JP4456883B2 - Dye-sensitized solar cell laminate film and dye-sensitized solar cell electrode using the same - Google Patents
Dye-sensitized solar cell laminate film and dye-sensitized solar cell electrode using the same Download PDFInfo
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- JP4456883B2 JP4456883B2 JP2004022840A JP2004022840A JP4456883B2 JP 4456883 B2 JP4456883 B2 JP 4456883B2 JP 2004022840 A JP2004022840 A JP 2004022840A JP 2004022840 A JP2004022840 A JP 2004022840A JP 4456883 B2 JP4456883 B2 JP 4456883B2
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- film
- dye
- sensitized solar
- layer
- solar cell
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- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- GKMXREIWPASRMP-UHFFFAOYSA-J dipotassium;oxalate;oxygen(2-);titanium(4+) Chemical compound [O-2].[K+].[K+].[Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O GKMXREIWPASRMP-UHFFFAOYSA-J 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Laminated Bodies (AREA)
Description
本発明は色素増感型太陽電池用積層フィルムおよび色素増感型太陽電池用電極に関し、更に詳しくは多孔質半導体層の加工性、およびその密着性を高めた色素増感型太陽電池用積層フィルム、それを用いた色素増感型太陽電池用電極に関するものである。 The present invention relates to a laminated film for a dye-sensitized solar cell and an electrode for a dye-sensitized solar cell, and more specifically, a laminated film for a dye-sensitized solar cell with improved workability and adhesion of a porous semiconductor layer. The present invention relates to a dye-sensitized solar cell electrode using the same.
色素増感型太陽電池は、色素増感半導体微粒子を用いた光電変換素子が提案されて以来（「ネイチャー（Ｎａｔｕｒｅ）」 第３５３巻、第７３７〜７４０ページ、（１９９１年））、シリコン系太陽電池に替る新たな太陽電池として注目されている。特に、支持体としてプラスチックフィルムを用いた色素増感型太陽電池は、柔軟化や軽量化が可能であり、数多くの検討がなされてきた。 The dye-sensitized solar cell has been proposed since a photoelectric conversion element using dye-sensitized semiconductor fine particles was proposed (“Nature”, Vol. 353, pages 737-740, (1991)). It is attracting attention as a new solar battery that replaces batteries. In particular, dye-sensitized solar cells using a plastic film as a support can be made flexible and lightweight, and many studies have been made.
しかしながら、プラスチックフィルムを支持体として用いた場合、透明導電層上への多孔質半導体層の加工が困難であり、透明導電層と多孔質半導体の密着性を確保することが難しく、ガラスを支持体として用いた場合に比べて多くの問題点がある。 However, when a plastic film is used as a support, it is difficult to process the porous semiconductor layer on the transparent conductive layer, and it is difficult to ensure adhesion between the transparent conductive layer and the porous semiconductor. There are many problems compared to the case of using as
プラスチックフィルムの中でもポリエステルフィルムは、安価でありながら高透明でかつ耐熱性を有するため、色素増感型太陽電池用の支持体として有用な素材である。しかしながら、透明導電層と多孔質半導体層との密着性を確保することはこれまで困難であり、光発電性能が低下するという問題がある。 Among plastic films, a polyester film is a material useful as a support for a dye-sensitized solar cell because it is inexpensive but highly transparent and has heat resistance. However, it has been difficult to secure the adhesion between the transparent conductive layer and the porous semiconductor layer, and there is a problem that the photovoltaic performance is deteriorated.
本発明は、かかる従来技術の問題を解決し、透明導電層と多孔質半導体層の密着性に優れ、光発電性能の高い色素増感太陽電池を作成することができる、色素増感型太陽電池用積層フィルムおよび色素増感型太陽電池用電極を提供することを目的とする。 The present invention solves the problems of the prior art and is excellent in the adhesion between the transparent conductive layer and the porous semiconductor layer, and can produce a dye-sensitized solar cell with high photovoltaic power generation performance. It is an object to provide a laminated film and a dye-sensitized solar cell electrode.
すなわち本発明は、２００℃で１０分間熱処理したときのフィルムの長手方向と幅方向における熱収縮率の差の絶対値が０．８％以下であるポリエステルフィルム、およびその片面に設けられた透明導電層からなり、透明導電層の表面張力が４０ｍＮ／ｍ以上である、色素増感型太陽電池用積層フィルムである。
以下、本発明を詳細に説明する。
That is, the present invention relates to a polyester film in which the absolute value of the difference in thermal shrinkage between the longitudinal direction and the width direction of the film when heat-treated at 200 ° C. for 10 minutes is 0.8% or less, and a transparent conductive film provided on one side thereof It is a laminated film for a dye-sensitized solar cell, comprising a layer and having a transparent conductive layer having a surface tension of 40 mN / m or more.
Hereinafter, the present invention will be described in detail.
[ポリエステルフィルム]
本発明において、ポリエステルフィルムを構成するポリエステルは、芳香族二塩基酸またはそのエステル形成性誘導体とジオールまたはそのエステル形成性誘導体とから合成される線状飽和ポリエステルである。
[Polyester film]
In the present invention, the polyester constituting the polyester film is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
かかるポリエステルの具体例として、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレンイソフタレート、ポリブチレンテレフタレート、ポリ（１，４−シクロヘキシレンジメチレンテレフタレート）、ポリエチレン−２，６−ナフタレート等を例示することができ、これらの共重合体またはこれと小割合の他樹脂とのブレンドであってもよい。これらのポリエステルのうち、ポリエチレンテレフタレート、ポリエチレン−２，６−ナフタレートが力学的物性や光学物性等のバランスが良いので好ましい。特にポリエチレン−２，６−ナフタレートは機械的強度の大きさ、熱収縮率の小ささ、加熱時のオリゴマー発生量の少なさなどの点でポリエチレンテレフタレートにまさっているので最も好ましい。 Specific examples of such polyesters include polyethylene terephthalate, polyethylene isophthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate, and the like. It may be a blend of these copolymers or a small proportion of other resins. Among these polyesters, polyethylene terephthalate and polyethylene-2,6-naphthalate are preferable because of a good balance between mechanical properties and optical properties. In particular, polyethylene-2,6-naphthalate is most preferable because it is superior to polyethylene terephthalate in terms of mechanical strength, small heat shrinkage, and a small amount of oligomer generated during heating.
ポリエステルは、ホモポリマーでも、第三成分を共重合したコポリマーでもよいが、ホモポリマーが好ましい。ポリエステルがポリエチレンテレフタレートである場合、コポリマーとしてイソフタル酸共重合ポリエチレンテレフタレートが最適である。このイソフタル酸共重合ポリエチレンテレフタレートは、イソフタル酸が５ｍｏｌ％以下であることが好ましい。ポリエステルにはイソフタル酸以外の共重合成分または共重合アルコール成分が、その特性を損なわない範囲、例えば全酸成分又は全アルコール成分に対して３モル％以下の割合で、共重合されていてもよい。該共重合酸成分としては、フタル酸、２，６−ナフタレンジカルボン酸等の如き芳香族ジカルボン酸、アジピン酸、アゼライン酸、セバシン酸、１，１０−デカンジカルボン酸等の如き脂肪族ジカルボン酸等が例示でき、またアルコール成分としては、１，４−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール等の如き脂肪族ジオール、１，４−シクロヘキサンジメタノールの如き脂環族ジオール等が例示できる。これらは単独または二種以上を使用することができる。 The polyester may be a homopolymer or a copolymer obtained by copolymerizing the third component, but a homopolymer is preferred. When the polyester is polyethylene terephthalate, isophthalic acid copolymerized polyethylene terephthalate is optimal as the copolymer. The isophthalic acid copolymerized polyethylene terephthalate preferably contains 5 mol% or less of isophthalic acid. The polyester may be copolymerized with a copolymer component or copolymer alcohol component other than isophthalic acid in a range that does not impair the properties thereof, for example, in a proportion of 3 mol% or less with respect to the total acid component or the total alcohol component. . Examples of the copolymer acid component include aromatic dicarboxylic acids such as phthalic acid and 2,6-naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and 1,10-decanedicarboxylic acid. Examples of the alcohol component include aliphatic diols such as 1,4-butanediol, 1,6-hexanediol and neopentyl glycol, and alicyclic diols such as 1,4-cyclohexanedimethanol. it can. These can be used alone or in combination of two or more.
ポリエステルがポリエチレン−２，６−ナフタレンジカルボキシレートである場合、主たるジカルボン酸成分としてナフタレンジカルボン酸が用いられ、主たるグリコール成分としてエチレングリコールが用いられる。ナフタレンジカルボン酸としては、たとえば２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸を挙げることができ、これらの中で２，６−ナフタレンジカルボン酸が好ましい。ここで「主たる」とは、本発明のフィルムの成分であるポリマーの構成成分において全繰返し単位の少なくとも９０ｍｏｌ％、好ましくは少なくとも９５ｍｏｌ％を意味する。 When the polyester is polyethylene-2,6-naphthalenedicarboxylate, naphthalenedicarboxylic acid is used as the main dicarboxylic acid component, and ethylene glycol is used as the main glycol component. Examples of naphthalenedicarboxylic acid include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. Among these, 2,6-naphthalenedicarboxylic acid is preferable. Here, “main” means at least 90 mol%, preferably at least 95 mol% of all repeating units in the constituent components of the polymer that is a component of the film of the present invention.
コポリマーである場合、コポリマーを構成する共重合成分としては、分子内に２つのエステル形成性官能基を有する化合物を用いることができ、かかる化合物としては例えば、蓚酸、アジピン酸、フタル酸、セバシン酸、ドデカンジカルボン酸、イソフタル酸、テレフタル酸、１，４−シクロヘキサンジカルボン酸、４，４'−ジフェニルジカルボン酸、フェニルインダンジカルボン酸、２，７−ナフタレンジカルボン酸、テトラリンジカルボン酸、デカリンジカルボン酸、ジフェニルエーテルジカルボン酸等の如きジカルボン酸、ｐ−オキシ安息香酸、ｐ−オキシエトキシ安息香酸の如きオキシカルボン酸、或いはプロピレングリコール、トリメチレングリコール、テトラメチレングリコール、ヘキサメチレングリコール、シクロヘキサンジメチレングリコール、ネオペンチルグリコール、ビスフェノールスルホンのエチレンオキサイド付加物、ビスフェノールＡのエチレンオキサイド付加物、ジエチレングリコール、ポリエチレングリコールの如き２価アルコールを好ましく用いることができる。 In the case of a copolymer, a compound having two ester-forming functional groups in the molecule can be used as a copolymer component constituting the copolymer. Examples of such a compound include oxalic acid, adipic acid, phthalic acid, and sebacic acid. , Dodecanedicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, phenylindanedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, tetralindicarboxylic acid, decalindicarboxylic acid, diphenylether Dicarboxylic acid such as dicarboxylic acid, oxycarboxylic acid such as p-oxybenzoic acid, p-oxyethoxybenzoic acid, or propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexanedi Divalent alcohols such as methylene glycol, neopentyl glycol, ethylene oxide adduct of bisphenol sulfone, ethylene oxide adduct of bisphenol A, diethylene glycol, and polyethylene glycol can be preferably used.
これらの化合物は１種のみ用いてもよく、２種以上を用いることができる。またこれらの中で好ましくは酸成分としては、イソフタル酸、テレフタル酸、４，４'−ジフェニルジカルボン酸、２，７−ナフタレンジカルボン酸、ｐ−オキシ安息香酸であり、グリコール成分としてはトリメチレングリコール、シクロヘキサンジメチレングリコール、ネオペンチルグリコール、ビスフェノールスルホンのエチレンオキサイド付加物である。 These compounds may be used alone or in combination of two or more. Of these, the acid component is preferably isophthalic acid, terephthalic acid, 4,4′-diphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, p-oxybenzoic acid, and the glycol component is trimethylene glycol. , Cyclohexanedimethylene glycol, neopentyl glycol, bisphenol sulfone ethylene oxide adduct.
また、ポリエチレン−２，６−ナフタレンジカルボキシレートは、例えば安息香酸、メトキシポリアルキレングリコールなどの一官能性化合物によって末端の水酸基および／またはカルボキシル基の一部または全部を封鎖したものであってよく、極く少量の例えばトリメリット酸、グリセリン、ペンタエリスリトール等の如き三官能以上のエステル形成性化合物で実質的に線状のポリマーが得られる範囲内で共重合したものであってもよい。 The polyethylene-2,6-naphthalenedicarboxylate may be one in which a terminal hydroxyl group and / or a carboxyl group is partially or entirely blocked with a monofunctional compound such as benzoic acid or methoxypolyalkylene glycol. Further, it may be one obtained by copolymerizing a very small amount of an ester-forming compound such as trimellitic acid, glycerin, pentaerythritol and the like within a range in which a substantially linear polymer is obtained.
本発明におけるポリエステルは従来公知の方法で、例えばジカルボン酸とグリコールの反応で直接低重合度ポリエステルを得る方法や、ジカルボン酸の低級アルキルエステルとグリコールとを従来公知のエステル交換触媒である、例えばナトリウム、カリウム、マグネシウム、カルシウム、亜鉛、ストロンチウム、チタン、ジルコニウム、マンガン、コバルトを含む化合物の一種または二種以上を用いて反応させた後、重合触媒の存在下で重合反応を行う方法で得ることができる。重合触媒としては、三酸化アンチモン、五酸化アンチモンのようなアンチモン化合物、二酸化ゲルマニウムで代表されるようなゲルマニウム化合物、テトラエチルチタネート、テトラプロピルチタネート、テトラフェニルチタネートまたはこれらの部分加水分解物、蓚酸チタニルアンモニウム、蓚酸チタニルカリウム、チタントリスアセチルアセトネートのようなチタン化合物を用いることができる。 The polyester in the present invention is a conventionally known method, for example, a method of directly obtaining a low polymerization degree polyester by reaction of dicarboxylic acid and glycol, or a lower alkyl ester of dicarboxylic acid and glycol are conventionally known transesterification catalysts, such as sodium It can be obtained by performing a polymerization reaction in the presence of a polymerization catalyst after reacting with one or more of compounds containing potassium, magnesium, calcium, zinc, strontium, titanium, zirconium, manganese, and cobalt. it can. As a polymerization catalyst, antimony compounds such as antimony trioxide and antimony pentoxide, germanium compounds represented by germanium dioxide, tetraethyl titanate, tetrapropyl titanate, tetraphenyl titanate or a partial hydrolyzate thereof, titanyl ammonium oxalate , Titanium compounds such as potassium titanyl oxalate and titanium trisacetylacetonate can be used.
エステル交換反応を経由して重合を行う場合は、重合反応前にエステル交換触媒を失活させる目的でトリメチルホスフェート、トリエチルホスフェート、トリ−ｎ−ブチルホスフェート、正リン酸等のリン化合物が通常は添加されるが、リン元素としてのポリエチレン−２，６−ナフタレンジカルボキシレート中の含有量が２０〜１００ｐｐｍであることがポリエステルの熱安定性の点から好ましい。 When polymerization is performed via a transesterification reaction, a phosphorus compound such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, or normal phosphoric acid is usually added for the purpose of deactivating the transesterification catalyst before the polymerization reaction. However, the content of polyethylene-2,6-naphthalenedicarboxylate as the phosphorus element is preferably 20 to 100 ppm from the viewpoint of thermal stability of the polyester.
なお、ポリエステルは、溶融重合後これをチップ化し、加熱減圧下または窒素などの不活性気流中において更に固相重合を施してもよい。 The polyester may be converted into chips after melt polymerization, and further subjected to solid phase polymerization under heating under reduced pressure or in an inert gas stream such as nitrogen.
本発明においてポリエステルは、エチレンテレフタレート単位またはエチレン−２，６−カルボキシレート単位を９０モル％以上、好ましくは９５％以上、更に好ましくは９７％以上有するポリエステルが好ましい。 In the present invention, the polyester is preferably a polyester having an ethylene terephthalate unit or an ethylene-2,6-carboxylate unit of 90 mol% or more, preferably 95% or more, more preferably 97% or more.
ポリエステルの固有粘度は０．４０ｄｌ／ｇ以上であることが好ましく、０．４０〜０．９０ｄｌ／ｇであることが更に好ましい。固有粘度が０．４０ｄｌ／ｇ未満では工程切断が多発することがある。また０．９ｄｌ／ｇより高いと溶融粘度が高いため溶融押出しが困難になり、重合時間が長く不経済であり好ましくない。 The intrinsic viscosity of the polyester is preferably 0.40 dl / g or more, and more preferably 0.40 to 0.90 dl / g. If the intrinsic viscosity is less than 0.40 dl / g, process cutting may occur frequently. On the other hand, if it is higher than 0.9 dl / g, melt viscosity is high and melt extrusion becomes difficult, and the polymerization time is long and uneconomical.
本発明におけるポリエステルフィルムは、実質的に粒子を含有しないことが好ましい。粒子を含有していると高透明性が損なわれたり、表面が粗面化し透明導電層の加工が困難になることがある。 It is preferable that the polyester film in the present invention contains substantially no particles. If the particles are contained, high transparency may be impaired, or the surface may become rough and it may be difficult to process the transparent conductive layer.
本発明におけるポリエステルフィルムは、２００℃で１０分間熱処理したときのフィルムの長手方向と幅方向における熱収縮率の差の絶対値が０．８％以下、好ましくは０．５％以下、更に好ましくは０．３％以下である。熱収縮率の差の絶対値が０．８％を越えると、積層フィルムの透明導電層と多孔質半導体の密着性が悪化し、色素増感型太陽電池を作成した際、十分な光発電性能が得られなくなる。なお、フィルムの長手方向の熱収縮率は小さい方がよく、好ましくは０％〜０．５％、更に好ましくは０〜０．３％である。 In the polyester film of the present invention, the absolute value of the difference in thermal shrinkage between the longitudinal direction and the width direction of the film when heat-treated at 200 ° C. for 10 minutes is 0.8% or less, preferably 0.5% or less, more preferably 0.3% or less. If the absolute value of the difference in thermal shrinkage exceeds 0.8%, the adhesion between the transparent conductive layer of the laminated film and the porous semiconductor deteriorates, and sufficient photovoltaic power generation performance is obtained when a dye-sensitized solar cell is created. Cannot be obtained. In addition, the one where the heat shrinkage rate of the longitudinal direction of a film should be small is preferable, Preferably it is 0%-0.5%, More preferably, it is 0-0.3%.
本発明におけるポリエステルフィルムは、より効率良く光発電を行うために、ヘーズ値が、好ましくは１．５％以下、更に好ましくは１．０％以下、特に好ましくは０．５％以下である。 The polyester film of the present invention has a haze value of preferably 1.5% or less, more preferably 1.0% or less, and particularly preferably 0.5% or less in order to perform photovoltaic power generation more efficiently.
本発明におけるポリエステルフィルムは、３次元中心線平均粗さが、両面共に好ましくは０．０００１〜０．０２μｍ、さらに好ましくは０．０００１〜０．０１５μｍ、特に好ましくは０．０００１〜０．０１０μｍである。特に、少なくとも片面の３次元中心線平均粗さが０．０００１〜０．００５μｍであると、透明導電層の加工がしやすくなるので好ましい。少なくとも片面の最も好ましい表面粗さは、０．０００５〜０．００４μｍである。 The polyester film in the present invention has a three-dimensional center line average roughness of preferably 0.0001 to 0.02 μm on both sides, more preferably 0.0001 to 0.015 μm, and particularly preferably 0.0001 to 0.010 μm. is there. In particular, it is preferable that the three-dimensional center line average roughness of at least one surface is 0.0001 to 0.005 μm because the transparent conductive layer can be easily processed. The most preferable surface roughness of at least one surface is 0.0005 to 0.004 μm.
本発明におけるポリエステルフィルムの厚みは、好ましくは１０〜５００μｍ、さらに好ましくは２０〜４００μｍ、特に好ましくは５０〜３００μｍである。 The thickness of the polyester film in the present invention is preferably 10 to 500 μm, more preferably 20 to 400 μm, and particularly preferably 50 to 300 μm.
次に、本発明のポリエステルフィルムの好ましい製造方法について説明する。なおガラス転位温度をＴｇと略記する。 Next, the preferable manufacturing method of the polyester film of this invention is demonstrated. The glass transition temperature is abbreviated as Tg.
本発明におけるポリエステルフィルムは、ポリエステルをフィルム状に溶融押出し、キャスティングドラムで冷却固化させて未延伸フィルムとし、この未延伸フィルムをＴｇ〜（Ｔｇ＋６０）℃で長手方向に１回もしくは２回以上合計の倍率が３倍〜６倍になるよう延伸し、その後Ｔｇ〜（Ｔｇ＋６０）℃で幅方向に倍率が３〜５倍になるように延伸し、必要に応じて更にＴｍ１８０℃〜２５５℃で１〜６０秒間熱処理を行うことにより得ることができる。ポリエステルフィルムの長手方向と幅方向における熱収縮率の差、および長手方向の熱収縮を小さくするためには、特開平５７−５７６２８号公報に示されるような、熱処理工程で縦方向に収縮せしめる方法や、特開平１−２７５０３１号公報に示されるような、フィルムを懸垂状態で弛緩熱処理する方法などを用いることができる。 In the polyester film of the present invention, the polyester is melt-extruded into a film shape, cooled and solidified with a casting drum to form an unstretched film, and this unstretched film is Tg to (Tg + 60) ° C. once or twice or more in the longitudinal direction. The film is stretched so that the magnification is 3 to 6 times, and then stretched so that the magnification is 3 to 5 times in the width direction at Tg to (Tg + 60) ° C., and further 1 to 1 at Tm 180 ° C. to 255 ° C. if necessary. It can be obtained by performing a heat treatment for 60 seconds. In order to reduce the difference in thermal shrinkage between the longitudinal direction and the width direction of the polyester film and the thermal shrinkage in the longitudinal direction, a method of shrinking in the longitudinal direction in a heat treatment step as disclosed in JP-A-57-57628 Alternatively, a method of relaxing heat treatment of the film in a suspended state as disclosed in JP-A-1-275031 can be used.
[透明導電層]
本発明において、ポリエステルフィルム上に形成する透明導電層としては、通常、導電性の金属酸化物（フッ素ドープ酸化スズ、インジウム−スズ複合酸化物（ＩＴＯ）、金属の薄膜（例えば白金、金、銀、銅、アルミニウムなど）、炭素材料を用いることができる。この透明導電層は２種以上を積層したり、複合化させたものでも良い。この中でＩＴＯは、光線透過率が高く低抵抗であるため、特に好ましい。表面抵抗の範囲は好ましくは１００Ω／□以下、更に好ましくは４０Ω／□以下である。
[Transparent conductive layer]
In the present invention, the transparent conductive layer formed on the polyester film is usually a conductive metal oxide (fluorine-doped tin oxide, indium-tin composite oxide (ITO), metal thin film (for example, platinum, gold, silver). , Copper, aluminum, etc.), carbon materials, etc. The transparent conductive layer may be a laminate or composite of two or more, among which ITO has high light transmittance and low resistance. The range of the surface resistance is preferably 100Ω / □ or less, more preferably 40Ω / □ or less.
透明導電層の厚みは好ましくは１００〜５００ｎｍである。１００ｎｍ未満であると十分に表面抵抗値を低くすることができず、５００ｎｍを超えると光線透過率が低下するとともに、透明導電層がわれやすくなり、好ましくない。 The thickness of the transparent conductive layer is preferably 100 to 500 nm. If it is less than 100 nm, the surface resistance value cannot be lowered sufficiently, and if it exceeds 500 nm, the light transmittance is lowered and the transparent conductive layer is easily broken, which is not preferable.
本発明における透明導電層の表面張力は４０ｍＮ／ｍ以上、好ましくは６５ｍＮ／ｍ以上である。表面張力が４０ｍＮ／ｍ未満であると、透明導電層と多孔質半導体の密着性が劣る。表面張力が６５ｍＮ／ｍ以上であると、溶媒の主成分が水である水性塗液の塗布による多孔質半導体層の形成が容易になり好ましい。透明導電層の表面張力は、完全水系塗剤の塗布が容易となる７５ｍＮ／ｍ程度が実用上の上限となる。 The surface tension of the transparent conductive layer in the present invention is 40 mN / m or more, preferably 65 mN / m or more. When the surface tension is less than 40 mN / m, the adhesion between the transparent conductive layer and the porous semiconductor is poor. When the surface tension is 65 mN / m or more, it is preferable because the porous semiconductor layer can be easily formed by application of an aqueous coating liquid in which the main component of the solvent is water. The practical upper limit of the surface tension of the transparent conductive layer is about 75 mN / m, which makes it easy to apply a complete aqueous coating material.
上記の表面張力を達成するための手段としては、例えば（１）透明導電性薄膜を酸性もしくはアルカリ性溶液で表面を活性化する方法、（２）紫外線や電子線を薄膜表面に照射して活性化する方法、（３）コロナ処理やプラズマ処理を施して活性化する方法、を適用することができる。この中でプラズマ処理により表面を活性化する方法は、高い表面張力が得られるため特に好ましい。 As means for achieving the above surface tension, for example, (1) a method of activating the surface of a transparent conductive thin film with an acidic or alkaline solution, (2) activation by irradiating the surface of the thin film with ultraviolet rays or electron beams And (3) a method of activating by applying corona treatment or plasma treatment can be applied. Among these, the method of activating the surface by plasma treatment is particularly preferable because high surface tension can be obtained.
[易接着層]
また、ポリエステルフィルムと透明導電層との密着性を向上させるために、ポリエステルフィルムと透明導電層の間に易接着層を設けることが好ましい。易接着層の厚みは好ましくは１０〜２００ｎｍ、さらに好ましくは２０〜１５０ｎｍである。易接着層の厚みが１０ｎｍ未満であると密着性を向上させる効果が乏しく、２００ｎｍを超えると易接着層の凝集破壊が発生しやすくなり密着性が低下することがあり好ましくない。
[Easily adhesive layer]
Moreover, in order to improve the adhesiveness of a polyester film and a transparent conductive layer, it is preferable to provide an easily bonding layer between a polyester film and a transparent conductive layer. The thickness of the easy adhesion layer is preferably 10 to 200 nm, more preferably 20 to 150 nm. If the thickness of the easy-adhesion layer is less than 10 nm, the effect of improving the adhesion is poor, and if it exceeds 200 nm, cohesive failure of the easy-adhesion layer tends to occur and the adhesion may be lowered.
易接着層を設ける方法としては、ポリエステルフィルムの製造過程で塗工により設ける方法が好ましく、さらには配向結晶化が完了する前のポリエステルフィルムに塗布するのが好ましい。ここで、結晶配向が完了する前のポリエステルフィルムとは、未延伸フィルム、未延伸フィルムを縦方向または横方向の何れか一方に配向せしめた一軸配向フィルム、さらには縦方向および横方向の二方向に低倍率延伸配向せしめたもの（最終的に縦方向また横方向に再延伸せしめて配向結晶化を完了せしめる前の二軸延伸フィルム）等を含むものである。なかでも、未延伸フィルムまたは一方向に配向せしめた一軸延伸フィルムに、上記組成物の水性塗液を塗布し、そのまま縦延伸および／または横延伸と熱固定とを施すのが好ましい。 As a method of providing the easy-adhesion layer, a method of providing by coating in the production process of the polyester film is preferable, and it is preferable to apply to the polyester film before the orientation crystallization is completed. Here, the polyester film before the crystal orientation is completed is an unstretched film, a uniaxially oriented film in which the unstretched film is oriented in either the longitudinal direction or the transverse direction, and further in two directions, the longitudinal direction and the transverse direction. And the like that have been oriented at a low magnification (biaxially stretched film before being finally re-stretched in the machine direction or the transverse direction to complete orientation crystallization). In particular, it is preferable to apply the aqueous coating liquid of the above composition to an unstretched film or a uniaxially stretched film oriented in one direction, and perform longitudinal stretching and / or lateral stretching and heat setting as it is.
易接着層の構成材としては、ポリエステルフィルムと透明導電層の双方に優れた接着性を示すものであることが好ましく、具体的には例えばポリエステル樹脂、アクリル樹脂、ウレタンアクリル樹脂、シリコンアクリル樹脂、メラミン樹脂、ポリシロキサン樹脂を用いることができる。これらの樹脂は単独で用いても良く、２種以上の混合物として用いてもよい。 As the constituent material of the easy-adhesion layer, it is preferable to exhibit excellent adhesion to both the polyester film and the transparent conductive layer. Specifically, for example, a polyester resin, an acrylic resin, a urethane acrylic resin, a silicon acrylic resin, Melamine resin and polysiloxane resin can be used. These resins may be used alone or as a mixture of two or more.
[ハードコート層]
ポリエステルフィルムと透明導電層との密着性、特に密着の耐久性を向上させるために、易接着層と透明導電層との間にハードコート層を設けてもよい。ハードコート層を設ける方法として、易接着層を設けたポリエステルフィルム上に塗工する方法が好ましい。ハードコート層の構成材としては、易接層および透明導電層の双方に優れた密着性を示すものであればよく、アクリル系樹脂、ウレタン系樹脂、シリコン系樹脂、ＵＶ硬化系樹脂、エポキシ系樹脂等の樹脂成分やこれらと無機粒子の混合物などが例示できる。無機粒子としては、例えばアルミナ、シリカ、マイカの粒子を用いることができる。ハードコート層の厚みは好ましくは０．０１〜２０μｍ、さらに好ましくは１〜１０μｍである。
[Hard coat layer]
In order to improve the adhesion between the polyester film and the transparent conductive layer, particularly the durability of the adhesion, a hard coat layer may be provided between the easy adhesion layer and the transparent conductive layer. As a method of providing a hard coat layer, a method of coating on a polyester film provided with an easy adhesion layer is preferable. The hard coat layer may be composed of any material that exhibits excellent adhesion to both the easy-contact layer and the transparent conductive layer, such as an acrylic resin, a urethane resin, a silicon resin, a UV curable resin, and an epoxy resin. Examples thereof include resin components such as resins and mixtures of these with inorganic particles. As the inorganic particles, for example, alumina, silica, and mica particles can be used. The thickness of the hard coat layer is preferably 0.01 to 20 μm, more preferably 1 to 10 μm.
[反射防止層]
本発明の積層フィルムには、光線透過率を上げて光発電効率を高めることを目的として、透明導電層とは反対側の面に反射防止層を設けることができる。反射防止層を設ける方法としては、ポリエステルフィルムの屈折率とは異なる屈折率を有する素材を単層もしくは２層以上に積層形成する方法が好ましい。単層構造の場合は、基材フィルムよりも小さな屈折率を有する素材を使用するのがよく、また２層以上の多層構造とする場合は、積層フィルムと隣接する層はポリエステルフィルムよりも大さな屈折率を有する素材とし、その上に積層される層には、これよりも小さな屈折率を有する素材を選択することが好ましい。
[Antireflection layer]
The laminated film of the present invention can be provided with an antireflection layer on the surface opposite to the transparent conductive layer for the purpose of increasing the light transmittance and increasing the photovoltaic power generation efficiency. As a method for providing the antireflection layer, a method in which a material having a refractive index different from the refractive index of the polyester film is laminated in a single layer or two or more layers is preferable. In the case of a single layer structure, it is better to use a material having a refractive index smaller than that of the base film, and in the case of a multilayer structure of two or more layers, the layer adjacent to the laminated film is larger than the polyester film. It is preferable to select a material having a refractive index smaller than that of a material having a high refractive index and a layer laminated thereon.
この様な反射防止処理層を構成する素材としては、有機材料、無機材料の如何を問わず上記屈折率の関係を満足するものであればよいが、好ましくは、ＣａＦ2，ＭｇＦ2，ＮａＡｌＦ4，ＳｉＯ2，ＴｈＦ4，ＺｒＯ2，Ｎｄ2Ｏ3，ＳｎＯ2，ＴｉＯ2，Ｃｅ、Ｏ2，ＺｎＳ，Ｉｎ2Ｏ3からなる群から選ばれる誘電体を用いる。 The material constituting such an antireflection treatment layer may be any material that satisfies the above-described refractive index relationship, regardless of whether it is an organic material or an inorganic material, but is preferably CaF 2 , MgF 2 , NaAlF 4. , SiO 2 , ThF 4 , ZrO 2 , Nd 2 O 3 , SnO 2 , TiO 2 , Ce, O 2 , ZnS, and In 2 O 3 are used.
上記反射防止処理層を積層する方法としては、真空蒸着法、スパッタリング法、ＣＶＤ法、イオンプレーテイング法などのドライコーティング法でも、グラビア方式、リバース方式、ダイ方式などのウェットコーティング法でも構わない。更に上記反射防止処理層の積層に先立って、コロナ放電処理、プラズマ処理、スパッタエッチング処理、電子線照射処理、紫外線照射処理、プライマ処理、易接着処理などの公知の前処理を施してもよい。 The method for laminating the antireflection treatment layer may be a dry coating method such as a vacuum deposition method, a sputtering method, a CVD method, or an ion plating method, or a wet coating method such as a gravure method, a reverse method, or a die method. Furthermore, prior to the lamination of the antireflection treatment layer, a known pretreatment such as a corona discharge treatment, a plasma treatment, a sputter etching treatment, an electron beam irradiation treatment, an ultraviolet ray irradiation treatment, a primer treatment, and an easy adhesion treatment may be performed.
[電極]
本発明の色素増感型太陽電池用電極は、上述の色素増感型太陽電池用積層フィルムの透明導電層の上に多孔質半導体層を積層して形成する。多孔質半導体層を構成する半導体の材料としては、ｎ型半導体である酸化チタン（ＴｉＯ2）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ2）を用いることが好ましい。これらの半導体の複数を複合させた半導体材料も用いることができる。
[electrode]
The electrode for the dye-sensitized solar cell of the present invention is formed by laminating a porous semiconductor layer on the transparent conductive layer of the above-mentioned laminated film for dye-sensitized solar cell. As a semiconductor material constituting the porous semiconductor layer, it is preferable to use titanium oxide (TiO 2 ), zinc oxide (ZnO), or tin oxide (SnO 2 ), which are n-type semiconductors. A semiconductor material obtained by combining a plurality of these semiconductors can also be used.
多孔質半導体層は半導体の超微粒子が焼結又は融着した構造を有し、その粒径は、一次粒子の平均粒径で、好ましくは５〜１００ｎｍ、さらに好ましくは５〜５０ｎｍのものを用いる。粒径分布の異なる２種類以上の微粒子を混合してもよく、入射光を散乱させて光捕獲率を向上させる目的で、粒径の大きな、例えば３００ｎｍ程度の半導体粒子を混合することもできる。 The porous semiconductor layer has a structure in which ultrafine particles of a semiconductor are sintered or fused, and the particle size thereof is an average particle size of primary particles, preferably 5 to 100 nm, more preferably 5 to 50 nm. . Two or more kinds of fine particles having different particle size distributions may be mixed, and semiconductor particles having a large particle size, for example, about 300 nm may be mixed for the purpose of scattering incident light and improving the light capture rate.
多孔質半導体層を構成する超微粒子は、例えば公知のゾル−ゲル法や気相熱分解法（２００１年技術教育出版社発行，柳田祥三監修，「色素増感太陽電池の基礎と応用」又は１９９５年技術情報協会発行，「ゾル−ゲル法による薄膜コーティング技術」参照）によって調製することができる。 Ultrafine particles constituting the porous semiconductor layer may be, for example, a known sol-gel method or gas phase pyrolysis method (published by Technical Education Publishing Co., 2001, supervised by Shozo Yanagida, “Basics and Applications of Dye-sensitized Solar Cells” or 1995. (See “Thin-film coating technology by sol-gel method” published by Japan Technical Information Association).
多孔質半導体層は、例えば塗布法、すなわち多孔質半導体を含む分散液を積層フィルムの透明導電層の上に塗布し、加熱乾燥することによって多孔質層を支持体上に固定化する方法で形成することができる。この際、半導体微粒子の分散液を調整するには、前述のゾルーゲル法の他に、例えば溶媒中で微粒子を化学反応の共沈生成物として析出させる方法、超音波照射や機械的粉砕によって超微粒子に粉砕して分散する方法を用いることができる。 The porous semiconductor layer is formed by, for example, a coating method, that is, a method of immobilizing the porous layer on a support by applying a dispersion containing the porous semiconductor on the transparent conductive layer of the laminated film and drying by heating. can do. In this case, in order to adjust the dispersion of the semiconductor fine particles, in addition to the sol-gel method described above, for example, a method of precipitating fine particles as a coprecipitation product of a chemical reaction in a solvent, ultrafine particles by ultrasonic irradiation or mechanical pulverization The method of pulverizing and dispersing can be used.
分散媒としては、水又は各種の有機溶媒を用い、分散の際、必要に応じて例えばポリエチレングリコール、ヒドロキシエチルセルロース、カルボキシメチルセルロースのようなポリマー、界面活性剤、酸又はキレート剤などを分散助剤として少量加えて、支持体上へ塗布し、製膜する。この塗布は、ローラ法、ディッブ法、エアーナイフ法、ブレード法、ワイヤーバー法、スライドホッパー法、エクストルージョン法、カーテン法など、これまで塗布加工に際し慣用されている任意の方法を用いて行うことができる。また汎用機によるスピン法やスプレー法も用いることができる。凸版、オフセット及びグラビアの３大印刷法をはじめ、凹版、ゴム版、スクリーン印刷のような湿式印刷を用いて塗布してもよい。これらの中から、液粘度やウェット厚さに応じて、好ましい製膜方法を選択する。 As a dispersion medium, water or various organic solvents are used. When dispersing, for example, a polymer such as polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, a surfactant, an acid or a chelating agent is used as a dispersion aid. Add a small amount, apply onto a support, and form a film. This coating should be performed using any method conventionally used for coating processing, such as the roller method, dipping method, air knife method, blade method, wire bar method, slide hopper method, extrusion method, and curtain method. Can do. Further, a spin method or a spray method using a general-purpose machine can be used. Application may be made using wet printing such as intaglio, rubber plate, screen printing, as well as the three major printing methods of letterpress, offset and gravure. From these, a preferred film forming method is selected according to the liquid viscosity and the wet thickness.
塗設した半導体微粒子の層に対し、半導体微粒子同士の電子的接触の強化と、支持体との密着性の向上のために、好ましくは１７０〜２５０℃、さらに好ましくは１８０〜２３０℃、特に好ましくは１９０〜２２０℃で加熱処理を施すことが好ましい。１７０〜２５０℃以下で加熱処理を行うことで、ポリエステルフィルム支持体の加熱による変形を防ぎながら多孔質半導体層の抵抗上昇を小さくすることができる。また更に、半導体微粒子に対して該微粒子が強く吸収する紫外光などを照射したり、マイクロ波を照射して微粒子層を加熱することにより、微粒子の間の物理的接合を強める処理を行うこともできる。 In order to reinforce the electronic contact between the semiconductor fine particles and to improve the adhesion to the support, it is preferably 170 to 250 ° C., more preferably 180 to 230 ° C., particularly preferably to the coated layer of semiconductor fine particles. Is preferably heat-treated at 190 to 220 ° C. By performing the heat treatment at 170 to 250 ° C. or less, it is possible to reduce the increase in resistance of the porous semiconductor layer while preventing deformation due to heating of the polyester film support. Furthermore, the semiconductor fine particles may be irradiated with ultraviolet light that is strongly absorbed by the fine particles, or the fine particle layer may be heated by irradiating the microwaves to enhance the physical bonding between the fine particles. it can.
多孔質半導体層の形成には、電着によって粒子の薄膜を担持する方法も用いることができる。すなわち、半導体微粒子を適当な低伝導度の溶媒、例えば純水、アルコールやアセトニトリル、ＴＨＦなどの極性有機溶媒、ヘキサン、クロロホルムなどの非極性有機溶媒、あるいはこれらの混合溶媒に添加し、凝集のないよう均一に分散し、電着すべき導電性樹脂シート電極と対極とを一定の間隔で平行に対向させ、この間隙に上記の分散液を注入し、両電極間に直流電圧を印加する。このようにして、分散液の濃度と電極間隔を選択することにより、基板電極に一定かつ均一な厚みの電着膜である多孔質半導体層が形成される。 For forming the porous semiconductor layer, a method of supporting a thin film of particles by electrodeposition can also be used. That is, the semiconductor fine particles are added to an appropriate low-conductivity solvent such as pure water, polar organic solvents such as alcohol, acetonitrile and THF, nonpolar organic solvents such as hexane and chloroform, or a mixed solvent thereof, so that there is no aggregation. The conductive resin sheet electrode to be electrodeposited and the counter electrode are made to face each other in parallel at a constant interval, the dispersion liquid is injected into the gap, and a DC voltage is applied between the electrodes. In this way, by selecting the concentration of the dispersion and the electrode interval, a porous semiconductor layer, which is an electrodeposition film having a constant and uniform thickness, is formed on the substrate electrode.
多孔質半導体層の厚さとしては、好ましくは１〜３０μｍ、さらに好ましくは２〜１０μｍの範囲で選ばれる。透明度を高める目的では２〜６μｍが好ましい。塗布量としては半導体微粒子の支持体１ｍ2当り０．５〜５〜２０ｇ／ｍ2、特に５〜１０ｇ／ｍ2が好ましい。 The thickness of the porous semiconductor layer is preferably selected in the range of 1 to 30 μm, more preferably 2 to 10 μm. For the purpose of increasing transparency, 2 to 6 μm is preferable. Support 1 m 2 per 0.5~5~20g / m 2 of the semiconductor fine particles as a coating amount, particularly 5 to 10 g / m 2 is preferred.
なお、多孔質半導体を担持する透明導電層が対極と電気的に短絡することを防止するな
どの目的のため、予め透明導電層の上に下塗り層を設けておくこともできる。この下塗り層としては、ＴｉＯ2、ＳｎＯ2、ＺｎＯ、Ｎｂ2Ｏ5、特にＴｉＯ2が好ましい。この下塗り層は、例えばＥｌｅｃｔｒｏｃｈｉｍ、Ａｃｔａ４０、６４３〜６５２（１９９５）に記載されているスプレーパイロリシス法の他、スパッタ法などにより設けることができる。この下塗り層の膜厚は、好ましくは５〜１０００ｎｍ以下、さらに好ましくは１０〜５００ｎｍである。
For the purpose of preventing the transparent conductive layer carrying the porous semiconductor from being electrically short-circuited with the counter electrode, an undercoat layer may be provided on the transparent conductive layer in advance. As the undercoat layer, TiO 2 , SnO 2 , ZnO, Nb 2 O 5 , particularly TiO 2 is preferable. This undercoat layer can be provided by, for example, a sputtering method in addition to the spray pyrolysis method described in Electrochim, Acta 40, 643 to 652 (1995). The thickness of the undercoat layer is preferably 5 to 1000 nm or less, more preferably 10 to 500 nm.
[色素増感太陽電池の作成]
本発明の電極を用いて色素増感型太陽電池を作成するには、公知の方法を用いることができる。具体的は例えば下記の方法で作成することができる。
（１）本発明の電極の多孔質半導体層に色素を吸着させる。ルテニウムビピリジン系錯体（ルテニウム錯体）に代表される有機金属錯体色素、シアニン系色素、クマリン系色素、キサンテン系色素、ポルフィリン系色素など、可視光領域および赤外光領域の光を吸収する特性を有する色素を、アルコールやトルエンなどの溶媒に溶解させて色素溶液を作成し、多孔質半導体層を浸漬するか、多孔質半導体層に噴霧または塗布する。（電極Ａ）
（２）対極としては、本発明の積層フィルムの透明導電層側に、薄い白金層をスパッタ法により形成したものを用いる。（電極Ｂ）
（３）上記電極Ａと電極Ｂを、熱圧着性のポリエチレンフィルム製フレーム型スペーサー（厚さ２０μｍ）を挿入して重ね合わせ、スペーサー部を１２０℃に加熱し、両電極を圧着する。さらに、そのエッジ部をエポキシ樹脂接着剤でシールする。
（４）シートのコーナー部にあらかじめ設けた電解液注入用の小孔を通して、ヨウ化リチウムとヨウ素（モル比３：２）ならびにスペーサーとして平均粒径２０μｍのナイロンビーズを３重量％含む電解質水溶液を注入する。内部の脱気を十分に行い、最終的に小孔をエポキシ樹脂接着剤で封じる。
[Preparation of dye-sensitized solar cell]
In order to produce a dye-sensitized solar cell using the electrode of the present invention, a known method can be used. Specifically, for example, it can be created by the following method.
(1) A dye is adsorbed on the porous semiconductor layer of the electrode of the present invention. It has the property of absorbing light in the visible and infrared regions, such as organometallic complex dyes represented by ruthenium bipyridine complexes (ruthenium complexes), cyanine dyes, coumarin dyes, xanthene dyes, porphyrin dyes, etc. A dye solution is prepared by dissolving a dye in a solvent such as alcohol or toluene, and the porous semiconductor layer is immersed, or sprayed or applied to the porous semiconductor layer. (Electrode A)
(2) As the counter electrode, a thin platinum layer formed by sputtering on the transparent conductive layer side of the laminated film of the present invention is used. (Electrode B)
(3) The electrode A and the electrode B are overlapped by inserting a thermocompression-bondable polyethylene film frame spacer (thickness 20 μm), the spacer portion is heated to 120 ° C., and both electrodes are pressure-bonded. Further, the edge portion is sealed with an epoxy resin adhesive.
(4) An electrolyte aqueous solution containing lithium iodide and iodine (molar ratio 3: 2) and 3% by weight of nylon beads having an average particle diameter of 20 μm as a spacer through a small hole for injecting an electrolyte provided in the corner of the sheet in advance. inject. Thoroughly deaerate the inside and finally seal the small holes with an epoxy resin adhesive.
本発明によれば、多孔質半導体層の加工性に優れ、密着性の高い色素増感型太陽電池用積層フィルムおよび色素増感型太陽電池用電極を製造することができる。この色素増感型太陽電池用積層フィルムまたは色素増感型太陽電池用電極を用いることにより光発電性能の高い色素増感型太陽電池を作成することができる。 ADVANTAGE OF THE INVENTION According to this invention, the laminated film for dye-sensitized solar cells and the electrode for dye-sensitized solar cells which are excellent in the workability of a porous semiconductor layer and have high adhesiveness can be manufactured. By using the laminated film for dye-sensitized solar cells or the electrode for dye-sensitized solar cells, a dye-sensitized solar cell with high photovoltaic power generation performance can be produced.
次に、実施例により本発明をさらに詳細に説明する。
なお、例中の各特性値は、下記の方法により測定した。
（１）固有粘度
固有粘度（［η］ｄｌ／ｇ）は、３５℃のｏ−クロロフェノール溶液で測定した。
（２）フィルム厚み
マイクロメーター（アンリツ（株）製のＫ−４０２Ｂ型）を用いて、フィルムの連続製膜方向および幅方向に各々１０ｃｍ間隔で測定を行い、全部で３００ヶ所のフィルム厚みを測定する。得られた３００ヶ所のフィルム厚みの平均値を算出してフィルム厚みとした。
（３）熱収縮率
２００℃に温度設定されたオーブンの中に無緊張状態で１０分間フィルムを保持し、フィルム長手方向（ＭＤ）および幅方向（ＴＤ）について各々の加熱処理前後での寸法変化を熱収縮率として下式により算出し、長手方向（ＭＤ）と幅方向（ＴＤ）の熱収縮率を求めた。
熱収縮率％＝（（Ｌ０−Ｌ）／Ｌ０）×１００
ただし、Ｌ０：熱処理前の標点間距離、Ｌ：熱処理後の漂点間距離
Next, the present invention will be described in more detail with reference to examples.
In addition, each characteristic value in an example was measured with the following method.
(1) Intrinsic viscosity Intrinsic viscosity ([η] dl / g) was measured with an o-chlorophenol solution at 35 ° C.
(2) Film thickness Using a micrometer (K-402B type manufactured by Anritsu Co., Ltd.), measurement is performed at 10 cm intervals in the continuous film forming direction and the width direction of the film, and a total of 300 film thicknesses are measured. To do. The average value of the film thicknesses of the obtained 300 locations was calculated and used as the film thickness.
(3) Heat shrinkage rate The film was held in an oven set at 200 ° C. for 10 minutes in an unstrained state, and the dimensional change before and after each heat treatment in the film longitudinal direction (MD) and width direction (TD) Was calculated by the following equation as the heat shrinkage rate, and the heat shrinkage rate in the longitudinal direction (MD) and the width direction (TD) was obtained.
Thermal shrinkage% = ((L0−L) / L0) × 100
However, L0: Distance between gauge points before heat treatment, L: Distance between floating points after heat treatment
（４）塗布層の厚み
フィルムの小片をエポキシ樹脂（リファインテック（株）製エポマウント）中に包埋し、Reichert-Jung社製Microtome2050を用いて包埋樹脂ごと５０ｎｍ厚さにスライスし、透過型電子顕微鏡（LEM-2000）にて加速電圧１００ＫＶ、倍率１０万倍にて観察し、塗膜層の厚みを測定した。
（５）表面抵抗値
４探針式表面抵抗率測定装置（三菱化学（株）製、ロレスタＧＰ）を用いて任意の５点を測定し、その平均値を代表値として用いた。
(4) Thickness of coating layer A small piece of film is embedded in an epoxy resin (Epomount manufactured by Refinetech Co., Ltd.), sliced to 50 nm thickness with the embedded resin using Microtome2050 manufactured by Reichert-Jung, and transmitted. The film was observed with a scanning electron microscope (LEM-2000) at an acceleration voltage of 100 KV and a magnification of 100,000, and the thickness of the coating layer was measured.
(5) Surface resistance value Any five points were measured using a 4-probe type surface resistivity measuring device (Made by Mitsubishi Chemical Corporation, Loresta GP), and the average value was used as a representative value.
（６）表面張力
表面張力が既知である水、およびヨウ化メテレンの透明導電性薄膜に対する接触角：θｗ、θｙを接触角計（協和界面科学社製「ＣＡ−Ｘ型」）を使用し、２５℃、５０％ＲＨの条件で測定した。これらの測定値を用い、以下の様にして透明導電性薄膜の表面張力γｓを算出した。
透明導電性薄膜の表面張力γｓは、分散性成分γｓｄと極性成分γｓｐとの和である。即ち、
γｓ＝γｓｄ＋γｓｐ （式１）
また、Ｙｏｕｎｇの式より、
γｓ＝γｓｗ＋γｗ・ｃｏｓθｗ （式２）
γｓ＝γｓｙ＋γｙ・ｃｏｓθｙ （式３）
ここで、γｓｗは透明導電性薄膜と水との間に働く張力、γｓｗは透明導電性薄膜とヨウ化メチレンとの間に働く張力、γｗは水の表面張力、γｙはヨウ化メチレンの表面張力である。
また、Ｆｏｗｋｅｓの式より、
γsw＝γs＋γw−２×（γsd・γwd）1/2−２×（γsp・γwp）1/2 （式４）
γsy＝γs＋γy−２×（γsd・γyd）1/2−２×（γsp・γyp）1/2 （式５）
である。ここで、γwdは水の表面張力の分散性成分、γwpは水の表面張力の極性成分、γydはヨウ化メテレンの表面張力の分散性成分、γypはヨウ化メチレンの表面張力の極性成分である。
(6) Surface tension Contact angles: θw and θy of water having a known surface tension and water-containing methylene to the transparent conductive thin film were measured using a contact angle meter (“CA-X type” manufactured by Kyowa Interface Science Co., Ltd.) It measured on 25 degreeC and 50% RH conditions. Using these measured values, the surface tension γs of the transparent conductive thin film was calculated as follows.
The surface tension γs of the transparent conductive thin film is the sum of the dispersive component γsd and the polar component γsp. That is,
γs = γsd + γsp (Formula 1)
From the Young equation,
γs = γsw + γw · cos θw (Formula 2)
γs = γsy + γy · cos θy (Formula 3)
Here, γsw is the tension acting between the transparent conductive thin film and water, γsw is the tension acting between the transparent conductive thin film and methylene iodide, γw is the surface tension of water, and γy is the surface tension of methylene iodide. It is.
From the Fowkes equation,
γ sw = γ s + γ w −2 × (γ sd · γ wd ) 1/2 −2 × (γ sp · γ wp ) 1/2 (Formula 4)
γ sy = γ s + γ y −2 × (γ sd · γ yd ) 1/2 −2 × (γ sp · γ yp ) 1/2 (Formula 5)
It is. Where γ wd is the dispersive component of the surface tension of water, γ wp is the polar component of the surface tension of water, γ yd is the dispersive component of the surface tension of methylene iodide, and γ yp is the surface tension of methylene iodide. It is a polar component.
式１〜５の連立方程式を解くことにより、透明導電性薄膜の表層張力γs＝γsd＋γspを算出できる。この時、水の表面張力（γw）：７２．８ｍＮ／ｍ、よう化メチレンの表面張力（γy）：５０．５ｍＮ／ｍ、水の表面張力の分散性成分（γwd）：２１．８ｍＮ／ｍ、水の表面張力の極性成分（γwp）：５１．０ｍＮ／ｍ、ヨウ化メチレンの表面張力の分散性成分（γyｄ）：４９．５ｍＮ／ｍ、ヨウ化メテレンの表面張力の極性成分（γyp）：１．３ｍＮ／ｍを用いた。 By solving the simultaneous equations of Equations 1 to 5, the surface tension γ s = γ sd + γ sp of the transparent conductive thin film can be calculated. At this time, the surface tension of water (γ w ): 72.8 mN / m, the surface tension of methylene iodide (γ y ): 50.5 mN / m, the dispersive component of the surface tension of water (γ wd ): 21. 8 mN / m, polar component of surface tension of water (γ wp ): 51.0 mN / m, dispersive component of surface tension of methylene iodide (γ y d): 49.5 mN / m, surface tension of methylene iodide Polar component (γ yp ): 1.3 mN / m was used.
（７）多孔質半導体層の密着性
多孔質半導体層表面にガーゼを５０g／ｃｍ２の加重で５往復し、剥離の程度を目指にて評価した。剥離が見られないものを○、部分的に剥離が見られるものを△、完全に剥離したものを×とした。
（８）Ｉ−Ｖ特性（光電流−電圧特性）
２５ｍｍ２大の色素増感太陽電池を形成し、下記の方法で光発電効率を算出した。５００Ｗのキセノンランプ（ウシオ電気社製）に太陽光シミュレーション用補正フィルター（オリエール社製ＡＭ１．５Ｇｌｏｂａｌ）を装着し、上記の光発電装置に対し、入射光強度が１００ｍＷ／ｃｍ２の模擬太陽光を、水平面に対する入射角度を様々変えて照射した。システムは屋内、気温１８℃、湿度５０％の雰囲気に静置した。電流電圧測定装置（ケースレー製ソースメジャーユニット２３８型）を用いて、システムに印加するＤＣ電圧を１０ｍＶ／秒の定速でスキャンし、素子の出力する光電流を計測することにより、光電流−電圧特性を測定し、光発電効率を算出した。
(7) Adhesiveness of porous semiconductor layer Gauze was reciprocated 5 times with a load of 50 g / cm 2 on the surface of the porous semiconductor layer, and the degree of peeling was evaluated with the aim. The case where peeling was not observed was indicated by ◯, the case where peeling was partially observed was indicated by Δ, and the case where peeling was completely observed was indicated by ×.
(8) IV characteristics (photocurrent-voltage characteristics)
A 25 mm 2 large dye-sensitized solar cell was formed, and the photovoltaic power generation efficiency was calculated by the following method. A 500 W xenon lamp (made by USHIO ELECTRIC CO., LTD.) Is equipped with a correction filter for sunlight simulation (AM1.5 Global made by Oriel), and simulated solar light with an incident light intensity of 100 mW / cm 2 is applied to the above photovoltaic power generation device. Irradiation was performed by changing the incident angle with respect to the horizontal plane. The system was left indoors at a temperature of 18 ° C. and a humidity of 50%. Using a current-voltage measuring device (Keutley source measure unit 238 type), the DC voltage applied to the system is scanned at a constant speed of 10 mV / second, and the photocurrent output from the device is measured, so that photocurrent-voltage The characteristics were measured, and the photovoltaic power generation efficiency was calculated.
[実施例１]
＜フィルム用ポリマーの作成＞
ナフタレン−２，６−ジカルボン酸ジメチル１００部、およびエチレングリコール６０部を、エステル交換触媒として酢酸マンガン四水塩０．０３部を使用し、１５０℃から２３８℃に徐々に昇温させながら１２０分間エステル交換反応を行なった。途中反応温度が１７０℃に達した時点で三酸化アンチモン０．０２４部を添加し、エステル交換反応終了後、リン酸トリメチル（エチレングリコール中で１３５℃、５時間０．１１〜０．１６ＭＰａの加圧下で加熱処理した溶液：リン酸トリメチル換算量で０．０２３部）を添加した。その後反応生成物を重合反応器に移し、２９０℃まで昇温し、２７Ｐａ以下の高真空下にて重縮合反応を行って、固有粘度が０．６３ｄｌ／ｇの、実質的に粒子を含有しない、ポリエチレン−２，６−ナフタレンジカルボキシレートを得た。
[Example 1]
<Creation of film polymer>
Using 100 parts of dimethyl naphthalene-2,6-dicarboxylate and 60 parts of ethylene glycol as a transesterification catalyst, 0.03 part of manganese acetate tetrahydrate, and gradually increasing the temperature from 150 ° C. to 238 ° C. for 120 minutes A transesterification reaction was performed. On the way, when the reaction temperature reached 170 ° C., 0.024 part of antimony trioxide was added, and after the transesterification reaction, trimethyl phosphate (135 ° C. in ethylene glycol, 0.11 to 0.16 MPa for 5 hours) was added. The solution heat-treated under pressure: 0.023 parts in terms of trimethyl phosphate was added. Thereafter, the reaction product is transferred to a polymerization reactor, heated to 290 ° C., subjected to a polycondensation reaction under a high vacuum of 27 Pa or less, and contains substantially no particles having an intrinsic viscosity of 0.63 dl / g. Polyethylene-2,6-naphthalenedicarboxylate was obtained.
＜ポリエステルフィルムの作成＞
このポリエチレン−２，６−ナフタレンジカルボキシレートのペレットを１７０℃で６時間乾燥後、押出機ホッパーに供給し、溶融温度３０５℃で溶融し、平均目開きが１７μｍのステンレス鋼細線フィルターで濾過し、３ｍｍのスリット状ダイを通して表面温度６０℃の回転冷却ドラム上で押出し、急冷して未延伸フィルムを得た。このようにして得られた未延伸フィルムを１２０℃にて予熱し、さらに低速、高速のロール間で１５ｍｍ上方より８５０℃のＩＲヒーターにて加熱して縦方向に３．２倍に延伸した。この縦延伸後のフィルムの片面に下記の塗剤Ａを乾燥後の塗膜厚みが０．２μｍになるようにロールコーターで塗工し易接層を形成した。
<Creation of polyester film>
The polyethylene-2,6-naphthalenedicarboxylate pellets were dried at 170 ° C. for 6 hours, then fed to an extruder hopper, melted at a melting temperature of 305 ° C., and filtered through a stainless steel fine wire filter having an average opening of 17 μm. The film was extruded through a 3 mm slit die on a rotary cooling drum having a surface temperature of 60 ° C. and rapidly cooled to obtain an unstretched film. The unstretched film thus obtained was preheated at 120 ° C., and further heated by an IR heater at 850 ° C. from above 15 mm between low-speed and high-speed rolls and stretched 3.2 times in the longitudinal direction. The following coating agent A was applied to one side of the film after the longitudinal stretching with a roll coater so that the coating thickness after drying was 0.2 μm, thereby forming an easy-contact layer.
続いてテンターに供給し、１４０℃にて横方向に．３．４倍に延伸した。得られた二軸配向フィルムを２４４℃の温度で５秒間熱固定し、固有粘度が０．５９ｄｌ／ｇ、厚み１２５μｍのポリエステルフィルムを得た。このフィルムの２００℃、１０分で処理した際のポリエステルフィルムの長手方向の熱収縮率は０．５８％、幅方向の熱収縮率は０．１２％、長手方向と幅方向の熱収縮率の差は０．４６％であり、ヘーズは０．８％、易着層の厚みは６０ｎｍであった。 Subsequently, it was supplied to the tenter and laterally at 140 ° C. Stretched by a factor of 3.4. The obtained biaxially oriented film was heat-set at a temperature of 244 ° C. for 5 seconds to obtain a polyester film having an intrinsic viscosity of 0.59 dl / g and a thickness of 125 μm. The thermal shrinkage in the longitudinal direction of the polyester film when treated at 200 ° C. for 10 minutes of this film is 0.58%, the thermal shrinkage in the width direction is 0.12%, and the thermal shrinkage in the longitudinal and width directions is The difference was 0.46%, the haze was 0.8%, and the thickness of the easy adhesion layer was 60 nm.
＜塗剤Ａ＞
四つ口フラスコに、界面活性剤としてラウリルスルホン酸ナトリウム３部、およびイオン交換水１８１部を仕込んで窒素気流中で６０℃まで昇温させ、次いで重合開始剤として過硫酸アンモニウム０．５部、亜硝酸水素ナトリウム０．２部を添加し、更にモノマー類である、メタクリル酸メチル３０．１部、２−イソプロペニル−２−オキサゾリン２１．９部、ポリエチレンオキシド（ｎ＝１０）メタクリル酸３９．４部、アクリルアミド８．６部の混合物を３時間にわたり、液温が６０〜７０℃になるよう調整しながら滴下した。滴下終了後も同温度範囲に２時間保持しつつ、攪拌下に反応を継続させ、次いで冷却して固形分が３５％重量のアクリルの水分散体を得た。
<Coating agent A>
A four-necked flask was charged with 3 parts of sodium lauryl sulfonate as a surfactant and 181 parts of ion-exchanged water and heated to 60 ° C. in a nitrogen stream, and then 0.5 part of ammonium persulfate as a polymerization initiator, 0.2 part of sodium hydrogen nitrate was added, and further monomers 30.1 parts of methyl methacrylate, 21.9 parts of 2-isopropenyl-2-oxazoline, polyethylene oxide (n = 10) methacrylic acid 39.4 A mixture of 8.6 parts of acrylamide was added dropwise over 3 hours while adjusting the liquid temperature to 60 to 70 ° C. After completion of dropping, the reaction was continued with stirring while maintaining the same temperature range for 2 hours, and then cooled to obtain an acrylic aqueous dispersion having a solid content of 35% by weight.
一方で、シリカフィラー（平均粒径：１００ｎｍ）（日産化学株式会社製 商品名スノーテックスＺＬ）を０．２重量％、濡れ剤として、ポリオキシエチレン（ｎ＝７）ラウリルエーテル（三洋化成株式会社製 商品名ナロアクティーＮ−７０）の０．３重量％添加した水溶液を作成した。
アクリルの水分散体１５重量部と水溶液８５重量部を混合して、塗剤Ａを作成した。
On the other hand, 0.2% by weight of silica filler (average particle size: 100 nm) (trade name Snowtex ZL manufactured by Nissan Chemical Co., Ltd.), polyoxyethylene (n = 7) lauryl ether (Sanyo Chemical Co., Ltd.) as a wetting agent An aqueous solution containing 0.3% by weight of the trade name NAROACTY N-70) was prepared.
A coating agent A was prepared by mixing 15 parts by weight of an acrylic aqueous dispersion and 85 parts by weight of an aqueous solution.
＜ハードコート＞
得られたポリエステルフィルムを用い、この易接層側にＵＶ硬化性ハードコート剤（ＪＳＲ製 デソライトＲ７５０１）を厚さ約５μｍになるよう塗布し、ＵＶ硬化させてハードコート層を形成した。
<Hard coat>
Using the obtained polyester film, a UV curable hard coat agent (Desolite R7501 manufactured by JSR) was applied to the easy-contact layer side so as to have a thickness of about 5 μm, and UV cured to form a hard coat layer.
＜透明導電層形成＞
ハードコート層が形成された片面に、ＩＴＯターゲット(錫濃度は二酸化錫換算で１０重量％)を用いた直流マグネトロンスパッタリング法により、膜厚４００ｎｍのＩＴＯからなる透明導電層を形成した。透明導電層のスパッタリング法による形成は、プラズマの放電前にチャンバー内を５×１０−４Ｐａまで排気した後、チャンバー内にアルゴンと酸素の混合ガス(酸素濃度は０．５体積％)を導入して圧力を０．３Ｐａとし、ＩＴＯターゲットに１０００Ｗ印加して行った。透明導電層の表面抵抗値は２０Ω／□であった。
<Transparent conductive layer formation>
A transparent conductive layer made of ITO having a thickness of 400 nm was formed on one surface on which the hard coat layer was formed by a direct current magnetron sputtering method using an ITO target (tin concentration was 10% by weight in terms of tin dioxide). The transparent conductive layer is formed by the sputtering method after the inside of the chamber is evacuated to 5 × 10 −4 Pa before plasma discharge, and then a mixed gas of argon and oxygen (oxygen concentration is 0.5 vol%) is introduced into the chamber. Then, the pressure was set to 0.3 Pa, and 1000 W was applied to the ITO target. The surface resistance value of the transparent conductive layer was 20Ω / □.
次いで、常圧プラズマ表面処理装置（積水化学工業製ＡＰ−Ｔ０３−Ｌ）を用いて、窒素気流下（６０Ｌ／分）、１ｍ／分にて透明導電層表面にプラズマ処理を施した。このとき、表面抵抗値２２Ω／□、表面張力は７２．３ｍＮ／ｍであった。 Next, using a normal pressure plasma surface treatment apparatus (AP-T03-L manufactured by Sekisui Chemical Co., Ltd.), the surface of the transparent conductive layer was subjected to plasma treatment at 1 m / min under a nitrogen stream (60 L / min). At this time, the surface resistance value was 22Ω / □ and the surface tension was 72.3 mN / m.
＜反射防止層＞
積層フィルムの透明導電層を形成した面とは反対側の面に、厚さ７５ｎｍで屈折率１．８９のＹ2Ｏ3層、その上に厚さ１２０ｎｍで屈折率２．３のＴｉＯ2層、更にその上に厚さ９０ｎｍで屈折率１．４６のＳｉＯ2を、夫々高周波スパッタリング法によって製膜し、反射防止処理層とした。各静電体薄膜を製膜するに際し、いずれも真空度は１×１０-3Ｔｏｒｒとし、ガスとしてＡｒ：５５ｓｃｃｍ、Ｏ2：５ｓｃｃｍを流した。また、基板は製膜行程中、加熱もしくは冷却をすることなく室温のままとした。
<Antireflection layer>
A Y 2 O 3 layer having a thickness of 75 nm and a refractive index of 1.89 is formed on the surface of the laminated film opposite to the surface on which the transparent conductive layer is formed, and a TiO 2 layer having a refractive index of 2.3 and a thickness of 120 nm is formed thereon. Further, SiO 2 having a thickness of 90 nm and a refractive index of 1.46 was formed thereon by high frequency sputtering to form an antireflection treatment layer. When forming each electrostatic thin film, the degree of vacuum was 1 × 10 −3 Torr, and Ar: 55 sccm and O 2 : 5 sccm were flowed as gases. The substrate was kept at room temperature without heating or cooling during the film forming process.
＜多孔質半導体層形成＞
積層フィルムの透明導電層の上に、市販されている低温形成型多孔質二酸化チタン層形成用ペースト(昭和電工製ＳＰ−２００)をバーコーターにて塗布し、大気中１８０℃で３０分間の熱処理を行って厚み５μｍになるように多孔質二酸化チタン層を形成し、色素増感型太陽電池の電極を作成した。密着性の評価を行ったところ、剥離はまったく見られず評価は○であった。
<Porous semiconductor layer formation>
On the transparent conductive layer of the laminated film, a commercially available paste for forming a low-temperature-forming porous titanium dioxide layer (SP-200 manufactured by Showa Denko) was applied with a bar coater and heat-treated at 180 ° C. for 30 minutes in the atmosphere. And a porous titanium dioxide layer was formed to a thickness of 5 μm, and an electrode of a dye-sensitized solar cell was prepared. When the adhesion was evaluated, no peeling was observed and the evaluation was good.
＜色素増感型太陽電池の作成＞
この電極をルテニウム錯体(Ｒｕ５３５ｂｉｓＴＢＡ、Ｓｏｌａｒｏｎｉｘ製)の３００μＭエタノール溶液中に２４時間浸漬し、光作用電極表面にルテニウム錯体を吸着させた。また、前記の積層フィルムの透明導電層上にスパッタリング法によりＰｔ膜を堆積して対向電極を作成した。電極と対向電極を、熱圧着性のポリエチレンフィルム製フレーム型スペーサー（厚さ２０μｍ）を介して重ね合わせ、スペーサー部を１２０℃に加熱し、両電極を圧着する。さらに、そのエッジ部をエポキシ樹脂接着剤でシールする。電解質溶液(０.５Ｍのヨウ化リチウムと０.０５Ｍのヨウ素と０.５Ｍのｔｅｒｔ−ブチルピリジン、平均粒径２０μｍのナイロンビーズ３重量％を含む３−メトキシプロピオニトリル溶液)を注入した後、エポキシ系接着剤でシールした。
<Creation of dye-sensitized solar cell>
This electrode was immersed in a 300 μM ethanol solution of ruthenium complex (Ru535bisTBA, manufactured by Solaronix) for 24 hours to adsorb the ruthenium complex on the surface of the photoactive electrode. A counter electrode was prepared by depositing a Pt film on the transparent conductive layer of the laminated film by sputtering. The electrode and the counter electrode are overlapped via a thermocompression-bondable polyethylene film frame spacer (thickness 20 μm), the spacer portion is heated to 120 ° C., and both electrodes are pressure-bonded. Further, the edge portion is sealed with an epoxy resin adhesive. After injecting an electrolyte solution (3-methoxypropionitrile solution containing 0.5% lithium iodide, 0.05M iodine, 0.5M tert-butylpyridine, 3% by weight of nylon beads having an average particle size of 20 μm) And sealed with an epoxy adhesive.
完成した色素増感 型太陽電池 のＩ−Ｖ特性の測定（有効面積２５ｍｍ２）を行った結果、開放電圧、短絡電流密度、曲線因子はそれぞれ、０.７２Ｖ、６．３ｍＡ／ｃｍ２、０．７２であり、その結果、光発電効率は３.２％であった。 As a result of measuring the IV characteristics (effective area 25 mm 2 ) of the completed dye-sensitized solar cell, the open circuit voltage, short circuit current density, and fill factor were 0.72 V, 6.3 mA / cm 2 , 0, respectively. As a result, the photovoltaic power generation efficiency was 3.2%.
[実施例２、３および比較例１]
ポリエステルフィルム作成時に、縦延伸倍率、横延伸倍率、熱固定温度を表１のように変えた他は実施例１と同様にして積層フィルム、電極および色素増感型太陽電池を得た。ポリエステルフィルムの縦方向、横方向の２００℃で１０分処理したあとの熱収縮率およびその差、多孔質半導体層の密着性、色素増感型太陽電池の光発電効率は、表１に示す通りであった。
[Examples 2 and 3 and Comparative Example 1]
A laminated film, an electrode, and a dye-sensitized solar cell were obtained in the same manner as in Example 1 except that the longitudinal stretch ratio, lateral stretch ratio, and heat setting temperature were changed as shown in Table 1 when the polyester film was prepared. Table 1 shows the thermal shrinkage ratio and the difference after treatment at 200 ° C. for 10 minutes in the longitudinal and lateral directions of the polyester film, the adhesion of the porous semiconductor layer, and the photovoltaic power generation efficiency of the dye-sensitized solar cell. Met.
[実施例４]
実施例１と同様にポリエステルフィルムを作成した後、フィルムを懸垂状態で、弛緩率０．８％、温度２０５℃で熱弛緩させた。２００℃、１０分で処理した際のポリエステルフィルムの長手方向の熱収縮率は０．１５％、幅方向の熱収縮率は０．０２％、長手方向と幅方向の熱収縮率の差は０．１３％であった。
[Example 4]
After producing a polyester film in the same manner as in Example 1, the film was heat relaxed in a suspended state at a relaxation rate of 0.8% and a temperature of 205 ° C. The thermal shrinkage in the longitudinal direction of the polyester film when treated at 200 ° C. for 10 minutes is 0.15%, the thermal shrinkage in the width direction is 0.02%, and the difference between the thermal shrinkage in the longitudinal direction and the width direction is 0. .13%.
更に、実施例１と同様に、ハードコート層、透明導電層の順に形成し、積層フィルムを得た。二酸化チタンペーストを塗布後の熱処理温度を２００℃にした他は実施例１と同様に多孔質半導体層を形成し、色素増感型太陽電池の電極を作成した。密着性評価を行ったところ、剥離は全く見られず評価は○であった。 Further, similarly to Example 1, a hard coat layer and a transparent conductive layer were formed in this order to obtain a laminated film. A porous semiconductor layer was formed in the same manner as in Example 1 except that the heat treatment temperature after applying the titanium dioxide paste was 200 ° C., and an electrode of a dye-sensitized solar cell was prepared. When the adhesion evaluation was performed, no peeling was observed, and the evaluation was good.
この電極を用いて実施例１と同様に色素増感太陽電池を作成した。Ｉ−Ｖ測定（有効面積２５ｍｍ２）を行った結果、開放電圧、短絡電流密度、曲線因子はそれぞれ、０.７１Ｖ、７．４ｍＡ／ｃｍ２、０．７５であり、その結果、光発電効率は３.９％であった。 Using this electrode, a dye-sensitized solar cell was prepared in the same manner as in Example 1. As a result of performing the IV measurement (effective area 25 mm 2 ), the open circuit voltage, the short circuit current density, and the fill factor are 0.71 V, 7.4 mA / cm 2 , and 0.75, respectively. Was 3.9%.
[実施例５，６および比較例２，３]
実施例１において、プラズマ処理をかけるときに用いるガスの、窒素と酸素の割合を表２のように変え、積層フィルムを作成した。なお、比較例３においてはプラズマ処理を実施しなかった。
[Examples 5 and 6 and Comparative Examples 2 and 3]
In Example 1, the ratio of nitrogen and oxygen in the gas used when performing the plasma treatment was changed as shown in Table 2 to prepare a laminated film. In Comparative Example 3, no plasma treatment was performed.
更に、実施例１と同様に、電極および色素増感型太陽電池を作成して、多孔質半導体層の密着性、電池の光発電効率を評価した。結果を表２に示す。 Furthermore, as in Example 1, electrodes and dye-sensitized solar cells were prepared, and the adhesion of the porous semiconductor layer and the photovoltaic power generation efficiency of the cells were evaluated. The results are shown in Table 2.
本発明は色素増感型太陽電池用積層フィルム、それを用いた色素増感型太陽電池用電極として利用することができる。 The present invention can be used as a dye-sensitized solar cell laminated film and a dye-sensitized solar cell electrode using the same.
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Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
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| JP2004022840A JP4456883B2 (en) | 2004-01-30 | 2004-01-30 | Dye-sensitized solar cell laminate film and dye-sensitized solar cell electrode using the same |
| CNB2005800037096A CN100524939C (en) | 2004-01-30 | 2005-01-28 | Laminated film for dye-sensitized solar cell, electrode for dye-sensitized solar cell and process for producing the same |
| US10/587,163 US8039735B2 (en) | 2004-01-30 | 2005-01-28 | Laminated film for dye-sensitized solar cell and electrode for dye-sensitized solar cell, and process for their production |
| PCT/JP2005/001641 WO2005074068A1 (en) | 2004-01-30 | 2005-01-28 | Laminated film for dye-sensitized solar cell, electrode for dye-sensitized solar cell and process for producing the same |
| KR1020067017465A KR101105183B1 (en) | 2004-01-30 | 2005-01-28 | Laminated film for dye-sensitized solar cell, electrode for dye-sensitized solar cell and process for producing the same |
| EP05704401A EP1717897B1 (en) | 2004-01-30 | 2005-01-28 | Laminated film for dye-sensitized solar cell and electrode for dye-sensitized solar cell |
| AU2005208615A AU2005208615B2 (en) | 2004-01-30 | 2005-01-28 | Laminated film for dye-sensitized solar cell, electrode for dye-sensitized solar cell and process for producing the same |
| TW094102765A TW200531330A (en) | 2004-01-30 | 2005-01-28 | Laminated film for dye-sensitized solar cell, electrode for dye-sensitized solar cell and process for producing the same |
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| JP2004022840A JP4456883B2 (en) | 2004-01-30 | 2004-01-30 | Dye-sensitized solar cell laminate film and dye-sensitized solar cell electrode using the same |
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| JP4456883B2 true JP4456883B2 (en) | 2010-04-28 |
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| JP2008039803A (en) * | 2006-08-01 | 2008-02-21 | Teijin Dupont Films Japan Ltd | Antireflection film |
| CN103833994B (en) * | 2012-11-22 | 2016-12-28 | 东丽纤维研究所（中国）有限公司 | A kind of alkali soluble copolymer polyester and its production and use |
| CN103903865A (en) * | 2012-12-27 | 2014-07-02 | 中国科学院上海硅酸盐研究所 | Dye-sensitized solar cell |
| CN104969305B (en) * | 2013-02-06 | 2017-03-22 | 三菱树脂株式会社 | Transparent stacked film, transparent conductive film, and gas barrier stacked film |
| JP6565683B2 (en) | 2014-11-28 | 2019-08-28 | 東レ株式会社 | Polyester film |
| JP7144318B2 (en) * | 2017-03-29 | 2022-09-29 | 積水化学工業株式会社 | Transparent conductive film for light control film and light control film |
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| JP2005216706A (en) | 2005-08-11 |
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