C) represented by the following general formula Styrenic thermoplastic elastomer 10 parts by weight or more
Figure 2005302564
 X1 and X2 in the formula represent an integer of 25 to 30 in total of X1 and X2, Y1 and Y2 represent an integer of 65 to 74 in total of Y1 and Y2, and Z is an integer of 1 to 5 Represents.
(D) Photoinitiator The said subject was solved by setting it as the photocurable dye-sensitized solar cell sealing agent which has said (A)-(D) as a main component.

以下本発明を詳細に説明する。色素増感型太陽電池の構造を図１を用いて簡単に説明すると、図１において、透明基板１の片方の面に透明導電膜２を形成しその上に酸化チタンの粒子を均一に塗布、加熱して多孔質膜３を設け、さらに多孔質膜に色素４を吸着させる。一方、透明基板１ａに透明導電膜２ａを形成した導電性基板が封止剤７を介して対向させ、両基板と封止剤によって形成された隙間には電解液５が注入されることにより製造させる。   The present invention will be described in detail below. The structure of the dye-sensitized solar cell will be briefly described with reference to FIG. 1. In FIG. 1, a transparent conductive film 2 is formed on one surface of a transparent substrate 1, and titanium oxide particles are uniformly applied thereon. The porous film 3 is provided by heating, and the dye 4 is adsorbed on the porous film. On the other hand, the conductive substrate having the transparent conductive film 2a formed on the transparent substrate 1a is opposed to each other through the sealant 7, and the electrolytic solution 5 is injected into the gap formed by both substrates and the sealant. Let

本発明のシール剤は、前記した色素増感型太陽電池の構造における封止剤７として主に使用されるものであるが、電解液の封止目的であればどのような部位にも使用可能である。なお、本発明では液状もしくは半液状の光硬化性シール剤としているので、固形のガスケットと比較して色素増感型太陽電池の構造変更にも容易に対応でき、また光硬化により生産性を向上させることができる。さらに、非シール部に対して化学的に接着しているので、界面からの電解液の漏れが生じにくく、また色素増感型太陽電池の強度的な信頼性を向上することができる。   The sealant of the present invention is mainly used as the sealant 7 in the structure of the dye-sensitized solar cell described above, but can be used for any part as long as the electrolyte is sealed. It is. In the present invention, since it is a liquid or semi-liquid photocurable sealant, it can easily cope with structural changes of dye-sensitized solar cells compared to solid gaskets, and also improves productivity by photocuring. Can be made. Furthermore, since it is chemically bonded to the non-seal portion, it is difficult for the electrolyte solution to leak from the interface, and the strength reliability of the dye-sensitized solar cell can be improved.

本発明で使用する（Ａ）の鎖状脂肪族アクリレート成分は、分子内に鎖状脂肪族炭化水素部位を有するアクリレートモノマーであることが必要であり、望ましくは単官能のアクリレートモノマーである。鎖状脂肪族単官能アクリレートモノマーとしては、脂肪族鎖部分の直鎖の炭素数が５〜２０のものが好ましく、８〜１６のものがより好ましい。脂肪族鎖部分の直鎖の炭素数が少なすぎると接着性が悪くなる。脂肪族直鎖部分の直鎖の炭素数が２０を超えると、本発明の成分（Ｃ）と相溶性が悪くなり接着強さが大きく低減してしまう。また添加量も硬化後の物性に大きく寄与し、本成分の量が少なすぎると硬化後に可撓性が不足し、多すぎると粘着性が強くなるため接着強度は低下する。鎖状脂肪族単官能アクリレートモノマーとしては、具体的には、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート等が例示される。   The chain aliphatic acrylate component (A) used in the present invention needs to be an acrylate monomer having a chain aliphatic hydrocarbon moiety in the molecule, and is preferably a monofunctional acrylate monomer. The chain aliphatic monofunctional acrylate monomer preferably has 5 to 20 linear carbon atoms in the aliphatic chain portion, and more preferably has 8 to 16 carbon atoms. If the straight chain carbon number of the aliphatic chain portion is too small, the adhesiveness is deteriorated. When the straight chain carbon number of the aliphatic straight chain portion exceeds 20, compatibility with the component (C) of the present invention is deteriorated and the adhesive strength is greatly reduced. Also, the added amount greatly contributes to the physical properties after curing. If the amount of this component is too small, the flexibility is insufficient after curing, and if it is too large, the tackiness becomes strong and the adhesive strength decreases. Specific examples of the chain aliphatic monofunctional acrylate monomer include 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, decyl (meth) acrylate, dodecyl ( Examples include (meth) acrylate, stearyl (meth) acrylate, hexadecyl (meth) acrylate and the like.

本発明で使用する（Ｂ）の脂環式（メタ）アクリレート成分とは、分子内に脂環式炭化水素基（脂環部やその他の部位に置換基を有していても良い）と少なくとも１つ以上（メタ）アクリロイル基を有する化合物で、脂環式アルコールとアクリル酸やメタクリル酸等とのエステル等が挙げられる。また、本発明においてアクリロイル基は、狭義のアクリレート基のほかにメタクリレート基やエタクリレート基なども含むが、硬化性の向上や酸素による硬化阻害の低減などから狭義のアクリレート基を有する脂環式アクリレートモノマーが好ましい。さらに添加量については成分（Ａ）１００重量部に対して５〜１５重量部が適量であり、好ましくは５〜１０重量部である。この範囲外では硬化後の接着性が大きく低下する。このような脂環式アクリレートモノマーの具体例としては、シクロヘキシル（メタ）アクリレート、ノルボニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、イソボニル（メタ）アクリレート、ヘキサシクロ−ヘプタデシル−４−アクリレート、１２−メチルヘキサシクロ−ヘプタデシル−４−アクリレート、オクタシクロ−ドコシル−５−アクリレート、１５−メチルオクタシクロ−ドコシル−５−アクリレート、テトラシクロ−ドデシル−３−アクリレート、２，７−ジメチルテトラシクロ−ドデシル−３−アクリレート等が挙げられる。   The alicyclic (meth) acrylate component (B) used in the present invention is an alicyclic hydrocarbon group (which may have a substituent at the alicyclic part or other site) in the molecule and at least A compound having one or more (meth) acryloyl groups, such as an ester of an alicyclic alcohol and acrylic acid or methacrylic acid. In the present invention, the acryloyl group includes a methacrylate group and an ethacrylate group in addition to the narrowly defined acrylate group. However, the cycloaliphatic acrylate monomer has a narrowly defined acrylate group in order to improve curability and reduce inhibition of curing by oxygen. Is preferred. Furthermore, about the addition amount, 5-15 weight part is a suitable quantity with respect to 100 weight part of component (A), Preferably it is 5-10 weight part. Outside this range, the adhesiveness after curing is greatly reduced. Specific examples of such alicyclic acrylate monomers include cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, hexacyclo -Heptadecyl-4-acrylate, 12-methylhexacyclo-heptadecyl-4-acrylate, octacyclo-docosyl-5-acrylate, 15-methyloctacyclo-docosyl-5-acrylate, tetracyclo-dodecyl-3-acrylate, 2,7 -Dimethyltetracyclo-dodecyl-3-acrylate and the like.

本発明におけるスチレン系熱可塑性エラストマー成分は下記一般式で示される化学構造で、スチレン骨格（Ｘ）とエチレン−ブチレン骨格（Ｙ１およびＹ２）を有し、かつ無水マレイン酸骨格（Ｚ）を有するＸＹＺＸブロック共重合体が最も有効である。本発明においては、熱可塑性エラストマーの数平均分子量は１０，０００〜５０、０００、好ましくは２０、０００〜３０、０００ものが適している。また、（Ｃ）成分中のＸの重合体ブロックとＹの重合体ブロックの比率は３０／７０が好ましく、さらにＹＺの重合ブロック中Ｚは１以上が好ましい。また添加量についても本発明の成分（Ａ）１００重量部に対して１０以上であり、好ましくは１０〜４０重量部、より好ましくは２０〜３５重量部であり、この範囲外では樹脂の物性である耐溶剤性、透湿度性、接着性が大きく低下する。   The styrenic thermoplastic elastomer component in the present invention has a chemical structure represented by the following general formula, and has styrene skeleton (X), ethylene-butylene skeleton (Y1 and Y2), and XYZX having maleic anhydride skeleton (Z). Block copolymers are most effective. In the present invention, the number average molecular weight of the thermoplastic elastomer is 10,000 to 50,000, preferably 20,000 to 30,000. Further, the ratio of the X polymer block to the Y polymer block in the component (C) is preferably 30/70, and Z in the YZ polymer block is preferably 1 or more. Further, the addition amount is 10 or more with respect to 100 parts by weight of the component (A) of the present invention, preferably 10 to 40 parts by weight, more preferably 20 to 35 parts by weight. Certain solvent resistance, moisture permeability and adhesion are greatly reduced.

Figure 2005302564
なお、式中のＸ１，Ｘ２は、Ｘ１及びＸ２の合計で２５〜３０整数を表し、またＹ１，Ｙ２は、Ｙ１及びＹ２の合計で６５〜７４の整数を表し、Ｚは１〜５の整数を表す。
Figure 2005302564
 X1 and X2 in the formula represent an integer of 25 to 30 in total of X1 and X2, Y1 and Y2 represent an integer of 65 to 74 in total of Y1 and Y2, and Z is an integer of 1 to 5 Represents.

本発明で使用する光重合開始剤は、特に限定されず公知の光ラジカル重合開始剤でよい。例えば、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシアセトフェノン、塩素化アセトフェノン、２−メチル−１−（４−メチルチオフェニル）−２−モルホリノ−プロパン−１−オン等のアセトフェノン類、ベンゾフェノン類、ベンジル、メチルオルソベンゾイルベンゾエート、ベンゾインアルキルエーテル等のベンゾイン類、α，α’−アゾビスイソブチロニトリル、２，２’−アゾビスプロパン、ヒドラゾン等のアゾ化合物、ベンゾイルパーオキサイド、ジターシャリーブチルパーオキサイド等の有機パーオキサイド類、ジフェニルジサルファイド、ジベンジルジサルファイド、ジベンゾイルジサルファイド等のジフェニルジサルファイド類等が挙げられる。また、イルガキュアー１８４（チバガイギー製、１−ヒドロキシシクロヘキシルフェニルケトン）等の市販の光重合開始剤も使用できる。   The photopolymerization initiator used in the present invention is not particularly limited and may be a known radical photopolymerization initiator. For example, acetophenone such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, chlorinated acetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one , Benzophenones, benzoins such as benzyl, methyl orthobenzoylbenzoate, benzoin alkyl ether, azo compounds such as α, α′-azobisisobutyronitrile, 2,2′-azobispropane, hydrazone, benzoyl peroxide And organic peroxides such as ditertiary butyl peroxide, and diphenyl disulfides such as diphenyl disulfide, dibenzyl disulfide, and dibenzoyl disulfide. Commercially available photopolymerization initiators such as Irgacure 184 (Ciba Geigy, 1-hydroxycyclohexyl phenyl ketone) can also be used.

本発明の組成物には発明の目的を損なわない範囲で、各種添加剤を添加してもよい。例えば、フェノール系やリン系等の老化防止剤、フェノール系等の熱劣化防止剤、ベンゾフェノン系等の紫外線安定剤、アミン系等の帯電防止剤、脂肪族アルコールのエステル、多価アルコールの部分エステル及び部分エーテル等の滑剤等の各種添加剤を添加してもよく、特に線膨張係数を小さくすることができるため、フィラーを添加することが好ましい。ただし、フィラーを添加すると樹脂の軽量性、透明性などが損なわれる場合もあるので、接着物の用途によって注意する必要がある。例えば、炭酸カルシウム、タルク、シリカ、カーボンブラックといった各種の無機充填剤が使用できる。しかし、本発明の硬化性組成物は光よる硬化を利用するため、その使用に当たっては、例えば極度に隠蔽性の高い無機充填剤を使用すると硬化性に支障をきたすことが考えられるので、硬化性低下の有無を考慮しなければならない。さらに、本発明の硬化物組成物には、必要に応じてギャップ保持のためのスペーサー、酸化防止剤、顔料、界面活性剤等を適宜添加することが出来る。   Various additives may be added to the composition of the present invention as long as the object of the invention is not impaired. For example, anti-aging agents such as phenols and phosphorus, anti-aging agents such as phenols, UV stabilizers such as benzophenones, antistatic agents such as amines, esters of aliphatic alcohols, partial esters of polyhydric alcohols In addition, various additives such as lubricants such as partial ethers may be added. In particular, since the linear expansion coefficient can be reduced, it is preferable to add a filler. However, if a filler is added, the lightness and transparency of the resin may be impaired, so care must be taken depending on the application of the adhesive. For example, various inorganic fillers such as calcium carbonate, talc, silica, and carbon black can be used. However, since the curable composition of the present invention utilizes curing by light, it is considered that the use of, for example, an inorganic filler with extremely high concealment may hinder the curability. The presence or absence of decline must be considered. Furthermore, a spacer for maintaining a gap, an antioxidant, a pigment, a surfactant, and the like can be appropriately added to the cured composition of the present invention as necessary.

本発明は接着性の向上を目的とした成分であるシランカップリング剤の添加も可能である。具体例としては、分子中にエポキシ基、メタクリル基、アクリル基、ビニル基、カルバメート基から選ばれる少なくとも１個の官能基と、ケイ素原子結合アルコール基を有するシランカップリング剤が望ましい。前記官能基については、中でも硬化性及び接着性の点から、分子中にエポキシ基、メタクリル基、アクリル基があるのが好ましい。具体的には、エポキシ官能基とケイ素原子結合アルコキシ基を有する有機ケイ素化合物として、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、−（３，４−エポキシシクロヘキシル）エチルトリエトキシシランが挙げられる。また、メタクリル基あるいはアクリル基とケイ素原子結合アルコキシ基を有する有機ケイ素化合物としては３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−アクリロキシプロピルトリエトキシシラン、メタクリロキシメチルトリメトキシシラン、メタクリロキシメチルトリエトキシシラン、アクリロキシメチルトリメトキシシラン、アクリロキシメチルトリエトキシシランが挙げられる。   In the present invention, it is also possible to add a silane coupling agent which is a component for the purpose of improving adhesiveness. As a specific example, a silane coupling agent having at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, a vinyl group, and a carbamate group in the molecule and a silicon atom-bonded alcohol group is desirable. About the said functional group, it is preferable that there exist an epoxy group, a methacryl group, and an acryl group in a molecule | numerator from the point of sclerosis | hardenability and adhesiveness especially. Specifically, as an organosilicon compound having an epoxy functional group and a silicon atom-bonded alkoxy group, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane,-(3,4-epoxycyclohexyl) ethyltriethoxysilane. Examples of the organosilicon compound having a methacryl group or an acryl group and a silicon atom-bonded alkoxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acrylonitrile. Examples include roxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

本発明のシール剤組成物は色素増感型太陽電池の電解液に対する耐性が高く、かつガラスとの接着性にも長けていることから、湿度の進入を妨げ、かつ高い耐薬品性が求められる箇所での使用において十分な封止が可能である。また封止する電極はガラスだけでなくＰＥＴやＰＥＮフィルムタイプなどのプラスチック製の電極における封止に関しても応用が可能である。   Since the sealing agent composition of the present invention has high resistance to the electrolyte solution of the dye-sensitized solar cell and has excellent adhesion to glass, it prevents moisture from entering and requires high chemical resistance. Enough sealing is possible in use at a location. Further, the electrode to be sealed is applicable not only to glass but also to sealing in a plastic electrode such as PET or PEN film type.

さらに、本発明のシール剤組成物は液状もしくは半液状であるため、色素増感型太陽電池の構造に左右されず様々の部位にも適用可能であり、また、光（紫外線）の照射により速やかに硬化するので生産性を向上させることができる。   Furthermore, since the sealing agent composition of the present invention is liquid or semi-liquid, it can be applied to various parts regardless of the structure of the dye-sensitized solar cell, and can be promptly irradiated with light (ultraviolet rays). Since it hardens rapidly, productivity can be improved.

以下実施例にて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。   EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

直鎖脂肪族（メタ）アクリレート（Ａ成分）としてイソステアリルアクリレート、イソノニルアクリレート、ラウリルアクリレートを、また、脂環式アクリレート（Ｂ成分）としてイソボロニルアクリレート、シクロヘキシルアクリレートを、スチレン系熱可塑エラストマー（Ｃ成分）としてタフテックＭ１９１３（旭化成社製）を（実施例１〜４）、また、本発明成分（Ｃ）の比較として無水マレイン酸骨格を持たないスチレン系熱可塑性エラストマー（セプトン８００７、クラレ社製）を（比較例６）、光開始剤（Ｄ）としてイルガキュアー１８４（チバ・スペシャルティ・ケミカルズ社製）を使用し、表１に示す通りに各成分を配合しミキサーを用いて５０℃で１時間攪拌し各シール剤を得た。   Isostearyl acrylate, isononyl acrylate, lauryl acrylate as linear aliphatic (meth) acrylate (component A), isobornyl acrylate, cyclohexyl acrylate as alicyclic acrylate (component B), styrene thermoplastic elastomer Tuftec M1913 (produced by Asahi Kasei Co., Ltd.) as (Component C) (Examples 1 to 4), and a styrene thermoplastic elastomer having no maleic anhydride skeleton (Septon 8007, Kuraray Co., Ltd.) as a comparison with the present component (C) (Comparative Example 6), Irgacure 184 (manufactured by Ciba Specialty Chemicals) is used as a photoinitiator (D), and each component is blended as shown in Table 1 and mixed at 50 ° C. using a mixer. Each sealant was obtained by stirring for 1 hour.

上記のとおり調整した光硬化性のシール剤を用いて下記の各試験をそれぞれ行った。その結果を表１に合わせて記載する。なお、各試験の詳細は次のとおりである。また、各試験に設定した目標値は色素増感型太陽電池用シール剤としての性能を満足するために必要十分条件であり、この目標値外のものは同シール剤に適さないものと思われる。   Each of the following tests was performed using the photocurable sealant prepared as described above. The results are shown in Table 1. The details of each test are as follows. In addition, the target values set for each test are necessary and sufficient conditions to satisfy the performance as a sealant for dye-sensitized solar cells, and those outside this target value are not suitable for the sealant. .

［相溶性試験］
各成分を混合した際に分離が見られるものを×とし、均一な液状を呈するものを○で評価した。 [Compatibility test]
The case where separation was observed when each component was mixed was evaluated as x, and the case where a uniform liquid was exhibited was evaluated as ◯.

［耐溶剤性試験］
各組成物約２ｇを２５φのポリキャップに入れ、３０．０Ｗ／ｍ２にて硬化させた後、重量測定する。ついでアセトニトリル溶液にそれぞれの硬化物を浸漬させた後（条件：６０℃×９６時間）、硬化物を取り出し、表面を軽くワイプして重量を測定し、浸漬前との重量変化率を求めた。なお、目標値を３０％以下としたが、この目標値を越えると水分が進入し易くなるため電解液の劣化を招く。 [Solvent resistance test]
About 2 g of each composition is put in a 25φ polycap, cured at 30.0 W / m 2 , and then weighed. Next, after each cured product was immersed in an acetonitrile solution (condition: 60 ° C. × 96 hours), the cured product was taken out, the surface was lightly wiped, the weight was measured, and the weight change rate before the immersion was determined. Note that the target value is set to 30% or less. However, if the target value is exceeded, moisture easily enters, leading to deterioration of the electrolytic solution.

［透湿度試験］
ＪＩＳ Ｚ ０２０８に基づき測定を行った（測定条件：４０℃×９５％ＲＨ）。測定膜の作成は、フッ素樹脂テープを貼ったガラス板上に樹脂をコーティングし（膜厚約３００ミクロン）、３０．０Ｗ／ｍ２にて硬化させたものを指定容器形状にカットし、塩化カルシウムを約１ｇ容器に入れて養生させた。測定は２４時間後の重量を基準値とし、その後経時で重量変化が飽和した時点を終点とした。なお、目標値を５０ｇ／ｍ２・２４ｈ以下としたが、この目標値を越えるとシール剤の硬化物が電解液による膨潤などで劣化するため、電解液の液漏れや破損を招く恐れがある。 [Moisture permeability test]
Measurement was performed based on JIS Z 0208 (measurement conditions: 40 ° C. × 95% RH). The measurement film is made by coating a resin on a glass plate with a fluororesin tape (film thickness of about 300 microns), curing it at 30.0 W / m 2, and cutting it into a specified container shape. Was put in a container of about 1 g and cured. The measurement was based on the weight after 24 hours, and the end point was when the weight change was saturated over time. The target value is set to 50 g / m 2 · 24 h or less. However, if this target value is exceeded, the cured product of the sealing agent deteriorates due to swelling by the electrolytic solution, which may cause leakage or breakage of the electrolytic solution. .

［引っ張り剪断接着強さ試験］
ＪＩＳ Ｋ ６８５０に基づき測定を行った（引っ張り速度：５０ｍｍ／ｍｉｎ）。試験片の作成は、５×２５×１００ｍｍのソーダガラスに樹脂を塗布面積２５ｍｍ２となるように貼り合わせを行い、紫外線照射装置（ウシオ電気社、ＵＶＬ−４００１Ｎ）を用いて約３０Ｗ／ｍ２の積算光量で硬化させた。なお、目標値を３ＭＰａ以上としたが、この目標値未満であると接着強度が不足し、剥離による電解液の漏れを生じやすくなる。 [Tensile shear strength test]
Measurement was performed based on JIS K 6850 (tensile speed: 50 mm / min). The test piece was prepared by bonding the resin to 5 × 25 × 100 mm soda glass so that the application area was 25 mm 2 and using an ultraviolet irradiation device (Ushio Electric Co., Ltd., UVL-4001N), about 30 W / m 2. Cured with the integrated light amount of The target value is set to 3 MPa or more. However, when the target value is less than this target value, the adhesive strength is insufficient, and the electrolyte solution is liable to leak due to peeling.

Figure 2005302564
Figure 2005302564

上記結果から、実施例で示したシール剤はいずれも試験項目においても十分な目標値を達成しており、色素増感型太陽電池用シール剤として有用である。一方、比較例１〜５では何れかの試験項目において極端な性能低下が見られ、電解液の漏洩と外部からの水分の進入を十分に満足できるものとは言えず、実施例と比較してトータルバランスに欠けることがわかる。また、Ｃ成分の添加量には相溶性においてその限界量が存在することがわかる。   From the above results, all of the sealing agents shown in the Examples have achieved sufficient target values in the test items, and are useful as sealing agents for dye-sensitized solar cells. On the other hand, in Comparative Examples 1 to 5, an extreme performance degradation was observed in any test item, and it cannot be said that the leakage of the electrolyte and the entry of moisture from the outside can be sufficiently satisfied, compared with the examples. It can be seen that the total balance is lacking. In addition, it can be seen that there is a limit amount in compatibility with the amount of component C added.

本発明は、色素増感型太陽電池用シール剤として好適に使用できるが、その他の用途であっても、耐溶剤性（耐電解液性）や耐透湿性が求められる部材に対する接着剤やシール材として使用可能である。   The present invention can be suitably used as a sealant for a dye-sensitized solar cell, but it can be used as an adhesive or a seal for members that require solvent resistance (electrolytic solution resistance) or moisture resistance even in other applications. It can be used as a material.

色素増感型太陽電池の一部構造を示した概略図である。It is the schematic which showed the partial structure of the dye-sensitized solar cell.

符号の説明Explanation of symbols

１ 透明基板
２ 透明電極
３ 多孔質膜
４ 色素層
５ 電解液
７ 封止剤 DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Transparent electrode 3 Porous film 4 Dye layer 5 Electrolyte 7 Sealant

Claims (3)

（Ａ）分子内に炭素数１０〜２０の直鎖脂肪族炭化水素を有する（メタ）アクリレート １００重量部
（Ｂ）脂環式（メタ）アクリレート ５〜１５重量部
（Ｃ）下記一般式で示されるスチレン系熱可塑性エラストマー １０重量部以上
Figure 2005302564
 なお、式中のＸ１，Ｘ２は、Ｘ１及びＸ２の合計で２５〜３０整数を表し、またＹ１，Ｙ２は、Ｙ１及びＹ２の合計で６５〜７４の整数を表し、Ｚは１〜５の整数を表す。
（Ｄ）光重合開始剤
上記（Ａ）〜（Ｄ）を主成分とする光硬化性の色素増感型太陽電池用シール剤。 (A) (meth) acrylate having a straight chain aliphatic hydrocarbon having 10 to 20 carbon atoms in the molecule 100 parts by weight (B) alicyclic (meth) acrylate 5 to 15 parts by weight (C) represented by the following general formula Styrenic thermoplastic elastomer 10 parts by weight or more
Figure 2005302564
 X1 and X2 in the formula represent an integer of 25 to 30 in total of X1 and X2, Y1 and Y2 represent an integer of 65 to 74 in total of Y1 and Y2, and Z is an integer of 1 to 5 Represents.
(D) Photopolymerization initiator A photocurable dye-sensitized solar cell sealing agent containing (A) to (D) as main components. 前記（Ａ）分子内に炭素数１０〜２０の直鎖脂肪族炭化水素を有する（メタ）アクリレートが単官能のモノマーである請求項１に記載の色素増感型太陽電池用シール剤。 2. The dye-sensitized solar cell sealing agent according to claim 1, wherein (A) (meth) acrylate having a linear aliphatic hydrocarbon having 10 to 20 carbon atoms in the molecule is a monofunctional monomer. 前記（Ｃ）スチレン系熱可塑性エラストマーの添加量が、１０〜４０重量部である請求項１に記載の色素増感型太陽電池用シール剤。 2. The dye-sensitized solar cell sealant according to claim 1, wherein the addition amount of the (C) styrene-based thermoplastic elastomer is 10 to 40 parts by weight.
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WO2011021647A1 (en) * 2009-08-21 2011-02-24 ソニー株式会社 Photocell module and process for production of photocell module
JP2015157912A (en) * 2014-02-25 2015-09-03 スリーボンドファインケミカル株式会社 curable resin composition
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